JP2010275446A - ETHYLENE-alpha-OLEFIN COPOLYMER FOR CALENDERING AND CALENDER MOLDED ARTICLE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene-α-olefin copolymer for calendering which is excellent in moldability, easy to release from a calendar roll when calendar-rolling, and which gives a molded article having excellent impact strength and anti-blocking property. <P>SOLUTION: The ethylene-α-olefin copolymer for calendering includes an ethylene-based monomer unit and a 3-20C α-olefin-based monomer unit, wherein a density (d) is 860-950 kg/m<SP>3</SP>, a melt flow rate (MFR) is 0.01-5 (g/10 minutes), a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4-30, a ratio (Mz/Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 2-5, and g* obtained by formula (I): g*=[η]/([η]<SB>GPC</SB>×g<SB>SCB</SB>*) is 0.79-0.95. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ethylene-α-olefin copolymer for calender molding and a calender molded product obtained by using the copolymer.

  Various sheets and tarpaulins have been produced by calendering ethylene-α-olefin copolymers.

  For example, Patent Document 1 describes a calender molded body obtained by calendering an ethylene-α-olefin copolymer produced using a vanadium-based catalyst. Patent Document 2 discloses a promoter component obtained by contacting silica, hexamethyldisilazane, diethyl zinc, pentafluorophenol and water, triisobutylaluminum, and racemic-ethylenebis (1-indenyl) zirconium diphenoxide. And calendering a composition containing an ethylene-α-olefin copolymer polymerized using a metallocene catalyst comprising:

JP 2001-114838 A JP 2007-51283 A

However, the calendar molded body made of the ethylene-α-olefin copolymer described in Patent Document 1 has been required to be further improved in terms of impact resistance and anti-blocking property. In addition, the composition described in Patent Document 2 may be difficult to peel off the molded body from the calendar roll when producing a wide molded body by calendering.
Under such circumstances, the problem to be solved by the present invention is an ethylene-α-olefin copolymer that is easily peeled from a calender roll during calender molding and has excellent moldability, and has impact strength and resistance. An object of the present invention is to provide an ethylene-α-olefin copolymer for calender molding from which a molded product having excellent blocking properties can be obtained, and a calender molded product using the copolymer.

That is, the first of the present invention has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, the density (d) is 860 to 950 kg / m ³ , The flow rate (MFR) is 0.01 to 5 (g / 10 min), the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4 to 30, and the Z average The ratio (Mz / Mw) between the molecular weight (Mz) and the weight average molecular weight (Mw) is 2 to 5, and g * obtained by the following formula (I) is 0.79 to 0.95. It is an ethylene-α-olefin copolymer.
g * = [η] / ([η] _GPC × g _SCB *) (I)
[In the formula, [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is defined by the following formula (I-I), and [η] _GPC is represented by the following formula ( G _SCB * is defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (I-III)
(In the formula, A can be obtained from the measurement of the content of short chain branches in the ethylene-α-olefin copolymer.)]

  The second of the present invention is a calendered molding obtained by using the ethylene-α-olefin copolymer.

  According to the present invention, a calendar molding is obtained which is an ethylene-α-olefin copolymer which is easily peeled off from a calender roll during calender molding and has excellent moldability, and which has excellent impact strength and anti-blocking properties. An ethylene-α-olefin copolymer for use, and a calender molded body using the copolymer can be provided.

  The ethylene-α-olefin copolymer of the present invention is an ethylene-α-olefin copolymer containing a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4 -Methyl- 1-hexene etc. are mention | raise | lifted and these may be used independently and 2 or more types may be used together. The α-olefin is preferably 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.

  The ethylene-α-olefin copolymer of the present invention, in addition to the above-described monomer units based on ethylene and monomer units based on α-olefins having 3 to 20 carbon atoms, does not impair the effects of the present invention. And may have a monomer unit based on another monomer. Examples of other monomers include conjugated dienes (for example, butadiene and isoprene), non-conjugated dienes (for example, 1,4-pentadiene), acrylic acid, acrylic acid esters (for example, methyl acrylate and ethyl acrylate), and methacrylic acid. Methacrylic acid esters (for example, methyl methacrylate and ethyl methacrylate), vinyl acetate and the like.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of the present invention is usually from 50 to 99.75 based on the total weight (100% by weight) of the ethylene-α-olefin copolymer. 5% by weight. The content of the monomer unit based on the α-olefin is usually 0.5 to 50% by weight with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer.

  The ethylene-α-olefin copolymer of the present invention is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms, more preferably. , A copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 5 to 20 carbon atoms, more preferably a monomer unit based on ethylene and 6 to 8 carbon atoms. It is a copolymer having monomer units based on α-olefin.

  Examples of the ethylene-α-olefin copolymer of the present invention include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-4-methyl-1-pentene copolymer, and ethylene-1. -Octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-octene copolymer, ethylene -1-hexene-1-octene copolymer and the like, preferably ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-hexene copolymer A polymer, an ethylene-1-butene-1-octene copolymer, and an ethylene-1-hexene-1-octene copolymer.

The density of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “d”) is 860 to 950 kg / m ³ . From the viewpoint of increasing the impact strength of the obtained calendered article, it is preferably 940 kg / m ³ or less, more preferably 935 kg / m ³ or less, and still more preferably 930 kg / m ³ or less. Further, in view of enhancing the anti-blocking property of the resulting molded article, preferably 870 kg / m ³ or more, more preferably 880 kg / m ³ or more, more preferably 890 kg / m ³ or more, particularly preferably 900 kg / m ³ or more. The density is measured according to the method defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. Moreover, the density of an ethylene-alpha-olefin copolymer can be changed with content of the monomer unit based on ethylene in an ethylene-alpha-olefin copolymer.

  The blocking of the molded body is a phenomenon in which the molded bodies adhere to each other over time in a state where the molded bodies are in direct contact with each other, such as being stacked in a sheet form or wound in a roll form. If the molded body is blocked, it may not be used as a molded body. In general, when the amount of components typified by cold xylene is reduced, the property of preventing blocking, that is, the anti-blocking property is improved. The amount of cold xylene solubles increases as the amount of low crystallinity components increases or the amount of low molecular weight components increases. The amount of the low crystallinity component in the ethylene-α-olefin copolymer depends on the copolymerization properties of ethylene and α-olefin determined by the catalyst component at the time of producing the copolymer.

  The melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene-α-olefin copolymer of the present invention is usually 0.01 to 5 (g / 10 minutes). The melt flow rate is preferably 0.05 g / 10 min or more, more preferably 0.1 g / 10 min or more, from the viewpoint of reducing the kneading load during molding. The melt flow rate is preferably 2 g / 10 minutes or less, more preferably 1 g / 10 minutes or less, from the viewpoint of improving antiblocking properties. The melt flow rate is a value measured by Method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. Further, the melt flow rate of the ethylene-α-olefin copolymer can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later. When the hydrogen concentration or the polymerization temperature is increased, the ethylene-α-olefin copolymer is changed. The melt flow rate of the copolymer is increased.

  The ratio of the weight average molecular weight (hereinafter sometimes referred to as “Mw”) and the number average molecular weight (hereinafter sometimes referred to as “Mn”) of the ethylene-α-olefin copolymer of the present invention. (Hereinafter, sometimes referred to as “Mw / Mn”) is 4 to 30, and is the Z average molecular weight (hereinafter sometimes referred to as “Mz”) and the weight average molecular weight (Mw). The ratio (hereinafter sometimes referred to as “Mz / Mw”) is 2-5. When Mw / Mn is too small, the kneading load at the time of calendar molding becomes high, and the peelability from the calendar roll may be deteriorated. Mw / Mn is preferably 4.5 or more, more preferably 5.5 or more, and further preferably 6 or more. If Mz / Mw is too large, a phenomenon may occur in which the molded body is torn off during calendar molding. Mz / Mw is preferably 4.5 or less. If Mw / Mn is too large or Mz / Mw is too small, the impact strength of the resulting molded product may be low. On the other hand, if Mw / Mn is too large, the anti-blocking property may be lowered. Mw / Mn is preferably 25 or less, more preferably 20 or less, still more preferably 18 or less, and particularly preferably 15 or less. Mz / Mw is preferably 2.5 or more. In addition, this Mw / Mn and this Mz / Mw measure the number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) by gel permeation chromatograph (GPC) method. And Mw is divided by Mn, and Mz is divided by Mw. The Mw / Mn can be changed by, for example, the hydrogen concentration or the polymerization temperature in the production method described later. When the hydrogen concentration or the polymerization temperature is increased, the Mw / Mn of the ethylene-α-olefin copolymer is increased. growing. The Mz / Mw can be changed by, for example, the use ratio of the transition metal compound (A1) and the transition metal compound (A2) in the production method described later, and the use ratio of the transition metal compound (A2) is lowered. This reduces the Mz / Mw of the ethylene-α-olefin copolymer.

  Mz / Mw represents the molecular weight distribution of the high molecular weight component. A smaller Mz / Mw compared to Mw / Mn means that the molecular weight distribution of the high molecular weight component is narrow and the proportion of the component having a very high molecular weight is small. It means that Mz / Mw is larger than Mw / Mn, which means that the molecular weight distribution of the high molecular weight component is wide and the component ratio of very high molecular weight is high. From the viewpoint of reducing the kneading load during calendar molding, preferably (Mw / Mn)-(Mz / Mw) is 1 or more, more preferably (Mw / Mn)-(Mz / Mw) is 2 or more. . (Mw / Mn)-(Mz / Mw) can be changed, for example, depending on the use ratio of the transition metal compound (A1) and the transition metal compound (A2), and the use ratio of the transition metal compound (A2) is increased. Then, (Mw / Mn)-(Mz / Mw) of the ethylene-α-olefin copolymer increases. Also, (Mw / Mn)-(Mz / Mw) can be increased by carrying out prepolymerization under appropriate conditions.

In the ethylene-α-olefin copolymer of the present invention, g * defined by the following formula (III) is 0.79 to 0.95 (for g *, the following document was referred to: Developments in Polymer) Characterization-4, JV Dawkins, Ed., Applied Science, London, 1983, Chapter I, “Characterization. Of Long Chain Branching in Polymers,” by Th. G. Scholte).
g * = [η] / ([η] _GPC × g _SCB *) (III)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer and is defined by the following formula (III-I). It was defined by the following formula (III-II). g _SCB * is defined by the following formula (III-III).
[Η] = 23.3 × log (ηrel) (III-I)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (III-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (III-III)
(In the formula, A can be determined directly from the measurement of the content of short chain branches in the ethylene-α-olefin copolymer.)]

[Η] _GPC is the intrinsic viscosity (unit: dl / g) of a polymer that is assumed to have the same molecular weight distribution as that of the ethylene-α-olefin copolymer and that the molecular chain is linear. Represents.
g _SCB * represents the contribution to g * produced by introducing short chain branching into the ethylene-α-olefin copolymer.
As the formula (III-II), the formula described in Journal of Polymer Science, 36, 130 (1959) pp. 287-294 by LH Tung was used.

  The relative viscosity (ηrel) of the ethylene-α-olefin copolymer is a sample prepared by dissolving 100 mg of an olefin polymer at 135 ° C. in 100 ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor. A solution is prepared, and is calculated from the falling time of the sample solution and a blank solution made of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor using an Ubbelohde viscometer.

で定義され、a＝０．７２５とした。 The viscosity average molecular weight (Mv) of the ethylene-α-olefin copolymer is represented by the following formula (III-IV)

And a = 0.725.

For A in formula (III-III), the number of short-chain branched carbons is n (for example, n = 2 when butene is used as the α-olefin, n = 4 when hexene is used), and NMR Or when the number of short chain branches per 1000 carbon atoms determined by infrared spectroscopy is y,
A = ((12 × n + 2n + 1) × y) / ((1000−2y−2) × 14 + (y + 2) × 15 + y × 13)
As estimated.

  g * is an index representing the degree of contraction of a molecule in a solution caused by long chain branching. When the amount of long chain branching per molecular chain is large, the contraction of the molecular chain increases. Get smaller. From the viewpoint of reducing the kneading load, g * of the ethylene-α-olefin copolymer is preferably 0.90 or less, more preferably 0.85 or less. When g * is large, long chain branching is not sufficiently contained, and thus the kneading load cannot be sufficiently reduced. Further, g * of the ethylene-α-olefin copolymer is preferably 0.80 or more, and more preferably 0.81 or more, from the viewpoint of improving the impact strength of the molded product. If g * is too small, the molecular chain spread when the crystal is formed is too small, so the probability of tie molecule formation decreases and the impact strength decreases. g * can be lowered, for example, by carrying out prepolymerization under suitable conditions.

  The activation energy of the flow of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “Ea”) reduces the kneading load at the time of calendering and improves the peelability from the calender roll. From the viewpoint of improvement, it is preferably 60 kJ / mol or more, more preferably 70 kJ / mol or more. Further, the activation energy of the flow is preferably 150 kJ / mol or less, more preferably 130 kJ / mol or less, and further preferably 110 kJ / mol or less in order to make the molded body difficult to tear at the time of calender molding. . In addition, the flow activation energy can be changed by, for example, the use ratio of the transition metal compound (A1) and the transition metal compound (A2) in the production method described later, and the use ratio of the transition metal compound (A2). When E is increased, Ea of the ethylene-α-olefin copolymer is increased.

The activation energy (Ea) of the flow is dependent on the angular frequency (unit: rad / sec) dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. based on the temperature-time superposition principle. It is a numerical value calculated by the Arrhenius type equation from the shift factor (a _T ) when creating the master curve shown, and is a value obtained by the method shown below. That is, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (the unit of melt complex viscosity is Pa · sec. The unit of the angular frequency is rad / sec.), Based on the temperature-time superposition principle, for each melt complex viscosity-angular frequency curve at each temperature (T), The shift factor (a _T ) at each temperature (T) obtained when superposed on the melt complex viscosity-angular frequency curve of the coalescence is obtained, and each temperature (T) and the shift factor at each temperature ( _T ) are obtained. From (a _T ), a first-order approximate expression (formula (I) below) of [ln (a _T )] and [1 / (T + 273.16)] is calculated by the method of least squares. Next, Ea is obtained from the slope m of the linear expression and the following expression (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. Moreover, the correlation coefficient when calculating | requiring (I) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

  The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1. It is performed under the conditions of 5 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.

  The melt flow rate ratio of the ethylene-α-olefin copolymer of the present invention (hereinafter sometimes referred to as “MFRR”) is preferably 70 or more from the viewpoint of further reducing the kneading load during the molding process. Yes, more preferably 80 or more, still more preferably 90 or more. Moreover, from a viewpoint which raises the impact strength of the molded object obtained more, Preferably it is 200 or less, More preferably, it is 180 or less. The MFRR is a melt flow rate (hereinafter sometimes referred to as “H-MFR”) measured under conditions of a load of 211.82 N and a temperature of 190 ° C. in the method defined in JIS K7210-1995. In the method defined in JIS K7210-1995, it is a value divided by the melt flow rate (MFR) measured under conditions of a load of 21.18 N and a temperature of 190 ° C. In addition, MFRR can be changed by, for example, the hydrogen concentration in the production method described later. When the hydrogen concentration is increased, the MFRR of the ethylene-α-olefin copolymer is decreased.

  The ethylene-α-olefin copolymer of the present invention has a single melting peak existing in the range from 25 ° C. to the end of melting temperature in the melting curve obtained from differential scanning calorimetry of the ethylene-α-olefin copolymer. It is preferable that it is a copolymer which is. The presence of a plurality of melting peaks means that there is a melting peak different from the maximum melting peak (melting peak having the highest peak height) in the melting curve of the ethylene-α-olefin copolymer, This means that the composition distribution of the ethylene-α-olefin copolymer (distribution of the content ratio of monomer units among the polymer components contained in the ethylene-α-olefin copolymer) is wide, and the crystal Contains ingredients with low properties. Ingredients having low crystallinity tend to volatilize during molding, and it is difficult to obtain a molded article having excellent cleanliness. Since the preferable ethylene-α-olefin copolymer of the present invention has a single melting peak, that is, a narrow composition distribution, it is possible to obtain a molded article having excellent cleanliness.

  In addition, the melting curve of the ethylene-α-olefin copolymer is measured by using a differential scanning calorimeter (for example, a differential scanning calorimeter DSC-7 manufactured by Perkin Elmer), for example, an aluminum pan in which about 10 mg of a sample is sealed. (1) held at 150 ° C. for 5 minutes, (2) lowered from 150 ° C. to 20 ° C. at 5 ° C./minute, (3) held at 20 ° C. for 2 minutes, and (4) 20 at 5 ° C./minute. It is obtained from the differential scanning calorimetry curve obtained in (4) by raising the temperature from 0 ° C. to the melting end temperature + about 20 ° C. (usually about 150 ° C.).

  As a manufacturing method of the ethylene-alpha-olefin copolymer of this invention, the transition metal compound (A1) represented by the following general formula (1) and the transition metal compound (A2) represented by the following general formula (3) ) And a cocatalyst component (B) to be described later, and a molar ratio of the transition metal compound (A1) to the transition metal compound (A2) ((A1) / (A2) )) At 0.5 to 50 in the presence of a polymerization catalyst to be contacted, the melt flow rate (MFR) of the copolymer is 0.01 (g / 10 min) or more to less than 1 (g / 10 min) The method of copolymerizing ethylene and a C3-C20 alpha olefin can be mentioned so that it may become. (A1) / (A2) is preferably 1 or more from the viewpoint of reducing the kneading load of the ethylene-α-olefin copolymer in the molten state and increasing the mechanical strength. Further, (A1) / (A2) is preferably 30 or less, more preferably 20 or less, from the viewpoint of enhancing the peelability from the calender roll during calendar molding.

［式中、Ｍ¹は元素周期律表の第４族の遷移金属原子を表し、Ｘ¹およびＲ¹は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＸ¹は互いに同じであっても異なっていてもよく、複数のＲ¹は互いに同じであっても異なっていてもよく、Ｑ¹は下記一般式（２）で表される架橋基を表す。

（式中、ｍは１〜５の整数であり、Ｊ¹は元素周期律表の第１４族の原子を表し、Ｒ²は、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＲ²は互いに同じであっても異なっていてもよい。）］

[Wherein, M ¹ represents a group 4 transition metal atom in the periodic table of the elements, and X ¹ and R ¹ are each independently a hydrogen atom, a halogen atom, or a C 1-20 substituted group. A good hydrocarbyl group, an optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of X ¹ May be the same as or different from each other, the plurality of R ¹ may be the same or different from each other, and Q ¹ represents a bridging group represented by the following general formula (2).

(In the formula, m is an integer of 1 to 5, J ¹ represents an atom belonging to Group 14 of the periodic table, and R ² is a hydrogen atom, a halogen atom, or a C 1-20 substituted atom. A hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group optionally having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of R ² may be the same or different from each other.)]

［式中、Ｍ²は元素周期律表の第４族の遷移金属原子を表し、Ｘ²、Ｒ³およびＲ⁴は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＸ²は互いに同じであっても異なっていてもよく、複数のＲ³は互いに同じであっても異なっていてもよく、複数のＲ⁴は互いに同じであっても異なっていてもよく、Ｑ²は、下記一般式（４）で表される架橋基を表す。

（式中、ｎは１〜５の整数であり、Ｊ²は元素周期律表の第１４族の原子を表し、Ｒ⁵は、水素原子、ハロゲン原子、炭素数１〜２０の置換されていてもよいハイドロカルビル基、炭素数１〜２０の置換されていてもよいハイドロカルビルオキシ基、炭素数１〜２０の置換シリル基または炭素数１〜２０の置換アミノ基であり、複数のＲ⁵は互いに同じであっても異なっていてもよい。）］

[Wherein, M ² represents a transition metal atom of Group 4 of the periodic table, and X ² , R ^3, and R ⁴ are each independently a hydrogen atom, a halogen atom, or a C 1-20 substituted group. A hydrocarbyl group optionally having 1 to 20 carbon atoms, a hydrocarbyloxy group optionally having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms. X ² may be the same or different from each other, the plurality of R ³ may be the same or different from each other, and the plurality of R ⁴ may be the same or different from each other. Q ² represents a crosslinking group represented by the following general formula (4).

(In the formula, n is an integer of 1 to 5, J ² represents an atom belonging to Group 14 of the periodic table, and R ⁵ is a hydrogen atom, a halogen atom, or a C 1-20 substituted atom. A hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group optionally having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of R ⁵ may be the same or different from each other.)]

M ^{1 in the} general formula (1) and M ^{2 in the} general formula (3) represent a transition metal atom of Group 4 of the periodic table of elements, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom.

X ¹ , R ^{1 in} the general formula ( ¹ ) and X ² , R ³ , R ^{4 in} the general formula (3) may each independently be a hydrogen atom, a halogen atom, or a C 1-20 substituent. A hydrocarbyl group, an optionally substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of X ¹ are The plurality of R ¹ may be the same or different from each other, the plurality of X ² may be the same or different from each other, and the plurality of R ³ May be the same or different from each other, and the plurality of R ⁴ may be the same or different from each other.

Examples of the halogen atom for X ¹ , R ¹ , X ² , R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the optionally substituted hydrocarbyl group having 1 to 20 carbon atoms of X ¹ , R ¹ , X ² , R ³ and R ⁴ include an alkyl group having 1 to 20 carbon atoms and a halogen having 1 to 20 carbon atoms. An alkyl group, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-dodecyl 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 and the like can be mentioned.

  Examples of the halogenated alkyl group having 1 to 20 carbon atoms include fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, and tribromomethyl. Group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group , Pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group Group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, Perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopenta group Examples include decyl group and perbromoeicosyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethylphenyl). ) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4 , 6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3 , 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4, -Tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropyl) (Phenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthra Cenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenyl Methyl, diphenylethyl group, diphenylpropyl group, diphenylbutyl group. Moreover, the halogenated aralkyl group etc. which these aralkyl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. Group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethyl Phenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2 , 3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, se -Butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl Examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Moreover, the halogenated aryl group etc. which these aryl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  The hydrocarbyl group having 1 to 20 carbon atoms which may be substituted includes a hydrocarbyl group substituted with a substituted silyl group, a hydrocarbyl group substituted with a substituted amino group, and a hydrocarbyloxy group. And hydrocarbyl groups substituted with.

  Hydrocarbyl groups substituted with substituted silyl groups include trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylpropyl, trimethylsilylbutyl, trimethylsilylphenyl, bis (trimethylsilyl) methyl, bis (trimethylsilyl) ethyl, bis ( Examples thereof include trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis (trimethylsilyl) phenyl group, and triphenylsilylmethyl group.

  Hydrocarbyl groups substituted with substituted amino groups include dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group, bis (dimethyl Amino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group, diphenylaminophenyl group and the like.

  Examples of the hydrocarbyl group substituted with a hydrocarbyloxy group include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxy group. Methyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl group, phenoxyethyl group, methoxy- n-propyl group, ethoxy-n-propyl group, n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propyl group, sec-butoxy-n-propyl group, tert-butoxy -N-propyl group, phenoxy-n-propyl group Methoxyisopropyl group, ethoxyisopropyl group, n-propoxyisopropyl group, isopropoxyisopropyl group, n-butoxyisopropyl group, sec-butoxyisopropyl group, tert-butoxyisopropyl group, phenoxyisopropyl group, methoxyphenyl group, ethoxyphenyl group, n -Propoxyphenyl group, isopropoxyphenyl group, n-butoxyphenyl group, sec-butoxyphenyl group, tert-butoxyphenyl group, phenoxyphenyl group and the like.

Examples of the optionally substituted hydrocarbyloxy group of X ¹ , R ¹ , X ² , R ³ and R ⁴ having 1 to 20 carbon atoms include an alkoxy group having 1 to 20 carbon atoms and a carbon number of 7 to 20 carbon atoms. Examples thereof include an aralkyloxy group and an aryloxy group having 6 to 20 carbon atoms.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neo Pentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyl group Examples include oxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosoxy group and the like. . Further, halogenated alkoxy groups in which these alkoxy groups are substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom can be mentioned.

  Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Enyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy Group, anthracenylmethoxy group and the like. In addition, a halogenated aralkyloxy group in which these aralkyloxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethyl Phenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5 -Tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethyl Ruphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n- Examples include decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. Moreover, the halogenated aryloxy group etc. which these aryloxy groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

Examples of the substituted silyl group having 1 to 20 carbon atoms of X ¹ , R ¹ , X ² , R ³ and R ⁴ include silyl groups substituted with hydrocarbyl groups such as alkyl groups and aryl groups. Specifically, for example, methylsilyl group, ethylsilyl group, n-propylsilyl group, isopropylsilyl group, n-butylsilyl group, sec-butylsilyl group, tert-butylsilyl group, isobutylsilyl group, n-pentylsilyl group, n- 1-substituted silyl groups such as hexylsilyl group and phenylsilyl group; dimethylsilyl group, diethylsilyl group, di-n-propylsilyl group, diisopropylsilyl group, di-n-butylsilyl group, di-sec-butylsilyl group, di- disubstituted silyl groups such as tert-butylsilyl group, diisobutylsilyl group, diphenylsilyl group; trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec- Butylsilyl group, tri-tert-butyl Examples include tri-substituted silyl groups such as rusilyl group, triisobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group. It is done.

Examples of the substituted amino group having 1 to 20 carbon atoms of X ¹ , R ¹ , X ² , R ³ and R ⁴ include an amino group substituted with two hydrocarbyl groups such as an alkyl group and an aryl group. I can. Specifically, for example, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group, isobutylamino group, n-hexyl Amino group, n-octylamino group, n-decylamino group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di -Sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group , Diphenylamino group, dibenzylamino group, tert-butylisopropylamino , Phenylethyl group, phenylpropyl group, phenylbutyl group, a pyrrolyl group, a pyrrolidinyl group, a piperidinyl group, a carbazolyl group, such as dihydroisoindolyl group.

X ¹ is preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group and a benzyl group.

R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom.

X ² is preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group and a benzyl group.

R ³ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.

R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom.

Q ¹ in the general formula (1) represents a crosslinking group represented by the general formula ( ² ), and Q ² in the general formula (3) represents a crosslinking group represented by the general formula (4).

  M in the general formula (2) and n in the general formula (4) are integers of 1 to 5. m is preferably 1-2, and n is preferably 1-2.

J ² of J ¹ and of the general formula (2) (4) represents a Group 14 transition metal atom of the periodic table of elements, carbon atoms, a silicon atom, such as a germanium atom. Preferably, they are a carbon atom or a silicon atom.

R ^{2 in} the general formula (2) and R ^{5 in the} general formula (4) are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, or 1 to carbon atoms. A 20-substituted hydrocarbyloxy group, a substituted silyl group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms, and a plurality of R ² may be the same or different from each other; The plurality of R ⁵ may be the same as or different from each other.

R ² and R ⁵ halogen atom, C 1-20 optionally substituted hydrocarbyl group, C 1-20 optionally substituted hydrocarbyloxy group, C 1-20 carbon atom Examples of the substituted silyl group and the substituted amino group having 1 to 20 carbon atoms include a halogen atom of X ¹ , R ¹ , X ² , R ³ and R ⁴ , and an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms. And those exemplified as the hydrocarbyloxy group having 1 to 20 carbon atoms which may be substituted, the substituted silyl group having 1 to 20 carbon atoms and the substituted amino group having 1 to 20 carbon atoms.

Q ¹ and Q ² are methylene group, ethylidene group, ethylene group, propylidene group, propylene group, butylidene group, butylene group, pentylidene group, pentylene group, hexylidene group, isopropylidene group, methylethylmethylene group, methylpropylmethylene group. Group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) methylene group, bis (trimethyl) Phenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) methylene group, bis (Dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group, di (biphenyl) methylene Group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group,

Silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group, bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutane Examples thereof include a diyl group, a silacyclohexanediyl group, a divinylsilanediyl group, a diallylsilanediyl group, a (methyl) (vinyl) silanediyl group, and an (allyl) (methyl) silanediyl group.

Q ¹ is preferably a methylene group, an ethylene group, an isopropylidene group, a bis (cyclohexyl) methylene group, a diphenylmethylene group, a dimethylsilanediyl group, or a bis (dimethylsilane) diyl group, and more preferably an ethylene group or a dimethyl group. Silane diyl group. Q ² is preferably a methylene group, ethylene group, isopropylidene group, bis (cyclohexyl) methylene group, diphenylmethylene group, dimethylsilanediyl group, or bis (dimethylsilane) diyl group, and more preferably diphenylmethylene. It is a group.

As the transition metal compound (A1) represented by the general formula (1), m ¹ is a zirconium atom, X ¹ is a chlorine atom, methylene bis (indenyl) zirconium dichloride, isopropylidenebis (indenyl) zirconium dichloride, (Methyl) (phenyl) methylenebis (indenyl) zirconium dichloride, diphenylmethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride,

Methylenebis (methylindenyl) zirconium dichloride, isopropylidenebis (methylindenyl) zirconium dichloride, (methyl) (phenyl) methylenebis (methylindenyl) zirconium dichloride, diphenylmethylenebis (methylindenyl) zirconium dichloride, ethylenebis (methyl Indenyl) zirconium dichloride,

Methylene (indenyl) (methylindenyl) zirconium dichloride, isopropylidene (indenyl) (methylindenyl) zirconium dichloride, (methyl) (phenyl) methylene (indenyl) (methylindenyl) zirconium dichloride, diphenylmethylene (indenyl) (methyl) Indenyl) zirconium dichloride, ethylene (indenyl) (methylindenyl) zirconium dichloride,

Methylenebis (2,4-dimethylindenyl) zirconium dichloride, isopropylidenebis (2,4-dimethylindenyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylindenyl) zirconium dichloride, diphenylmethylenebis (2,4-dimethylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl) zirconium dichloride,

Dimethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (indenyl) zirconium dichloride, di (n-propyl) silanediylbis (indenyl) zirconium dichloride, diisopropylsilanediylbis (indenyl) zirconium dichloride, dicyclohexylsilanediylbis (indenyl) Zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, di (p-tolyl) silanediylbis (indenyl) zirconium dichloride, divinylsilanediylbis (indenyl) zirconium dichloride, diallylsilanediylbis (indenyl) zirconium dichloride, (methyl) ( Vinyl) silanediylbis (indenyl) zirconium dichloride, Allyl) (methyl) silanediylbis (indenyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (indenyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (indenyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (indenyl) Zirconium dichloride, (cyclohexyl) (methyl) bis (indenyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (indenyl) zirconium dichloride,

Dimethylsilanediylbis (methylindenyl) zirconium dichloride, diethylsilanediylbis (methylindenyl) zirconium dichloride, di (n-propyl) silanediylbis (methylindenyl) zirconium dichloride, diisopropylsilanediylbis (methylindenyl) zirconium dichloride , Dicyclohexylsilanediylbis (methylindenyl) zirconium dichloride, diphenylsilanediylbis (methylindenyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (methylindenyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis ( Methylindenyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (methylindenyl) zyl Niumujikurorido, (cyclohexyl) (methyl) bis (methylindenyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (methylindenyl) zirconium dichloride,

Dimethylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, diethylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, di (n-propyl) silanediyl (indenyl) (methylindenyl) zirconium dichloride, diisopropylsilanediyl ( Indenyl) (methylindenyl) zirconium dichloride, dicyclohexylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, diphenylsilanediyl (indenyl) (methylindenyl) zirconium dichloride, (ethyl) (methyl) silanediyl (indenyl) (methyl) Indenyl) zirconium dichloride, (methyl) (n-propyl) silanediyl (indenyl) (methylindenyl) zirconium Dichloride, (methyl) (isopropyl) silanediyl (indenyl) (methylindenyl) zirconium dichloride, (cyclohexyl) (methyl) (indenyl) (methylindenyl) zirconium dichloride, (methyl) (phenyl) silanediyl (indenyl) (methylindene) Nil) zirconium dichloride,

Dimethylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, di (n-propyl) silanediylbis (2,4-dimethylindenyl) zirconium dichloride Diisopropylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, dicyclohexylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride, ( Ethyl) (methyl) silanediylbis (2,4-dimethylindenyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,4-dimethylindenyl) zirconium Dichloride, (methyl) (isopropyl) silanediylbis (2,4-dimethylindenyl) zirconium dichloride, (cyclohexyl) (methyl) bis (2,4-dimethylindenyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (2, 4-dimethylindenyl) zirconium dichloride and the like can be exemplified.

In the above exemplification, when the bridging group is in the 1-position, the η ⁵ -indenyl group is substituted in the 2-position, 3-position, 4-position, 5-position, 6-position and 7 Including all substitutions in the -position, including bridged positions other than the 1-position. Bi- or higher substituents similarly include all combinations of substituents and crosslinks. Further, X ¹ dichloride of the above transition metal compound is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, dipropoxide, dibutoxide, bis (trifluoromethoxide), diphenyl, diphenoxide, bis (2, 6-di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide) Examples thereof include compounds changed to dibenzyl and the like. Furthermore, the zirconium M ¹ of the transition metal compound may be exemplified compound was changed to titanium or hafnium.

  The transition metal compound (A1) represented by the general formula (1) is preferably ethylene bis (indenyl) zirconium diphenoxide, ethylene bis (indenyl) zirconium dichloride, or dimethylsilylene bis (indenyl) zirconium dichloride.

As the transition metal compound (A2) represented by the general formula (3), M ² is a zirconium atom, X ² is a chlorine atom, and the bridging group Q ² is a diphenylmethylene group. Pentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2, , 5-Trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetramethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2, , 5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tri-n-propyl-1-cyclo) Pentadienyl) (9-fluorenyl) zyl Nium dichloride, diphenylmethylene (2,3,5-tri-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium Chloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmeth Len (2,3,5-triphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclo Ntadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris ( Trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Trimethyl-1- Clopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclo) Pentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Triethyl-1- Clopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopenta Dienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7 -Dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Di-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (2 , 7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmeth Len (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tri-n-propyl- 1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1-cyclopentadienyl) (2,7-dimethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) ( 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-trif Nyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5- Tetraphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9- Fluorenyl) Jill Nium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) ) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Trimethyl-1- Clopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclo) Pentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-Triethyl-1- Clopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopenta Dienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7 -Diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Di-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-di-n-propyl-1-cyclopentadienyl) (2 , 7-diethyl-9-fluorenyl) zirconium dichloride, diphenylme Len (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tri-n-propyl- 1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1-cyclopentadienyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) ( 2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadi) Enyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 3,4-trif Nyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5- Tetraphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-diethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9- Fluorenyl) Jill Nium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) ) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene 2,3,4-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2,5-di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4 -Di-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirco Um dichloride, diphenylmethylene (2,3,4-tri-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4) 5-tri-n-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tri-n-propyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetra-n-propyl-1-cyclopentadienyl) (2, 7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1-cyclopentadienyl) (2 , 7-Di-t-butyl-9-fluorenyl) zirconium Chloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triisopropyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride,

Diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, dipheny Methylene (2,3,4-triphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-di-t -Butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,

Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7 -Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl)- 1-cyclopentadienyl) (2,7-di-t- Til-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) ( 2,7-di-t-butyl-9-fluorenyl) zirconium dic It can be exemplified Lido like.

X ² dichloride of the above transition metal compound is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, dimethoxide, diethoxide, dipropoxide, dibutoxide, bis (trifluoromethoxide), diphenyl, diphenoxide, bis (2,6 -Di-tert-butylphenoxide), bis (3,4,5-trifluorophenoxide), bis (pentafluorophenoxide), bis (2,3,5,6-tetrafluoro-4-pentafluorophenylphenoxide), Examples include compounds changed to dibenzyl and the like. Further, the diphenylmethylene group of Q ² of the transition metal compound is a methylene group, ethylene group, isopropylidene group, methylphenylmethylene group, dimethylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, etc. Examples of the compound can be exemplified. Furthermore, the zirconium M ² of the transition metal compound may be exemplified compound was changed to titanium or hafnium.

  The transition metal compound (A2) represented by the general formula (3) is preferably diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride.

The promoter component (B) used for the preparation of the polymerization catalyst used in the production of the ethylene-α-olefin copolymer of the present invention includes the following component (b1), the following component (b2), and the following component (b3). And a solid catalyst component formed by contacting the following component (b4).
(B1): Compound represented by the following general formula (5)
M ³ L _x (5)
[Wherein M ³ is lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom, lead atom, antimony Represents an atom or a bismuth atom, and x represents a number corresponding to the valence of M ³ . L represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbyl group, and when a plurality of L are present, they may be the same as or different from each other. ]
(B2): Compound represented by the following general formula (6)
R ⁶ _t-1 T ¹ H (6)
[Wherein T ¹ represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and t represents a number corresponding to the valence of T ¹ . R ⁶ represents a halogen atom, an electron-withdrawing group, a group containing a halogen atom or a group having an electron-withdrawing group, and when a plurality of R ⁶ are present, they may be the same or different from each other. ]
(B3): Compound represented by the following general formula (7)
R ⁷ _s-2 T ² H ₂ (7)
[Wherein T ² represents an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and s represents a number corresponding to the valence of T ² . R ⁷ represents a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group. ]
(B4): particulate carrier

M ^{3 in the} general formula (5) is lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom, lead An atom, an antimony atom or a bismuth atom. Preferred is a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, more preferred is a magnesium atom, zinc atom, tin atom or bismuth atom, still more preferred. It is a zinc atom.

X in the general formula (5) represents a number corresponding to the valence of M ³ . For example, when M ³ is a zinc atom, x is 2.

  L in the general formula (5) represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbyl group, and when a plurality of L are present, they may be the same or different from each other.

  Examples of the halogen atom for L include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the optionally substituted hydrocarbyl group for L include an alkyl group, an aralkyl group, an aryl group, and a halogenated alkyl group.

  As the alkyl group for L, an alkyl group having 1 to 20 carbon atoms is preferable. Group, n-pentyl group, neopentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-nonyl group, n-decyl group, n-dodecyl group, n -Dodecyl 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 and the like. Preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group.

  As the halogenated alkyl group of L, a halogenated alkyl group having 1 to 20 carbon atoms is preferable, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a bromomethyl. Group, dibromomethyl group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl Group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, per group Fluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, Perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group Group, perbromopentadecyl group, perbromoeicosyl group and the like.

  As the aralkyl group of L, an aralkyl group having 7 to 20 carbon atoms is preferable. (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl) Phenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) ) Methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group , (N-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) Methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n- Tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, phenylethyl group, phenylpropyl group Phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group. Preferably, it is a benzyl group. Moreover, the C7-20 halogenated aralkyl group etc. which these aralkyl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  The aryl group of L is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, and 2,4-xylyl group. Group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,4-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6 -Tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, -Butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl Group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like. Preferably, it is a phenyl group. Moreover, the C6-C20 halogenated aryl group etc. which these aryl groups substituted by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are mention | raise | lifted.

  L is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and still more preferably an alkyl group.

T ^{1 in the} general formula (6) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom.

The t in the general formula (6) represents a valence of T ^1, if T ¹ is an oxygen atom or a sulfur atom, t is 2, if T ¹ is a nitrogen atom or phosphorus atom, t is 3 .

R ^{6 in the} general formula (6) represents a halogen atom, an electron-withdrawing group, a group containing a halogen atom, or a group having an electron-withdrawing group, and represents a group containing an electron-withdrawing group or an electron-withdrawing group. , R ⁶ may be the same as or different from each other. As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known, and functional groups having positive Hammett's rule substituent constant σ are listed as electron withdrawing groups.

Examples of the halogen atom for R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the electron-withdrawing group for R ⁶ include a cyano group, a nitro group, a carbonyl group, a hydrocarbyloxycarbonyl group, a sulfone group, and a phenyl group.

Examples of the halogen-containing group represented by R ⁶ include halogenated hydrocarbyl groups such as halogenated alkyl groups, halogenated aralkyl groups, halogenated aryl groups, and (halogenated alkyl) aryl groups; halogenated hydrocarbyloxy groups; And halogenated hydrocarbyloxycarbonyl group. Examples of the group having an electron-withdrawing group of R ⁶ include a cyanated hydrocarbyl group such as a cyanated aryl group and a nitrated hydrocarbyl group such as a nitrated aryl group.

Examples of the halogenated alkyl group for R ⁶ include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, a trichloromethyl group, and a tribromomethyl group. Group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2,3 , 3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1-trichloromethyl Til group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2,2, 2-trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group, 1 , 1-bis (triiodomethyl) -2,2,2-triiodoethyl group, and the like.

As the halogenated aryl group for R ⁶ , 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2,6- Chlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, penta Chlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, perchloro-2- Naphtyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromo Phenyl group, 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6-tetrabromophenyl Phenyl group, pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group Perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenyl group, 3,4-diiodo Phenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentaiodophenyl Group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, periodate 1-naphthyl group, etc. Payodo-2-naphthyl group.

As the (halogenated alkyl) aryl group of R ⁶ , 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (trimethyl) Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoromethyl) phenyl group, etc. can give.

Examples of the cyanated aryl group for R ⁶ include a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group.

Examples of the nitrated aryl group for R ⁶ include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4-nitrophenyl group.

Examples of the hydrocarbyloxycarbonyl group for R ⁶ include an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, and the like. More specifically, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, Examples thereof include an isopropoxycarbonyl group and a phenoxycarbonyl group.

Examples of the halogenated hydrocarbyloxycarbonyl group for R ⁶ include a halogenated alkoxycarbonyl group, a halogenated aralkyloxycarbonyl group, a halogenated aryloxycarbonyl group, and the like. More specifically, a trifluoromethoxycarbonyl group, And pentafluorophenoxycarbonyl group.

R ⁶ is preferably a halogenated hydrocarbyl group, more preferably a halogenated alkyl group or a halogenated aryl group, still more preferably a fluorinated alkyl group, a fluorinated aryl group, a chlorinated alkyl group or A chlorinated aryl group, particularly preferably a fluorinated alkyl group or a fluorinated aryl group. The fluorinated alkyl group is preferably a fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2 , 2-trifluoro-1-trifluoromethylethyl group or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, more preferably trifluoromethyl group, 2,2 , 2-trifluoro-1-trifluoromethylethyl group or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group. As the fluorinated aryl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2, 3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group or perfluoro-2-naphthyl group More preferably a 3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group or a penta group. Is a Ruorofeniru group. The chlorinated alkyl group is preferably a chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2 -Trichloro-1-trichloromethylethyl group or 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group. The chlorinated aryl group is preferably a 4-chlorophenyl group, a 2,6-dichlorophenyl group, a 3.5-dichlorophenyl group, a 2,4,6-trichlorophenyl group, a 3,4,5-trichlorophenyl group or a pentachlorophenyl group. It is.

T ^{2 in the} general formula (7) is an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably a nitrogen atom or an oxygen atom, more preferably an oxygen atom.

The s of the general formula (7) represents a valence of T ^2, if T ² is an oxygen atom or a sulfur atom, s is 2, if T ² is a nitrogen atom or a phosphorus atom, s is 3 .

R ^{7 in the} general formula (7) represents a hydrocarbyl group or a halogenated hydrocarbyl group. Examples of the hydrocarbyl group for R ⁷ include an alkyl group, an aralkyl group, an aryl group, and the like, and examples thereof include the groups exemplified as the alkyl group, the aralkyl group, and the aryl group for L. The halogenated hydrocarbyl group R ^7, a halogenated alkyl group, halogenated aralkyl group, halogenated aryl group, and halogenated hydrocarbyl groups, such as (halogenated alkyl) aryl group and the like, the R ⁶ The groups exemplified as the halogenated alkyl group, the halogenated aryl group, and the (halogenated alkyl) aryl group can be exemplified.

R ⁷ is preferably a halogenated hydrocarbyl group, and more preferably a fluorinated hydrocarbyl group.

As the compound represented by the general formula (5) of the component (b1), as a compound in which M ³ is a zinc atom, dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc Dialkyl zinc such as diisobutyl zinc and di-n-hexyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; Methyl zinc, ethyl zinc chloride, n-propyl zinc chloride, isopropyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, n-hexyl zinc chloride, methyl zinc bromide, ethyl zinc bromide, n-propyl zinc bromide, Isopropyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl zinc bromide, yo Alkyl zinc halides such as methyl zinc iodide, ethyl zinc iodide, n-propyl zinc iodide, isopropyl zinc iodide, n-butyl zinc iodide, isobutyl zinc iodide, n-hexyl zinc iodide; zinc fluoride, Examples thereof include zinc halides such as zinc chloride, zinc bromide and zinc iodide.

  The compound represented by the general formula (5) of the component (b1) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc. Diisobutylzinc or di-n-hexylzinc, particularly preferably dimethylzinc or diethylzinc.

  Examples of the compound represented by the general formula (6) of the component (b2) include amines, phosphines, alcohols, thiols, phenols, thiophenols, naphthols, naphthylthiols, and carboxylic acid compounds.

  Examples of the amine include di (fluoromethyl) amine, bis (difluoromethyl) amine, bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3, 3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl ) Amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) Amine, bis (2,4,6-trifluorophenyl) amine, bis (3,4,5-trifluorophenyl) amine, bis (penta Fluorophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di) (Trifluoromethyl) phenyl) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) Amine, (3-cyanophenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine, bis (1H, 1H-perfluorobutyl) amine, bis (1H, 1H-perfluoropentyl) amine, bis (1H, 1H-per Fluorohexyl) amine, bis (1H, 1H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoropentadecyl) amine, bis (1H, 1H-perfluoroeico) Syl) amine and the like. Further, amines in which the fluoro of these amines is changed to chloro, bromo or iodo can be mentioned.

  Examples of the phosphine include compounds in which the nitrogen atom of the amine is changed to a phosphorus atom. Those phosphines are compounds represented by replacing the amine in the amine with phosphine.

  Examples of the alcohol include fluoromethanol, difluoromethanol, trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoro Fluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1H, 1H-perfluorobutanol, 1H, 1H-perfluoropentanol, 1H, 1H-perfluorohexanol, Examples thereof include 1H, 1H-perfluorooctanol, 1H, 1H-perfluorododecanol, 1H, 1H-perfluoropentadecanol, 1H, 1H-perfluoroeicosanol and the like. Moreover, the alcohol which changed fluoro of these alcohol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of the thiol include compounds in which the oxygen atom of the alcohol is changed to a sulfur atom. Those thiols are compounds represented by substituting the thiols in the alcohol with thiols.

  As phenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4 , 6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethylphenol 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol and the like. Moreover, the phenol which changed fluoro of these phenol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of the thiophenol include compounds in which the oxygen atom of the phenol is changed to a sulfur atom. Those thiophenols are compounds represented by replacing the phenol in the phenol with thiophenol.

  As naphthol, perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7,8-pentafluoro-2-naphthol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) ) Phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, Examples include 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol. Moreover, the naphthol which changed fluoro of these naphthol into chloro, bromo, or iodo can be mention | raise | lifted.

  Examples of naphthyl thiol include compounds in which the oxygen atom of the naphthol is changed to a sulfur atom. Those naphthols are compounds represented by replacing naphthol in the naphthol with naphthylthiol.

  Examples of carboxylic acid compounds include pentafluorobenzoic acid, perfluoroethanolic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoro. Examples include heptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid.

  The compound represented by the general formula (6) of the component (b2) is preferably an amine, alcohol or phenol compound, and the amine is preferably bis (trifluoromethyl) amine, bis (2,2,2-trimethyl). Fluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (Trifluoromethyl) -2,2,2-trifluoroethyl) amine or bis (pentafluorophenyl) amine, and the alcohol is preferably trifluoromethanol, 2,2,2-trifluoroethanol, 2,2 , 3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol Is 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, preferably 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol as phenol 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol or 3,4 , 5-tris (trifluoromethyl) phenol.

  More preferably, the compound represented by the general formula (6) of the component (b2) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3 , 5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol Or 2,4,6-tris (trifluoromethyl) phenol More preferably 3,5-difluorophenol, 3,4,5-fluorophenol, pentafluorophenol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol.

  Examples of the compound represented by the general formula (7) of the component (b3) include water, hydrogen sulfide, amine, aniline compound and the like.

  Examples of the amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, n-hexylamine, alkylamines such as n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine; benzylamine, (2-methylphenyl) methylamine, (3-methylphenyl) methylamine , (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) ) Methylamine, (3, -Dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3,4-trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) methylamine, (2,3,6) -Trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2,4,6-trimethylphenyl) methylamine, (2,3,4,5-tetramethylphenyl) methylamine, ( 2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n-propyl) Phenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (s c-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (neopentylphenyl) methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methyl Aralkylamines such as amine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthracenylmethylamine; allylamine; cyclopentadienylamine and the like.

  Examples of the amine include fluoromethylamine, difluoromethylamine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2- Trifluoro-1-trifluoromethylethylamine, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, Examples thereof include halogenated alkylamines such as perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, and perfluoroeicosylamine. Further, amines in which the fluoro of these amines is changed to chloro, bromo or iodo can be mentioned.

  Examples of aniline compounds include aniline, naphthylamine, anthracenylamine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2 , 6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4 , 6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline , Pentamethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-diethylaniline 2,4-diethylaniline, 2,5-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline, 2,3,4-triethylaniline, 2,3,5 -Triethylaniline, 2,3,6-triethylaniline, 2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline, 2,3,4,6- Examples thereof include tetraethylaniline, 2,3,5,6-tetraethylaniline, pentaethylaniline and the like. Moreover, the ethyl of these aniline compounds is n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n -An aniline compound changed to tetradecyl and the like.

  Examples of aniline compounds include 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4, 5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3 , 5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) aniline, 3,4,5-tri (trifluoromethyl) aniline, and the like. Moreover, the aniline compound which changed fluoro of these aniline compounds into chloro, bromo, iodo etc. can be mention | raise | lifted.

  The compound represented by the general formula (7) of the component (b3) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutyl. Amine, n-octylamine, aniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluoro Butylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroanily 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2 -(Trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4,6-tris (trifluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine , Perfluoropentadecylamine, 2-fluoroaniline, 3-fur Roaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoro Methyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, 2,4, 6-Tris (trifluoromethyl) aniline or 3,4,5-tris (trifluoromethyl) aniline, most preferably water or pentafluoroaniline.

  As the particulate carrier of component (b4), a solvent for preparing a polymerization catalyst or a solid substance insoluble in the polymerization solvent is preferably used, a porous substance is more preferably used, and an inorganic substance or an organic polymer is used. More preferably, inorganic substances are particularly preferably used.

  The particulate carrier of component (b4) is preferably of a uniform particle size, and the volume standard geometric standard deviation of the particle size of the particulate carrier of component (b4) is preferably 2.5 or less. More preferably, it is 2.0 or less, More preferably, it is 1.7 or less.

  Examples of the inorganic substance of the particulate carrier of the component (b4) include inorganic oxides, clays, clay minerals and the like. A plurality of these may be mixed and used.

As the inorganic _{oxide, SiO 2, Al 2 O 3} , MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO 2, SiO 2 -MgO, SiO 2 -Al 2 O 3, SiO _{2 -TiO 2, SiO 2 -V 2} O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO, and, can be mentioned mixtures of two or more of these. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ (silica) is particularly preferable. The inorganic oxide is a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. Carbonic acid salts such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

  In addition, a hydroxyl group is usually generated and present on the surface of the inorganic oxide, but as the inorganic oxide, modified inorganic oxides in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used. . Examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane; triarylchlorosilanes such as triphenylchlorosilane; dialkyldichlorosilanes such as dimethyldichlorosilane; diaryldichlorosilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as methyltrichlorosilane; aryltrichlorosilanes such as phenyltrichlorosilane; trialkylalkoxysilanes such as trimethylmethoxysilane; triarylalkoxysilanes such as triphenylmethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane; ; Diaryl dialkoxysilanes such as diphenyldimethoxysilane; Alkyltria such as methyltrimethoxysilane Coxysilane; aryltrialkoxysilane such as phenyltrimethoxysilane; tetraalkoxysilane such as tetramethoxysilane; alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane; tetrachlorosilane; methanol, ethanol Examples thereof include: alcohols such as phenol; dialkylmagnesium such as dibutylmagnesium, butylethylmagnesium and butyloctylmagnesium; and inorganic oxides contacted with alkyllithium such as butyllithium.

  Furthermore, after contact with a trialkylaluminum, an inorganic oxide contacted with a dialkylamine such as diethylamine and diphenylamine, an alcohol such as methanol and ethanol, or phenol.

  In addition, the strength of the inorganic oxide itself may increase due to hydrogen bonding between hydroxyl groups. In that case, if all the active hydrogens of the surface hydroxyl group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxyl group is not particularly limited. As this method, the method of changing the usage-amount of the compound used for a contact can be illustrated, for example.

  Clay or clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophyllite, talc, unmo group, smectite, montmorillonite group, hectorite, laponite, saponite, vermiculite, ryokdeite group, Examples include palygorskite, kaolinite, nacrite, dickite and halloysite. Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

  An inorganic oxide is preferably used as the inorganic substance. The inorganic substance is preferably dried to substantially remove moisture, and is preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which an inert gas (for example, nitrogen or argon) dried during heating is circulated and dried at a constant flow rate, a method in which heat is reduced under reduced pressure, and the like.

The average particle diameter of the inorganic substance is usually 1 to 5000 μm, preferably 5 to 1000 μm, more preferably 10 to 500 μm, and further preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  The organic polymer of the particulate carrier of component (b4) is preferably a polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group.

  As functional groups having active hydrogen, primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group Sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, carbazolyl group and the like. Preferred are primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group and thiol group. Particularly preferred are a primary amino group, a secondary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  The non-proton-donating Lewis basic functional group is a functional group having a Lewis base portion that does not have an active hydrogen atom, and includes pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, N -Substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group , Alkoxy groups, alkyloxycarbonyl groups, N, N-substituted carbamoyl groups, thioalkoxy groups, substituted sulfinyl groups, substituted sulfonyl groups, substituted sulfonic acid groups, and the like. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.

  In the organic polymer, the content of the functional group having active hydrogen or the non-proton-donating Lewis basic functional group is preferably 0.01 to as the molar amount of the functional group per gram of polymer unit constituting the organic polymer. 50 mmol / g, more preferably 0.1 to 20 mmol / g.

  Examples of the method for producing a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group include, for example, a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and 1 Examples thereof include a method of homopolymerizing a monomer having one or more polymerizable unsaturated groups, and a method of copolymerizing the monomer and another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

  Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group; alkynyl groups such as ethyne group.

  Examples of monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, vinyl group-containing hydroxy compounds, and the like. be able to. Specific examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methyl. Amine, 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-butene-1- For example, all.

  Examples of the monomer having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole and the like. be able to.

  Examples of other monomers having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound, and cyclic olefin. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentadiene. Two or more of these monomers may be used. Preferably, they are ethylene and styrene. Examples of the crosslinkable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle diameter of the organic polymer is usually 1 to 5000 μm, preferably 5 to 1000 μm, and more preferably 10 to 500 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 50 to 500 m ² / g.

  The organic polymer is preferably dried and substantially free of moisture, and is preferably dried by heat treatment. The temperature of the heat treatment is usually 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which a dry inert gas (for example, nitrogen or argon) is circulated and dried at a constant flow rate during heating, a method in which heat is dried under reduced pressure, and the like.

The promoter component (B) is formed by bringing the component (b1), the component (b2), the component (b3), and the component (b4) into contact with each other. The contact order of the component (b1), the component (b2), the component (b3) and the component (b4)) includes the following order.
<1> The component (b1) and the component (b2) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b4).
<2> The component (b1) and the component (b2) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b3).
<3> The component (b1) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b2), and the contact product resulting from the contact is brought into contact with the component (b4).
<4> The component (b1) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b2).
<5> The component (b1) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b2), and the contact product resulting from the contact is brought into contact with the component (b3).
<6> The component (b1) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b2).
<7> The component (b2) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b4).
<8> The component (b2) and the component (b3) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b4), and the contact product resulting from the contact is brought into contact with the component (b1).
<9> The component (b2) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b3).
<10> The component (b2) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b3), and the contact product resulting from the contact is brought into contact with the component (b1).
<11> The component (b3) and the component (b4) are brought into contact with each other, the contact product resulting from the contact is contacted with the component (b1), and the contact product resulting from the contact is brought into contact with the component (b2).
<12> The component (b3) and the component (b4) are brought into contact with each other, the contact with the contact is brought into contact with the component (b2), and the contact with the contact is brought into contact with the component (b1).

  The contact with the component (b1), the component (b2), the component (b3) and the component (b4) is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Further, a solvent may be used for the contact, and these compounds may be directly contacted without being used.

  When a solvent is used, a component that does not react with the component (b1), the component (b2), the component (b3), the component (b4), and their contacts is used. However, as described above, when each component is contacted step by step, even if the solvent reacts with a component at a certain stage, the solvent does not react with each component at another stage. The solvent can be used in other stages. That is, the solvents in each stage are the same or different from each other. Examples of the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, nitrile solvents. Examples include polar solvents such as solvents, nitro compounds, amine solvents, and sulfur compounds. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; dichloromethane, difluoromethane , Halogenated solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene Dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran Ether solvents such as tetrahydropyran; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Alcohol solvents such as ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, and glycerol; phenol solvents such as phenol and p-cresol; acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride Carbonyl solvents such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; Phosphoric acid derivatives such as oxamethylphosphoric triamide and triethyl phosphate; nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile; nitro compounds such as nitromethane and nitrobenzene; amine solvents such as pyridine, piperidine and morpholine; Examples thereof include sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When the contact (c) formed by bringing the component (b1), the component (b2) and the component (b3) into contact with the component (b4), that is, the above <1>, <3>, In each method of <7>, as the solvent (s1) for producing the contact product (c), the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent is preferable.

On the other hand, the solvent (s2) when the contact product (c) and the component (b4) are contacted is preferably a polar solvent. As an index representing the polarity of the solvent, E _T ^N value (C.Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988).) And the like are known, 0.8 ≧ A solvent satisfying the range of E _T ^N ≧ 0.1 is particularly preferable.

  Examples of the polar solvent include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol Cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, Examples thereof include ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide, sulfolane and the like.

  More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). ) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, particularly preferably di-n-butyl ether, methyl- ert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol Most preferred are tetrahydrofuran, methanol, ethanol, 1-propanol, and 2-propanol.

  As the solvent (s2), a mixed solvent of these polar solvents and hydrocarbon solvents can be used. As the hydrocarbon solvent, compounds exemplified as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are used. Examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, heptane / methanol mixed solvent, heptane. / Ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent, xylene / Methanol mixed solvent, xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, xylene / 2-propanol mixed solvent and the like. Preferably, hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent It is. More preferred are a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent, and a toluene / ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent. Moreover, the preferable range of the ethanol fraction in a toluene / ethanol mixed solvent is 10-50 volume%, More preferably, it is 15-30 volume%.

  When the contact (c) obtained by contacting the component (b1), the component (b2), and the component (b3) and the component (b4) are contacted, that is, the above <1>, <3>, < In each of the methods 7>, a hydrocarbon solvent may be used as the solvent (s1) and the solvent (s2). In this case, after the component (b1), the component (b2) and the component (b3) are contacted, it is preferable that the time until the obtained contact product (c) and the component (b4) are contacted is short. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Moreover, the temperature at which the contact (c) and the component (b4) are contacted is usually −100 ° C. to 40 ° C., preferably −20 ° C. to 20 ° C., and most preferably −10 ° C. to 10 ° C. It is.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, any of the above nonpolar solvents and polar solvents should be used. Can do. Preferably, it is a nonpolar solvent. This is because a contact object between component (b1) and component (b3), or a contact object between component (b1) and component (b2) and component (b3) is generally non-contact. Since the solubility in the polar solvent is low, when the component (b4) is present in the reaction system when these contact products are formed, the contact product precipitates on the surface of the component (b4) and is more easily immobilized. Because it is considered.

The amount of component (b2) and component (b3) used per mole of component (b1) is preferably satisfied by the following relational formula (IV).
| Valence of M ³ -molar amount of component (b2) -2 × molar amount of component (b3) | ≦ 1 (IV)
Moreover, the usage-amount of the component (b2) per 1 mol of usage-amount of a component (b1) becomes like this. Preferably it is 0.01-1.99 mol, More preferably, it is 0.1-1.8 mol, Furthermore, Preferably it is 0.2-1.5 mol, Most preferably, it is 0.3-1 mol. Use amount of component (b1) Preferred use amount, more preferred use amount, more preferred use amount, and most preferred use amount of component (b3) per mole are the valence of M ^{3 and} the use of the above component (b1). It is calculated by the amount of component (b2) used per 1 mol and the above relational expression (IV).

  The amount of component (b1) and component (b2) used is the number of moles of metal atoms contained per 1 g of promoter component (B) by the amount of metal atoms derived from component (b1) contained in promoter component (B). The amount is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol.

  In order to advance the reaction faster, a heating step at a higher temperature may be added after the contact as described above. In the heating step, it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. In performing the heating step, the solvent used in the contact may be replaced with another solvent having a higher boiling point.

  As a result of such contact, the cocatalyst component (B) may be the raw material component (b1), component (b2), component (b3) and / or component (b4) remaining as an unreacted substance. However, it is preferable to perform a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Moreover, after such a contact or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 0 ° C. or higher. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., and particularly preferably 2 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 4 to 18 hours at a temperature of 15 ° C to 160 ° C.

  The total amount of the transition metal compound (A1) and the transition metal compound (A2) used is usually 1 to 10000 μmol / g, preferably 10 to 1000 μmol / g, per 1 g of the promoter component (B). Preferably it is 20-500 micromol / g.

  In the preparation of the polymerization catalyst, the organoaluminum compound (C) may be contacted in addition to the transition metal compound (A1), the transition metal compound (A2) and the promoter component (B). The amount of the organoaluminum compound (C) used is preferably as the number of moles of aluminum atoms in the organoaluminum compound (C) per mole of the total number of moles of the transition metal compound (A1) and the transition metal compound (A2), It is 0.1-1000, More preferably, it is 0.5-500, More preferably, it is 1-100.

  Examples of the organoaluminum compound (C) include trialkylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like. Aluminum: Dialkylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride, etc .; methylaluminum dichloride, ethylaluminum dichloride , N-propylaluminum dichloride, n-butylaluminum dichloride, isobutyl Alkyl aluminum dichlorides such as rualuminum dichloride and n-hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride Dialkylaluminum hydrides such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, alkyl (dialkoxy) aluminum such as methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, methyl ( dialkyl (alkoxy) al such as tert-butoxy) aluminum Aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, methyl bis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl (2,6- Examples thereof include dialkyl (aryloxy) aluminum such as diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum. These organoaluminum compounds may be used alone or in combination of two or more.

  The organoaluminum compound (C) is preferably trialkylaluminum, more preferably trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. More preferred are triisobutylaluminum and tri-n-octylaluminum.

  In the preparation of the polymerization catalyst, the electron donating compound (D) may be contacted in addition to the transition metal compound (A1), the transition metal compound (A2) and the promoter component (B). The amount of the electron-donating compound (D) used is preferably 0.1 as the number of moles of the electron-donating compound (D) per mole of the total number of moles of the transition metal compound (A1) and the transition metal compound (A2). It is 01-100, More preferably, it is 0.1-50, More preferably, it is 0.25-5.

  Examples of the electron donating compound (D) include triethylamine and trinormaloctylamine.

  The transition metal compound (A1), the transition metal compound (A2), the promoter component (B), and, if necessary, the contact between the organoaluminum compound (C) and the electron donating compound (D) is performed in an inert gas atmosphere. It is preferably carried out below. The contact temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The contact time is usually 1 minute to 200 hours, preferably 30 minutes to 100 hours. In addition, the contact may be performed in the polymerization reactor with each component separately charged into the polymerization reaction tank.

  Examples of the method for producing the ethylene-α-olefin copolymer of the present invention include a method of copolymerizing ethylene and α-olefin by a gas phase polymerization method, a slurry polymerization method, a bulk polymerization method or the like. A gas phase polymerization method is preferable, and a continuous gas phase polymerization method is more preferable. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method for supplying the polymerization catalyst and each catalyst component to the polymerization reaction tank, a method for supplying the catalyst in a moisture-free state using an inert gas such as nitrogen or argon, hydrogen, ethylene, etc. A method of dissolving or diluting and supplying in a solution or slurry state is used.

  In the case of vapor phase polymerization of ethylene and α-olefin, the polymerization temperature is usually less than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C, more preferably 30 to 100. ° C. An inert gas may be introduced into the polymerization reaction tank, and hydrogen may be introduced as a molecular weight regulator. Further, an organoaluminum compound (C) and an electron donating compound (D) may be introduced.

  The α-olefin used for the polymerization is propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene. And α-olefins having 3 to 20 carbon atoms such as 4-methyl-1-hexene. These may be used independently and may use 2 or more types together. 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred. Examples of combinations of ethylene and α-olefin include ethylene / 1-butene, ethylene / 1-hexene, ethylene / 4-methyl-1-pentene, ethylene / 1-octene, ethylene / 1-butene / 1-hexene, ethylene / 1 / butene / 4-methyl-1-pentene, ethylene / 1-butene / 1-octene, ethylene / 1-hexene / 1-octene, etc., preferably ethylene / 1-hexene, ethylene / 4-methyl -1-pentene, ethylene / 1-butene / 1-hexene, ethylene / 1-butene / 1-octene, and ethylene / 1-hexene / 1-octene.

  In the copolymerization of ethylene and α-olefin, if necessary, another monomer is introduced into the polymerization reaction vessel, and the other monomer is copolymerized within a range not impairing the effects of the present invention. It may be polymerized. Examples of the other monomers include diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, α, β-unsaturated carboxylic acids, and the like.

  Specific examples thereof include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2 -Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene , 1,3-cyclooctadiene, 1,3-cyclohexadiene and other diolefins; cyclopentene, Chlohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclo Hexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene Cyclic olefins such as 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; Alkenylbenzene such as tylene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, p-second Alkyl styrene such as grade butyl styrene, bisalkenyl benzene such as divinylbenzene, alkenyl aromatic hydrocarbon such as alkenyl naphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride Acid, bicyclo (2,2,1) -5-heptene-2, Α, β-unsaturated carboxylic acids such as 3-dicarboxylic acids; metal salts of α, β-unsaturated carboxylic acids such as sodium, potassium, lithium, zinc, magnesium, calcium; methyl acrylate, ethyl acrylate, acrylic acid α such as n-propyl, isopropyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Β-unsaturated carboxylic acid alkyl esters; unsaturated dicarboxylic acids such as maleic acid and itaconic acid; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. Vinyl ester; acrylic acid Rishijiru, glycidyl methacrylate, and unsaturated carboxylic acid glycidyl ester of itaconic acid monoglycidyl ester.

  As the method for producing the ethylene-α-olefin copolymer of the present invention, a transition metal compound (A1), a transition metal compound (A2), a promoter component (B), and, if necessary, an organoaluminum compound ( A prepolymerized solid component obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization) using C) and an electron donating compound (D) is used as a polymerization catalyst component or a polymerization catalyst. Thus, a method of copolymerizing ethylene and α-olefin is preferable.

  Examples of the olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene and cyclohexene. These can be used alone or in combination of two or more. Preferably, ethylene alone, or a combination of ethylene and α-olefin, more preferably ethylene alone, or at least one α-olefin selected from 1-butene, 1-hexene and 1-octene, and ethylene Is used in combination.

  The content of the prepolymerized polymer in the prepolymerized solid component is preferably 0.01 to 1000 g, more preferably 0.05 to 500 g, and still more preferably, per 1 g of the promoter component (B). 0.1 to 200 g.

  The preliminary polymerization method may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous slurry polymerization method, and a continuous gas phase polymerization method. In a polymerization reaction tank for performing prepolymerization, a transition metal compound (A1), a transition metal compound (A2), a promoter component (B), and, if necessary, an organoaluminum compound (C) and an electron donating compound (D) As a method of charging, normally, an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is used in a moisture-free state, each component is dissolved or diluted in a solvent, and a solution or slurry A method of charging in a state is used.

  When the prepolymerization is performed by a slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as the solvent, and examples thereof include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane and the like. . These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  Moreover, when prepolymerization is performed by the slurry polymerization method, as the slurry concentration, the amount of the promoter component (B) per liter of the solvent is usually 0.1 to 600 g, preferably 0.5 to 300 g. . The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed. Moreover, the partial pressure of olefins in the gas phase part during the prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  As a method of supplying the prepolymerized prepolymerized solid catalyst component to the polymerization reaction tank, a method of supplying an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in a state free from moisture, each component Is dissolved or diluted in a solvent and supplied in a solution or slurry state.

  The calendar-forming ethylene-α-olefin copolymer of the present invention can be calendered together with known additives and polyolefins as necessary. Examples of the additive include antioxidants, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, dripping agents, pigments, fillers, and release agents. Known polyolefins include, for example, high density polyethylene, low density polyethylene, very low density polyethylene, very low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer. Examples thereof include a polymer, an ethylene-methacrylic acid copolymer, an ethylene-methacrylic acid ester copolymer, and a polyolefin rubber.

  Single-screw extrusion after ethylene-α-olefin copolymer or a composition containing the copolymer and additives and other polyolefins is heated and melted on a calender roll or dry blended with a tumbler blender or Henschel mixer A material that has been melt-kneaded by a machine or a multi-screw extruder, or melt-kneaded by a kneader or a Banbury mixer is used for calendering.

  As a processing machine used for calendering, a known calendering machine is used, and usually the molten resin composition melt-kneaded by an extruder or a Banbury mixer is transferred to a receiving roll, and then transferred to a supply roll by an appropriate amount. Further, it is transferred to 2 to 6 calender rolls, and is gradually spread into a sheet shape, and is composed of an apparatus that can be wound up through a take-out roll or a cooling / stretching roll. The calender roll includes 4 to 6 reverse L-type, horizontal type, Z-type, and composite type, and the roll temperature is usually 120 to 180 ° C. although it depends on the melting point of the resin composition to be used.

  Examples of the calendar molded body of the present invention include a waterproof sheet, a waterproof sheet, a desk mat, a flooring material, a wallpaper, a laminated glass interlayer film, a solar cell interlayer film, a tarpaulin, a waterproof cloth, a bag cloth, a flexible container, a canvas, Examples include raincoats, boots, waterproof pants, and waterproof apron.

  The calender molded product in the present invention may be a molded product of a single composition comprising the above-described ethylene-α-olefin copolymer or a composition containing the copolymer, and may be other resin, metal, cloth, non-woven fabric. It may be a multilayer molded body bonded to the above.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

(1) Density (d, unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(2) Melt flow rate (MFR, unit: g / 10 minutes)
In the method defined in JIS K7210-1995, measurement was performed by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(3) Melt flow rate ratio (MFRR)
In the method specified in JIS K7210-1995, the test load is 211.82N, the melt flow rate (H-MFR) measured at a measurement temperature of 190 ° C., and the method specified in JIS K7210-1995 is the load 21 The melt flow rate (MFR) measured under the conditions of .18 N and a temperature of 190 ° C. was measured, and a value obtained by dividing H-MFR by MFR was obtained.

(4) Molecular weight distribution (Mw / Mn, Mz / Mw)
Using gel permeation chromatograph (GPC) method, measure z-average molecular weight (Mz), weight-average molecular weight (Mw) and number-average molecular weight (Mn) under the following conditions (1) to (8) Mw / Mn and Mz / Mw were obtained. The baseline on the chromatogram is a stable horizontal region with a sufficiently long retention time than the appearance of the sample elution peak and a stable horizontal region with a sufficiently long retention time than the solvent elution peak was observed. A straight line formed by connecting the points.
(1) Equipment: Waters 150C manufactured by Waters
(2) Separation column: TOSOH TSKgelGMH6-HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refraction
(8) Molecular weight reference material: Standard polystyrene

(5) Number of DSC melting peaks The ethylene-α-olefin copolymer was pressed for 5 minutes at a pressure of 10 MPa with a hot press at 150 ° C. and then cooled for 5 minutes with a cooling press at 30 ° C. The sheet was molded into a 100 μm sheet, and a sample of about 10 mg was cut out from the sheet and sealed in an aluminum pan. Next, the aluminum pan in which the sample was sealed was held at a differential scanning calorimeter (differential scanning calorimeter DSC-7 manufactured by Perkin Elmer Co., Ltd.) (1) at 150 ° C. for 5 minutes, and (2) 5 ° C. (3) Hold at 20 ° C. for 2 minutes, (4) Increase the temperature from 20 ° C. to 150 ° C. at 5 ° C./minute, and calculate the melting curve in (4) It was measured. From the obtained melting curve, the number of melting peaks existing in the range from 25 ° C. to the melting end temperature (the temperature at which the melting curve returns to the high-temperature side baseline) was determined.

(6) Flow activation energy (Ea, unit: kJ / mol)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software Rhios V. Using 4.4.4, a master curve of a melt complex viscosity-angular frequency curve at 190 ° C. was created, and activation energy (Ea) was determined.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(7) Melt complex viscosity (η *, unit: Pa · sec)
In the measurement of the flow activation energy of (6), the melt complex viscosity measured at a temperature of 190 ° C. and an angular frequency of 100 rad / sec was determined. The lower the melt complex viscosity, the better the kneading load during calendar molding.

(8) Number of short chain branches (N _SCB , unit: 1 / 1000C)
The number of short chain branches in the ethylene-α-olefin copolymer was determined from an infrared absorption spectrum. Measurement and calculation were carried out by utilizing characteristic absorption derived from α-olefin according to the method described in the literature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, MA, Madams, WF). The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation).

(9) g *
G * was determined by the formula (III).
[Η] represents the relative viscosity (ηrel) of the ethylene-α-olefin copolymer in 100 ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor, and ethylene-α-olefin. A sample solution was prepared by dissolving 100 mg of the copolymer at 135 ° C., and using a Ubbelohde viscometer, the sample solution and a blank solution composed of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor Calculated from the fall time and determined by the formula (III-I), [η] _GPC is determined by the formula (III-II) from the measurement of the molecular weight distribution of the ethylene-α-olefin copolymer of (4), g _SCB * was calculated | required by Formula (III-III) from the measurement of the number of short chain branches of the ethylene-alpha-olefin copolymer of (7).

(10) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, an ethylene-α-olefin copolymer was melt-extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm at a temperature of 190 ° C. and an extrusion speed of 0.32 g / min. The melted ethylene-α-olefin copolymer was drawn into a filament by a take-up roll at a take-up rate of 6.3 (m / min) / min, and the tension during take-up was measured. The maximum tension from the start of take-up until the filamentous ethylene-α-olefin copolymer was cut was defined as the melt tension.
The higher this value, the better the peelability from the roll during calendar molding and the easier it is to mold. If MT is 12 cN or more, even if it is a wide molded object, it will be easy to peel and shaping | molding will be easy.

(11) Maximum take-up speed (MTV, unit: m / min)
In the measurement of the melt tension of (10), the take-up speed when the filamentous ethylene-α-olefin copolymer was cut was defined as the maximum take-up speed. The higher this value is, the more difficult the molded body is torn during extrusion molding, and the better the take-up property is.

(12) Impact strength (unit: kJ / m ² )
The measurement of impact strength was performed at 23 ° C. in an S-type dumbbell shape according to ASTM D1822-61T. The sample piece was molded by hot pressing at 150 ° C., stored in a temperature-controlled room at 23 ° C. and 50% humidity for 24 hours or more, and then used for measurement.

(13) Cold xylene soluble part (unit: wt%)
In a 200 mL flat bottom flask equipped with a reflux condenser, about 0.5 g of an ethylene copolymer sample and 100 mL of xylene were charged and refluxed for 30 minutes. After refluxing, the flat bottom flask was allowed to stand in an atmosphere of about 25 ° C. for 20 minutes, and then left in a water bath adjusted to 25 ° C. for 1 hour. After standing, the solution in the flat bottom flask was filtered with a filter paper (for No. 50 chromatography). The obtained filtrate was subjected to liquid chromatographic analysis under the following conditions (1) to (7), the amount of the copolymer dissolved in the solution was calculated, and the cold xylene-dissolved component ratio was determined from the sample weight.
(1) Apparatus: Degasser DG-2080-53 manufactured by JASCO Corporation
(2) Column: SHODEX GPC KF-801
(3) Column oven: CO-2065Plus manufactured by JASCO Corporation, setting 30 ° C
(4) Eluent: Tetrahydrofuran (for liquid chromatograph)
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 110 μL
(7) Detector: differential refractometer The smaller this value, the better the anti-blocking property.

Example 1
(1) Preparation of solid catalyst component In a reactor equipped with a nitrogen-replaced stirrer, silica heat-treated at 300 ° C. under nitrogen flow (Sypolol 948 manufactured by Devison; 50% volume average particle size = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 1.73 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 1.02 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of 3,4,5-trifluorophenol and 1.44 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then cooled to 22 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.11kg the temperature of the reactor 22 ° C.. After completion of dropping, the mixture was stirred at 22 ° C. for 1.5 hours, then heated to 40 ° C., stirred at 40 ° C. for 2 hours, further heated to 80 ° C., and stirred at 80 ° C. for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the solid catalyst component was obtained by drying.

(2) Preparation of prepolymerization catalyst component 836 g of butane was charged into an autoclave equipped with a stirrer with an internal volume of 5 liters previously purged with nitrogen, then the autoclave was heated to 50 ° C., and then 28 g of ethylene was charged. Stabilized. Next, 0.25 g of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] in a 50 ml flask under a nitrogen atmosphere, and racemic-ethylenebis (1-indenyl) ) 0.52 g of zirconium diphenoxide [corresponding to transition metal compound (A1)] and 4.3 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL are mixed and stirred at 50 ° C. for 4 hours. The solution was put into an autoclave. Thereafter, 10.3 g of the solid catalyst component obtained in Example 1 (1) was added to initiate polymerization. While continuously supplying a mixed gas of ethylene and hydrogen having a hydrogen concentration of 0.2%, prepolymerization was carried out at 50 ° C. for 100 minutes. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 15.9 g of polyethylene per 1 g of the solid catalyst component.

(3) Polymerization The inside of a 5 liter autoclave equipped with a stirrer was vacuum-dried after drying under reduced pressure, and hydrogen was added so that the partial pressure became 0.037 MPa, and 200 mL of 1-hexene and 1065 g of butane were charged. After the temperature was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 2.05 mol%. To this, 2.0 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 358 mg of the prepolymerized catalyst component obtained in Example 1 (2) was added. During the polymerization, the polymerization was carried out at 70 ° C. for 160 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.44 mol%) so as to keep the total pressure and the hydrogen concentration in the gas constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 156 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 2
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.015 MPa, 180 ml of 1-hexene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.99 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.2 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and a concentration adjusted to 0.1 μmol / ml 0.3 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to the transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above. 21.8 mg of the catalyst component was added. During the polymerization, the polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.20 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 215 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 3
(1) Preparation of prepolymerization catalyst component After adding 833 g of butane to an autoclave equipped with a stirrer with an internal volume of 5 liters previously purged with nitrogen, the autoclave was heated to 50 ° C. and diphenylmethylene (cyclopentadienyl) ( 9-fluorenyl) zirconium dichloride [equivalent to transition metal compound (A2)] 0.26 g and racemic-ethylenebis (1-indenyl) zirconium diphenoxide [equivalent to transition metal compound (A1)] 0.50 g in powder form The mixture was added and stirred at 50 ° C. for 75 minutes. Next, 28 g of ethylene was charged, and after the system was stabilized, 10.6 g of the solid catalyst component obtained in Example 1 (1) was added. Subsequently, the concentration of triisobutylaluminum as the organoaluminum compound (C) was increased. Polymerization was initiated by adding 4.2 mL of a heptane solution of triisobutylaluminum at 1 mmol / mL. Prepolymerization was carried out at 50 ° C. for 130 minutes while continuously supplying a mixed gas of ethylene and hydrogen having a hydrogen concentration of 0.2%. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 17.5 g of polyethylene per 1 g of the solid promoter component.

(2) Polymerization The inside of a 5 liter autoclave equipped with a stirrer was vacuum-dried after drying under reduced pressure, hydrogen was added so that the partial pressure became 0.055 MPa, and 200 ml of 1-hexene and 1066 g of butane were charged. After the temperature was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 3.14 mol%. To this, 1.0 mL of a toluene solution of triethylamine having a triethylamine concentration of 0.1 mmol / mL was added, and then a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was used as the organoaluminum compound (C). 2.0 mL was added. Next, 401 mg of the prepolymerized catalyst component prepared in Example 9 (1) was added. During the polymerization, the polymerization was carried out at 70 ° C. for 210 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.49 mol%) so as to keep the total pressure and the hydrogen concentration in the gas constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 171 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 4
(1) Polymerization The inside of a 5 liter autoclave equipped with a stirrer was vacuum-dried after drying under reduced pressure, and hydrogen was added so that the partial pressure became 0.029 MPa, and 200 ml of 1-hexene and 1065 g of butane were charged. After the temperature was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 1.58 mol%. To this, 2.0 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C) was added. Next, 374 mg of the prepolymerized catalyst component prepared in Example 3 (1) was added. During the polymerization, the polymerization was carried out at 70 ° C. for 220 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.20 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 106 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 5
(1) Preparation of prepolymerization catalyst component After adding 833 g of butane to an autoclave equipped with a stirrer with an internal volume of 5 liters previously purged with nitrogen, the autoclave was heated to 50 ° C., and then 28 g of ethylene was charged. Stabilized. Next, 57 mg of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to the transition metal compound (A2)] and racemic-ethylenebis (1-indenyl) zirconium in a 50 ml flask under a nitrogen atmosphere. Diphenoxide [corresponding to the transition metal compound (A1)] 0.67 g and 4.1 mL of triisobutylaluminum hexane solution having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C) were mixed at 50 ° C. The solution stirred and mixed for 4 hours was put into an autoclave. Subsequently, 10.4 g of the solid catalyst component prepared in Example 1 was added to initiate polymerization. Prepolymerization was carried out at 50 ° C. for 80 minutes while continuously supplying a mixed gas of ethylene and hydrogen having a hydrogen concentration of 0.2%. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was dried at room temperature to obtain a prepolymerized catalyst component containing 17.5 g of polyethylene per 1 g of the solid catalyst component.
(2) Polymerization The inside of a 3 liter autoclave equipped with a stirrer was dried under reduced pressure and purged with argon, hydrogen was added so that the partial pressure became 0.015 MPa, and 180 ml of 1-hexene and 650 g of butane were charged. After the temperature was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 0.93 mol%. To this was added 0.9 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C). Next, 363 mg of the prepolymerized catalyst component obtained in Example 11 (1) was added. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.23 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 214 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 6
(1) Polymerization The inside of a 3 liter autoclave equipped with a stirrer that was dried under reduced pressure and replaced with argon was evacuated, hydrogen was added so that the partial pressure was 0.025 MPa, and 180 ml of 1-hexene and 650 g of butane were charged. After the temperature was raised to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 2.26 mol%. To this was added 0.9 mL of a hexane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL as the organoaluminum compound (C). Next, 364 mg of the prepolymerized catalyst component obtained in Example 5 (1) was added. During the polymerization, polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.21 mol%). Thereafter, butane, ethylene and hydrogen were purged to obtain 172 g of an ethylene-1-hexene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Example 7
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.025 MPa, 55 g of 1-butene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was as follows: hydrogen = 1.08 mol% and 1-butene = 2.48 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml and a concentration adjusted to 0.1 μmol / ml 0.25 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to the transition metal compound (A2)] was added, and then the solid obtained in Example 1 (1) above. 10.0 mg of the catalyst component was added. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.33 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 112 g of an ethylene-1-butene copolymer. Table 1 shows the physical properties of the obtained copolymer.

Comparative Example 1
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was dried under reduced pressure and replaced with argon, was evacuated, hydrogen was added so that the partial pressure became 0.08 MPa, 31 g of 1-butene, butane as a polymerization solvent 720 g was charged and the temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was as follows: hydrogen = 4.57 mol%, 1-butene = 1.83 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.75 ml of a toluene solution of racemic dimethylsilylene bis (1-indenyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 0.2 μmol / ml and a concentration of 2 μmol / ml were adjusted. 0.75 ml of a toluene solution of diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to transition metal compound (A2)] was added, and then the solid catalyst component obtained in Example 1 (1) above 11.8 mg was charged. During the polymerization, the polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 1.24 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 38 g of an ethylene-1-butene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Comparative Example 2
(1) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, hydrogen was added so that the partial pressure became 0.025 MPa, 56 g of 1-butene, butane as a polymerization solvent Was heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.10 mol% and 1-butene = 2.96 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide adjusted to a concentration of 2 μmol / ml was added, and then the solid catalyst component 3 obtained in Example 1 (1) above was added. 4 mg was charged. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.32 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant. Thereafter, butane, ethylene and hydrogen were purged to obtain 65 g of an ethylene-1-butene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

Comparative Example 3
(1) Preparation of solid catalyst component (S) In a reactor equipped with a stirrer substituted with nitrogen, component (b) silica heat-treated at 300 ° C. under a nitrogen flow as a solid carrier (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 9.68 kg was added. After adding 100 liters of toluene, it was cooled to 2 ° C. To this, 26.3 liters of a toluene solution of methylalumoxane (2.9M) was added dropwise over 1 hour. After stirring at 5 ° C. for 30 minutes, the mixture was heated to 95 ° C. over 90 minutes and stirred for 4 hours. After cooling to 40 ° C., the mixture was allowed to stand for 40 minutes to allow the solid component to settle, and the upper slurry portion was removed. As a washing operation, 100 liters of toluene was added thereto, and the mixture was stirred for 10 minutes. Then, the stirring was stopped and the mixture was allowed to stand to settle the solid component. Similarly, the upper slurry portion was removed. The above washing operation was repeated 3 times in total. Furthermore, after adding 100 liters of toluene and stirring, it filtered simultaneously with stopping stirring. After repeating this operation once more, 110 liters of hexane was added, and filtration was performed in the same manner. This operation was repeated once more. Then, 12.6 kg of solid catalyst components were obtained by performing drying at 70 degreeC under nitrogen distribution for 7 hours. As a result of elemental analysis, it was Al = 4.4 mmol / g.

(2) Preparation of slurry catalyst component (Cat-1) 200 mg of the solid catalyst component (S) prepared in (1) above was added to a nitrogen-substituted 100 ml glass flask. Next, 12.5 ml of a toluene solution of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride [corresponding to a transition metal compound (A1)] adjusted to a concentration of 2 μmol / ml, and diphenyl adjusted to a concentration of 2 μmol / ml 1 ml of a toluene solution of methylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride [corresponding to the transition metal compound (A2)] was added and reacted at room temperature for 5 minutes. Thereafter, the supernatant was removed by decantation and then washed twice with hexane to obtain 6 ml of hexane slurry.

(3) Polymerization The inside of an autoclave with a stirrer with an internal volume of 3 liters, which was substituted with argon after drying under reduced pressure, was evacuated, charged with 180 ml of 1-hexene and 650 g of butane as a polymerization solvent, and heated to 70 ° C. Thereafter, an ethylene / hydrogen mixed gas (hydrogen = 0.33 mol%) was added so that the partial pressure of the mixed gas was 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.15 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 6 ml of the slurry catalyst component (Cat-1) prepared in the above (2) was added. During the polymerization, polymerization was performed at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.33 mol%). Thereafter, butane, ethylene, and hydrogen were purged to obtain 71 g of an ethylene-1-hexene copolymer. The physical properties of the obtained copolymer are shown in Table 2.

（注１）：150℃で測定

(Note 1): Measured at 150 ° C

Claims (3)

It has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, has a density (d) of 860 to 950 kg / m ³ , and a melt flow rate (MFR) of 0.00. 01 to 5 (g / 10 min), the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4 to 30, the Z average molecular weight (Mz) and the weight average molecular weight (Mw) ratio (Mz / Mw) is 2-5, g * calculated | required by following formula (I) is 0.79-0.95, the ethylene-alpha-olefin copolymer for calendar moldings .
g * = [η] / ([η] _GPC × g _SCB *) (I)
[In the formula, [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is defined by the following formula (I-I), and [η] _GPC is represented by the following formula ( G _SCB * is defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (I-III)
(In the formula, A can be obtained from the measurement of the content of short chain branches in the ethylene-α-olefin copolymer.)]   The ethylene-α-olefin copolymer for calendering according to claim 1, wherein the activation energy (Ea) of flow is 60 kJ / mol or more.   A calendered molding obtained by using the calendar-forming ethylene-α-olefin copolymer according to claim 1 or 2.