JP2009197226A - Ethylene copolymer, thermoplastic resin composition containing the ethylene copolymer, and molded product obtained from them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene copolymer excellent in moldability and mechanical strength and a thermoplastic resin composition containing the copolymer, and a molded product, a film, and a laminate film containing the film, which are formed from them. <P>SOLUTION: The ethylene copolymer is a copolymer of ethylene with 4-10C α-olefin which satisfies requirements (I)-(VI): (I) MFR (190°C, 2.16 kg load): 0.1-100 g/10 min, (II) density: 875-936 kg/m<SP>3</SP>, (III) the ratio of melt tension to shear viscosity: 2.50×10<SP>-4</SP>-9.00×10<SP>-4</SP>, (IV) the sum of the numbers of methyl branches and ethyl branches: 1.8 or less, (V) the relationship between zero shear viscosity [η<SB>0</SB>(P), 200°C] and weight-average molecular weight (Mw) measured by the GPC-viscosity detector method: 0.01×10<SP>-13</SP>×Mw<SP>3.4</SP>≤ηo≤4.50×10<SP>-13</SP>×Mw<SP>3.4</SP>, and (VI) the molecular weight at the maximum weight fraction on its molecular weight distribution curve by a GPC measurement: 1.0×10<SP>4.20</SP>-1.0×10<SP>4.50</SP>. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is an ethylene copolymer that is excellent in moldability and particularly excellent in mechanical strength as compared with a conventionally known ethylene copolymer, and a thermoplastic resin composition containing the ethylene copolymer. The present invention relates to a molded article, a film, and a laminate film comprising the ethylene copolymer and a thermoplastic resin composition containing the ethylene copolymer.

  Ethylene copolymers are molded by various molding methods and used for various purposes. Depending on these molding methods and applications, the properties required for ethylene copolymers also differ. For example, when a cast film is formed in T-die molding, a neck-in in which the film end portion shrinks in the center direction occurs. When neck-in occurs, the film width becomes small and the thickness of the film end becomes thicker than that of the central part of the film, so that the product yield deteriorates. In order to minimize neck-in, an ethylene copolymer having a high melt tension must be selected for the molecular weight. Similar properties are necessary to prevent sagging or tearing in hollow molding or to prevent bubble swaying or tearing in blown film.

  In addition, when a cast film is formed in T-die molding, regular thickness fluctuations that occur in the film take-off direction called take-up surging (sometimes referred to as draw resonance) occur. When take-up surging occurs, thickness unevenness occurs in the film, and as a result, the mechanical strength varies from place to place. For this reason, in order to stably produce a film having a uniform film thickness, occurrence of take-up surging must be avoided. In order to suppress this take-up surging, it is considered that a resin characteristic is required such that the strain hardening degree of the extension viscosity increases as the strain rate increases (for example, see Non-Patent Document 1).

  An ethylene copolymer obtained using a metallocene catalyst is excellent in mechanical strength such as tensile strength, tear strength or impact strength strength, but has a low melt tension, resulting in a large neck-in. Further, since the extension viscosity does not show strain rate curability, take-up surging occurs.

  The high-pressure method low-density polyethylene has a higher melt tension than an ethylene copolymer obtained using a metallocene catalyst, and thus is excellent in moldability such as neck-in. Further, since the extension viscosity shows strain rate curability, take-up surging does not occur. However, the high-pressure low-density polyethylene has a complicated long-chain branched structure, and therefore is inferior in mechanical strength such as tensile strength, tear strength or impact strength.

  Therefore, an ethylene copolymer obtained by using a metallocene catalyst and a high-pressure low-density polyethylene as an ethylene copolymer having improved moldability such as neck-in and take-off surging and having mechanical strength. And a composition proposed in Patent Document 1 and the like. However, when the content of the high pressure method low density polyethylene is large, it is expected that the mechanical strength such as tensile strength, tear strength or impact strength is inferior. In addition, when the content of the high-pressure method low-density polyethylene is small, the melt tension is not sufficiently improved, so that the moldability is expected to deteriorate due to a large neck-in.

In order to solve such problems, various ethylene copolymers into which long chain branching is introduced by a metallocene catalyst have been disclosed. Patent Document 2 discloses an ethylene copolymer obtained by solution polymerization in the presence of a catalyst composed of ethylenebis (indenyl) hafnium dichloride and methylalumoxane, and Patent Document 3 discloses ethylenebis (indenyl) supported on silica. An ethylene copolymer obtained by gas phase polymerization in the presence of a catalyst comprising zirconium dichloride and methylalumoxane is disclosed in Patent Document 4, and an ethylene copolymer obtained by solution polymerization in the presence of a constrained geometric catalyst is disclosed in Patent Document 4. Patent Document 5 discloses an ethylene copolymer obtained by gas phase polymerization in the presence of a catalyst comprising a racemic and meso isomer of Me ₂ Si (2-Me-Ind) ₂ supported on silica and methylalumoxane. Is disclosed. These ethylene copolymers are described as having improved melt tension and excellent moldability compared to linear ethylene copolymers without long-chain branching, but still have a large neck-in, This improvement is expected to be insufficient. Further, these ethylene copolymers, unlike the high-pressure low-density polyethylene, are not expected to improve take-up surging because the extensional viscosity does not exhibit strain rate curability.

  Patent Document 6 discloses an ethylene copolymer in which zero shear viscosity and weight average molecular weight satisfy a specific relationship. This ethylene copolymer has improved take-up surging because the elongational viscosity exhibits strain rate curability by satisfying a specific relationship between zero shear viscosity and weight average molecular weight. Further, the neck-in is improved as compared with the conventional ethylene copolymer in which long chain branching is introduced using a metallocene catalyst, and the mechanical strength of the film is also superior to that of the high-pressure method low-density polyethylene. However, when an ethylene copolymer is used for packaging materials, bottles, tanks, etc., further mechanical strength improvement is desired in order to protect the contents. Further, in order to further improve the product yield, improvement of neck-in is also desired.

  As described above, it has been difficult to efficiently obtain an ethylene copolymer that has improved problems in moldability such as neck-in and take-off surging, and that is particularly excellent in mechanical strength, from the conventional known techniques. .

  As a result of intensive studies in view of such circumstances, the present inventors have given a specific melting characteristic and molecular structure to the polymer, so that the neck-in in T-die molding is small and there is no occurrence of take-up surging, In addition, the inventors have found an ethylene copolymer particularly excellent in mechanical strength, and have completed the present invention.

JP 7-26079 A JP-A-2-276807 JP-A-4-213309 International Publication No. 93/08221 Pamphlet JP-A-8-311260 JP 2006-233206 A

Toshitaka Kanai and Akira Funaki "Journal of the Textile Society of Japan (Volume 41)", 1986, T-1

  The present invention relates to an ethylene copolymer excellent in moldability and particularly excellent in mechanical strength as compared with conventionally known ethylene copolymers, a thermoplastic resin composition containing the ethylene copolymer, and the ethylene It is an object of the present invention to provide a molded body obtained from a copolymer and the thermoplastic resin composition, a film, and a laminate film comprising the film.

The ethylene copolymer of the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and is characterized by satisfying the following requirements (I) to (VI) simultaneously.
(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 100 g / 10 min.
(II) The density (d) is in the range of 875 to 936 kg / m ³ .
(III) The ratio [MT / η ^* (g / P)] of the melt tension [MT (g)] at 190 ° C. and the shear viscosity [η ^* (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec. The range is from 2.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ .
(IV) Sum of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR [(A + B) (/ 1000C )] Is 1.8 or less.
(V) Zero shear viscosity [η ₀ (P)] at 200 ° C. and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .

(VI) The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is in the range of 1.0 × 10 ^{4.20 to} 1.0 × 10 ^4.50 .
Further, by blending the ethylene copolymer according to the present invention with another thermoplastic resin, a thermoplastic resin composition excellent in moldability and particularly excellent in mechanical strength can be obtained. By processing the ethylene copolymer according to the present invention and a resin composition containing the ethylene copolymer, a molded body, a film, and a laminate film comprising the film, which have excellent moldability and mechanical strength Is obtained.

  The ethylene copolymer of the present invention and the thermoplastic resin composition containing the ethylene copolymer have a small neck-in in T-die molding, no occurrence of take-up surging, and a molded body and film particularly excellent in mechanical strength A laminate film comprising the film can be produced.

Hereinafter, the ethylene copolymer according to the present invention will be specifically described.
The ethylene copolymer according to the present invention comprises ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 4 to 10 carbon atoms (however, when butene-1 is used as a comonomer, A copolymer of ethylene and an α-olefin having 6 to 10 carbon atoms is more preferable. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.

Such an ethylene copolymer has the characteristics shown in the following (I) to (VI).
(I) Melt flow rate (MFR) is 0.1 to 100 g / 10 minutes, preferably 1.0 to 50 g / 10 minutes, more preferably 1.0 to 30 g / 10 minutes, and particularly preferably 4 to 30 g / 10. The range of minutes. When the melt flow rate (MFR) is 0.1 g / 10 min or more, the shear viscosity of the ethylene copolymer is not too high and the moldability is good. When the melt flow rate (MFR) is 100 g / 10 min or less, the tensile strength and heat seal strength of the ethylene copolymer are good.

  The melt flow rate (MFR) strongly depends on the molecular weight. The smaller the melt flow rate (MFR), the larger the molecular weight, and the larger the melt flow rate (MFR), the smaller the molecular weight. In addition, it is known that the molecular weight of an ethylene copolymer is determined by the composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system (for example, Kazuo Soga et al., “Catalytic Olefin Polymerization”, Kodansha Scientific, 1990, p.376). For this reason, it is possible to increase / decrease the melt flow rate (MFR) of an ethylene copolymer by increasing / decreasing hydrogen / ethylene.

Melt flow rate (MFR) is measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89.
(II) The density (d) is in the range of 875 to 936 kg / m ³ , preferably 885 to 930 kg / m ³ , more preferably 903 to 930 kg / m ³ . When the density (d) is 875 kg / m ³ or more, there is little stickiness on the surface of the film formed from the ethylene copolymer, and when the density (d) is 936 kg / m ³ or less, the heat seal strength, bag breaking strength, etc. Good mechanical strength.

  The density depends on the α-olefin content of the ethylene copolymer. The smaller the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. Further, it is known that the α-olefin content in the ethylene copolymer is determined by the composition ratio (α-olefin / ethylene) of α-olefin and ethylene in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p.606 (1992)). For this reason, the ethylene copolymer which has the density of the said range can be manufactured by increasing / decreasing (alpha) -olefin / ethylene.

The density (d) is measured by heat treating the measurement sample at 120 ° C. for 1 hour, linearly cooling to room temperature over 1 hour, and then using a density gradient tube.
(III) Ratio [MT / η ^* (g / Poise)] of melt tension [MT (g)] and shear viscosity [η ^* (Poise)] at 200 ° C. and angular velocity of 1.0 rad / sec is 2.50. × 10 ^{−4 to} 9.00 × 10 ⁻⁴ , preferably 2.50 × 10 ^{−4 to} 7.00 × 10 ⁻⁴ , more preferably 3.00 × 10 ^{−4 to} 5.00 × 10 ⁻⁴ It is a range.

When MT / η ^* is 2.50 × 10 ⁻⁴ or more, the neck-in is good, and when MT / η ^* is 9.00 × 10 ⁻⁴ or less, the drawdown property is good.
MT / η ^* depends on the long chain branching content of the ethylene-based polymer. MT / η ^* increases as the long chain branching content increases, and MT / η ^* decreases as the long chain branching content decreases. Long chain branching is defined as a branched structure with a length greater than the molecular weight (Me) between the entanglement points contained in the ethylene polymer. By introducing long chain branching, the melt properties and molding processability of the ethylene polymer are It is known that it changes significantly (for example, Kazuo Matsuura et al., “Polyethylene Technology Reader”, Industrial Research Committee, 2001, p. 32, 36). As will be described later, the ethylene polymer according to the present invention comprises component (A), component (B), and component (C), in the presence of an olefin polymerization catalyst characterized by comprising ethylene and carbon number. It can be produced by polymerizing 4 to 10 α-olefins. In the mechanism in which the ethylene-based polymer of the present invention is produced, the present inventors are present in the presence of a catalyst component for olefin polymerization containing components (A) and (C), and optionally component (S). It has terminal vinyl having a number average molecular weight of 4000 to 20000, preferably 4000 to 15000 by polymerizing ethylene or ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 4 to 10 carbon atoms. A “macromonomer” which is a polymer is produced, and then ethylene and a catalyst component for olefin polymerization containing component (B) and component (C), and optionally component (S), are used. It is considered that long chain branching is generated in the ethylene polymer of the present invention by copolymerizing the macromonomer competitively with the polymerization of α-olefin. To have. The long chain branching content in the ethylene polymer of the present invention depends on the composition ratio ([macromonomer] / [ethylene]) of the macromonomer and ethylene in the polymerization system, and [macromonomer] / [ethylene ] Is higher, the long chain branching content in the ethylene polymer is increased. Since the ratio of component (A) in the olefin polymerization catalyst ([A] / [A + B]) can be increased, [macromonomer] / [ethylene] can be increased, so [A] / [A + B] By increasing or decreasing, an ethylene-based polymer having MT / η ^* in the above range can be produced. In the example described later, when Example 11 ([A] / [A + B] = 0.40) and Example 16 ([A] / [A + B] = 0.18) are compared, [A ] / [A + B] in Example 11 where MT / η ^* is closer to the upper limit of the claims.

  The melt tension (MT) is a value measured by the following method. Melt tension (MT) is determined by measuring the stress when the molten polymer is stretched at a constant rate. An MT measuring machine manufactured by Toyo Seiki Seisakusho is used for the measurement. The conditions are as follows: resin temperature 190 ° C., melting time 6 minutes, barrel diameter 9.55 mmφ, extrusion speed 15 mm / minute, winding speed 24 mm / minute (if the molten filament breaks, the winding speed is 5 m / minute) The nozzle diameter is 2.095 mmφ and the nozzle length is 8 mm.

Also, 200 ° C., the angular velocity 1.0 rad / shear viscosity in seconds (eta ^*) is the angular velocity [omega (rad / sec)] of the shear viscosity at a measurement temperature 200 ° C. (eta ^*) dispersed 0.02512 ≦ ω ≦ 100 It is determined by measuring in the range. A dynamic stress rheometer SR-5000 manufactured by Rheometrics is used for the measurement. The sample holder uses a 25 mmφ parallel plate and the sample thickness is about 2.0 mm. There are 5 measurement points per ω digit. The amount of strain is appropriately selected within a range of 3 to 10% so that the torque in the measurement range can be detected and torque is not exceeded. The sample used for the shear viscosity measurement was a press molding machine manufactured by Shin-Fuji Metal Industry Co., Ltd., preheating temperature 190 ° C., preheating time 5 minutes, heating temperature 190 ° C., heating time 2 minutes, heating pressure 100 kgf / cm ² , cooling temperature The measurement sample is prepared by press molding to a thickness of 2 mm under the conditions of 20 ° C., cooling time of 5 minutes, and cooling pressure of 100 kg weight / cm ² .

(IV) The sum [(A + B) (/ 1000C)] of the number of methyl branches [A (/ 1000C)] and the number of ethyl branches [B (/ 1000C)] measured by ¹³ C-NMR is 1.8. Hereinafter, it is preferably 1.3 or less, more preferably 0.8 or less, and even more preferably 0.5 or less. The number of methyl branches and the number of ethyl branches defined in the present invention are defined by the number per 1000 carbons as described later.

  If there are short chain branches such as methyl branch and ethyl branch in the ethylene copolymer, the short chain branch is incorporated into the crystal and the interplanar spacing of the crystal widens, which may reduce the mechanical strength of the resin. It is known (eg, supervised by Zenjiro Osawa et al., “Technology for predicting and extending the life of polymers”, NTS Corporation, 2002, p. 481). Therefore, when the sum of the number of methyl branches and the number of ethyl branches (A + B) is 1.8 or less, the mechanical strength of the ethylene copolymer is good.

  The number of methyl branches and the number of ethyl branches in the ethylene copolymer strongly depend on the polymerization method of the ethylene copolymer, and the ethylene copolymer obtained by high-pressure radical polymerization is obtained by coordination polymerization using a Ziegler type catalyst system. The number of methyl branches and the number of ethyl branches are larger than the obtained ethylene copolymer. In the case of coordination polymerization, the number of methyl branches and the number of ethyl branches in the ethylene copolymer strongly depend on the composition ratio of propylene, 1-butene and ethylene (propylene / ethylene, 1-butene / ethylene) in the polymerization system. To do. For this reason, it is possible to increase / decrease the sum (A + B) of the number of methyl branches and the number of ethyl branches of an ethylene copolymer by increasing / decreasing 1-butene / ethylene.

^The number of methyl branches and the number of ethyl branches measured by ¹³ C-NMR are determined as follows. The measurement was carried out using an ECP500 type nuclear magnetic resonance apparatus (1H: 500 MHz) manufactured by JEOL Ltd. at a cumulative number of 10,000 to 30,000. The main chain methylene peak (29.97 ppm) was used as the chemical shift standard. A mixture of PE sample 250-400mg and Wako Pure Chemical Industries, Ltd. special grade o-dichlorobenzene: ISOTEC benzene-d6 = 5: 1 (volume ratio) in a commercial NMR measurement quartz glass tube with a diameter of 10mm 3 ml was added and heated at 120 ° C. for uniform dispersion. Assignment of each absorption in the NMR spectrum was carried out according to Chemical Region No. 141 NMR-Review and Experiment Guide [I], p. The number of methyl branches per 1,000 carbons is calculated from the integrated intensity ratio of the absorption of methyl groups derived from methyl branches (19.9 ppm) to the integrated sum of absorptions appearing in the range of 5 to 45 ppm. The number of ethyl branches is calculated from the integrated intensity ratio of the absorption of ethyl groups derived from ethyl branches (10.8 ppm) to the integrated sum of absorptions appearing in the range of 5 to 45 ppm.

(V) Zero shear viscosity [η ₀ (P)] at 200 ° C. and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .

Preferably, the following relational expression (Eq-2) is satisfied.

More preferably, the following relational expression (Eq-3) is satisfied.

Particularly preferably, the following relational expression (Eq-4) is satisfied.

When logarithm plotting zero shear viscosity [η ₀ (P)] against weight average molecular weight (Mw), the extensional viscosity is strain-hardening like a linear ethylene copolymer with no long chain branching. The resin with no slope follows the power law with a slope of 3.4, whereas the resin exhibiting a strain rate curable elongational viscosity like the high-pressure low-density polyethylene has a zero shear viscosity [η ₀ (P )] Is known (C Gabriel, H. Munstedt, J. Rheol., 47 (3), 619 (2003)). When the zero shear viscosity [η ₀ (P)] at 200 ° C. is 4.50 × 10 ⁻¹³ × Mw ^3.4 or less, the elongation viscosity of the resulting ethylene copolymer exhibits strain rate curability, so that take-up surging occurs. do not do.

The relationship between the zero shear viscosity [η ₀ (P)] and the weight average molecular weight (Mw) is considered to depend on the long chain branch content and the length of the long chain branch in the ethylene polymer. The greater the chain branch content and the shorter the long chain branch length, the closer the zero shear viscosity [η ₀ (P)] is to the lower limit of the claims. The smaller the long chain branch content, the longer the long chain branch content. The longer the length, the zero shear viscosity [η ₀ (P)] is considered to be closer to the upper limit of the claims. As described above, the long chain branching content is increased by increasing the ratio ([A] / [A + B]) of the component (A) in the olefin polymerization catalyst. Further, in the ethylene polymer of the present invention, when the composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system is increased, the molecular weight of the macromonomer is decreased, so that a long chain introduced into the ethylene polymer. The length of the branch is shortened. From this, it is possible to produce an ethylene polymer having a zero-shear viscosity [η ₀ (P)] as claimed by increasing or decreasing [A] / [A + B] and hydrogen / ethylene. In an example described later, when Example 15 ([A] / [A + B] = 0.28) and Example 16 ([A] / [A + B] = 0.18) are compared, [A ] / [A + B] in Example 15 having a high zero shear viscosity [η ₀ (P)] is closer to the lower limit of the claims.

The fact that the ethylene copolymer of the present invention satisfies the above relational expression (Eq-1) means that log (η ₀ ) and logMw are expressed by the following relational expression (logarithmic plot of η ₀ and Mw of the ethylene copolymer: It is synonymous with existing in the region defined by Eq-1 ′).

3.4Log (Mw) -15.0000 ≦ Log ( η 0) ≦ 3.4Log (Mw) -12.3468 -------- (Eq-1 ')
The zero shear viscosity [η ₀ (P)] at 200 ° C. is determined as follows. The angular velocity [ω (rad / sec)] dispersion of the shear viscosity (η ^* ) at a measurement temperature of 200 ° C. is measured in the range of 0.02512 ≦ ω ≦ 100. A dynamic stress rheometer SR-5000 manufactured by Rheometrics is used for the measurement. The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 2.0 mm. There are 5 measurement points per ω digit. The amount of strain is appropriately selected within a range of 3 to 10% so that the torque in the measurement range can be detected and torque is not exceeded. The sample used for the shear viscosity measurement was a press molding machine manufactured by Shin-Fuji Metal Industry Co., Ltd., preheating temperature 190 ° C., preheating time 5 minutes, heating temperature 190 ° C., heating time 2 minutes, heating pressure 100 kgf / cm ² , cooling temperature The measurement sample is prepared by press molding to a thickness of 2 mm under the conditions of 20 ° C., cooling time of 5 minutes, and cooling pressure of 100 kg weight / cm ² .

The zero shear viscosity η ₀ is calculated by fitting the Carreau model of the following formula (Eq-5) to an actually measured rheological curve [angular velocity (ω) dispersion of shear viscosity (η ^* )] by the nonlinear least square method.

  Here, λ represents a parameter having a time dimension, and n represents a power law index of the material. Note that the fitting by the nonlinear least square method is performed so that d in the following equation (Eq-6) is minimized.

Here, η _exp (ω) represents the measured shear viscosity, and η _calc (ω) represents the shear viscosity calculated from the Carreau model.
The weight average molecular weight (Mw) by GPC-VISCO method is measured as follows using GPC / V2000 manufactured by Waters. The guard column uses Shodex AT-G, the analytical column uses two AT-806, the column temperature is 145 ° C., the mobile phase uses o-dichlorobenzene and BHT 0.3 wt% as an antioxidant, 1. The sample is moved at 0 ml / min, the sample concentration is 0.1% by weight, and a differential refractometer and 3-capillary viscometer are used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. In the molecular weight calculation, an actual viscosity is calculated from a viscometer and a refractometer, and a weight average molecular weight (Mw) is calculated from an actual universal calibration.

(VI) The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is 1.0 × 10 ^{4.20 to} 1.0 × 10 ^4.50 , preferably 1.0 × 10 ^4.20 to 1 It is 0.0 × 10 ^4.40 , more preferably 1.0 × 10 ^{4.30 to} 1.0 × 10 ^4.40 .

It is known that a low molecular weight component has a strong influence on the mechanical strength of an ethylene copolymer. The presence of low molecular weight components is thought to decrease the mechanical strength due to an increase in molecular ends that are thought to be the starting point of destruction (edited by Kazuo Matsuura and Naotaka Mikami, “Polyethylene Technology Reader”, Inc. Industrial Research Committee, 2001, p.45). When the molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is 1.0 × 10 ^4.20 or more, there are few low molecular weight components that adversely affect the mechanical strength. Excellent.

  It is known that the molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system. (For example, Kazuo Soga et al., “Catalytic Olefin Polymerization”, Kodansha Scientific, 1990, p.376). Therefore, by increasing / decreasing hydrogen / ethylene, it is possible to increase / decrease the molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve.

  The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve is calculated as follows using a gel permeation chromatograph alliance GPC2000 (high temperature size exclusion chromatograph) manufactured by Waters.

[Devices and conditions]
Analysis software: Chromatographic data system Empower (Waters)
Column: TSKgel GMH ₆ -HT x 2 + TSKgel GMH _6- HTL x 2
(Inner diameter 7.5mm x length 30cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene (Wako Pure Chemicals special grade reagent)
Detector: Differential refractometer (built-in device)
Column temperature; 140 ° C
Flow rate: 1.0 mL / min injection volume: 500 μL
Sampling time interval; 1 second sample concentration; 0.15% (w / v)
Molecular weight calibration: Monodisperse polystyrene (Tosoh Corp.) / Molecular weight 495 ~ Molecular weight 20.6 million
A molecular weight distribution curve is prepared in terms of polyethylene molecular weight according to the procedure of general calibration described in Z. Crubisic, P. Rempp, H. Benoit, J. Polym. Sci., B5 , 753 (1967). From this molecular weight distribution curve, the molecular weight (peak top M) at the maximum weight fraction is calculated.

Next, the manufacturing method of the ethylene copolymer in this invention is demonstrated.
The ethylene copolymer according to the present invention comprises component (A), component (B), component (C), ethylene, in the presence of an olefin polymerization catalyst, and having 6 to 20 carbon atoms. It can be efficiently produced by polymerizing α-olefin.

Component (A) : A bridged metallocene compound represented by the following general formula (I).

However, in formula (I), R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, Selected from a silicon-containing group, a germanium-containing group and a tin-containing group, which may be the same or different from each other, but not all are simultaneously hydrogen atoms, Q ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, Selected from a silicon-containing group, a germanium-containing group and a tin-containing group, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, or a nitrogen-containing group. It is a group selected from a group and a phosphorus-containing group. M is titanium, zirconium or hafnium.

Component (B) : A bridged metallocene compound represented by the following general formula (II).

However, in the formula (II), R ^{7 to} R ¹⁰ and R ^{13 to} R ²⁰ are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, or a sulfur-containing group. Selected from a group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and may be the same or different from each other, and adjacent substituents may be bonded to each other to form a ring.
Q ² is a group selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. M is selected from titanium, zirconium and hafnium, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and It is a group selected from phosphorus-containing groups.

Component (C) : at least one compound selected from the group consisting of the following (c-1) to (c-3).
(C-1) Organometallic compound represented by the following general formula (III), (IV) or (V) R ^a _m Al (OR ^b ) _n H _p X _q (III)
(In the formula (III), R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, and m represents 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.
_{^{M a AlR a 4 ... (IV}} )
(In formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms.)
R ^a R ^b M ^b (V)
(In the formula (V), R ^a and R ^b may be the same as or different from each other, each represent a hydrocarbon group having 1 to 15 carbon atoms, and M ^b is Mg, Zn or Cd.)
(C-2) Organoaluminum oxy compound (c-3) Compound which reacts with component (A) and component (B) to form an ion pair The olefin polymerization catalyst according to the present invention further comprises a solid carrier (S) As such a catalyst, the solid support (S), the component (C), the solid catalyst component (K1) formed from the component (A), and the solid support (S ), A catalyst for olefin polymerization comprising the solid catalyst component (K2) formed from the component (C) and the component (B), a solid support (S), the component (A), the component (B) and the component There is an olefin polymerization catalyst comprising a solid catalyst component (K3) formed from (C).

  As a mechanism for producing the ethylene copolymer of the present invention by the above-mentioned catalyst for olefin polymerization, the present inventors have made use of the components (A) and (C) and, if necessary, the component (S) for olefin polymerization. In the presence of a catalyst component, ethylene or ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 4 to 10 carbon atoms are polymerized to polymerize a number average molecular weight of 4000 to 20000, preferably 4000 A “macromonomer” which is a polymer having 15,000 terminal vinyls is produced, and then ethylene and a catalyst component for olefin polymerization containing component (B) and component (C), and optionally component (S). By copolymerizing the macromonomer competitively with the polymerization of an α-olefin having 6 to 20 carbon atoms, the long-chain branched ethylene of the present invention is obtained. We believe that emissions copolymer is produced.

Next, each component of the olefin polymerization catalyst used when producing the ethylene copolymer of the present invention will be described in detail.
The bridged metallocene compound of component (A) used in the present invention is a metallocene compound belonging to Group 4 of the periodic table represented by the following general formula (I). The metallocene compound of Group 4 of the periodic table represented by the following general formula (I) will be described in detail.

In general formula (I), M represents a group 4 transition metal atom in the periodic table, specifically titanium, zirconium, or hafnium, preferably zirconium.
R ^{1 to} R ⁴ are hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups. They may be the same or different from each other, but not all are hydrogen atoms at the same time. Moreover, R < ¹ > -R < ⁴ > may combine the adjacent group mutually and may form the aliphatic ring.

  The hydrocarbon group means an alkyl group composed of 1 to 20 carbon atoms and hydrogen, a cycloalkyl group, an alkenyl group, an aryl group, and an arylalkyl group. For example, as an alkyl group, a methyl group, an ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, nonyl group, dodecyl group, eicosyl group Etc. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group. Examples of the aryl group include phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, Examples include anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, and arylalkyl groups include benzyl, phenylethyl, phenylpropyl, and the like.

Examples of the halogen-containing group include groups in which one or more hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, such as a trifluoromethyl group.
Examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a thiol group and a sulfonic acid group. Examples of the nitrogen-containing group include a dimethylamino group. Examples thereof include a phenylphosphine group. Examples of the boron-containing group include a boranediyl group, a boranetriyl group, and a diboranyl group.

  Silicon-containing groups include silyl, methylsilyl, dimethylsilyl, diisopropylsilyl, methyl-t-butylsilyl, dicyclohexylsilyl, methylcyclohexylsilyl, methylphenylsilyl, diphenylsilyl, methylnaphthylsilyl, dinaphthylsilyl, cyclodimethylenesilyl, cyclo Examples include trimethylene silyl, cyclotetramethylene silyl, cyclopentamethylene silyl, cyclohexamethylene silyl, cycloheptamethylene silyl, and the like. Germanium and tin-containing groups include groups obtained by converting silicon into germanium and tin in the silicon-containing groups. Etc.

Examples of the case where adjacent groups of R ^{1 to} R ⁴ are bonded to each other to form an aliphatic ring include tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,2,4-trimethyltetrahydroindenyl, 4-phenyltetrahydroindenyl, 2-methyl-4-phenyltetrahydroindenyl, substituted cyclopenta in which R ³ and R ⁴ are cyclically bonded via a tetramethylene group and R ¹ and R ² are cyclically bonded via a tetramethylene group A dienyl group etc. are mentioned.

Q ¹ is a divalent group that binds two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, or an alkylidene group, a halogen-containing group, a silicon-containing group, germanium It is a group selected from a containing group and a tin-containing group.

  Specific examples of the alkylene group having 1 to 20 carbon atoms, the substituted alkylene group, and the alkylidene group include alkylene groups such as methylene, ethylene, propylene, and butylene, isopropylidene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, and methyl. Ethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1, Substituted alkylene groups such as 2-dimethylethylene and 1-ethyl-2-methylethylene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylide , Cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthyl dust Den, cycloalkylene groups such as dihydroindolyl mites isopropylidene, ethylidene, propylidene, and the like alkylidene group such as butylidene.

  Silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methyl Naphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like, and germanium and tin-containing groups include the above Examples of the silicon-containing group include a group obtained by converting silicon into germanium or tin.

  As the halogen-containing group, a group in which one or more hydrogen atoms in the above-mentioned alkylene group, substituted alkylene group, alkylidene group or silicon-containing group are substituted with an appropriate halogen atom is selected. For example, bis (trifluoromethyl) Examples include methylene, 4,4,4-trifluorobutylmethylmethylene, bis (trifluoromethyl) silylene, 4,4,4-trifluorobutylmethylsilylene and the like.

Among these, preferred groups for Q ¹ include alkylene groups having 1 to 20 carbon atoms, substituted alkylene groups, alkylidene groups, halogen-containing alkylene groups, halogen-containing substituted alkylene groups, halogen-containing alkylidene groups, silicon-containing groups, and halogen-containing silicon-containing groups. And a particularly preferred group is a silicon-containing group or a halogen-containing silicon.

Q ¹ may have a structure represented by either the following general formula [1] or [2].

Here, Y is selected from a carbon atom, a silicon atom, a germanium atom, and a tin atom. R ⁵ and R ⁶ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, and a halogen-containing group, and may be the same or different. A represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, and A may contain two or more ring structures including a ring formed with Y. A black circle (●) represents a point of attachment to a substituted cyclopentadienyl group or cyclopentadienyl group.

In the general formulas [1] and [2], Y is preferably a carbon atom or a silicon atom, and particularly preferably a silicon atom.
The hydrocarbon group, silicon-containing group, germanium-containing group, tin-containing group, and halogen-containing group of R ⁵ and R ^{6 in} the general formula [1] are the same as those for R ¹ , R ² , R ³ , and R ^4. It can be mentioned as an example. Among the hydrocarbons, methyl group, chloromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, cycloheptyl It is preferably a group selected from a group, a phenyl group, an m-tolyl group, and a p-tolyl group, and particularly preferably selected from a methyl group, a chloromethyl group, an n-butyl group, an n-pentyl group, and a phenyl group. .

  In the general formula [2], A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, Y is bonded to this A, and a 1-silacyclopentylidene group or the like Configure. In the present specification, the 1-silacyclopentylidene group represents the following formula [3].

(In the above formula [3], the black circle (●) is the same as the general formula [2].)
A may contain two or more ring structures including a ring formed with Y.
Among these, preferred groups for Q ¹ include alkylene groups having 1 to 20 carbon atoms, substituted alkylene groups, alkylidene groups, halogen-containing alkylene groups, halogen-containing substituted alkylene groups, halogen-containing alkylidene groups, silicon-containing groups, and halogen-containing silicon-containing groups. And a particularly preferred group is a silicon-containing group or a halogen-containing silicon-containing group.

  X independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group (for example, a halogen-containing hydrocarbon group), a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group. The selected group is preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, hydrocarbon group, halogen-containing group (for example, halogen-containing hydrocarbon group), silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus. Examples of the containing group include the same groups as described above.

A preferred group of R ^{1 to} R ⁴ is a group selected from a hydrogen atom, a hydrocarbon group, and a halogen-containing group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, and still more preferably, Three of the substituents of R ^{1 to} R ⁴ are hydrogen atoms, the remaining one is a hydrocarbon group having 1 to 15 carbon atoms, and more preferably, three of the substituents of R ^{1 to} R ⁴ are hydrogen. An atom, the remaining one being a hydrocarbon group having 3 to 15 carbon atoms, particularly preferably three of the substituents of R ^{1 to} R ⁴ are hydrogen atoms, and the remaining one is a carbon group having 3 to 8 carbon atoms. hydrocarbon is a group, very preferably, wherein R ¹ and R ⁴ are hydrogen atoms among the substituents of R ¹ to R ^4, one of either R ² and R ³ is a hydrocarbon group having 3 to 8 carbon atoms And the other is a hydrogen atom.

Specific examples of the transition metal compound of the component (A) represented by the general formula (I) are shown below.
Specific examples include ethylene (cyclopentadienyl) (2-methylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl). (2-ethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2-n-propylcyclopentadienyl) zirconium Dichloride, ethylene (cyclopentadienyl) (2-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, ethylene (cycl Pentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-pentylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-hexyl) Cyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-decylcyclopentadienyl) zirconium dichloride, Ethylene (cyclopentadienyl) (2,3-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,4-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) ) (2,5-dimethylcyclopentadienyl) zirconium dichloride,
Ethylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3,4-di-n-propylcyclopentadienyl) zirconium dichloride, ethylene (cyclopenta Dienyl) (3,4-di-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,4-ethylmethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-methyl, 4 -N-propylcyclopen Dienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) Zirconium dichloride, ethylene (cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,5-dimethyl, 3-n-propylcyclopentadienyl) Zirconium dichloride, ethylene (cyclopentadienyl) (2,5-dimethyl, 3-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene Cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-propylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,5-dimethyl, 3,4-di-n -Bridged cyclopentadienyl) bridged asymmetric metallocene compound having an alkylene group such as zirconium dichloride at the crosslinking site;
Isopropylidene (cyclopentadienyl) (2-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2 -Ethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-n-propylcyclopentadienyl) zirconium Dichloride, isopropylidene (cyclopentadienyl) (2-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-propylcyclopentadienyl) Zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-pentylcyclopentadienyl) zirconium dichloride, isopropylidene ( Cyclopentadienyl) (3-n-hexylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ( 3-n-decylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ) (2,4-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,5-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4- Dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-di-n-propylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-di-) n-butylcyclopentadienyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,4-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclo Pentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methyl, 4-n-propylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopenta Dienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) zirconium dichloride, isopropyl Pyridene (cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,5-dimethyl, 3-n-propylcyclopentadienyl) zirconium dichloride Isopropylidene (cyclopentadienyl) (2,5-dimethyl, 3-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (Cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-propylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,5-dimethyl, 3,4-di -N-Butylcyclopentadie Bridged asymmetric metallocene compounds having a substituted alkylene group such as Le) zirconium dichloride crosslinking site;
Dimethylsilylene (cyclopentadienyl) (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2 -Ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2-n-propylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (2-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) Zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-pentylcyclopentadienyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl) (3-n-hexylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ( 3-n-decylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ) (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4- Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-di-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-di-) n-butylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene (cyclopentadienyl) (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclo Pentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl, 4-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopenta Dienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethyl, 3-n-propylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (2,5-dimethyl, 3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (Cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethyl, 3,4-di -N-Butylcyclopentadie Le) bridged asymmetric metallocene compounds having a silicon-containing group, such as zirconium dichloride crosslinking site.

  In addition, a crosslinked asymmetric metallocene in which the isopropylidene crosslinking group of the substituted alkylene group is changed to a di-n-butylmethylene crosslinking group, and a crosslinked type in which the dimethylsilylene crosslinking group of the silicon-containing group is changed to a di-n-butylsilylene crosslinking group Asymmetric metallocenes, bridged asymmetric metallocenes in which one or more of the hydrogen atoms in the bridging group are changed to halogen atoms, bridges in which one or more of the hydrogen atoms of the substituent bonded to the cyclopentadienyl ring is changed to halogen atoms Type asymmetric metallocenes. Moreover, although the metallocene compound etc. whose center metal of the said compound is titanium or hafnium are mentioned, it is not limited to these.

  Among these, as a preferable compound, a crosslinked asymmetric metallocene having a silicon-containing group such as a dimethylsilylene group at a crosslinking site is selected. Among them, a particularly preferable compound is dimethylsilylene (cyclopentadienyl) (3-ethyl). Cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, Methylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene ( Cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene ( Cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride and the like. In the present invention, two or more kinds of metallocene compounds represented by the general formula (I) having different structures are used, or metallocenes having the same structure and comprising an optical isomer mixture (for example, meso / racemic mixture). There is no restriction on the use of the compound.

Such a bridged metallocene compound represented by the general formula (I) can be produced by the method disclosed in WO 01/27124.
The bridged metallocene compound of component (B) used in the present invention is a group 4 metallocene compound represented by the following general formula (II). The metallocene compound of Group 4 of the periodic table represented by the following general formula (II) will be described in detail.

In the general formula (II), M is a transition metal selected from titanium, zirconium and hafnium, preferably zirconium.
R ^{7 to} R ¹⁰ , R ^{13 to} R ²⁰ are hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing Selected from a group and a tin-containing group, which may be the same or different from each other, and two adjacent groups may be linked to each other to form a ring.

Q ² is a divalent group that binds two ligands, and includes a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, and an alkylidene group, a halogen-containing group, a silicon-containing group, germanium It is a group selected from a containing group and a tin-containing group. Specific examples of these groups include those described for Q ¹ above.

Q ² may have a structure represented by any of the following general formulas [4] and [5].

Here, Y is selected from a carbon atom, a silicon atom, a germanium atom, and a tin atom. R ²¹ and R ²² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, and a halogen-containing group, and may be the same or different. A ′ represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, and A ′ may contain two or more ring structures including a ring formed with Y. Good. A black circle (●) represents a point of attachment to the substituted cyclopentadienyl group and the substituted fluorenyl group.

In the above general formulas [4] and [5], Y is preferably a carbon atom or a silicon atom, particularly preferably a carbon atom.
The hydrocarbon group, silicon-containing group, germanium-containing group, tin-containing group, and halogen-containing group of R ²¹ and R ^{22 in} the general formula [4] are the same as R ^{7 to} R ¹⁰ and R ^{13 to} R ^20. It can be mentioned as an example. Among the hydrocarbon groups, methyl group, chloromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, cyclohexane It is preferably a group selected from a heptyl group, a phenyl group, an m-tolyl group, and a p-tolyl group, and particularly preferably selected from a methyl group, a chloromethyl group, an n-butyl group, an n-pentyl group, and a phenyl group. preferable.

  In the general formula [5], A ′ is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, Y binds to this A ′, and 1-silacyclopentylidene Configure the group. In the present specification, the 1-silacyclopentylidene group represents the following formula [6].

(In the above formula [6], the black circle (●) is the same as the general formula [5].)
A ′ may contain two or more ring structures including a ring formed with Y.
Among these, preferred groups for Q ² include alkylene groups having 1 to 20 carbon atoms, substituted alkylene groups, alkylidene groups, halogen-containing alkylene groups, halogen-containing substituted alkylene groups, halogen-containing alkylidene groups, silicon-containing groups, and halogen-containing silicon-containing groups. And a particularly preferred group is an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, an alkylidene group, or a silicon-containing group.

  X independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group (for example, a halogen-containing hydrocarbon group), a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group. The selected group is preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, hydrocarbon group, halogen-containing group (for example, halogen-containing hydrocarbon group), silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus. Examples of the containing group include the same groups as described above.

Hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing R ^{7 to} R ¹⁰ and R ^{13 to} R ²⁰ As for the group or tin-containing group, those specifically described in R ^{1 to} R ⁴ in the general formula (I) can be used without limitation, and X is also described for X in the general formula (I). Can be used without limitation. Also, R ^{7 to} R ¹⁰ on the cyclopentadienyl ring are bonded to each other to form a ring, for example, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group. R ^{13 to} R ²⁰ on the fluorene ring may be bonded to each other to form a ring, for example, a benzofluorenyl group or a dibenzofluorenyl group. An octahydrodibenzofluorenyl group, an octamethyloctahydrodibenzofluorenyl group, or the like may be formed.

As the above preferred group form, R ^{7 to} R ¹⁰ are selected from hydrogen atoms, R ^{13 to} R ²⁰ are selected from hydrogen atoms and hydrocarbon groups, and at least of the adjacent hydrocarbon groups. An octahydrodibenzofluorenyl group and an octamethyloctahydrodibenzofluorenyl group in which one set is bonded to each other to form a ring are also selected as preferred groups. With respect to Q ² , groups represented by general formula [4] and general formula [5] are selected, Y is a carbon atom, and R ²¹ and R ²² are each preferably a hydrocarbon group. When these substituents and crosslinking groups are used, the improvement in molecular weight is relatively suppressed, and the amount of macromonomer generated from component (A) increases due to the reduction in the amount of hydrogen necessary to adjust the molecular weight. Is expected to increase the number of long chain branches.

Specific examples of such metallocene compounds belonging to Group 4 of the periodic table represented by the general formula (II) are shown below, but the present invention is not limited thereto.
Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3 6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, Dibutylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) Luconium dichloride, dibutylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2 , 7-Di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octa Methyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium Dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) ( 2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclope Tadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (2,7-di-tert-butylfluorene) Nyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium Dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfullyl) Rhenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (octa Methyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (2,7-di) -tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl) Le cyclopentadienyl) (octamethyl octa hydride blunder benz fluorenyl) zirconium dichloride,
Cyclohexylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, Cyclohexylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride , Cyclohexylidene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butylcyclopentadienyl) (octamethylocta Hydridodibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (2,7-di -tert- Tylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (Octamethyloctahydridodibenzfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclohexane) Pentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorene) Nyl) zirconium di Loride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (Fluorenyl) zirconium dichloride,
Diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) ) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohex Silidene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert- Butylfluorenyl) zirconium dichloride, cyclohexylide (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopentadienyl) (Octamethyloctahydrido-dibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5) -Methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert -Butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, and dibromide compounds, dialkyl compounds, diaralkyl compounds, disilyl compounds, dialkoxy compounds of the above metallocene compounds, Examples thereof include a dithiol compound, a disulfonic acid compound, a diamino compound, a diphosphine compound, or a metallocene compound in which the central metal of the above compound is titanium or hafnium.

  Among these, preferred metallocene compounds include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene ( Cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadi) Enyl) (fluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) ) Zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-tert-butylfull) Olenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride Dimethylsilyl (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, Examples include dimethylsilyl (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride.

Further, as specific examples of preferred metallocene compounds having adjacent groups of R ^{7 to} R ¹⁰ on the cyclopentadienyl ring to form a ring and having an indenyl ring and a substituted indenyl ring, isopropylidene (indenyl) (Fluorenyl) zirconium dichloride, isopropylidene (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, Isopropylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (fluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (2,7-di-tert-butylfluorenyl) Zirconium dichloride, cyclohexylidene (indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (indenyl) ) (Fluorenyl) zirconium dichloride, dimethylsilyl (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride And dimethylsilyl (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride. In the present invention, the use of two or more kinds of metallocene compounds represented by the general formula (II) having different structures is not limited.

Such a bridged metallocene compound represented by the general formula (II) is disclosed in WO 01/27124.
Next, the component (C) will be specifically described.

In the olefin polymerization catalyst according to the present invention, the component (C) used together with the compound represented by the component (A) and the component (B),
(C-1) an organometallic compound represented by the following general formula (III), (IV) or (V),
R ^a _m Al (OR ^b ) _n H _p X _q (III)
[In the general formula (III), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ]
_{^{M a AlR a 4 ... (IV}} )
[In General Formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (V)
[In General Formula (V), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, and may be the same or different from each other, and M ^b is selected from Mg, Zn and Cd. , X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]
(C-2) an organoaluminum oxy compound, and (c-3) a compound that reacts with component (A) and component (B) to form an ion pair,
At least one compound selected from the group consisting of:

As the compound (c-1), compounds disclosed in JP-A-11-315109 and EP0874005A by the present applicant can be used without limitation.
(C-1) Among the organometallic compounds represented by the general formula (III), (IV) or (V), those represented by the general formula (III) are preferable, specifically, trimethylaluminum, triethyl Trialkylaluminum such as aluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide Dialkylaluminum halide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum Alkyl aluminum sesquihalides such as cyclochloride and ethylaluminum sesquibromide, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, alkylaluminum dihalides such as ethylaluminum dibromide, dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropyl Aluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, di-sec-nonylaluminumhigh Examples thereof include alkyl aluminum hydrides such as dride, dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum methoxide and diisobutyl aluminum ethoxide.

These are used singly or in combination of two or more.
(C-2) The organoaluminum oxy compound is preferably an aluminoxane prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum. Such organoaluminum oxy compounds are used singly or in combination of two or more.

  (C-3) As compounds that react with component (A) and component (B) to form ion pairs, JP-A-1-501950, JP-A-1-503636, JP-A-3-179005 Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. Furthermore, heteropoly compounds and isopoly compounds can be used without limitation.

  In the olefin polymerization catalyst according to the present invention, when an organoaluminum oxy compound such as methylaluminoxane is used in combination as a co-catalyst component, the olefin compound exhibits not only very high polymerization activity but also active hydrogen in the solid support. Since a solid carrier component that reacts and contains a cocatalyst component can be easily prepared, it is preferable to use (c-2) an organoaluminum oxy compound as the component (C).

Next, the solid carrier (S) will be described in detail. The solid carrier (S) may be simply expressed as “component (S)”.
The solid carrier (S) that may be used in the present invention is an inorganic or organic compound and is a granular or particulate solid, and the above-described components are converted into the following solid carrier. It is supported.

  Among these, examples of the inorganic compound include inorganic oxides such as porous oxides and inorganic chlorides, clays, clay minerals, and ion-exchangeable layered compounds. Preferably, the porous oxides and inorganic chlorides described below are used. Inorganic halides such as can be used.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or a composite or mixture containing these is used. For example, natural or synthetic zeolite, 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, etc. Can be used. Of these, those containing SiO ₂ as the main component are preferred.

Note that the inorganic oxide includes 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 , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 0.2 to 300 μm, preferably 1 to 200 μm, and a specific surface area of 50 to 1200 m. ² / g, preferably in the range of 100 to 1000 m ² / g, and the pore volume is in the range of 0.3 to ³⁰ cm ³ / g. Such a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use an inorganic halide dissolved in a solvent such as alcohol and then precipitated into fine particles by a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchange layered compound is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

In addition, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂・ H ₂ O, α-Sn (HPO ₄ ) ₂・ H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 20 cc or more and a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, as measured by a mercury intrusion method. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ⁴に よ り by a mercury intrusion method using a mercury porosimeter.

When a pore volume with a radius of 20 mm or more and a pore volume smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface, a treatment that affects the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+ and} other metal hydroxide ions Etc. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _2, etc. can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane, styrene, divinyl. Examples thereof include (co) polymers and reactants produced with benzene as a main component, and modified products thereof.

It describes about the preparation method of the catalyst for olefin polymerization in this invention.
The first olefin polymerization catalyst according to the present invention is prepared by adding the component (A), the component (B) and the component (C) in an inert hydrocarbon or a polymerization system using an inert hydrocarbon. it can.

The order of adding each component is arbitrary, but as a preferred order, for example,
i) Method of adding component (C), component (A), and component (B) to the polymerization system in this order
ii) A method of adding component (C), component (B), and component (A) to the polymerization system in this order.
iii) A method in which a contact product obtained by mixing and contacting component (A) and component (C) is added to the polymerization system, and then component (B) is added to the polymerization system.
iv) A method in which a contact product obtained by mixing and contacting component (B) and component (C) is added to the polymerization system, and then component (A) is added to the polymerization system. v) Component (C) is added to the polymerization system. And then adding a contact product obtained by mixing and contacting the component (A) and the component (B) into the polymerization system
vi) A method in which component (C), component (A) and component (B) are added to the polymerization system in this order, and component (C) is added again to the polymerization system.
vii) A method in which component (C), component (B), and component (A) are added to the polymerization system in this order, and component (C) is added again to the polymerization system.
viii) A contact product obtained by mixing and contacting component (A) and component (C) is added to the polymerization system, then component (B) is added to the polymerization system, and component (C) is added again to the polymerization system. how to
ix) A contact product obtained by mixing and contacting component (B) and component (C) is added to the polymerization system, then component (A) is added to the polymerization system, and component (C) is added again to the polymerization system. Method x) Component (C) is added to the polymerization system, and then a contact product obtained by mixing and contacting component (A) and component (B) is added to the polymerization system, and then component (C) is added again to the polymerization system. The method of adding in is mentioned. Among these, particularly preferable contact orders include i), ii), and v).

  The second olefin polymerization catalyst according to the present invention comprises a solid support (S), the solid catalyst component (K1) formed from the component (C) and the component (A), and the solid support (S). The solid catalyst component (K2) formed from the component (C) and the component (B) can be prepared by adding it into an inert hydrocarbon or a polymerization system using an inert hydrocarbon.

Although the contact order of each component is arbitrary, as a preferable method, for example,
xi) The component (C) and the component (S) are contacted, then the solid catalyst component (K1) prepared by contacting the component (A), the component (C) and the component (S) are contacted, and then the component (B ) Using a solid catalyst component (K2) prepared by contacting
xii) Mixing contact of the component (A) and the component (C), then contacting the component (S), the solid catalyst component (K1), the component (B) and the component (C) are mixed and contacted, and then the component Method using solid catalyst component (K2) prepared by contacting with (S)
xiii) The solid catalyst component (K1), the component (C), and the component (S) prepared by bringing the component (C) and the component (S) into contact with each other and then contacting the contact product of the component (A) with the component (C). Using the solid catalyst component (K2) prepared by bringing the catalyst into contact with each other and then bringing the contact product of component (B) and component (C) into contact with each other
xiv) Solid catalyst component (K1), component (C), and component (C) prepared by bringing component (C) and component (S) into contact, then contacting component (A), and then contacting component (C) again. Examples thereof include a method using a solid catalyst component (K2) prepared by contacting S), then contacting component (B), and again contacting component (C). Among these, particularly preferable contact order includes xi) and xiii).

  The third olefin polymerization catalyst (K3) according to the present invention can be prepared by contacting the component (A), the component (B), the component (C) and the solid carrier (S) in an inert hydrocarbon. .

The order of contacting the components is arbitrary, but as a preferred order, for example,
xv) A method in which component (S) is mixed and contacted with component (S), then contacted with component (A), and then contacted with component (B)
xvi) A method in which component (S) is mixed and contacted with component (S), then contacted with component (B), and then contacted with component (A)
xvii) a method in which component (C) is mixed and contacted with component (S), and then a contact mixture of component (A) and component (B) is contacted;
xviii) a method in which component (A) and component (B) are mixed and contacted, then contacted with component (C), and subsequently contacted with component (S);
xix) A method of contacting the component (S) with the component (C), further contacting the component (C), and then contacting the component (A) and then the component (B) in this order,
xx) A method of contacting the component (S) with the component (C), further contacting the component (C), and then contacting the component (B) and then the component (A) in this order,
xxi) A method in which the component (S) is contacted with the component (C), the component (C) is further contacted, and then the contact mixture of the component (A) and the component (B) is contacted.
xxii) a method in which component (C) is mixed and contacted with component (S), and then a contact mixture of component (A), component (B) and component (C) is contacted;
xxiii) A method in which the component (S) is mixed and contacted with the component (S), then the contact mixture of the component (A) and the component (C) is contacted, and the component (B) is further contacted.
xxiv) A method in which component (C) is mixed and contacted with component (S), then a contact mixture of component (B) and component (C) is contacted, and further component (A) is contacted,
xxv) After contacting component (S) with component (C) and further contacting component (C), then contact mixture of component (A) and component (C), component (B) and component (C) A method of contacting in the order of the contact mixture,
xxvi) After contacting component (S) with component (C) and further contacting component (C), the contact mixture of component (B) and component (C), then component (A) and component (C) A method of contacting in the order of the contact mixture,
xxvii) a method of contacting the component (S) with the component (C), further contacting the component (C), and then contacting the contact mixture of the component (A), the component (B) and the component (C);
xxviii) a method in which a mixture of component (A) and component (C) and a mixture of component (B) and component (C) are premixed and contacted with the contact product of component (S) and component (C),
xxix) A mixture of component (A) and component (C) and a mixture of component (B) and component (C) are mixed in advance, and this is brought into contact with component (S), component (C), and further component (C). The method of making it contact with the contacted thing etc. is mentioned. When a plurality of components (C) are used, the components (C) may be the same or different. Among these, particularly preferable contact orders include xv), xvi), xvii), xxii), xxiii), and xxiv), and more preferably xvii) and xxii).

  In each method showing the contact order form, the step (P1) including the contact between the component (S) and the component (C), the step (P2) including the contact between the component (S) and the component (A), and the component (S ) And component (B) contact (P3), component (S), component (A) and step including contact (B) component (G) (g-1) polyalkylene oxide block , (G-2) higher aliphatic amide, (g-3) polyalkylene oxide, (g-4) polyalkylene oxide alkyl ether, (g-5) alkyldiethanolamine and (g-6) polyoxyalkylenealkylamine At least one selected compound may coexist. By allowing the component (G) to coexist, fouling during the polymerization reaction is suppressed, and the particle properties of the produced polymer are improved. Among the components (G), (g-1), (g-2), (g-3) and (g-4) are preferable, and (g-1) and (g-2) are particularly preferable.

Examples of the solvent used for the preparation of the solid catalyst component of the present invention include an inert hydrocarbon solvent,
Specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene Aromatic hydrocarbons such as ethylene chloride, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof.

  The contact between the component (C) and the component (S) is chemically combined by the reaction between the reaction site in the component (C) and the reaction site in the component (S), and the contact between the component (C) and the component (S) A contact is formed. The contact time between component (C) and component (S) is usually 0 to 20 hours, preferably 0 to 10 hours, and the contact temperature is usually -50 to 200 ° C, preferably -20 to 120 ° C. Is called. When the initial contact between the component (C) and the component (S) is suddenly performed, the component (S) collapses due to the reaction heat generation or reaction energy, and the morphology of the resulting solid catalyst component deteriorates, and this is used for polymerization. In many cases, continuous operation becomes difficult due to poor polymer morphology. Therefore, the initial contact temperature between the component (C) and the component (S) can be maintained at a low temperature of −20 to 30 ° C. for the purpose of suppressing the reaction exotherm, or the initial contact temperature can be maintained by controlling the reaction exotherm. It is preferable to react at a moderate rate. The same applies to the case where the component (C) and the component (S) are contacted and the component (C) is further contacted. The molar ratio of contact between the component (C) and the component (S) (component (C) / component (S)) can be arbitrarily selected, but the higher the molar ratio, the higher the component (A) and the component (B). Can be increased, and the activity per solid catalyst component can be improved.

  As a preferred range, the molar ratio of the component (C) to the component (S) [= molar amount of the component (C) / molar amount of the component (S)] is usually 0.2 to 2.0, particularly preferably 0. .4 to 2.0. Regarding the contact between the contact product of component (C) and component (S), and component (A) and component (B), the contact time is usually 0 to 5 hours, preferably 0 to 2 hours, and the contact temperature is Usually, it is carried out within a range of -50 to 200 ° C, preferably -50 to 100 ° C. The contact amount of component (A) and component (B) largely depends on the type and amount of component (C). In the case of component (c-1), all transitions in component (A) and component (B) The molar ratio [(c-1) / M] of the metal atom (M) and the component (c-1) is usually 0.01 to 100,000, preferably 0.05 to 50,000, Component (c-2) is a molar ratio [(c-2) / M] of aluminum atoms in component (c-2) and all transition metal atoms (M) in components (A) and (B). Is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. Component (c-3) has a molar ratio [(c-3) / M] of component (c-3) to all transition metal atoms (M) in component (A) and component (B). The amount used is 1 to 10, preferably 1 to 5. The ratio of component (C) to all transition metal atoms (M) in component (A) and component (B) can be determined by inductively coupled plasma emission analysis (ICP analysis).

  The use ratio of the component (A) to the component (B) can be arbitrarily determined from the molecular weight and molecular weight distribution of the polyolefin to be produced. As a preferred range, the ratio of the polymer produced from the component (A) and the component (B) [= Component (A) produced polymer amount / component (B) produced polymer amount] is usually 40/60 to 95/5, preferably 50/50 to 95/5, particularly preferably 60/40 to 95 /. 5. Here, it is preferable that the amount of the polymer derived from the component (A) is large because the macromonomer is generated from the component (A), and the amount of the generated amount is more advantageous for generating a long chain branch. is there. In addition, the molar ratio of the component (A) and the component (B) to be used per transition metal compound should satisfy the above-mentioned polymer ratio, and the ratio is approximately the contact between the component (S) and the component (C). It can be arbitrarily selected depending on the activity ratio expressed from the solid catalyst component in which the component (A) or the component (B) is contacted independently. In addition, the ratio of the polymer produced | generated from a component (A) and a component (B) can be calculated | required from the below-mentioned peak separation.

  The polymer is substantially composed of two or three peaks, and the first peak is a peak derived from the component (A) (sometimes referred to as “component (A) peak”), The second peak is a peak due to component (B) (may be described as “component (B) peak”), and the third peak is for both component (A) and component (B). It is a peak that is generated only for the first time (sometimes referred to as “third peak”). The abundance ratio of each peak can be clearly confirmed by separation according to the peak separation method described below.

  In addition, regarding the determination of the generation ratio when each peak is overlapped and observed as a single peak or a shoulder, if the separation is performed by the method described later, the peak is caused by the component (A) and the component (B). The presence of the peak as well as the third peak can be clearly confirmed.

The peak separation of the molecular weight curve (G1) of the ethylene polymer produced by the polymerization method according to the present invention is the component (A), component (C), component polymerized under the same polymerization conditions as the ethylene polymer. Molecular weight curve (G2) of ethylene polymer [may be described as a polymer containing only component (A)] obtained using the particulate catalyst comprising (S), component (B), component (C) The molecular weight curve (G3) of an ethylene polymer [may be described as a polymer containing only the component (B)] obtained by using a particulate catalyst comprising the component (S) is carried out by the following method. did. In addition, the molecular weight curve used what was obtained by GPC measurement mentioned above, and the calculation of peak separation used Excel (trademark) 97 by Microsoft Corporation.
[1] In the numerical data of (G1), (G2), (G3), Log (molecular weight) is divided into 0.02 intervals, and the intensity [dwt / d (log Molecular weight)] is normalized.
[2] A composite curve (G4) of (G2) and (G3) is created.
[3] The intensity at each molecular weight of (G2) and (G3) at a certain ratio so that the absolute value of the difference between the intensity of (G1) and the intensity of (G4) at each molecular weight is 0.0004 or less. Change it arbitrarily. Note that, on the high molecular weight side, the absolute value of the difference between the intensity of (G1) and the intensity of (G4) becomes larger than 0.0004 due to the influence of the third peak to be generated, and therefore on the lower molecular weight side (G1 The intensity of (G2) and (G3) is changed so that the absolute value of the difference between the intensity of (G) and the intensity of (G4) is 0.0004 or less.
[4] The portion (G5) [(G1)-(G4)] where (G1) and (G4) do not overlap each other on the high molecular weight side from the peak top is defined as the third peak. The polymer polymerization ratio Wa caused by the component (A), the polymer weight ratio Wb caused by the component (B), and the third peak weight ratio W ₃ are calculated as follows.

Wa = S (G2) / S (G1)
Wb = S (G3) / S (G1)
W ₃ = S (G5) / S (G1)
Here, S (G2) and S (G3) are peak areas of (G2) and (G3) after the intensity is changed, and S (G1) and S (G5) are those of (G1) and (G5). Peak area.
The ratio of the polymer produced from component (A) and component (B) (component (A) / component (B)) can be determined from Wa / Wb.

The preferred ranges are 40% <Wa ≦ 95%, 5% <Wb ≦ 60%, 0% ≦ W ₃ ≦ 30%, and the particularly preferred range is 60% <Wa ≦ 95%, 5% < Wb ≦ 40%, 2% ≦ W ₃ ≦ 20%.

In the (co) polymerization of olefins, the solid catalyst component as described above can be used as it is, but it can also be used after prepolymerizing the olefin with this solid catalyst component to form a prepolymerized solid catalyst component.

  The prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin in the presence of the solid catalyst component, usually in an inert hydrocarbon solvent, and can be prepared by any of batch, semi-continuous and continuous methods. Can also be carried out under reduced pressure, normal pressure or increased pressure. Furthermore, it is desirable that the prepolymerized solid catalyst component is produced by prepolymerization in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of the solid catalyst component.

  After separating the prepolymerized solid catalyst component produced in the inert hydrocarbon solvent from the suspension, it may be suspended again in the inert hydrocarbon, and the olefin may be introduced into the resulting suspension. Further, olefin may be introduced after drying.

  In the prepolymerization, the prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. In the prepolymerization, an olefin similar to the olefin used in the polymerization described later is used, but an olefin mainly composed of ethylene is preferable.

  As the form of the solid catalyst component used for the prepolymerization, those already described can be used without limitation. In addition, component (C) is used as necessary, and an organoaluminum compound represented by general formula (III) in (c-1) is particularly preferred and used. When the component (C) is used, the molar ratio of the aluminum atom (Al-C) and the transition metal compound in the component (C) (component (C) / transition metal compound) is 0.1 to 10,000, Preferably it is used in an amount of 0.5 to 5000.

  The concentration of the solid catalyst component in the prepolymerization system is preferably 1 to 1000 g / liter, more preferably 10 to 500 g / liter, in a ratio of solid catalyst component / polymerization volume of 1 liter. At the time of prepolymerization, the component (G) can be present together for the purpose of suppressing fouling or improving particle properties.

  In addition, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, heat spot sheeting during polymerization, and suppressing the generation of polymer lumps, the component (G) is brought into contact with the prepolymerized solid catalyst component once produced by prepolymerization. Also good. In this case, as the component (G) to be used, (g-1), (g-2), (g-3), (g-4) are preferable, and (g-1), (g-2) are particularly preferable. preferable.

The temperature at which the component (G) is mixed and contacted is usually −50 to 50 ° C., preferably −20 to 50 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.
In mixing and contacting the solid catalyst component and the component (G), the component (G) is 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the solid catalyst component. Preferably it is used in an amount of 0.4-5 parts by weight.

The mixed contact of the solid catalyst component and the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same as described above.
The olefin polymerization catalyst according to the present invention can be used as a dry prepolymerization catalyst by drying a prepolymerized solid catalyst component. The prepolymerized solid catalyst component is usually dried after removing the hydrocarbon as a dispersion medium from the suspension of the prepolymerized catalyst obtained by filtration or the like.

  Drying of the prepolymerized solid catalyst component is carried out by maintaining the prepolymerized solid catalyst component at a temperature in the range of 70 ° C. or lower, preferably 20 to 50 ° C. under the flow of inert gas. The amount of volatile components of the obtained dry prepolymerization catalyst is 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile components in the dry prepolymerization catalyst is preferably as small as possible, and there is no particular lower limit, but it is practically 0.001% by weight. The drying time is usually 3 to 8 hours depending on the drying temperature.

  When the amount of the volatile component of the dry prepolymerization catalyst exceeds 2.0% by weight, the fluidity of the dry prepolymerization catalyst is lowered, and it may be impossible to stably supply the polymerization reactor. The angle of repose of the dry prepolymerized catalyst is 50 ° or less, preferably 5 to 47 °, more preferably 10 to 45 °. When the angle of repose of the dry prepolymerized catalyst exceeds 50 °, the fluidity of the dry prepolymerized catalyst is lowered, and it may not be possible to stably supply the polymerization reactor.

Here, the amount of volatile components of the dry prepolymerization catalyst is measured by, for example, a weight loss method, a method using gas chromatography, or the like.
In the weight loss method, the weight loss when the dried prepolymerized catalyst is heated at 110 ° C. for 1 hour in an inert gas atmosphere is determined and expressed as a percentage of the dried prepolymerized catalyst before heating.

  In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dry prepolymerization catalyst, a calibration curve is prepared according to the internal standard method, and then calculated from the GC area as weight%.

  As a method for measuring the amount of volatile components in the dry prepolymerized catalyst, when the amount of volatile components in the dry prepolymerized catalyst is about 1% by weight or more, a weight reduction method is adopted, and the amount of volatile components in the dry prepolymerized catalyst is about 1 When the content is not more than% by weight, a method using gas chromatography is employed.

  Examples of the inert gas used for drying the prepolymerized solid catalyst component include nitrogen gas, argon gas, and neon gas. Such an inert gas has an oxygen concentration of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (volume basis), and a moisture content of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (weight basis). ) Is desirable. If the oxygen concentration and water content in the inert gas exceed the above ranges, the olefin polymerization activity of the dry prepolymerization catalyst may be greatly reduced.

  Since the dry prepolymerization catalyst is excellent in fluidity, it can be stably supplied to the polymerization reactor. Further, since it is not necessary to entrain the solvent used for suspension in the gas phase polymerization system, the polymerization can be stably performed.

  Next, the method for polymerizing an ethylene polymer according to the present invention will be described. Ethylene polymers are obtained by polymerizing or copolymerizing olefins in the presence of the above-mentioned catalyst for olefin polymerization. The ethylene-based polymer in the present invention refers to a polymer having an ethylene content of 10 mol% or more in the polymer.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method, but the solution polymerization method is used under the first catalyst for olefin polymerization according to the present invention. In the presence of the solid catalyst component according to the second and third inventions, it is preferable to use a suspension polymerization method or a gas phase polymerization method.

  Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the like, and using the olefin itself as a solvent You can also.

When the olefin polymerization is performed using the above-mentioned catalyst for olefin polymerization, the component (A) and the component (B) are usually 10 ⁻¹² to 10 ⁻¹ mol, preferably 10 ⁻⁸ to It is used in such an amount that it becomes 10 ⁻² mol. Component (C) is used, and an organoaluminum compound represented by general formula (III) in (c-1) is particularly preferred and used.

Moreover, the polymerization temperature of the olefin using the above-mentioned solid catalyst component is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C., particularly preferably 60 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can do. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions.

  The molecular weight of the resulting ethylene polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. At the time of polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving particle properties.

  In the present invention, the olefin supplied to the polymerization reaction can be polymerized or copolymerized with ethylene and, if necessary, an olefin having 4 to 20 carbon atoms. Specific examples of the olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene. , 1-hexadecene, 1-octadecene, α-olefin such as 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano Examples include cyclic olefins such as -1,2,3,4,4a, 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc .; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid, etc. can also be used. .

  In general, the reactivity of olefin polymerization catalysts to ethylene polymers increases as the molecular weight of the ethylene polymer decreases and the proportion of terminal double bonds increases, producing many long chain branches. I can do it. Since component (A) has a relatively low molecular weight and can produce a polymer having a number of double bonds at its terminals, it can be efficiently incorporated by component (B), and has a longer length than that of conventionally known polymers. A polymer having a chain branch can be produced. In addition, a polymer having a long chain branch can be produced with high productivity derived from the polymerization activity of the component (A).

  In order to suppress variations in physical property values, the ethylene copolymer particles obtained by the polymerization reaction and other components added as desired are melted by an arbitrary method and subjected to kneading, granulation, or the like.

  By blending the ethylene copolymer according to the present invention with another thermoplastic resin, a thermoplastic resin composition having excellent moldability and excellent mechanical strength can be obtained. The blend ratio of the ethylene copolymer according to the present invention and another thermoplastic resin is 99.1 / 0.1 to 0.1 / 99.9.

  Other thermoplastic resins include crystalline thermoplastic resins such as polyolefins, polyamides, polyesters and polyacetals; amorphous heats such as polystyrene, acrylonitrile / butadiene / styrene copolymers (ABS), polycarbonates, polyphenylene oxides, polyacrylates, etc. A plastic resin is used. Polyvinyl chloride is also preferably used.

  Specific examples of the polyolefin include ethylene copolymers, propylene polymers, butene polymers, 4-methyl-1-pentene polymers, 3-methyl-1-butene polymers, hexene polymers, and the like. Is mentioned. Of these, ethylene copolymers, propylene polymers, and 4-methyl-1-pentene polymers are preferred. When ethylene copolymers are used, even if the ethylene copolymer according to the present invention is used, a conventional ethylene copolymer is used. Although it may be a polymer or an ethylene / polar group-containing vinyl copolymer, a conventional ethylene copolymer is more preferred.

  Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycaprolactone, polyhydroxybutyrate, and the like.

  Specific examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Can be mentioned.

  Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like. Among these, polyformaldehyde is particularly preferable.

The polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene.
The ABS includes a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. Is preferably used in an amount of 40 to 60 mol%.

  Examples of the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). ) A polymer obtained from butane or the like. Of these, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.

As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferably used.
As the polyacrylate, polymethyl methacrylate or polybutyl acrylate is preferably used.

  The thermoplastic resins as described above may be used alone or in combination of two or more. Particularly preferred thermoplastic resins are polyolefins, and ethylene copolymers are more particularly preferred.

  In addition to the above thermoplastic resin, the ethylene copolymer of the present invention is a weather resistance stabilizer, heat resistance stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, as long as the object of the present invention is not impaired. Additives such as agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants may be blended.

  By processing the ethylene copolymer according to the present invention and the thermoplastic resin composition containing the ethylene copolymer, a molded body excellent in moldability and mechanical strength, preferably a film, more preferably A laminate film comprising the film is obtained.

  The ethylene copolymer of the present invention and the thermoplastic resin composition containing the ethylene copolymer are processed by general film molding, sheet molding, blow molding, injection molding and extrusion molding. Examples of film molding include extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multistage cooling, high speed processing) and the like. Although the obtained film can be used as a single layer, various functions can be imparted by forming a multilayer. In that case, the coextrusion method in each said shaping | molding method is mentioned. On the other hand, lamination with paper and barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrusion by laminating molding methods such as extrusion laminating and dry laminating are listed. It is done. Production of high-functional products by multilayering by co-extrusion methods in blow molding, injection molding, and extrusion molding is possible in the same manner as film molding.

  Examples of the molded body obtained by processing the ethylene copolymer of the present invention and the thermoplastic resin composition containing the ethylene copolymer include films, sheets, blown infusion bags, blow bottles, gasoline tanks, and extrusion molding. Examples include tubes, pipes, tear-off caps, injection molded products such as daily goods, fibers, and large molded products by rotational molding.

  Furthermore, the film obtained by processing the ethylene copolymer of the present invention and the thermoplastic resin composition containing the ethylene copolymer includes a water packaging bag, a liquid soup bag, a liquid paper container, a lami raw fabric, a special film Suitable for liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, food packaging packaging films, protective films, infusion bags, agricultural materials, etc. is there. Further, it can be used as a multilayer film by being bonded to a base material such as nylon, polyester or polyolefin film.

〔Example〕
EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. Among the methods for analyzing and evaluating the ethylene copolymer of the present invention, methods not described in the above description are as follows.

[Intrinsic viscosity ([η])]
The intrinsic viscosity [[η] (dl / g)] was measured as follows using a decalin solvent. About 20 mg of ethylene copolymer was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η _sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (η _sp / C) (C → 0)
[Number average molecular weight (Mn), Z average molecular weight (Mz), ratio of weight average molecular weight to number average molecular weight (Mw / Mn), ratio of Z average molecular weight to weight average molecular weight (Mz / Mw)]
Number average molecular weight (Mn), Z average molecular weight (Mz), ratio of weight average molecular weight to number average molecular weight (Mw / Mn), ratio of Z average molecular weight to weight average molecular weight (Mz / Mw) are GPC manufactured by Waters Using / V2000, measurement was performed as follows. The guard column uses Shodex AT-G, the analytical column uses two AT-806, the column temperature is 145 ° C., the mobile phase uses o-dichlorobenzene and BHT 0.3 wt% as an antioxidant, 1. The sample was moved at 0 ml / min, the sample concentration was 0.1% by weight, and a differential refractometer and a three-capillary viscometer were used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. The molecular weight was calculated by measuring the measured viscosity from a viscometer and a refractometer, and calculating from the measured universal calibration.

[Neck-in]
The obtained ethylene copolymer was extrusion laminated on 50 g / m ² kraft paper as a substrate under the following conditions using a 65 mmφ extruder and a Laminator manufactured by Sumitomo Heavy Industries having a T die with a die width of 500 mm. .
・ Air gap: 130mm
-Resin temperature under die: 295 ° C
・ Take-up speed: 50 m / min, 80 m / min, 120 m / min, 200 m / min ・ Film thickness: 20 μm at take-up speed of 80 m / min, 13 μm at take-up speed of 120 m / min, and take-up speed at 200 m / min Is 8μm
When the width of the T die is L ₀ and the width of the film laminated on the kraft paper at each take-off speed is L, the neck-in is calculated by L ₀ -L.

[Membrane cutting speed, take-off surging generation speed]
The obtained ethylene copolymer was placed on a 50 g / m ² kraft paper as a base material using a 65 mmφ extruder and a T die with a die width of 500 mm on a base material of 50 g / m ² craft paper. Extrusion lamination was performed under the condition of a resin temperature of 295 ° C. The amount of extrusion was set so that the film thickness was 20 μm when the take-up speed was 80 m / min.

The take-up speed was increased, and the take-off speed when the molten film was cut (including when only the end of the molten film was cut) was taken as the film-cut speed.
Also, increase the take-up speed, measure the neck-in at each take-up speed 5 times, take-up speed when the value that becomes ± 1.5mm or more with respect to the average value of the neck-in is measured twice or more Was taken as the rate of occurrence of surging.

[Resin pressure]
The obtained ethylene copolymer was placed on a 50 g / m ² kraft paper as a base material using a 65 mmφ extruder and a T die with a die width of 500 mm on a base material of 50 g / m ² craft paper. Extrusion lamination was carried out so that the film thickness was 20 μm under the conditions of a resin temperature of 295 ° C. and a take-up speed of 80 m / min. The resin pressure of the crosshead part at that time was measured.

[Heat seal strength]
Using the obtained ethylene copolymer, a laminator manufactured by Sumitomo Heavy Industries, Ltd. having a 65 mmφ extruder and a T die having a die width of 500 mm, an air gap of 130 mm, a resin temperature under the die of 295 ° C., a take-off speed of 80 m / The film was extruded and laminated to a film thickness of 25 μm under the conditions of minutes. The base material was coated with a urethane anchor coating agent on one side of a biaxially stretched nylon film (trade name: Emblem ONM, manufactured by Unitika Co., Ltd.) having a thickness of 15 μm, and then a linear chain obtained by a Ziegler catalyst. A laminate obtained by extrusion laminating an ethylene-based mixed resin obtained by blending 50 parts by weight of each of low-density polyethylene and high-pressure low-density polyethylene into a thickness of 25 μm was used. The ethylene copolymer is extrusion-laminated to the ethylene mixed resin layer side of the laminate.

The heat seal strength between the ethylene copolymer layers of this extruded laminate film was measured or evaluated according to the following method.
Use single-side heated bar sealer Heat seal pressure: 2kg / cm ²
Heat sealing time: 0.5 seconds Seal bar width: 10 mm
Specimen width: 15mm
Peeling angle: 180 degrees Peeling speed: 300 mm / min [Synthesis Example 1]
[Preparation of dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A-1)]
<Step 1> Synthesis of (3-n-butylcyclopentadienyl) chlorodimethylsilane
50 ml of THF was added to 30.1 g (61.5 mmol) of a 25 wt% -butylcyclopentadiene-tetrahydrofuran (THF) solution. The solution was cooled to 0 ° C., and 38.4 ml (58.4 mol) of a 1.52 M-n-butyllithium / hexane solution was added dropwise. The mixture was stirred at room temperature for 2 hours, and dropwise added to dimethylsilyl dichloride (14.3 g, 110 mmol) and THF (50 ml) at -78 ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, the filtrate was distilled under reduced pressure. Distillation under reduced pressure was performed to obtain 8.09 g (yield 64%) of (3-n-butylcyclopentadienyl) chlorodimethylsilane.

The target product was identified by GC-MS. The results are shown below.
GC-MS; 214 (MS)
<Step 2> Synthesis of dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl)
50 ml of THF was added to 8.8 ml (16.6 mmol) of 2M-sodium cyclopentadienide in THF and cooled to -78 ° C. 1.89 g (8.8 mmol) of (3-n-butylcyclopentadienyl) chlorodimethylsilane was dissolved in 20 ml of THF and added dropwise to the reactor. The mixture was stirred at room temperature for 2 hours and then stirred at 50 ° C. for 2 hours. The completion of the reaction was confirmed by TLC, and the reaction was stopped by adding water at 0 ° C. Extraction was performed with hexane, and the organic layer was washed with saturated brine. It dried with magnesium sulfate and concentrated the solution obtained after filtration under reduced pressure. Distillation under reduced pressure was performed to obtain 1.07 g (yield 50%) of dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl).

^The target product was identified by ¹ H-NMR and GC-MS. The results are shown below.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-6.0 (br, 7H), 3.2 (d, 1H), 2.9 (d, 1H), 2.3 (t, 2H), 1.4 (m, 4H) 0.9 ( t, 3H), 0.1 (t, 3H), -0.2ppm (s, 3H),
GC-MS; 244 (MS)
<Step 3> Synthesis of dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A-1) Dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl) 0.58 g (2.38 mmol) was dissolved in 30 ml of diethyl ether. After cooling to −78 ° C., 3.16 ml (4.99 mmol) of 1.57M-nBuLi was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 6 ml of hexane. The obtained white solid was suspended in 60 ml of hexane, and 500 mg (2.15 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure to obtain 510 mg of a crude product. The solid obtained after washing with diethyl ether and pentane was dried under reduced pressure, and dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A-1) 190 mg (yield 20%) Got.

^The target product was identified by ¹ H-NMR and FD-MS. The results are shown below.
¹ H-NMR (CDCl ₃ , TMS standard); 6.9 (d, 2H), 6.6 (s, 1H), 5.9 (t, 3H), 5.5 (s, 1H), 2.6 (m, 2H), 1.4 (m , 2H), 1.3 (m, 2H), 0.9 (t, 3H), 0.8ppm (m, 3H),
FD-MS; 404 (MS)

[Synthesis Example 2]
[Preparation of dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A-2)]
<Step 1> Synthesis of chloro (cyclopentadienyl) dimethylsilane 100 ml of THF was added to 14.3 g (110 mmol) of dimethylsilyl dichloride and cooled to -78 ° C. 38.7 ml (77.4 mmol) of a THF solution of 2M-sodium cyclopentadienide was added dropwise over 30 minutes, the temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration under reduced pressure was performed, and sodium chloride was removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure, and the resulting chloro (cyclopentadienyl) dimethylsilane was used in the next step.

<Step 2> Synthesis of dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl)
100 ml of THF was added to 2.16 g (20 mmol) of n-propylcyclopentadiene and cooled to -78 ° C. 13.3 ml (22 mmol) of 1.57M-n-butyllithium / hexane solution was slowly added dropwise and stirred at room temperature for 3 hours. The reactor was cooled again to −78 ° C., and 3.97 g (25 mmol) of chloro (cyclopentadienyl) dimethylsilane was dissolved in 20 ml of THF and added dropwise to the reactor. After stirring for 18 hours at room temperature, the completion of the reaction was confirmed by TLC. The reaction was stopped by adding water at 0 ° C. Extraction was performed with hexane, and the organic layer was washed with saturated brine. After drying with magnesium sulfate, the solution obtained after filtration was concentrated under reduced pressure. Purification by silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v) and vacuum distillation, 1.73 g (yield) of dimethylsilylyl (3-n-propylcyclopentadienyl) (cyclopentadienyl) Rate 38%).

^The target product was identified by ¹ H-NMR and GC-MS. The results are shown below.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-6.0 (br, 7H), 3.0 (s, 1H), 2.9 (s, 1H), 2.3 (m, 2H), 1.6 (m, 2H) 0.9 ( t, 3H), 0.1 (t, 3H), -0.2ppm (s, 3H),
GC-MS; 230 (MS)
<Step 3> Synthesis of dimethylsilylene (3-n-propylcyclopentadienyl ) (cyclopentadienyl) zirconium dichloride (A-2) Dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl) 0.90 g (3.9 mmol) was dissolved in 40 ml of diethyl ether. After cooling to −78 ° C., 5.09 ml (8.0 mmol) of 1.57 M-n-butyllithium / hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 13 ml of hexane. The resulting white solid was suspended in 50 ml of hexane, and 820 mg (3.5 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure and washed with pentane. The obtained solid was dried under reduced pressure to obtain 210 mg (yield 14%) of dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A-2).

^The target product was identified by ¹ H-NMR and FD-MS. The results are shown below. ¹ H-NMR (CDCl ₃ , TMS standard); 7.1-6.9 (m, 2H), 6.6 (s, 1H), 6.0-5.8 (m, 3H), 5.5 (s, 1H), 2.6 (m, 2H) , 1.5 (m, 2H), 0.9 (t, 3H), 0.8-0.7ppm (d, 6H),
FD-MS; 388 (MS)

[Synthesis Example 3]
(B-1) represented by the following structural formula was synthesized based on the method described in JP-A-4-69394.

[Example 1]
Preparation of solid component (S) After suspending 10 kg of silica (SiO ₂ : average particle diameter 12 μm) dried at 250 ° C. for 10 hours under nitrogen atmosphere in 66.5 L of toluene in a reactor with an internal volume of 200 L and with a stirrer. And cooled to 0-5 ° C. 19.8 L of a toluene solution of methylalumoxane (3.575 mmol / mL in terms of Al atom) was diluted with 30.2 L of toluene. Diluted toluene solution of methylalumoxane was added dropwise to this suspension over 1 hour. At this time, the temperature in the system was kept at 0 to 5 ° C. The reaction was continued at 0-5 ° C for 30 minutes, then the temperature was raised to 95-100 ° C over about 1.5 hours, and the reaction was continued at 95-100 ° C for 4 hours. Thereafter, the temperature was lowered, and the supernatant was removed by decantation. The solid component thus obtained was washed 4 times with toluene. Toluene was added to a total volume of 140 L to prepare a solid component (S) toluene slurry. A part of the obtained solid component was collected and examined for concentration. As a result, the slurry concentration was 98.04 g / L and the Al concentration was 0.471 mol / L.

Preparation of solid catalyst component (X-1) In a reactor with a stirrer having an internal volume of 150 L, under a nitrogen atmosphere, 36.2 L of toluene and 3.1 L of a toluene slurry of the solid component (S) prepared above (304 g as a solid component) Was loaded. Next, 1.35 g (3.35 mmol in terms of Zr atoms) and 2.23 g (4 in terms of Zr atoms) of the metallocene compound (B-1) in a 2 L glass reactor under a nitrogen atmosphere. (.09 mmol) was collected (molar ratio (A-1) / (B-1) = 45/55), dissolved in 2.0 L of toluene, and pumped to the reactor. After pumping, the mixture is reacted at an internal temperature of 20 to 25 ° C. for 1 hour, the supernatant liquid is removed by decantation, the solid catalyst component is washed twice with hexane, hexane is added to a total volume of 35 L, and the solid catalyst component ( A hexane slurry of X-1) was prepared.

Preparation of prepolymerization catalyst (XP-1) After cooling the hexane slurry of the solid catalyst component (X-1) obtained above to 10.8 ° C, ethylene is continuously fed into the system for several minutes under normal pressure. did. During this time, the temperature in the system was maintained at 10 to 15 ° C., and then 0.6 mol of diisobutylaluminum hydride (DiBAl—H) and 19 mL of 1-hexene were added. After the addition of 1-hexene, ethylene supply was started at 0.43 kg / hour, and prepolymerization was performed at a system temperature of 32 to 37 ° C. 38 minutes after the start of prepolymerization, 11.0 mL of 1-hexene was added, 11.0 mL of 1-hexene was also added 100 minutes later, and 153 minutes after the start of prepolymerization, when ethylene supply reached 912 g, The ethylene supply was stopped. Thereafter, the supernatant was removed by decantation, and the solid catalyst component was washed three times with hexane, and then hexane was added to make the total volume 42 L.

  Next, a hexane solution of Chemistad 2500 (3.0 g) was pumped into the reactor at a system temperature of 34 to 36 ° C., and then kept at 34 to 36 ° C. for 1 hour, and the prepolymerized catalyst was used as Chemistad 2500. Was supported. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed with hexane three times.

  Next, 25 L of the prepolymerized catalyst hexane slurry (1255 g as a solid prepolymerized catalyst) was transferred to an evaporator having an internal volume of 43 L with a stirrer under a nitrogen atmosphere. After the liquid transfer, the inside of the dryer was depressurized to -65 KPaG over about 3.5 hours, and when it reached -65 KPaG, vacuum drying was performed for about 4.0 hours to remove volatile components of hexane and the prepolymerized catalyst. The pressure was further reduced to 100 KPaG, and when it reached −100 KPaG, vacuum drying was performed for 6 hours to obtain a prepolymerized catalyst (XP-1) in which 3 g of polymer was polymerized per 1 g of the solid catalyst component.

A part of the obtained prepolymerization catalyst component was dried and the composition was examined. As a result, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.
In a fluidized bed gas phase polymerization reactor having a polymerization internal volume of 1.7 m ³ , an ethylene copolymer was produced using the prepolymerization catalyst (XP-1).

  The prepolymerization catalyst component (XP-1) is supplied into the reactor at a rate of 0.038 mol / hour in terms of Zr atoms, the total pressure is 2.0 MPa · G, the partial pressure of ethylene is 1.2 MPa · A, and the gas in the reactor. Copolymerization was carried out under the conditions of a linear velocity of 0.8 m / sec, a polymerization temperature of 80 ° C., and a residence time of 6.9 hours. Nitrogen, ethylene, and 1-hexene were supplied so that the gas composition was constant. The supply amount was performed according to the conditions shown in Table 1. The polymer was continuously extracted from the polymerization reactor and dried with a drying apparatus to obtain an ethylene copolymer at 3.5 kg / hour.

  Irganox 1076 (manufactured by Ciba Specialty Chemicals) 0.1% by weight and Irgafos168 (manufactured by Ciba Specialty Chemicals) 0.1% by weight are added to the obtained ethylene copolymer as a heat stabilizer, and a single shaft made by Plako Co., Ltd. Using a 65 mmφ extruder, melt kneading was carried out under the conditions of a preset temperature of 180 ° C. and a screw rotation speed of 50 rpm, and then extruded into a strand and pelletized with a cutter as a measurement sample. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

[Example 2]
Preparation of solid catalyst component (X-2) To a reactor equipped with a stirrer with an internal volume of 150 L, in a nitrogen atmosphere, 50.1 L of toluene and 12.9 L of toluene slurry of the solid component (S) prepared above (1265 g as a solid component) Was loaded. Next, in a 2 L glass reactor, under a nitrogen atmosphere, 5.72 g (14.65 mmol in terms of Zr atoms) and 9.00 g of metallocene compound (B-1) in terms of Zr atoms (16.65 in terms of Zr atoms). 52 mmol) was collected (molar ratio (A-2) / (B-1) = 47/53), dissolved in 2.0 L of toluene, and pumped to the reactor. After pumping, the mixture is reacted at an internal temperature of 20 to 25 ° C. for 1 hour, the supernatant liquid is removed by decantation, and the solid catalyst component is washed twice using hexane, and then hexane is added to make a total volume of 50 L. -2) hexane slurry was prepared.

Preparation of prepolymerized catalyst (XP-2) Subsequently, the hexane slurry of the solid catalyst component (X-2) obtained above was cooled to 10.0 ° C., and then ethylene was continuously added to the system under normal pressure. Feed for minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C., and then 2.7 mol of diisobutylaluminum hydride (DiBAl—H) and 84 mL of 1-hexene were added. After the addition of 1-hexene, ethylene supply was started at 1.82 kg / hour, and prepolymerization was performed at a system temperature of 32 to 37 ° C. 58 minutes after the start of prepolymerization, 43.0 mL of 1-hexene was added, and 43.0 mL of 1-hexene was also added 111 minutes later. After 153 minutes from the start of prepolymerization, the ethylene supply reached 3827 g. Supply was stopped. Thereafter, the supernatant was removed by decantation, and the solid catalyst component was washed three times with hexane, and then hexane was added to make the total volume 66 L.

  Next, a hexane solution of Chemistad 2500 (13.1 g) was pumped into the reactor at a system temperature of 34 to 36 ° C., and then kept at 34 to 36 ° C. for 1 hour, and ChemStud 2500 was added to the prepolymerized catalyst. Supported. Thereafter, the supernatant was removed by decantation, and the prepolymerized catalyst was washed four times with hexane.

  Next, 25 L of the prepolymerized catalyst hexane slurry (5269 g as a solid prepolymerized catalyst) was transferred to an evaporator having an internal volume of 43 L with a stirrer under a nitrogen atmosphere. After the liquid transfer, the inside of the dryer was depressurized to -65 KPaG over about 3.5 hours, and when it reached -65 KPaG, it was vacuum dried for about 4.0 hours to remove volatile components of hexane and the prepolymerized catalyst. The pressure was further reduced to 100 KPaG, and when it reached −100 KPaG, vacuum drying was performed for 6 hours to obtain a prepolymerized catalyst (XP-2) in which 3 g of polymer was polymerized per 1 g of the solid catalyst component. A part of the obtained prepolymerization catalyst component was dried and the composition was examined. As a result, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

In the polymerization of Polymerization Example 1, an ethylene / hexene copolymer was obtained in the same manner as in the polymerization method of Example 1, except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

[Example 3]
In the polymerization of Example 2, an ethylene / hexene copolymer was obtained in the same manner as in the polymerization method of Example 2, except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

[Example 4]
Preparation of solid catalyst component (X-3) In a reactor with a stirrer with an internal volume of 150 L, in a nitrogen atmosphere, 31.3 L of toluene and 8.3 L of the toluene slurry of the solid component (S) prepared above (814 g as a solid component) Was loaded. Next, 3.27 g (8.38 mmol in terms of Zr atoms) and 6.32 g (11 in terms of Zr atoms) of the metallocene compound (B-1) in a 2 L glass reactor under a nitrogen atmosphere. 57 mmol) was collected ((A-2) / (B-1) molar ratio = 42/58), dissolved in 2.0 L of toluene, and pumped to the reactor. After pumping, the mixture is reacted at an internal temperature of 20 to 25 ° C. for 1 hour, the supernatant liquid is removed by decantation, the solid catalyst component is washed twice with hexane, and hexane is added to make a total volume of 50 L. A hexane slurry of X-3) was prepared.

Preparation of prepolymerized catalyst (XP-3) Subsequently, the hexane slurry of the solid catalyst component (X-3) obtained above was cooled to 10.0 ° C., and then ethylene was continuously added to the system under normal pressure. Feed for minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C., and then 1.7 mol of diisobutylaluminum hydride (DiBAl—H) and 53 mL of 1-hexene were added. After the addition of 1-hexene, ethylene supply was started at 1.67 kg / hour, and prepolymerization was performed at a system temperature of 32 to 37 ° C. 35 minutes after the start of prepolymerization, 28.0 mL of 1-hexene was added, 28.0 mL of 1-hexene was also added 102 minutes later, and 139 minutes after the start of prepolymerization, the ethylene supply reached 2450 g. Supply was stopped. Thereafter, the supernatant was removed by decantation, and the solid catalyst component was washed three times with hexane, and then hexane was added to make the total volume 42 L.

  Next, at a system temperature of 34 to 36 ° C., a hexane solution of Chemistad 2500 (8.4 g) was pumped into the reactor, and subsequently kept at 34 to 36 ° C. for 1 hour. Was supported. Thereafter, the supernatant was removed by decantation, and the prepolymerized catalyst was washed four times with hexane.

  Next, 25 L of the prepolymerized catalyst hexane slurry (3372 g as a solid prepolymerized catalyst) was transferred to a 43 L internal evaporator with a stirrer under a nitrogen atmosphere. After the liquid transfer, the inside of the dryer was depressurized to -65 KPaG over about 3.5 hours, and when it reached -65 KPaG, it was vacuum dried for about 4.0 hours to remove volatile components of hexane and the prepolymerized catalyst. The pressure was further reduced to 100 KPaG, and when it reached −100 KPaG, vacuum drying was performed for 6 hours to obtain a prepolymerized catalyst (XP-3) in which 3 g of polymer was polymerized per 1 g of the solid catalyst component.

A part of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.
In the polymerization of Polymerization Example 1, an ethylene / hexene copolymer was obtained in the same manner as in the polymerization method of Example 1, except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

[Example 5]
In the polymerization of Example 4, an ethylene / hexene copolymer was obtained in the same manner as in the polymerization method of Example 4 except that the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

[Example 6]
In the polymerization of Example 4, an ethylene copolymer was obtained in the same manner as in the polymerization method of Example 4 except that the polymerization conditions were changed to those shown in Table 1. Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

[Example 7]
In the polymerization of Example 1, an ethylene / hexene copolymer was obtained in the same manner as in the polymerization method of Example 1, except that the polymerization conditions were changed to those shown in Table 1. Irganox 1076 (manufactured by Ciba Specialty Chemicals) 0.1% by weight and Irgafos 168 (manufactured by Ciba Specialty Chemicals) 0.1% by weight as heat resistance stabilizers were added to the obtained ethylene copolymer. Using a 20 mmφ extruder with different axial directions, melt kneading was performed under the conditions of a set temperature of 220 ° C. and a screw rotation speed of 100 rpm, and then extruded into a strand and pelletized with a cutter as a measurement sample. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

[Example 8]
Preparation of solid catalyst component (X-4) 50 mL of toluene was placed in a 200 mL glass flask purged with nitrogen, and the toluene slurry of the solid component (S) prepared above (1.0 g in terms of solid part) was charged. Next, 7.6 mL of a toluene solution of metallocene compound (A-1) (0.002 mmol / mL in terms of Zr atoms) and a toluene solution of metallocene compound (B-1) (0.002 mmol / mL in terms of Zr atoms) 5 .1 mL was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with heptane to obtain a 100 ml heptane slurry (solid catalyst component X-4). A part of the resulting heptane slurry of the solid catalyst component (X-4) was collected to examine the concentration. As a result, the Zr concentration was 0.023 mg / mL and the Al concentration was 1.3 mg / mL.

Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, 10 mL of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and further 15 mg of the solid catalyst component (X-4) was charged in terms of solid component, the temperature was raised to 80 ° C., and 0.78 MPa · G For 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 60.2 g of an ethylene / 1-hexene copolymer. Irganox 1076 (manufactured by Ciba Specialty Chemicals) 0.1 wt% and Irgafos168 (manufactured by Ciba Specialty Chemicals) 0.1 wt% as heat resistance stabilizers were added to the obtained ethylene copolymer, and Laboplast mill manufactured by Toyo Seiki Seisakusho was The mixture was melt kneaded for 5 minutes at a resin temperature of 180 ° C. and a rotation speed of 50 rpm. Further, this molten polymer was cooled using a press molding machine manufactured by Shindo Metal Industries under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm ² . Table 2 shows the results of physical property measurement using the sample.

[Example 9]
The polymerization of Example 8 was carried out in the same manner as Example 8 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.05 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 55.1 g of an ethylene / 1-hexene copolymer. A measurement sample was prepared by the same method as in Example 8 using the obtained ethylene copolymer. Table 2 shows the results of physical property measurement using the sample.

[Example 10]
Preparation of solid catalyst component (X-5) In the preparation of the solid catalyst component (X-1) of Example 1, the reaction ratio of the metallocene compound (A-1) and the metallocene compound (B-1) was changed to (A-1). Solid catalyst component (X-1) except that ((A-1) / (B-1) = 40/60 (molar ratio) instead of / (B-1) = 45/55 (molar ratio) A hexane slurry of the solid catalyst component (X-5) was synthesized by the same method as described above.

Preparation of pre-polymerization catalyst component (XP-5) Preparation of pre-polymerization catalyst component (XP-1) was carried out except that the solid catalyst component (X-5) was used instead of the solid catalyst component (X-1). A prepolymerized catalyst component (XP-5) was obtained in the same manner as the polymerization catalyst component (XP-1). When the composition of the obtained prepolymerized catalyst component was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

In the polymerization of Polymerization Example 1, an ethylene / hexene copolymer was obtained in the same manner as in Example 1 except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 8, and physical properties were measured. The results are shown in Table 2.

[Example 11]
In the polymerization of Polymerization Example 10, an ethylene / hexene copolymer was obtained in the same manner as in Example 10 except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 8, and physical properties were measured. Further, using the obtained ethylene polymer, a sample was prepared in the same manner as in Example 1, and extrusion lamination was performed. The results are shown in Tables 2 and 3.

[Example 12]
Preparation of solid catalyst component (X-6) In the preparation of the solid catalyst component (X-2) of Example 2, the reaction ratio of the metallocene compound (A-2) and the metallocene compound (B-1) was changed to (A-2). / (B-1) = 47/53 (molar ratio) instead of (A-2) / (B-1) = 39/61 (molar ratio) A hexane slurry of the solid catalyst component (X-6) was synthesized in the same manner.

Preparation of Preliminary Polymerization Catalyst Component (XP-6) Preliminary polymerization catalyst component (XP-2) was prepared except that solid catalyst component (X-6) was used instead of solid catalyst component (X-2). A prepolymerized catalyst component (XP-6) was obtained in the same manner as the polymerization catalyst component (XP-2). When the composition of the obtained prepolymerized catalyst component was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

In the polymerization of Polymerization Example 1, an ethylene / hexene copolymer was obtained in the same manner as in Example 1 except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 8, and physical properties were measured. The results are shown in Table 2.

[Example 13]
In the polymerization of Polymerization Example 1, an ethylene / hexene copolymer was obtained in the same manner as in Example 1 except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 8, and physical properties were measured. Further, using the obtained ethylene polymer, a sample was prepared in the same manner as in Example 1, and extrusion lamination was performed. The results are shown in Tables 2 and 3.

[Example 14]
Preparation of solid catalyst component (X-7) To a reactor equipped with a stirrer with an internal volume of 150 L, under a nitrogen atmosphere, toluene and a toluene slurry of solid component (S) prepared above (1575 g as a solid component) were charged. The amount was adjusted to 33L. Next, 5.8 g of metallocene compound (A-2) (14.9 mmol in terms of Zr atoms) and 36.9 g of metallocene compound (B-1) (in terms of Zr atoms 67.67 g) in a 2 L glass reactor under a nitrogen atmosphere. 7 mmol) was collected (molar ratio of (A-2) / (B-1) = 28/72), dissolved in 2.0 L of toluene, and pumped to the reactor. After pumping, the mixture is reacted at an internal temperature of 73 to 76 ° C. for 2 hours. The supernatant is removed by decantation, and the solid catalyst component is washed three times with hexane, and then hexane is added to make a total volume of 25 L. A hexane slurry of -7) was prepared.

[Preparation of prepolymerization catalyst component (XP-7)]
Subsequently, the hexane slurry of the solid catalyst component (X-7) obtained above was cooled to 10.8 ° C., and then a hexane solution of Chemistad 2500 (15.9 g) was pumped into the reactor, and then diisobutylaluminum hydride. 1.4 mol of (DiBAl-H) was added. Further, ethylene was continuously fed into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C., and then 103 mL of 1-hexene was added. After the addition of 1-hexene, ethylene supply was started at 1.5 kg / h, and prepolymerization was performed at a system temperature of 32 to 37 ° C. After 85 minutes from the start of prepolymerization, 52 mL of 1-hexene was added, and after 155 minutes, 52 mL of 1-hexene was also added. After 217 minutes from the start of prepolymerization, ethylene supply reached 4643 g, and ethylene supply was stopped. . Thereafter, the supernatant was removed by decantation and the solid catalyst component was washed four times with hexane, and then hexane was added to make the total volume 25 L.

  Next, a hexane solution of Chemistad 2500 (63.8 g) was pumped into the reactor at a system temperature of 34 to 36 ° C., and then kept at 34 to 36 ° C. for 2 hours to prepare Chemistad 2500 as a prepolymerized catalyst component. Was supported. Thereafter, the supernatant was removed by decantation, and the prepolymerized catalyst component was washed four times with hexane.

  Next, 25 L of the prepolymerized catalyst hexane slurry (6456 g as a solid prepolymerized catalyst) was transferred to an evaporator with an internal volume of 43 L with a stirrer under a nitrogen atmosphere. After the liquid transfer, the inside of the dryer was depressurized to -68 KPaG over about 60 minutes, and when it reached -68 KPaG, it was vacuum-dried for about 4.3 hours to remove volatile components of hexane and the prepolymerized catalyst. The pressure was further reduced to −100 KPaG, and when the pressure reached −100 KPaG, vacuum drying was performed for 8 hours to obtain a prepolymerized catalyst component (XP-7) in which 3 g of polymer was polymerized per 1 g of the solid catalyst component.

A part of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.5 mg of Zr atom was contained per 1 g of the solid catalyst component.
In the polymerization of Polymerization Example 1, an ethylene / hexene copolymer was obtained in the same manner as in Example 1 except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 8, and physical properties were measured. The results are shown in Table 2.

[Example 15]
In the polymerization of Polymerization Example 14, an ethylene / hexene copolymer was obtained in the same manner as in Example 14 except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 8, and physical properties were measured. The results are shown in Table 2.

[Example 16]
Preparation of solid catalyst component (X-8) In the preparation of the solid catalyst component (X-7) of Example 14, the reaction ratio of the metallocene compound (A-2) and the metallocene compound (B-1) was changed to (A-1). The solid catalyst component (X-7) was used except that (A-2) / (B-1) = 18/82 (molar ratio) instead of / (B-1) = 28/72 (molar ratio) A hexane slurry of the solid catalyst component (X-8) was synthesized in the same manner.

Preparation of prepolymerization catalyst component (XP-8) Preparation of prepolymerization catalyst component (XP-7) was carried out except that solid catalyst component (X-8) was used instead of solid catalyst component (X-7). A prepolymerized catalyst component (XP-8) was obtained in the same manner as the polymerization catalyst component (XP-7). When the composition of the obtained prepolymerized catalyst component was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

In the polymerization of Polymerization Example 1, an ethylene / hexene copolymer was obtained in the same manner as in Example 1 except that the catalyst components and the polymerization conditions were changed to the conditions shown in Table 1. Using the obtained ethylene polymer, a measurement sample was prepared in the same manner as in Example 8, and physical properties were measured. The results are shown in Table 2.

[Comparative Example 1]
The product pellets of ethylene 4-methyl-1-pentene copolymer (trade name: ULTZEX 20100J) by solution polymerization method marketed by Prime Polymer Co., Ltd. were used as measurement samples, and physical properties were evaluated and extrusion lamination was performed. . The results are shown in Tables 2 and 3.

In Comparative Example 1, the neck-in was large and the MT / η * value was also small compared to the Example.
[Comparative Example 2]
The product pellets of polyethylene (trade name: Mirason 11) obtained by the high pressure radical polymerization method commercially available from Prime Polymer Co., Ltd. were used as measurement samples, and physical properties were evaluated and extrusion lamination was performed. The results are shown in Tables 2 and 3.

In Comparative Example 2, the heat seal strength was inferior, and the sum (A + B) of the number of methyl branches and the number of ethyl branches (A + B) was larger than in the Example.
[Comparative Example 3]
Preparation of solid catalyst component (X-9) To a reactor with a stirrer having an internal volume of 114 L, 11.8 L of toluene slurry of the solid component (S) prepared above (1000 g as a solid component) was added under a nitrogen atmosphere. Under stirring, 14.7 liters of a toluene solution of ethylenebis (indenyl) zirconium dichloride (0.0017 mmol / mL in terms of Zr atoms) was added dropwise at 78 to 80 ° C. over 30 minutes, and the reaction was carried out at this temperature for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane, and then hexane was added to make a total volume of 25 L to prepare a hexane slurry of the solid catalyst component (X-9).

Preparation of Prepolymerization Catalyst (XPV-9) After cooling the hexane slurry of the solid catalyst component (X-9) obtained above to 5 ° C., ethylene was continuously supplied into the system under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 1.9 L of a hexane solution of triisobutylaluminum (40.0 mmol / L in terms of Al atom) and 65.3 mL of 1-hexene were added to start prepolymerization. After 1 hour, the temperature in the system rose to 35 ° C, but thereafter, the temperature in the system was maintained at 34 to 35 ° C. 70 minutes after the start of prepolymerization, 65.3 mL of 1-hexene was added again.

  Thereafter, 4 hours after the start of prepolymerization, the system was replaced with nitrogen, and the prepolymerization was stopped. Next, the supernatant was removed and washed four times with hexane to obtain a prepolymerized catalyst (XP-9) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component (X-9). Thereafter, the system temperature was raised to 34 to 35 ° C., and 10 L of hexane solution of Emulgen 108 (polyoxyethylene lauryl ether manufactured by Kao Corporation) (1.0 g / L in the concentration of Emulgen) was added. The mixture was stirred at this temperature for 2 hours to obtain a prepolymerized catalyst (XPV-9) in which the prepolymerized catalyst (XP-9) was supported with emulgen.

Using a continuous polymerization fluidized bed gas phase polymerization apparatus, copolymerization of ethylene and 1-hexene was carried out at a total pressure of 2.0 MPa-G, a polymerization temperature of 70 ° C., and a gas linear velocity of 0.8 m / sec. The pre-polymerized catalyst (XPV-9) prepared above is dried and fed continuously at a rate of 25-30 g / hr to maintain a constant gas composition during the polymerization, ethylene, 1-hexene, hydrogen and Nitrogen was continuously supplied (gas composition: 1-hexene / ethylene = 1.1 to 1.3 × 10 ⁻² , ethylene concentration = 71.4%). The yield of the obtained ethylene copolymer was 5.3 kg / hour.

Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1. Using this sample, physical properties were measured and extrusion lamination was performed.
The results are shown in Tables 2 and 3.

In Comparative Example 3, the neck-in was large and the MT / η * value was small. Further, take-up surging occurred, and the zero shear viscosity (η ₀ ) did not satisfy the relational expression (Eq-1).
[Comparative Example 4]
Preparation of solid catalyst component (X-10) 100 mL of toluene was placed in a 200 mL glass flask purged with nitrogen and stirred, and the toluene slurry of the solid component (S) prepared above (2.0 g in terms of solid part) was loaded. I entered. Next, 32.1 mL of a toluene solution of Me ₂ Si (Ind) ₂ ZrCl ₂ (0.0015 mmol / mL in terms of Zr atom) was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with decane to obtain a 100 mL decane slurry (solid catalyst component X-10). A part of the resulting decane slurry of the solid catalyst component (X-10) was collected to examine the concentration. As a result, the Zr concentration was 0.043 mg / mL, and the Al concentration was 2.49 mg / mL.

Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, after substituting the inside of the system using a hydrogen-ethylene mixed gas (hydrogen concentration: 0.54 vol%), 1-hexene 15 mL, triisobutylaluminum 0.375 mmol, solid catalyst component (X-10) 0. 5 g was charged in this order. The temperature was raised to 80 ° C., and polymerization was carried out at 0.78 MPa · G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 86.7 g of an ethylene copolymer.

Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1.
The results are shown in Tables 2 and 3.
[Comparative Example 5]
The ethylene / 1-octene copolymer (trade name: Affinity PF1140) obtained by a solution polymerization method commercially available from Dow Chemical Company was evaluated for physical properties using a product pellet as a measurement sample. The results are shown in Table 2.

In Comparative Examples 4 and 5, the MT / η * value was small, and the zero shear viscosity (η ₀ ) did not satisfy the relational expression (Eq-1). For this reason, it is presumed that neck-in is large and takeover surging occurs.

[Comparative Example 6]
Preparation of solid component (S-1) In a reactor equipped with a stirrer with an internal volume of 260 L, 10 kg of silica (SiO ₂ : average particle size 12 μm) dried at 250 ° C. for 10 hours in a nitrogen atmosphere was suspended in 90.5 L of toluene. And then cooled to 0-5 ° C. To this suspension, 45.5 L of a toluene solution of methylalumoxane (3.0 mmol / mL in terms of Al atom) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 5 ° C. The reaction was continued at 0-5 ° C for 30 minutes, then the temperature was raised to 95-100 ° C over about 1.5 hours, and the reaction was continued at 95-100 ° C for 4 hours. Thereafter, the temperature was lowered to room temperature, and the supernatant was removed by decantation. The solid component thus obtained was washed twice with toluene, and then toluene was added to make a total amount of 129 L to prepare a toluene slurry of the solid component (S-1). A part of the obtained solid component was collected and examined for concentration. As a result, the slurry concentration was 137.5 g / L and the Al concentration was 1.1 mol / L.

Preparation of solid catalyst component (X-11) To a reactor equipped with a stirrer with an internal volume of 114 L, in a nitrogen atmosphere, 21.0 L of toluene and 15.8 L of toluene slurry of the solid component (S-1) prepared above (in solid component) 2400 g) was added. On the other hand, in a reactor with a stirrer having an internal volume of 100 L, 31.0 L of toluene was put under a nitrogen atmosphere, and under stirring, a toluene solution of metallocene compound (A-3) (8.25 mmol / L in terms of Zr atoms) 10.0 Next, 2.0 L of a toluene solution of metallocene compound (B-2) (2.17 mmol / L in terms of Zr atom) was added and mixed for several minutes ((A-3) / (B-2) Molar ratio = 95/5). Subsequently, the prepared mixed solution was pumped to the reactor in which the toluene slurry of the solid component (S-1) was previously put. After pumping, the reaction was carried out at an internal temperature of 20 to 25 ° C. for 1 hour. Thereafter, the supernatant was removed by decantation.

The solid catalyst component thus obtained was washed three times with hexane, and then hexane was added to a total volume of 56 L to prepare a hexane slurry of the solid catalyst component (X-11).
In addition, (A-3) represented by the following structural formula uses the product made by STREM, and the compound represented by the following formula (B-2) is based on the method described in Japanese Patent No. 2813057. And synthesized.

Preparation of prepolymerized catalyst (XP-11) Subsequently, the hexane slurry of the solid catalyst component (X-11) obtained above was cooled to 10 ° C., and then ethylene was continuously fed into the system for several minutes under normal pressure. did. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 2.8 mol of triisobutylaluminum (TiBAl) and 157 mL of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg / hour to start prepolymerization. After 40 minutes from the start of the prepolymerization, the system temperature rose to 24 ° C, and the subsequent system temperature was maintained at 24-26 ° C. 70 minutes after the start of the prepolymerization, 79.0 mL of 1-hexene was added, and 79.0 mL of 1-hexene was added 140 minutes later.

  220 minutes after the start of prepolymerization, the ethylene supply was stopped, the inside of the system was replaced with nitrogen, and the prepolymerization was stopped. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed six times with hexane to obtain a prepolymerized catalyst (XP-11) in which 2.87 g of polymer was polymerized per 1 g of the solid catalyst component. A part of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.72 mg of Zr atom was contained per 1 g of the solid catalyst component.

In a completely stirred and mixed polymerization tank having a polymerization internal volume of 290 L, an ethylene copolymer was produced using the prepolymerized catalyst (XP-11).

  In the polymerization tank, the solvent hexane is 45 L / hour, the prepolymerization catalyst is converted to Zr atom, 0.32 mmol / hour, triisobutylaluminum is 20.0 mmol / hour, ethylene is 8.0 kg / hour, 1-hexene is It supplied continuously so that it might become a rate of 700 g / hour. Further, the polymer slurry is continuously withdrawn from the polymerization tank so that the amount of solvent in the polymerization tank is constant, and polymerization is performed under the conditions of a total pressure of 0.8 MPa-G, a polymerization temperature of 80 ° C., and a residence time of 2.6 hours. went. From the polymer slurry continuously extracted from the polymerization tank, unreacted ethylene is substantially removed by a flash drum. Thereafter, hexane in the polymer slurry was removed with a solvent separator and dried to obtain an ethylene copolymer at 5.6 kg / hour.

Using the obtained ethylene copolymer, a measurement sample was prepared in the same manner as in Example 1. Using this sample, physical properties were measured and extrusion lamination was performed. The results are shown in Tables 2 and 3.
Since Comparative Example 6 had a high density, the heat seal strength was lower than that of the Example.

[Comparative Example 7]
Preparation of solid catalyst component (X-12) In a reactor with an internal volume of 114 L, with a stirrer, 18.6 L of toluene and 7.9 L of toluene slurry of the solid component (S-1) prepared above (in solid components) 1200 g) was added. On the other hand, 14.5 L of toluene was put into a reactor with a stirrer having an internal volume of 100 L under a nitrogen atmosphere. Under stirring, a toluene solution of metallocene compound (A-3) (7.81 mmol / L in terms of Zr atom) 5.0 Then, 2.0 L of a toluene solution of metallocene compound (B-2) (2.17 mmol / L in terms of Zr atom) was added and mixed for several minutes ((A-3) / (B-2 ) Molar ratio = 85/15). Subsequently, the prepared mixed solution was pumped to the reactor in which the toluene slurry of the solid component (S-1) was previously put. After pumping, the reaction was carried out at an internal temperature of 20 to 25 ° C. for 1 hour. Thereafter, the supernatant was removed by decantation. The solid catalyst component thus obtained was washed three times with hexane, and then hexane was added to a total volume of 30 L to prepare a hexane slurry of the solid catalyst component (X-12).

Preparation of Prepolymerization Catalyst (XP-12) Subsequently, the hexane slurry of the solid catalyst component (X-12) was cooled to 10 ° C., and then ethylene was continuously supplied into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, 1.6 mol of triisobutylaluminum and 80 mL of 1-hexene were added. After the addition of 1-hexene, ethylene was supplied again at 1.8 kg / hour to start prepolymerization. 25 minutes after the start of prepolymerization, the system temperature rose to 24 ° C, and the system temperature thereafter was maintained at 24-26 ° C. 35 minutes after the start of prepolymerization, 39.0 mL of 1-hexene was added, and 39.0 mL of 1-hexene was also added 60 minutes later.

  85 minutes after the start of prepolymerization, the ethylene supply was stopped and the system was replaced with nitrogen to stop the prepolymerization. Thereafter, the supernatant was removed by decantation. The prepolymerized catalyst thus obtained was washed four times with hexane to obtain a prepolymerized catalyst (XP-12) in which 2.93 g of polymer was polymerized per 1 g of the solid catalyst component. A part of the obtained prepolymerized catalyst component was dried and the composition was examined. As a result, 0.72 mg of Zr atom was contained per 1 g of the solid catalyst component.

In a completely stirred and mixed polymerization tank having a polymerization internal volume of 290 L, an ethylene copolymer was produced using the preliminary polymerization catalyst (XP-12).

In the polymerization tank, the solvent hexane is 45 L / hour, the prepolymerization catalyst is converted to Zr atom, 0.10 mmol / hour, triisobutylaluminum is 20.0 mmol / hour, ethylene is 5.0 kg / hour, 1-hexene is It supplied continuously so that it might become a rate of 1900 g / hour. Further, the polymer slurry is continuously withdrawn from the polymerization tank so that the amount of solvent in the polymerization tank is constant, and polymerization is performed under the conditions of a total pressure of 1.0 MPa-G, a polymerization temperature of 65 ° C., and a residence time of 2.7 hours. went. From the polymer slurry continuously extracted from the polymerization tank, unreacted ethylene is substantially removed by a flash drum. Thereafter, hexane in the polymer slurry was removed with a solvent separator and dried to obtain an ethylene copolymer at 3.1 kg / hour. However, when the density of the polymer is less than 935 kg / m ³ , the supernatant of the polymer slurry extracted from the polymerization tank becomes cloudy, and after 8 hours from the time when the density of the polymer reaches 920 kg / m ^3. Since the polymer and the solvent were not separated and the slurry properties deteriorated, the continuous operation was stopped. A measurement sample was prepared in the same manner as in Example 1 using the ethylene copolymer obtained before the operation was stopped. Tables 2 and 3 show the results of physical property measurement and extrusion lamination molding using the sample.

  In Comparative Example 7, the molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement was small, and the heat seal strength was small as compared with the Example.

  The ethylene copolymer of the present invention has a sufficiently high melt tension and is particularly excellent in mechanical strength as a molded body as compared with existing ethylene copolymers produced with a Ziegler-Natta catalyst or a metallocene catalyst. Therefore, the ethylene copolymer of the present invention is suitably used for forming a homogeneous quality plastic molded article having sufficient mechanical strength.

Claims (6)

An ethylene copolymer, which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and simultaneously satisfies the following requirements (I) to (VI).
(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 100 g / 10 min.
(II) The density (d) is in the range of 875 to 936 kg / m ³ .
(III) The ratio [MT / η ^* (g / P)] of the melt tension [MT (g)] at 190 ° C. and the shear viscosity [η ^* (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec. The range is from 2.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ .
(IV) Sum of methyl branch number [A (/ 1000C)] and ethyl branch number [B (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR [(A + B) (/ 1000C )] Is 1.8 or less.
(V) Zero shear viscosity [η ₀ (P)] at 200 ° C. and weight average molecular weight (Mw) measured by GPC-viscosity detector method (GPC-VISCO) satisfy the following relational expression (Eq-1) .

(VI) The molecular weight (peak top M) at the maximum weight fraction in the molecular weight distribution curve obtained by GPC measurement is in the range of 1.0 × 10 ^{4.20 to} 1.0 × 10 ^4.50 .   A thermoplastic resin composition comprising the ethylene copolymer according to claim 1.   The molded object obtained from the ethylene copolymer of Claim 1.   A molded product obtained from the thermoplastic resin composition according to claim 2.   The film which consists of a molded object of Claim 3 or 4.   A laminate film comprising the film according to claim 5.