JP5428399B2 - Olefin polymerization catalyst and process for producing olefin polymer - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same.

  Low density polyethylene (hereinafter abbreviated as HP-LDPE) produced by a high pressure radical polymerization method is excellent in molding processability, transparency and flexibility, but has a problem of low mechanical strength.

Among copolymers of ethylene and α-olefin produced using a Ziegler catalyst or a metallocene catalyst, those having a density in the range of 0.910 to 0.940 g / cm ³ are linear low density polyethylene (hereinafter referred to as “low-density polyethylene”). , Abbreviated as LLDPE), and has higher transparency than high-density polyethylene (hereinafter abbreviated as HDPE) with a density exceeding 0.940 g / cm ³ and higher mechanical strength than HP-LDPE. Therefore, it is used in various applications where transparency and mechanical strength are required. However, when used for products including heat treatment in production processes such as medical and food applications, heat resistance may be required in addition to transparency and mechanical strength. Although heat resistance can be improved by increasing the density of LLDPE, since transparency decreases, it is difficult to achieve both transparency and heat resistance with LLDPE alone. Therefore, a method of blending HP-LDPE and LLDPE (see, for example, Patent Document 1), LLDPE (m-LLDPE) having a narrow molecular weight distribution and composition distribution produced using a metallocene catalyst and a relatively high molecular weight ethylene alone A method of blending a polymer or an ethylene / α-olefin copolymer has been proposed (for example, see Patent Document 2).

  In recent years, by copolymerizing ethylene and α-olefin using a catalyst composition in which two types of olefin polymerization catalysts having different comonomer incorporation ability and a reversible chain transfer agent are combined, a multi-block copolymer is produced, The resulting multi-block copolymer is excellent in heat resistance, and it has been reported that transparency is improved by increasing the average number of blocks (see, for example, Patent Document 3 and Non-Patent Document 1). The catalyst composition used herein is “preferably for ease of use and to produce narrow molecular weight polymer segments in solution, the catalyst used in the present invention is a relatively pure organometallic. The compound or metal complex, in particular, a homogeneous catalyst containing a compound or complex mainly containing a metal selected from Group 3 to 10 of the periodic table or a lanthanide series. A system catalyst is preferable (for example, see Patent Document 3). In general, when a homogeneous catalyst is used, the particle shape is poor and application to a slurry polymerization process is difficult.

  As an example of producing an olefin polymer using a heterogeneous catalyst containing two or more kinds of transition metal compounds, a catalyst for olefin polymerization in which a small amount of comonomer-incorporated metallocene compound and a large amount of comonomer-incorporated metallocene compound are supported on silica is used. A method of producing an olefin polymer having a bimodal composition distribution and excellent tear strength by copolymerization of ethylene and one or more comonomers (see, for example, Patent Document 4), a transition metal compound for synthesizing a macromonomer, A transition metal compound for copolymerization of an olefin and a macromonomer, ethylene alone or ethylene and one or more comonomers using an olefin polymerization catalyst comprising a modified clay mineral treated with an organic compound as an activation promoter Produced olefin polymers with long chain branching and good particle shape by copolymerization of If, Patent Document 5.) Have been disclosed.

JP-A-3-168231 Japanese Patent Laid-Open No. 9-077921 JP 2007-529617 A JP 2007-286991 A JP 2007-169341 A

Science, 2006, 312, 714

  The problem to be solved by the present invention from the above situation is that an olefin polymer produced using a Ziegler catalyst and an olefin polymerization catalyst comprising one kind of transition metal compound (metallocene, etc.) as a constituent component are produced. Suitable for heterogeneous olefin polymerization, suitable for slurry polymerization process, capable of producing olefin polymers with excellent heat resistance and mechanical strength equivalent to olefin polymers and their blends It is an object of the present invention to provide a catalyst and a method for producing an olefin polymer using the catalyst.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that the component (A), the component (B) are two types of metallocene compounds belonging to Group 4 of the periodic table, and the component (C) is an organic compound as an activation promoter. Manufactured using a Ziegler catalyst by using a modified clay mineral, component (D) organozinc metal compound, component (E) organoaluminum compound, and optionally component (H) a catalyst for olefin polymerization comprising a solid support. Olefin polymer, heat resistance and mechanical strength equivalent to those of olefin polymers produced using olefin polymerization catalysts composed of one kind of transition metal compound and their blends, and transparency It has been found that an excellent olefin polymer can be obtained.

  Hereinafter, the present invention will be described in detail. Although a specific example is given, it is not limited to them.

  Component (A) and component (B) of the present invention are Group 4 metallocene compounds of the periodic table. Preferably, the following general formulas (a-1) and (b-1)

で表される遷移金属化合物を挙げることができる。一般式（ａ−１）中、Ｍ^１は周期表第４族の遷移金属原子を示し、具体的にはチタン原子、ジルコニウム原子またはハフニウム原子である。Ｘ^１は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げることができる。炭素数１〜２０の炭化水素基としては、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、ベンジル基、オクチル基、フェニルエチル基、ノニル基、フェニルプロピル基、クミル基、デシル基、アダマンチル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、トリフェニルメチル基、アラキジル基等のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基等のシクロアルキル基；ビニル基、プロペニル基、ブテニル基、シクロヘキセニル基等のアルケニル基；フェニル基、トリル基、２，６−ジメチルフェニル基、メシチル基、２，６−ジイソプロピルフェニル基、ビフェニル基、ナフチル基、アセナフチル基、アントラセニル基、フェナントリル基、ピレニル基等のアリール基を挙げることができる。炭素数１〜２０のアルコキシ基としては、メトキシ基、エトキシ基、ノルマルプロポキシ基、イソプロポキシ基、ノルマルブトキシ基、イソブトキシ基、ターシャリーブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等を挙げることができる。炭素数６〜２０のアリールオキシ基としては、フェノキシ基、パラメチルフェノキシ基、パラメトキシフェノキシ基、２，６−ジメチルフェノキシ基、１−ナフトキシ基等を挙げることができる。炭素数１〜２０のシリル基としては、トリメチルシリル基、ジメチルフェニルシリル基、トリイソプロピルシリル基、ジメチルメトキシシリル基、ジメチル−ｔ−ブチルシリル基、ジフェニルメチルシリル基、トリフェニルシリル基等を挙げることができる。炭素数１〜２０のアミノ基としては、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、ジフェニルアミノ基等を挙げることができる。水素原子がシリル基によって置換された炭素数１〜２０の炭化水素基としては、トリメチルシリルメチル基、トリメチルシリルエチル基等をあげることができる。水素原子がアミノ基によって置換された炭素数１〜２０の炭化水素基としては、ジメチルアミノメチル基、ジエチルアミノメチル基、ジメチルアミノフェニル基、２−ジイソプロピルアミノフェニル基等を挙げることができる。水素原子がアルコキシ基によって置換された炭素数２〜２０の炭化水素基としては、メトキシフェニル基、２−エトキシフェニル基等を挙げることができる。水素原子がアリールオキシ基によって置換された炭素数７〜２０の置換炭化水素基としては、フェノキシフェニル基等を挙げることができる。水素原子がハロゲン原子によって置換された炭素数１〜２０の炭化水素基としては、トリフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロフェニル基等を挙げることができる。
Ｒ^１からＲ^８は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、炭素数１〜２０のアミノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリールオキシ基を示し（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）、互いに同じでも異なっていてもよい。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げることができる。炭素数１〜２０の炭化水素基としては、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、ベンジル基、オクチル基、フェニルエチル基、ノニル基、フェニルプロピル基、クミル基、デシル基、アダマンチル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、トリフェニルメチル基、アラキジル基等のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基等のシクロアルキル基；ビニル基、プロペニル基、ブテニル基、シクロヘキセニル基等のアルケニル基；フェニル基、トリル基、２，６−ジメチルフェニル基、メシチル基、２，６−ジイソプロピルフェニル基、ビフェニル基、ナフチル基、アセナフチル基、アントラセニル基、フェナントリル基、ピレニル基等のアリール基を挙げることができる。炭素数１〜２０のアルコキシ基としては、メトキシ基、エトキシ基、ノルマルプロポキシ基、イソプロポキシ基、ノルマルブトキシ基、イソブトキシ基、ターシャリーブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等を挙げることができる。炭素数６〜２０のアリールオキシ基としては、フェノキシ基、パラメチルフェノキシ基、パラメトキシフェノキシ基、２，６−ジメチルフェノキシ基、１−ナフトキシ基等を挙げることができる。炭素数１〜２０のシリル基としては、トリメチルシリル基、ジメチルフェニルシリル基、トリイソプロピルシリル基、ジメチルメトキシシリル基、ジメチル−ｔ−ブチルシリル基、ジフェニルメチルシリル基、トリフェニルシリル基等を挙げることができる。炭素数１〜２０のアミノ基としては、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、ジフェニルアミノ基等を挙げることができる。水素原子がシリル基によって置換された炭素数１〜２０の炭化水素基としては、トリメチルシリルメチル基、トリメチルシリルエチル基等をあげることができる。水素原子がアミノ基によって置換された炭素数１〜２０の炭化水素基としては、ジメチルアミノメチル基、ジエチルアミノメチル基、ジメチルアミノフェニル基、２−ジイソプロピルアミノフェニル基等を挙げることができる。水素原子がアルコキシ基によって置換された炭素数２〜２０の炭化水素基としては、メトキシフェニル基、２−エトキシフェニル基等を挙げることができる。水素原子がアリールオキシ基によって置換された炭素数７〜２０の置換炭化水素基としては、フェノキシフェニル基等を挙げることができる。水素原子がハロゲン原子によって置換された炭素数１〜２０の炭化水素基としては、トリフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロフェニル基等を挙げることができる。また、同一シクロペンタジエニル基上に存在するＲ^１からＲ^４もしくはＲ^５からＲ^８のうち隣接する１組以上の置換基が互いに連結し、インデニル基、フルオレニル基を形成しても良い。Ｙ^１は、下記一般式（ａ−２）または（ａ−３）

The transition metal compound represented by these can be mentioned. In general formula (a-1), M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom. X ¹ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms may be substituted by a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom); ). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, and benzyl. Group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, alkyl group such as triphenylmethyl group and arachidyl group; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; alkenyl group such as vinyl group, propenyl group, butenyl group and cyclohexenyl group Phenyl group, Group, 2,6-dimethylphenyl group, mesityl group, 2,6-diisopropylphenyl group, a biphenyl group, a naphthyl group, acenaphthyl group, an anthracenyl group, a phenanthryl group, and an aryl group such as a pyrenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a diisopropylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a trimethylsilylethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C2-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, a methoxyphenyl group, 2-ethoxyphenyl group, etc. can be mentioned. Examples of the substituted hydrocarbon group having 7 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluorophenyl group.
R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. An alkoxy group, an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is substituted by a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom); They may be the same or different. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, and benzyl. Group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, alkyl group such as triphenylmethyl group and arachidyl group; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; alkenyl group such as vinyl group, propenyl group, butenyl group and cyclohexenyl group Phenyl group, Group, 2,6-dimethylphenyl group, mesityl group, 2,6-diisopropylphenyl group, a biphenyl group, a naphthyl group, acenaphthyl group, an anthracenyl group, a phenanthryl group, and an aryl group such as a pyrenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a diisopropylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a trimethylsilylethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C2-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, a methoxyphenyl group, 2-ethoxyphenyl group, etc. can be mentioned. Examples of the substituted hydrocarbon group having 7 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluorophenyl group. Further, one or more adjacent substituents of R ¹ to R ⁴ or R ⁵ to R ⁸ existing on the same cyclopentadienyl group may be linked to each other to form an indenyl group or a fluorenyl group. Y ¹ represents the following general formula (a-2) or (a-3)

で表される。一般式（ａ−２）（ａ−３）中、Ｒ^９は各々独立して水素原子、炭素数１〜２０の炭化水素基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。また、Ｒ^９は互いに同じでも異なっていてもよく、互いに連結し環を形成していても良い。炭素数１〜２０の炭化水素基としては、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、ベンジル基、オクチル基、フェニルエチル基、ノニル基、フェニルプロピル基、クミル基、デシル基、アダマンチル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、トリフェニルメチル基、アラキジル基等のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基等のシクロアルキル基；ビニル基、プロペニル基、ブテニル基、シクロヘキセニル基等のアルケニル基；フェニル基、トリル基、２，６−ジメチルフェニル基、メシチル基、２，６−ジイソプロピルフェニル基、ビフェニル基、ナフチル基、アセナフチル基、アントラセニル基、フェナントリル基、ピレニル基等のアリール基を挙げることができる。水素原子がシリル基によって置換された炭素数１〜２０の炭化水素基としては、トリメチルシリルメチル基、トリメチルシリルエチル基等をあげることができる。水素原子がアミノ基によって置換された炭素数１〜２０の炭化水素基としては、ジメチルアミノメチル基、ジエチルアミノメチル基、ジメチルアミノフェニル基、２−ジイソプロピルアミノフェニル基等を挙げることができる。水素原子がアルコキシ基によって置換された炭素数２〜２０の炭化水素基としては、メトキシフェニル基、２−エトキシフェニル基等を挙げることができる。水素原子がアリールオキシ基によって置換された炭素数７〜２０の置換炭化水素基としては、フェノキシフェニル基等を挙げることができる。水素原子がハロゲン原子によって置換された炭素数１〜２０の炭化水素基としては、トリフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロフェニル基等を挙げることができる。Ｅ^１は炭素原子、ケイ素原子、ゲルマニウム原子または錫原子である。ｎは０から４の整数を示し、好ましくは０もしくは２から４の整数であり、より好ましくは０もしくは３から４の整数である。Ｙ^１の具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ジメチルメチレン基、ジフェニルメチレン基、シクロヘキシリデン基、テトラメチルエチレン基、フェニレン基、ブテニレン基、シリレン基、ジメチルシリレン基、ジフェニルシリレン基、１，１−ジメチル−１−シラエタン−１，２−ジイル基、テトラメチルジシラン−１，２−ジイル基、１，１，３，３−テトラメチルジシロキサン−１，３−ジイル基、上記化合物のケイ素原子をゲルマニウム原子あるいはスズ原子に置き換えた化合物を挙げることができる。好ましくは、エチレン基、プロピレン基、ブチレン基、テトラメチルエチレン基、フェニレン基、ブテニレン基、１，１−ジメチル−１−シラエタン−１，２−ジイル基、テトラメチルジシラン−１，２−ジイル基、１，１，３，３−テトラメチルジシロキサン−１，３−ジイル基等であり、より好ましくは、プロピレン基、ブチレン基、ブテニレン基、１，１−ジメチル−１−シラエタン−１，２−ジイル基、テトラメチルジシラン−１，２−ジイル基、１，１，３，３−テトラメチルジシロキサン−１，３−ジイル基等である。ｎが０の場合、非架橋メタロセン化合物を示す。

It is represented by In general formulas (a-2) and (a-3), each R ⁹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (here, hydrogen of a hydrocarbon group having 1 to 20 carbon atoms). The atoms may be substituted by silyl groups, amino groups, alkoxy groups, aryloxy groups or halogen atoms). R ⁹ may be the same as or different from each other, and may be connected to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, and benzyl. Group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, alkyl group such as triphenylmethyl group and arachidyl group; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; alkenyl group such as vinyl group, propenyl group, butenyl group and cyclohexenyl group Phenyl group, Group, 2,6-dimethylphenyl group, mesityl group, 2,6-diisopropylphenyl group, a biphenyl group, a naphthyl group, acenaphthyl group, an anthracenyl group, a phenanthryl group, and an aryl group such as a pyrenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a trimethylsilylethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C2-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, a methoxyphenyl group, 2-ethoxyphenyl group, etc. can be mentioned. Examples of the substituted hydrocarbon group having 7 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluorophenyl group. E ¹ is a carbon atom, a silicon atom, a germanium atom or a tin atom. n represents an integer of 0 to 4, preferably 0 or an integer of 2 to 4, more preferably 0 or an integer of 3 to 4. Specific examples of Y ¹ include a methylene group, an ethylene group, a propylene group, a butylene group, a dimethylmethylene group, a diphenylmethylene group, a cyclohexylidene group, a tetramethylethylene group, a phenylene group, a butenylene group, a silylene group, and a dimethylsilylene group. , Diphenylsilylene group, 1,1-dimethyl-1-silaethane-1,2-diyl group, tetramethyldisilane-1,2-diyl group, 1,1,3,3-tetramethyldisiloxane-1,3- Examples thereof include a diyl group and a compound in which the silicon atom of the above compound is replaced with a germanium atom or a tin atom. Preferably, ethylene group, propylene group, butylene group, tetramethylethylene group, phenylene group, butenylene group, 1,1-dimethyl-1-silaethane-1,2-diyl group, tetramethyldisilane-1,2-diyl group 1,1,3,3-tetramethyldisiloxane-1,3-diyl group, etc., more preferably, propylene group, butylene group, butenylene group, 1,1-dimethyl-1-silaethane-1,2. -Diyl group, tetramethyldisilane-1,2-diyl group, 1,1,3,3-tetramethyldisiloxane-1,3-diyl group and the like. When n is 0, it represents a non-bridged metallocene compound.

  Specific examples of the metallocene compounds belonging to Group 4 of the periodic table represented by formula (a-1) are shown below.

  Specifically, methylene bis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylmethylene bis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, Dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethyl) Cyclopentadienyl) zirconium dichloride, dimethylsilylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium di Loride, diphenylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (tetramethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadi) Enyl) (indenyl) zirconium dichloride, tetramethylethylenebis (cyclopentadienyl) zirconium dichloride, (propane-1,3-diyl-bis (cyclopentadienyl)) zirconium dichloride, (1,1,3,3- Tetramethylpropane-1,3-diyl-bis (cyclopentadienyl)) zirconium dichloride, (2,2-dimethylpropane-1,3-diyl-bis (cyclopentadienyl) Zirconium dichloride, (butane-1,4-diyl-bis (cyclopentadienyl)) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl-bis (cyclopentadienyl)) Zirconium dichloride, (1,1,2,2-tetraphenyldisilane-1,2-diyl-bis (cyclopentadienyl)) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl- Bis (cyclopentadienyl)) zirconium dichloride, (1,1,3,3-tetramethyldisiloxane-1,3-diyl-bis (cyclopentadienyl)) zirconium dichloride, (1,1,3,3) -Tetraisopropyldisiloxane-1,3-diyl-bis (cyclopentadienyl)) zirconium Transition metal compounds having a bridged bis (substituted cyclopentadienyl) ligand such as dichloride, (cis-2-butene-1,4-diyl-bis (cyclopentadienyl)) zirconium dichloride; Non-bridged metallocene compounds such as enyl) zirconium dichloride, (cyclopentadienyl) (indenyl) zirconium dichloride, bis (indenyl) zirconium dichloride; methylene (cyclopentadienyl) (indenyl) zirconium dichloride, methylene (tetramethylcyclopentadidi) Enyl) (indenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylmethylene (tetramethylcyclopentadienyl) (indenyl) di Conium dichloride, diphenylmethylene (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (Cyclopentadienyl) (2-methyl-indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (4,7-dimethyl-indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4,7 -Trimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4,7-trimethyl-indenyl) zirconium dichloride Dimethylsilylene (cyclopentadienyl) (2,3,4,7-tetramethyl-indenyl) zirconium dichloride, dimethylsilylene (3,4-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (3 , 4-Cyclopentadienyl) (2-methyl-indenyl) zirconium dichloride, dimethylsilylene (3,4-cyclopentadienyl) (4,7-dimethyl-indenyl) zirconium dichloride, dimethylsilylene (3,4-cyclo Pentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylene (3,4-cyclopentadienyl) (3,4,7-trimethyl-indenyl) zirconium dichloride, dimethylsilylene (3,4) -Cyclopentadienyl) (2,3,4,7-tetramethyl-indenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) ( 2-methyl-indenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (4,7-dimethyl-indenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (2,4,7-trimethylindene) Nyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,4,7-trimethyl-indenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclo Ntadienyl) (2,3,4,7-tetramethyl-indenyl) zirconium dichloride, ethylene (cyclopentadienyl) (indenyl) zirconium dichloride, ethylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride, ethylene (cyclo Pentadienyl) (4,7-dimethyl-indenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,4,7-trimethyl-indenyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1, 2-diyl) (cyclopentadienyl) (indenyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl) (tetramethylcyclopentadienyl) (indenyl) zirconium dichlora (1,1-dimethyl-1-silaethane-1,2-diyl) (cyclopentadienyl) (4,7-dimethyl-indenyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1, 2-diyl) (cyclopentadienyl) (2,4,7-trimethyl-indenyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl) (cyclopentadienyl) ( Indenyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl) (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane) -1,2-diyl) (cyclopentadienyl) (4,7-dimethyl-indenyl) zirconium dichloride (1,1,2,2-tetramethyldisilane-1,2-diyl) (cyclopentadienyl) (2,4,7-trimethyl-indenyl) zirconium dichloride, (propane-1,3-diyl) ( Cyclopentadienyl) (indenyl) zirconium dichloride, (propane-1,3-diyl) (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride, (propane-1,3-diyl) (cyclopentadienyl) ( 4,7-dimethyl-indenyl) zirconium dichloride, (propane-1,3-diyl) (cyclopentadienyl) (2,4,7-trimethyl-indenyl) zirconium dichloride, (1,1,3,3-tetra Methylpropane-1,3-diyl) (cyclopentadienyl) (indenyl) zyl Nium dichloride, (butane-1,4-diyl) (cyclopentadienyl) (indenyl) zirconium dichloride, (cis-2-butene-1,4-diyl) (cyclopentadienyl) (indenyl) zirconium dichloride, etc. Transition metal compounds having a bridged (substituted cyclopentadienyl) (substituted indenyl) ligand; methylene bis (fluorenyl) zirconium dichloride, dimethylmethylene bis (fluorenyl) zirconium dichloride, diphenylmethylene bis (fluorenyl) zirconium dichloride, dimethylsilylene bis ( Fluorenyl) zirconium dichloride, diphenylsilylene bis (fluorenyl) zirconium dichloride, ethylene bis (fluorenyl) zirconium dichloride, tetramethyl Tylene bis (fluorenyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl) (fluorenyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl) bis (Fluorenyl) zirconium dichloride, (propane-1,3-diyl) bis (fluorenyl) zirconium dichloride, (1,1,3,3-tetramethylpropane-1,3-diyl) bis (fluorenyl) zirconium dichloride, (butane Transition metal compounds having bridged bis (substituted fluorenyl) ligands such as -1,4-diyl) bis (fluorenyl) zirconium dichloride, (cis-2-butene-1,4-diyl) bis (fluorenyl) zirconium dichloride, and The transition metal compound Examples include til, diethyl, dihydro, diphenyl, and dibenzyl. Furthermore, the metallocene compound which replaced the zirconium atom of the said transition metal compound with the titanium atom and the hafnium atom can be illustrated.

In general formula (b-1), M ² is a transition metal atom of Group 4 of the periodic table, specifically a titanium atom, a zirconium atom or a hafnium atom. X ² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms may be substituted by a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom); ). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, and benzyl. Group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, alkyl group such as triphenylmethyl group and arachidyl group, cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, alkenyl group such as vinyl group, propenyl group, butenyl group and cyclohexenyl group , Phenyl group, Group, 2,6-dimethylphenyl group, mesityl group, 2,6-diisopropylphenyl group, a biphenyl group, a naphthyl group, acenaphthyl group, an anthracenyl group, a phenanthryl group, and an aryl group such as a pyrenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a diisopropylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a trimethylsilylethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C2-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, a methoxyphenyl group, 2-ethoxyphenyl group, etc. can be mentioned. Examples of the substituted hydrocarbon group having 7 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluorophenyl group. R ¹⁰ to R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an amino group having 1 to 20 carbon atoms, or an amino group having 1 to 20 carbon atoms. An alkoxy group, an aryloxy group having 6 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is substituted by a silyl group, an amino group, an alkoxy group, an aryloxy group or a halogen atom); May be). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, and benzyl. Group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, alkyl group such as triphenylmethyl group and arachidyl group, cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, alkenyl group such as vinyl group, propenyl group, butenyl group and cyclohexenyl group , Phenyl group, Group, 2,6-dimethylphenyl group, mesityl group, 2,6-diisopropylphenyl group, a biphenyl group, a naphthyl group, acenaphthyl group, an anthracenyl group, a phenanthryl group, and an aryl group such as a pyrenyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, tertiary butoxy group, pentyloxy group, and hexyloxy group. . Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. Examples of the silyl group having 1 to 20 carbon atoms include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group. it can. Examples of the amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a diisopropylamino group, and a diphenylamino group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a trimethylsilylethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C2-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, a methoxyphenyl group, 2-ethoxyphenyl group, etc. can be mentioned. Examples of the substituted hydrocarbon group having 7 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluorophenyl group. R ¹⁰ to R ¹⁹ may be the same as or different from each other. Further, a pair of adjacent substituents of R ¹⁰ to R ^{13 in} the cyclopentadienyl ring may be linked to each other to form an indenyl group, and R ¹⁸ and R ¹⁹ on the indenyl ring are linked to each other. A fluorene group may be formed. Y ² represents the following general formula (b-2)

で表される。一般式（ｂ−２）中、Ｒ^２０は各々独立して水素原子、炭素数１〜２０の炭化水素基を示す（ここで、炭素数１〜２０の炭化水素基の水素原子はシリル基、アミノ基、アルコキシ基、アリールオキシ基またはハロゲン原子によって置換されていても良い）。炭素数１〜２０の炭化水素基としては、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、ベンジル基、オクチル基、フェニルエチル基、ノニル基、フェニルプロピル基、クミル基、デシル基、アダマンチル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、トリフェニルメチル基、アラキジル基等のアルキル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基等のシクロアルキル基、ビニル基、プロペニル基、ブテニル基、シクロヘキセニル基等のアルケニル基、フェニル基、トリル基、２，６−ジメチルフェニル基、メシチル基、２，６−ジイソプロピルフェニル基、ビフェニル基、ナフチル基、アセナフチル基、アントラセニル基、フェナントリル基、ピレニル基等のアリール基を挙げることができる。水素原子がシリル基によって置換された炭素数１〜２０の炭化水素基としては、トリメチルシリルメチル基、トリメチルシリルエチル基等をあげることができる。水素原子がアミノ基によって置換された炭素数１〜２０の炭化水素基としては、ジメチルアミノメチル基、ジエチルアミノメチル基、ジメチルアミノフェニル基、２−ジイソプロピルアミノフェニル基等を挙げることができる。水素原子がアルコキシ基によって置換された炭素数２〜２０の炭化水素基としては、メトキシフェニル基、２−エトキシフェニル基等を挙げることができる。水素原子がアリールオキシ基によって置換された炭素数７〜２０の置換炭化水素基としては、フェノキシフェニル基等を挙げることができる。水素原子がハロゲン原子によって置換された炭素数１〜２０の炭化水素基としては、トリフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロフェニル基等を挙げることができる。また、Ｒ^２２は互いに同じでも異なっていてもよく、互いに連結し環を形成していても良い。Ｅ^２は炭素原子、ケイ素原子、ゲルマニウム原子または錫原子である。ｍは１から２の整数を示す。Ｙ^２の具体例としては、メチレン基、エチレン基、ジメチルメチレン基、ジフェニルメチレン基、シリレン基、ジメチルシリレン基、ジフェニルシリレン基、ジビニルシリレン基、ジプロペニルシリレン基、上記化合物のケイ素原子をゲルマニウム原子あるいは錫原子に置き換えた基を挙げることができる。好ましくは、ジメチルメチレン基、ジフェニルメチレン基、エチレン基、ジメチルシリレン基、ジフェニルシリレン基などである。
一般式（ｂ−１）で表される周期表第４族のメタロセン化合物の具体例を以下に示す。
具体的には、ジメチルメチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド、ジメチルシリレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド、ジメチルメチレン（シクロペンタジエニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジメチルシリレン（シクロペンタジエニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジフェニルシリレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド、エチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド、（１，１−ジメチル−１−シラエタン−１，２−ジイル）（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド、（１，１，２，２−テトラメチルジシラン−１，２−ジイル）（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド等の架橋（置換シクロペンタジエニル）（置換フルオレニル）配位子を有する遷移金属化合物；ジメチルメチレン（インデニル）（フルオレニル）ジルコニウムジクロライド、ジフェニルメチレン（インデニル）（フルオレニル）ジルコニウムジクロライド、ジフェニルメチレン（２−メチル−インデニル）（フルオレニル）ジルコニウムジクロライド、ジフェニルメチレン（４−フェニル−インデニル）（フルオレニル）ジルコニウムジクロライド、ジメチルシリレン（インデニル）（フルオレニル）ジルコニウムジクロライド、ジメチルメチレン（インデニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジフェニルメチレン（インデニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジフェニルメチレン（２−メチルインデニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジフェニルメチレン（４−フェニル−インデニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジメチルシリレン（インデニル）（２，７−ジターシャリーブチル）ジルコニウムジクロライド、ジフェニルシリレン（インデニル）（フルオレニル）ジルコニウムジクロライド、エチレン（インデニル）（フルオレニル）ジルコニウムジクロライド、（１，１−ジメチル−１−シラエタン−１，２−ジイル）（インデニル）（フルオレニル）ジルコニウムジクロライド、（１，１，２，２−テトラメチルジシラン−１，２−ジイル）（インデニル）（フルオレニル）ジルコニウムジクロライド等の架橋（置換インデニル）（置換フルオレニル）配位子を有する遷移金属化合物；ジメチルメチレンビス（インデニル）ジルコニウムジクロライド、ジフェニルメチレンビス（インデニル）ジルコニウムジクロライド、ジメチルシリレンビス（インデニル）ジルコニウムジクロライド、ジフェニルシリレンビス（インデニル）ジルコニウムジクロライド、エチレンビス（インデニル）ジルコニウムジクロライド、（１，１−ジメチル−１−シラエタン−１，２−ジイル）ビス（インデニル）ジルコニウムジクロライド、（１，１，２，２−テトラメチルジシラン−１，２−ジイル）ビス（インデニル）ジルコニウムジクロライド、等の架橋ビス（置換インデル）配位子を有する遷移金属化合物および上記遷移金属化合物のジメチル体、ジエチル体、ジヒドロ体、ジフェニル体、ジベンジル体を挙げることができる。さらに、上記遷移金属化合物のジルコニウム原子をチタン原子、ハフニウム原子に置き換えた遷移金属化合物を例示することができる。

It is represented by In general formula (b-2), each R ²⁰ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (wherein the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms is a silyl group, An amino group, an alkoxy group, an aryloxy group or a halogen atom may be substituted). Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, and benzyl. Group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, alkyl group such as triphenylmethyl group and arachidyl group, cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, alkenyl group such as vinyl group, propenyl group, butenyl group and cyclohexenyl group , Phenyl group, Group, 2,6-dimethylphenyl group, mesityl group, 2,6-diisopropylphenyl group, a biphenyl group, a naphthyl group, acenaphthyl group, an anthracenyl group, a phenanthryl group, and an aryl group such as a pyrenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a silyl group include a trimethylsilylmethyl group and a trimethylsilylethyl group. As a C1-C20 hydrocarbon group by which the hydrogen atom was substituted by the amino group, a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylaminophenyl group, 2-diisopropylaminophenyl group etc. can be mentioned. As a C2-C20 hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, a methoxyphenyl group, 2-ethoxyphenyl group, etc. can be mentioned. Examples of the substituted hydrocarbon group having 7 to 20 carbon atoms in which a hydrogen atom is substituted with an aryloxy group include a phenoxyphenyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluorophenyl group. R ²² may be the same as or different from each other, and may be connected to each other to form a ring. E ² is a carbon atom, a silicon atom, a germanium atom or a tin atom. m represents an integer of 1 to 2. Specific examples of Y ² include a methylene group, an ethylene group, a dimethylmethylene group, a diphenylmethylene group, a silylene group, a dimethylsilylene group, a diphenylsilylene group, a divinylsilylene group, a dipropenylsilylene group, and a silicon atom of the above compound as a germanium atom. Or the group substituted by the tin atom can be mentioned. Preferred are dimethylmethylene group, diphenylmethylene group, ethylene group, dimethylsilylene group, diphenylsilylene group and the like.
Specific examples of the metallocene compounds belonging to Group 4 of the periodic table represented by formula (b-1) are shown below.
Specifically, dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene ( Cyclopentadienyl) (2,7-ditertiarybutyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditertiarybutyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7- Ditertiary butyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadiene) ) (Fluorenyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl) (cyclopentadienyl) (fluorenyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane-) 1,2-diyl) (cyclopentadienyl) (fluorenyl) zirconium dichloride and other transition metal compounds having a bridged (substituted cyclopentadienyl) (substituted fluorenyl) ligand; dimethylmethylene (indenyl) (fluorenyl) zirconium dichloride , Diphenylmethylene (indenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-indenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-indenyl) (fluorenyl) Luconium dichloride, dimethylsilylene (indenyl) (fluorenyl) zirconium dichloride, dimethylmethylene (indenyl) (2,7-ditertiary butyl) zirconium dichloride, diphenylmethylene (indenyl) (2,7-ditertiary butyl) zirconium dichloride, diphenyl Methylene (2-methylindenyl) (2,7-ditertiarybutyl) zirconium dichloride, diphenylmethylene (4-phenyl-indenyl) (2,7-ditertiarybutyl) zirconium dichloride, dimethylsilylene (indenyl) (2,7 -Ditertiary butyl) zirconium dichloride, diphenylsilylene (indenyl) (fluorenyl) zirconium dichloride, ethylene (indenyl) (Luolenyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1,2-diyl) (indenyl) (fluorenyl) zirconium dichloride, (1,1,2,2-tetramethyldisilane-1,2-diyl) Transition metal compounds having a bridged (substituted indenyl) (substituted fluorenyl) ligand such as (indenyl) (fluorenyl) zirconium dichloride; dimethylmethylene bis (indenyl) zirconium dichloride, diphenylmethylene bis (indenyl) zirconium dichloride, dimethylsilylene bis ( Indenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, (1,1-dimethyl-1-silaethane-1) 2-diyl) bis (indenyl) zirconium dichloride, bridged bis (substituted indel) ligands such as (1,1,2,2-tetramethyldisilane-1,2-diyl) bis (indenyl) zirconium dichloride A transition metal compound and the dimethyl body, diethyl body, dihydro body, diphenyl body, dibenzyl body of the said transition metal compound can be mentioned. Furthermore, the transition metal compound which replaced the zirconium atom of the said transition metal compound with the titanium atom and the hafnium atom can be illustrated.

  The comonomer uptake capacity means the comonomer content of an olefin polymer formed by copolymerization of ethylene and a comonomer under the same conditions. For example, when the comonomer is an α olefin, it is generated with respect to a molar ratio of α olefin / ethylene. The number of short chain branches per 1000 carbons of the olefin polymer is used as an index.

  Compared to the comonomer uptake capacity of component (A), the comonomer uptake capacity of component (B) is higher. When the α-olefin / ethylene molar ratio is 0.25, the comonomer uptake capacity of component (B) is preferably at least twice the comonomer uptake capacity of component (A).

  The component (C) activation co-catalyst is a compound that can form a polymerization active species capable of polymerizing an olefin by acting or reacting with the component (A) and the component (B). An activation co-catalyst is a compound that provides a compound that, after forming a polymerization active species, coordinates weakly or interacts with the generated polymerization active species but does not react directly with the active species.

  Examples of the activation promoter for the component (C) used in the present invention include clay minerals, modified clay minerals treated with organic compounds, alkylaluminoxanes, ionized ionic compounds having non-coordinating anions, Lewis acids, sulfones And acid salts and carboxylic acid compounds. When the activation promoter (C) is a modified clay mineral treated with an organic compound, the catalyst becomes a heterogeneous catalyst. The resulting olefin polymer has a high bulk density and a good particle shape.

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

  The clay mineral may be used as it is, or may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. The clay mineral is preferably subjected to chemical treatment such as acid treatment, alkali treatment, salt treatment and the like. Acid treatment uses, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, and other acids to remove impurities on the surface of clay minerals and to elute some or all of the cations such as Al, Fe, Mg in the crystal structure. To increase the surface area. In the alkali treatment, for example, an alkali such as sodium hydroxide is used to destroy the crystal structure of the clay mineral and cause a structural change. For example, lithium chloride, sodium phosphate, sodium sulfate, sodium acetate, sodium formate, sodium citrate, sodium nitrate, sodium oxalate, magnesium chloride, magnesium sulfate, magnesium phosphate, magnesium perchlorate, magnesium oxalate Swellability by replacing exchangeable ions between clay mineral layers with other ions using salts such as magnesium nitrate, magnesium acetate, magnesium succinate, aluminum sulfate, aluminum phosphate, aluminum oxalate, aluminum nitrate, etc. Increase interlayer distance.

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

[R ²¹ R ²² _x-1 GH] _y [J] _z (c-1)
[R ²¹ R ²² _x-1 GH] in the general formula (c-1) is a cation, and G is an atom selected from Group 15 or Group 16 of the periodic table. Examples of the group 15 atom of the periodic table include a nitrogen atom, a phosphorus atom, an antimony atom, and examples of the group 16 atom of the periodic table include an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Preferred examples of G are a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. R ²¹ is a hydrocarbon group having 1 to 30 carbon atoms. Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl. Group, benzyl group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group Group, nonadecyl group, triphenylmethyl group, eicosanyl group, docosyl group, tricosyl group, tetracosyl group, hexacosyl group, octacosyl group, alkyl group such as triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. The Loalkyl group, vinyl group, propenyl group, butenyl group, cyclohexenyl group, myristoyl group, palmitoyl group, oleyl group, elaidyl group, alkenyl group such as linoleyl, phenyl group, tolyl group, 2,6-dimethylphenyl group, mesityl group And aryl groups such as 2,6-diisopropylphenyl group, biphenyl group, naphthyl group, acenaphthyl group, anthracenyl group, phenanthryl group, and pyrenyl group. R ²² is each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl. Group, benzyl group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group Group, nonadecyl group, triphenylmethyl group, eicosanyl group, docosyl group, tricosyl group, tetracosyl group, hexacosyl group, octacosyl group, alkyl group such as triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. The Loalkyl group, vinyl group, propenyl group, butenyl group, cyclohexenyl group, myristoyl group, palmitoyl group, oleyl group, elaidyl group, alkenyl group such as linoleyl, phenyl group, tolyl group, 2,6-dimethylphenyl group, mesityl group And aryl groups such as 2,6-diisopropylphenyl group, biphenyl group, naphthyl group, acenaphthyl group, anthracenyl group, phenanthryl group, and pyrenyl group. R ²¹ and R ²² may be bonded to each other. When G is a Group 15 element, x = 3, and when G is a Group 16 element, x = 2. Among the compounds represented by formula (c-1), those in which G is a nitrogen atom include methylamine hydrochloride, ethylamine hydrochloride, normal propylamine hydrochloride, isopropylamine hydrochloride, normal butylamine hydrochloride, and isobutyl. Amine hydrochloride, tertiary butylamine hydrochloride, normal pentylamine hydrochloride, isopentylamine hydrochloride, 2-methylbutylamine hydrochloride, neopentylamine hydrochloride, tertiary pentylamine hydrochloride, normal hexylamine hydrochloride, isohexyl Amine hydrochloride, normal heptylamine hydrochloride, normal octylamine hydrochloride, normal nonylamine hydrochloride, normal decylamine hydrochloride, normal undecylamine hydrochloride, normal dodecylamine hydrochloride, normal tetradecylamine hydrochloride, normal Ruhexadecylamine hydrochloride, normal octadecylamine hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, laurylamine hydrochloride, myristylamine hydrochloride, palmitylamine hydrochloride, stearylamine hydrochloride, behenylamine hydrochloride, oleylamine hydrochloride Salt, dimethylamine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-normal butylamine hydrochloride, triallylamine hydrochloride, hexylamine hydrochloride, 2-aminoheptane hydrochloride, 3-aminoheptane hydrochloride, Normal heptylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, normal octylamine hydrochloride, tertiary octylamine hydrochloride, nonylamine hydrochloride, decylami Hydrochloride, undecylamine hydrochloride, dodecylamine hydrochloride, tridecylamine hydrochloride, tetradecylamine hydrochloride, pentadecylamine hydrochloride, hexadecylamine hydrochloride, heptadecylamine hydrochloride, octadecylamine hydrochloride, nonadecylamine Hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride, cyclododecyl Amine hydrochloride, 2- (1-cyclohexenyl) ethylamine hydrochloride, geranylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride, bis (2-ethylhexyl) amine hydrochloride, dioctylamine hydrochloride, di Decylamine hydrochloride, N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, N-tertiarybutylcyclohexylamine hydrochloride, N-allylcyclohexylamine hydrochloride, N-methyldioctyl Amine hydrochloride, N-methyldiundecylamine hydrochloride, N-methyldidodecylamine hydrochloride, N-methyldineral tetradecylamine hydrochloride, N-methyldineral hexadecylamine hydrochloride, N-methyldineral octadecyl Amine hydrochloride, N-methyldinormaleicosylamine hydrochloride, N-methyldilaurylamine hydrochloride, N-methyldimyristylamine hydrochloride, N-methyldipalmitylamine hydrochloride, N-methyldistearylamine hydrochloride Salt, N Methyl dibehenylamine hydrochloride, N-methyldioleylamine hydrochloride, N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N- Dimethyl-normal tetradecylamine hydrochloride, N, N-dimethyl-normal hexadecylamine hydrochloride, N, N-dimethyl-normal octadecylamine hydrochloride, N, N-dimethyl-normal eicosylamine hydrochloride, N, N -Dimethyl-normaldocosylamine hydrochloride, N, N-dimethyllaurylamine hydrochloride, N, N-dimethylmyristylamine hydrochloride, N, N-dimethylpalmitylamine hydrochloride, N, N-dimethylstearylamine hydrochloride N, N-dimethylbehenylamine hydrochloride, N, N-dimethyloleylamine hydrochloride , Trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tridodecylamine hydrochloride, N-methyl-dioctadecylamine hydrochloride, N, N-dimethylcyclohexylamine Hydrochloride, N, N-dimethylcyclohexylmethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride, pyrrolidine hydrochloride, piperidine hydrochloride, 2,5-dimethylpyrrolidine hydrochloride, 2-methylpiperidine hydrochloride, 3- Methylpiperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride, 3,3-dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2-ethylpiperidine hydrochloride, 2,2, 6,6-tetramethylpiperidine hydrochloride, 1-methylpyrrolidine Hydrochlorides of aliphatic amines such as hydrochloride, 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpyrrolidine hydrochloride, 1,2,2,6,6-pentamethylpiperidine hydrochloride, aniline hydrochloride Salt, N-methylaniline hydrochloride, N-ethylaniline hydrochloride, N-allylaniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N, N-dimethylaniline hydrochloride, N-methyl-o-toluidine hydrochloride, N-methyl-m-toluidine hydrochloride, N-methyl-p-toluidine hydrochloride, N-ethyl-o-toluidine hydrochloride, N-ethyl-m-toluidine hydrochloride, N-ethyl-p-toluidine hydrochloride, N-allyl-o-toluidine hydrochloride, N-allyl-m-toluidine hydrochloride, N-allyl-p-toluidine hydrochloride, N Propyl-o-toluidine hydrochloride, N-propyl-m-toluidine hydrochloride, N-propyl-p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5- Dimethylaniline hydrochloride, 2,6-dimethylaniline hydrochloride, 3,4-dimethylaniline hydrochloride, 3,5-dimethylaniline hydrochloride, 2-ethylaniline hydrochloride, 3-ethylaniline hydrochloride, 4-ethylaniline Hydrochloride, N, N-diethylaniline hydrochloride, 2-isopropylaniline hydrochloride, 4-isopropylaniline hydrochloride, 2-tertiary butylaniline hydrochloride, 4-normal butylaniline hydrochloride, 4-secondary butylaniline hydrochloride 4-tert-butylaniline hydrochloride, 2,6-diethylaniline hydrochloride, 2-isopropyl -6-methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, 4-chloroaniline hydrochloride, 2-bromoaniline hydrochloride, 3-bromoaniline hydrochloride, 4-bromoaniline hydrochloride, o-anisidine hydrochloride, m-anisidine hydrochloride, p-anisidine hydrochloride, o-phenetidine hydrochloride, m-phenetidine hydrochloride, p-phenetidine hydrochloride, 1-aminonaphthalene hydrochloride, 2-aminonaphthalene hydrochloride, 1-aminofluorene hydrochloride, 2-aminofluorene hydrochloride, 3-aminofluorene hydrochloride, 4-aminofluorene hydrochloride, 5-aminoindan hydrochloride, 2-aminobiphenyl hydrochloride, 4-aminobiphenyl hydrochloride, N , 2,3-Trimethylaniline hydrochloride, N, 2,4-trimethylaniline hydrochloride, N, 2,5-trime Tyraniline hydrochloride, N, 2,6-trimethylaniline hydrochloride, N, 3,4-trimethylaniline hydrochloride, N, 3,5-trimethylaniline hydrochloride, N-methyl-2-ethylaniline hydrochloride, N- Methyl-3-ethylaniline hydrochloride, N-methyl-4-ethylaniline hydrochloride, N-methyl-6-ethyl-o-toluidine hydrochloride, N-methyl-2-isopropylaniline hydrochloride, N-methyl-4 -Isopropylaniline hydrochloride, N-methyl-2-tertiary butylaniline hydrochloride, N-methyl-4-normal butylaniline hydrochloride, N-methyl-4-secondary butylaniline hydrochloride, N-methyl-4-tersia Libutylaniline hydrochloride, N-methyl-2,6-diethylaniline hydrochloride, N-methyl-2-isopropyl-6-methylani Hydrochloride, N-methyl-p-anisidine hydrochloride, N-ethyl-2,3-anisidine hydrochloride, N, N-dimethyl-o-toluidine hydrochloride, N, N-dimethyl-m-toluidine hydrochloride, N, N-dimethyl-p-toluidine hydrochloride, N, N, 2,3-tetramethylaniline hydrochloride, N, N, 2,4-tetramethylaniline hydrochloride, N, N, 2,5-tetramethyl Aniline hydrochloride, N, N, 2,6-tetramethylaniline hydrochloride, N, N, 3,4-tetramethylaniline hydrochloride, N, N, 3,5-tetramethylaniline hydrochloride, N, N- Dimethyl-2-ethylaniline hydrochloride, N, N-dimethyl-3-ethylaniline hydrochloride, N, N-dimethyl-4-ethylaniline hydrochloride, N, N-dimethyl-6-ethyl-o-toluidine hydrochloride , N, N-dimethyl 2-isopropylaniline hydrochloride, N, N-dimethyl-4-isopropylaniline hydrochloride, N, N-dimethyl-2-tert-butylaniline hydrochloride, N, N-dimethyl-4
Normal n-butylaniline hydrochloride, N, N-dimethyl-4-secondary butylaniline hydrochloride, N, N-dimethyl-4-tertiary butylaniline hydrochloride, N, N-dimethyl-2,6-diethylaniline hydrochloride N, N-dimethyl-2-isopropyl-6-methylaniline hydrochloride, N, N-dimethyl-2-chloroaniline hydrochloride, N, N-dimethyl-3-chloroaniline hydrochloride, N, N-dimethyl- 4-chloroaniline hydrochloride, N, N-dimethyl-2-bromoaniline hydrochloride, N, N-dimethyl-3-bromoaniline hydrochloride, N, N-dimethyl-4-bromoaniline hydrochloride, N, N- Dimethyl-o-anisidine hydrochloride, N, N-dimethyl-m-anisidine hydrochloride, N, N-dimethyl-p-anisidine hydrochloride, N, N-dimethyl-o-fe Tidine hydrochloride, N, N-dimethyl-m-phenethidine hydrochloride, N, N-dimethyl-p-phenethidine hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2-amino Naphthalene hydrochloride, N, N-dimethyl-1-aminofluorene hydrochloride, N, N-dimethyl-2-aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4 -Aminofluorene hydrochloride, N, N-dimethyl-5-aminoindan hydrochloride, N, N-dimethyl-2-aminobiphenyl hydrochloride, N, N-dimethyl-4-aminobiphenyl hydrochloride, N, N-dimethyl Aromatic amine hydrochlorides such as p-trimethylsilylaniline hydrochloride and hydrochlorides of the above compounds are hydrofluoric acid, hydrobromide, hydroiodide or sulfuric acid It can be exemplified the replaced compound is not limited thereto.

  Among the compounds represented by formula (c-1), those in which G is an oxygen atom include compounds such as methyl ether hydrochloride, ethyl ether hydrochloride, normal butyl ether hydrochloride, tetrahydrofuran hydrochloride, and phenyl ether hydrochloride Examples thereof include, but are not limited to, compounds in which the hydrochloride of the above compound is replaced with hydrofluoride, hydrobromide, hydroiodide, or sulfate. Among the compounds represented by the formula (c-1), those in which G is a sulfur atom include diethylsulfonium fluoride, diethylsulfonium chloride, diethylsulfonium bromide, diethylsulfonium iodide, dimethylsulfonium fluoride, and dimethyl chloride. Examples thereof include, but are not limited to, sulfonium, dimethylsulfonium bromide, and dimethylsulfonium iodide.

  Among the compounds represented by formula (c-1), those in which G is a phosphorus atom include triphenylphosphine hydrochloride, tri (o-tolyl) phosphine hydrochloride, tri (p-tolyl) phosphine hydrochloride, Examples include compounds such as trimesityl phosphine hydrochloride and compounds obtained by replacing hydrochlorides of the above compounds with hydrofluoric acid salts, hydrobromide salts, hydroiodide salts or sulfate salts, but are not limited thereto. Is not to be done. [J] is an anion, such as fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, succinate ion, tetrafluoro ion. A borate ion or a hexafluorophosphate ion can be used, but is not limited thereto. Furthermore, y and z are integers chosen to balance the charges.

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

  When the component (C) is an alkylaluminoxane, the structure is preferably a compound represented by the following general formula (c-2) and / or (c-3).

ここで、Ｒ^２３は各々同一でも異なっていてもよく、水素原子、メチル基、エチル基、プロピル基、イソブチル基、ターシャリーブチル基などの炭素数１〜２０の炭化水素基である。また、ｑは２〜６０の整数である。なお、アルキルアルミノキサンには有機アルミニウム化合物の単量体、そのニ量体およびオリゴマー等の有機金属化合物が含まれていてもよい。

Here, R ²³ may be the same or different and is a hydrocarbon group having 1 to 20 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isobutyl group, or a tertiary butyl group. Moreover, q is an integer of 2-60. The alkylaluminoxane may contain organometallic compounds such as organoaluminum compound monomers, dimers and oligomers thereof.

  When component (C) is an ionized ionic compound having a non-coordinating anion, the structure is any of the following general formulas (c-4), (c-5), and (c-6) A compound having the following structure is desirable.

_{^{[R 25 R 26 a-1}} M 4 H] [Q (R 24) 4] (c-4)
[M ⁵ L ¹ _b ] [Q (R ²⁴ ) ₄ ] _c (c-5)
[D] [Q (R ²⁴ ) ₄ ] _d (c-6)
Here, [Q (R ²⁴ ) ₄ ] represents a non-coordinating anion, and Q represents a boron atom or an aluminum atom. R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms and a halogen-substituted aryl group having 6 to 20 carbon atoms. M ⁴ is an element selected from Group 15 or 16 of the periodic table, R ²⁵ is a hydrocarbon group having 1 to 30 carbon atoms, and R ²⁶ is independently a hydrogen atom or a carbon atom having 1 to 30 carbon atoms. Indicates a hydrogen group. If M ⁴ is of the periodic table Group 15 element a is 3, if M ⁴ is an element of the periodic table Group 16 a shows a 2.

M ⁵ is a metal cation selected from lithium, sodium, potassium, iron or silver, and c represents the valence of the cation. L ¹ is a Lewis base such as ethers, aliphatic amines, aromatic amines, phosphines, a cyclopentadienyl group, or a hydrocarbon group-substituted cyclopentadienyl group having 1 to 20 carbon atoms.

  D represents an organic cation such as carbonium cation or tropylium cation, and d represents the valence of the organic cation.

  Specific examples of the compound represented by the general formula (c-4) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, and tetramethyleneoxonium tetrakis (pentafluorophenyl). ) Borate, hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-N-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminum , Dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) al Nate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, trinormalbutylammonium tetrakis (pentafluorophenyl) aluminate, and the like. It is not limited.

  Specific examples of the compound represented by the general formula (c-5) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, or ether complexes thereof, sodium tetrakis ( Sodium salt such as pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) aluminate, ferrocenium salt such as ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) aluminate, silver tetrakis ( Examples thereof include, but are not limited to, silver salts such as pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) aluminate.

  Specific examples of the compound represented by the general formula (c-6) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, tropylium. Examples thereof include tetrakis (pentafluorophenyl) aluminate, but are not limited thereto.

When the component (C) is a Lewis acid, examples include compounds represented by the following general formula (c-7) Q (R ²⁴ ) ₃ (c-7)
Here, Q represents a boron atom or an aluminum atom, and R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms and a halogen-substituted aryl group having 6 to 20 carbon atoms.

  Specific examples of the compound represented by the general formula (c-7) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4). , 5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum and the like. It is not limited to this.

  Specific examples when component (C) is a sulfonate include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, bis (trifluoromethanesulfonate) calcium, bis (trifluoromethanesulfonate) Barium, tris (trifluoromethanesulfonate) titanium, tetrakis (trifluoromethanesulfonate) titanium, tetrakis (trifluoromethanesulfonate) zirconium, tetrakis (trifluoromethanesulfonate) hafnium, pentakis (trifluoromethanesulfonate) niobium, pentakis (trifluoro) Lomethanesulfonate) tantalum, tris (trifluoromethanesulfonate) iron, trifluoromethanesulfone Silver, tris (trifluoromethanesulfonate) boron, tris (trifluoromethanesulfonate) aluminum, tris (trifluoromethanesulfonate) gallium, tetrakis (trifluoromethanesulfonate) tin, lithium pentafluorobenzenesulfonate, pentafluorobenzene Sodium sulfonate, potassium pentafluorobenzenesulfonate, bis (pentafluorobenzenesulfonate) magnesium, bis (pentafluorobenzenesulfonate) calcium, bis (pentafluorobenzenesulfonate) barium, tris (pentafluorobenzenesulfonate) titanium , Tetrakis (pentafluorobenzenesulfonate) zirconium, tetrakis (pentafluorobenzenesulfonate) G) Hafnium, pentakis (pentafluorobenzene sulfonate) niobium, pentakis (pentafluorobenzene sulfonate) tantalum, tris (pentafluorobenzene sulfonate) iron, pentafluorobenzene sulfonate silver, tris (pentafluorobenzene sulfonate) boron , Tris (pentafluorobenzenesulfonate) aluminum, tris (pentafluorobenzenesulfonate) gallium, tetrakis (pentafluorobenzenesulfonate) tin, bis (trifluoromethanesulfonate) magnesium, pentakis (trifluoromethanesulfonate) niobium, bis (Pentafluorobenzenesulfonate) magnesium, tetrakis (pentafluorobenzenesulfonate) titanium and pentakis (Pentafluorobenzenesulfonate) niobium and the like can be exemplified.

  Specific examples when component (C) is a carboxylic acid compound include trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluorobenzoic acid, tetrafluorotoluic acid, 2,4- (trifluoromethyl) benzoic acid, penta A fluorophenylacetic acid etc. can be illustrated.

Component (D) is represented by the following general formula (d)
Zn (R ′) ₂ (d)
It is an organic zinc compound represented by these.

In general formula (d), R ′ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. These may be the same as or different from each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, normal butyl group, pentyl group, hexyl group, heptyl group, benzyl group, octyl group, phenylethyl group, nonyl group, and phenylpropyl. Group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, arachidyl group and other alkyl groups, vinyl group, propenyl group, butenyl group, cyclohexenyl As an aryl group such as an alkenyl group such as a group, and an alkoxy group having 1 to 20 carbon atoms, a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, an isobutoxy group, a tertiary butoxy group, a pentyloxy group , Hexyloxy group, etc. Door can be. Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, paramethylphenoxy group, paramethoxyphenoxy group, 2,6-dimethylphenoxy group, 1-naphthoxy group and the like. R ^″ may be the same as or different from each other, and may be connected to each other to form a ring.

Specific examples of the component (D) represented by the general formula (d) are shown below.
Specific examples include zinc compounds such as dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, divinyl zinc, diallyl zinc, methyl zinc chloride, and ethyl zinc chloride.

Component (E) is used for alkylation of components (A) and (B) and has the following general formula (e)
Al (R ^″ ) ₃ (e)
It is an organoaluminum compound represented by. In general formula (e), R ^″ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, and benzyl. Group, octyl group, phenylethyl group, nonyl group, phenylpropyl group, cumyl group, decyl group, adamantyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, alkyl group such as triphenylmethyl group and arachidyl group, cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, alkenyl group such as vinyl group, propenyl group, butenyl group and cyclohexenyl group , Phenyl group, Group, 2,6-dimethylphenyl group, mesityl group, 2,6-diisopropylphenyl group, a biphenyl group, a naphthyl group, acenaphthyl group, an anthracenyl group, a phenanthryl group, and an aryl group such as a pyrenyl group.
R ^″ may be the same as or different from each other, and may be connected to each other to form a ring.
Specific examples of the component (E) represented by the general formula (e) include trimethylaluminum, dimethylaluminum hydride, triethylaluminum, diethylaluminum hydride, trinormalpropylaluminum, dinormalpropylaluminum hydride, triisopropylaluminum, diisopropylaluminum. Hydride, tri-normal butyl aluminum, di-normal butyl aluminum hydride, triisobutyl aluminum, diisobutyl aluminum hydride, tritertiary butyl aluminum, ditertiary butyl aluminum hydride, trinormal hexyl aluminum, dinormal hexyl aluminum hydride, triisohexyl aluminum, di Isohexyl aluminum hydride, tri-normal octide Aluminum, di-n-octyl aluminum hydride, tri-isooctyl aluminum, and the like diisooctyl aluminum hydride. Triethylaluminum and triisobutylaluminum are preferred.

You may use a component (H) solid support | carrier as needed. Examples of the solid support of the component (H) include inorganic oxides of typical elements such as SiO ₂ , Al ₂ O ₃ , MgO, inorganic oxides of transition metal elements such as TiO ₂ and ZrO ₂ , mixtures thereof, and MgCl _2. Inorganic halides can be exemplified.

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

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

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

  The amount of each component used in the olefin polymerization catalyst of the present invention will be described.

  The molar ratio [= (number of moles of component (A)) / (number of moles of component (B))] of the component (A) and the component (B) used in the present invention is 0.001 to 1000. Preferably, it is 0.01-100. The amount of component (A) and component (B) used relative to component (C) is 0.0001 to 10 mmol of the sum of the number of moles of component (A) and component (B) relative to 1 g of component (C). Is more preferable, and 0.001-1 mmol is more preferable.

  The amount of component (D) used in the present invention is the ratio of the number of moles of component (D) to the sum of the number of moles of component (A) and the number of moles of component (B) [= mol of component (D). Number) / [(number of moles of component (A)) + (number of moles of component (B))]] is preferably 500 to 100,000, more preferably 1,000 to 20,000, and particularly preferably 2500 to 10,000. is there.

  The amount of component (E) used in the present invention is the ratio of the number of moles of component (E) to the sum of the number of moles of component (A) and the number of moles of component (B) [= mol of component (E). Number) / [(number of moles of component (A)) + (number of moles of component (B))]] is preferably 1 to 10,000, more preferably 1 to 1000, and particularly preferably 1 to 500. It is.

  A method for preparing the olefin polymerization catalyst of the present invention will be described.

In the catalyst for olefin polymerization of the present invention, the component (A), the component (B), the component (C), the component (D), the component (E) and, if necessary, the component (H) are contacted in an organic solvent. Can be adjusted by.

There are no particular restrictions on the contact method,
i-1) A method in which the contact product of component (A) and component (B) is contacted with component (C), and then component (D) is contacted.
i-2) Method of contacting component (C) with component (A), then contacting component (B) and then contacting component (D) i-3) Component (C) with component (B) Method of contacting component (A) and then contacting component (D) ii-1) A catalyst component (F) in which component (C) and component (D) are contacted is prepared. A method in which the contact product of component (A) and component (B) is contacted with catalyst component (F), and then component (D) is contacted.
ii-2) The catalyst component (F) is prepared by bringing the component (C) and the component (D) into contact with each other. A method of contacting the component (D) after contacting the component (A) with the catalyst component (F), then contacting the component (B).
ii-3) The component (C) and the component (D) are contacted to prepare the catalyst component (F). A method of bringing the component (B) into contact with the catalyst component (F), then bringing the component (A) into contact with the catalyst component (F), and then bringing the component (D) into contact therewith.
iii) A component (A) and a component (C) are made to contact and a catalyst component (G-1) is prepared. Separately, the component (B) and the component (C) are contacted to prepare the catalyst component (G-2). Subsequently, after preparing the catalyst component (G) which made the catalyst component (G-1) and the catalyst component (G-2) contact, the method which makes a component (D) contact.
iv) The component (C) and the component (D) are contacted to prepare the catalyst component (F). The catalyst component (F) and the component (A) are contacted to prepare the catalyst component (F-1), and the catalyst component (F) and the component (B) are contacted to prepare the catalyst component (F-2). F-1) and a catalyst component (F-2) are contacted.

  A method of using a contact product of component (A) and component (E) instead of component (A) in the above preparation method, and using a contact product of component (B) and component (E) instead of component (B). It can be illustrated.

  Moreover, the method including the process which contacts a component (H) in the said preparation method can be illustrated.

  Preferably, preparation methods i-1) to i-3), ii-1) to ii-3) and contact products of component (A) and component (E) in place of component (A) in these preparation methods Is a method using a contact product of component (B) and component (E) instead of component (B).

  Examples of the solvent used in preparing the olefin polymerization catalyst of the present invention include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; benzene, toluene, xylene, and the like. Aromatic hydrocarbons; ethers such as ethyl ether or normal butyl ether; halogenated hydrocarbons such as methylene chloride or chloroform; 1,4-dioxane; acetonitrile or tetrahydrofuran. The temperature for preparing the olefin polymerization catalyst of the present invention is preferably selected from -20 to 200 ° C for the treatment. The prepared catalyst for olefin polymerization may be used without washing, or may be used after washing with the above organic solvent.

  The manufacturing method of the olefin polymer of this invention is demonstrated.

  In the method for producing an olefin polymer of the present invention, an olefin polymer is obtained by homopolymerizing ethylene or copolymerizing ethylene and at least one comonomer in the presence of the olefin polymerization catalyst.

  As a polymerization method used in the method for producing an olefin polymer of the present invention, any of liquid phase polymerization such as slurry polymerization, gas phase polymerization, and high pressure polymerization can be used. The solvent used in the liquid phase polymerization may be any organic solvent that is generally used. Specific examples thereof include benzene, toluene, xylene, pentane, hexane, heptane, and the like. Propylene, 1-butene, 1- Olefins such as octene and 1-hexene can themselves be used as a solvent. A preferred polymerization method is liquid phase polymerization such as slurry polymerization.

  Examples of the comonomer used in the method for producing an olefin polymer of the present invention include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. Α-olefins such as 1-eicosene, 4-methyl-1-pentene, 3-methyl-1-butene or vinylcycloalkane; cyclic olefins such as norbornene or norbornadiene; dienes such as butadiene or 1,4-hexadiene or styrene Examples thereof include polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Further, two or more kinds of these comonomers can be mixed and used.

  There is no restriction | limiting in particular about polymerization conditions, such as the polymerization temperature in the manufacturing method of the olefin polymer of this invention, polymerization time, a polymerization pressure, and a monomer concentration. The polymerization temperature can be performed in the range of −100 to 120 ° C., preferably in the range of 40 to 100 ° C., and more preferably in the range of 60 to 90 ° C. The polymerization time can be carried out in the range of 10 seconds to 20 hours. The polymerization pressure can be performed in the range of 0.001 MPa to 300 MPa, preferably in the range of 0.005 MPa to 50 MPa, and more preferably in the range of 0.01 MPa to 10 MPa. As a supply ratio of ethylene and comonomer, a range of comonomer / ethylene (molar ratio) of 0.0001 to 5 can be used, a range of 0.001 to 2 is preferable, and a range of 0.01 to 1 is more preferable. is there. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The olefin polymer can be obtained by separating and recovering from the polymerization solvent by a conventionally known method after completion of the polymerization and drying.

The density of the olefin polymer produced in the present invention is 880 kg / ^{m 3} or more 980 kg / ^{m 3} or less.
The number average molecular weight (Mn) is from 1,000 to 1,000,000, preferably from 5,000 to 500,000. The ratio of weight average molecular weight (Mw) to Mn (Mw / Mn) is 2 or more and 20 or less, preferably 3.5 or more and 15 or less, more preferably 3.5 or more and 10 or less.

The olefin polymer produced using the olefin polymerization catalyst of the present invention is an olefin polymer produced using a Ziegler catalyst, and an olefin polymerization catalyst comprising one kind of transition metal compound (metallocene etc.) as a constituent component. The transparency at the same density is better compared to the olefin polymers produced and blends thereof. Moreover, the transparency in the same density is favorable compared with the olefin polymer obtained using the catalyst which does not contain the component (D) of this invention. In particular, the transparency in the high-density polyethylene region (density of 940 kg / m ³ or more) is good.

  Examples of fields to which the olefin polymer produced in the present invention can be applied include fields such as injection molded products, films, sheets, blows, laminates, foams, and fibers. The olefin polymer produced in the present invention includes, for example, a heat stabilizer, a weather stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, a nucleating agent, a pigment, carbon black, talc, glass powder, Known additives such as inorganic fillers or reinforcing agents such as glass fibers, organic fillers or reinforcing agents, flame retardants, and neutron shielding agents can be blended. Moreover, it can also be used by mixing with other thermoplastic resins. Examples include tackifying resins, waxes, high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymer Examples thereof include a copolymer, an ethylene / vinyl alcohol copolymer, polystyrene, or a maleic anhydride graft product thereof.

  By using the catalyst for olefin polymerization of the present invention, it is possible to produce an olefin polymer having high transparency while maintaining heat resistance and mechanical strength.

It is the figure which plotted the density and haze of the olefin polymer obtained by the Example and the comparative example. It is the figure which plotted the density and Vicat softening temperature of the olefin polymer obtained by the Example and the comparative example. It is the figure which plotted the density and durometer D hardness of the olefin polymer obtained by the Example and the comparative example. It is the figure which plotted the haze and Vicat softening temperature of the olefin polymer obtained by the Example and the comparative example. It is the figure which plotted 1-butene / ethylene molar ratio and the number of short chain branches.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  Preparation of the olefin polymerization catalyst, polymerization reaction and solvent purification were all carried out in an inert gas atmosphere. As the preparation of the olefin polymerization catalyst and the solvent used for the polymerization reaction, all the solvents that had been purified, dried, and deoxygenated by a known method in advance were used. Tosoh Finechem Co., Ltd. was used for the hexane solution of triethylaluminum and the hexane solution of triisobutylaluminum. A diethyl zinc hexane solution manufactured by Kanto Chemical Co., Ltd. was used.

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

  The melt flow rate (MFR) was measured by a method according to ASTM D1238 Condition E.

The weight average molecular weight (Mw), the number average molecular weight (Mn) and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) were measured by gel permeation chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgelGMHhr-H (20) HT is used, the column temperature is set to 140 ° C., and 1 and 2 are used as eluents. , 4-trichlorobenzene was used for measurement. A measurement sample was prepared at a concentration of 1.0 mg / mL, and 0.3 mL was injected and measured. The calibration curve of the molecular weight is calibrated using a polystyrene sample having a known molecular weight by the universal calibration method. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion. The melting point Tm and heat of fusion ΔH of the obtained polymer were measured using DSC (Differential Scanning Calorimeter) SEIKO SC-5000.
The number of short chain branches (SCB) in the molecular chain is an absorption band corresponding to the bending vibration of the methyl group located at 1378 cm ⁻¹ using a Fourier transform infrared absorption spectrometer [SPECTRUM ONE manufactured by Perkin Elmer Co., Ltd.]. Obtained from the strength of

  Haze was measured with a Nippon Denshoku Industries Co., Ltd. haze meter (model number 300A) in accordance with JIS K7105 (1981). For the measurement, a sheet having a thickness of about 0.2 mm obtained by compression molding was used.

  The durometer D hardness was measured according to JISK6760 (D).

  The Vicat softening temperature is 10 mm x 10 mm x 4 mm test piece prepared in accordance with JISK7206. The test piece is put in a heating tank and heated at a rate of 50 ° C / hour while applying a 1 kg load. The temperature when entering 1 mm was defined as the Vicat softening temperature.

The density (kg / m ³ ) was measured by a density gradient tube method according to JISK6760 (1995).

  In the blending experiment, Irganox 1010TM (manufactured by Ciba Specialty Chemicals) 1,500 ppm and Irgaphos 168TM (manufactured by Ciba Specialty Chemicals) 1,500 ppm were added as heat stabilizers in advance, and an internal mixer (manufactured by Toyo Seiki Seisakusho, trade name) : Laboplast mill), and melt kneading was performed for 30 minutes at 190 ° C. and a rotation speed of 30 rpm under a nitrogen stream.

Example 1
[Preparation of component (C)]
After adding 60 mL of ethanol and 2.0 mL of 37% concentrated hydrochloric acid to 60 mL of water, 6.6 g (0.022 mol) of N, N-dimethyl-octadecylamine was added to the resulting solution and heated to 60 ° C. A hydrochloride solution was prepared. To this solution was added 20 g of hectorite. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 1 L of 60 ° C. water. Then, it dried at 60 degreeC and 10 < ^-3 > torr for 24 hours, and the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill. As a result of elemental analysis, the amount of ions per gram of modified hectorite was 0.85 mmol.
[Preparation of catalyst component for olefin polymerization]
Component (A): (1,1,3,3-tetramethyldisiloxane-1,3-diyl) bis (1-cyclopentadienyl) zirconium dichloride (complex A-1, 25.3 mg, 60 μmol) in hexane Suspended in (7 mL), hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (A) and component (E). Component (B): (diphenylmethylene) (4-phenyl-indenyl) (2,7-ditertiarybutylfluorenyl) zirconium dichloride (complex B-1, 47.7 mg, 60 μmol) is suspended in hexane (7 mL). The mixture was made turbid, and a hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (B) and component (E). These contact products were added to a hexane suspension of the modified hectorite (3.0 g) of the above component (C) and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (30 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Hexane was added to adjust the slurry concentration (100 g of the solid catalyst component per liter), and an olefin polymerization catalyst component containing component (A), component (B), component (C), and component (E) was obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the above olefin polymerization catalyst component (0.30 mL) was added, and ethylene gas and 1-butene (12.0 g) were introduced to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 211 g, Mn = 28,300, Mw / Mn = 4.48, MFR = 0.41 g / 10 min. The melting point was 132.0 ° C., the heat of fusion was 194 mJ / mg, the density was 949 kg / m ³ , the Vicat softening temperature was 127 ° C., the durometer D hardness was 67, and the haze was 46.2%.

Example 2
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc hexane solution (1.06 M, 3.8 mL, 4 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the catalyst component for olefin polymerization (0.20 mL) described in Example 1 was added, and an ethylene / hydrogen mixed gas (containing 3000 ppm of hydrogen) and 1-butene (12.0 g) were introduced to initiate polymerization. did. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of the ethylene / hydrogen mixed gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 191 g, Mn = 12,900, Mw / Mn = 5.43, MFR = 4.59 g / 10 min. The melting point was 128.2 ° C., the heat of fusion was 193 mJ / mg, the density was 946 kg / m ³ , the Vicat softening temperature was 120 ° C., the durometer D hardness was 65, and the haze was 45.9%.

Example 3
[Production of olefin polymer]

Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.30 mL) described in Example 1 was added, and ethylene gas and 1-butene (12.0 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 189 g, Mn = 27,100, Mw / Mn = 4.58, MFR = 0.46 g / 10 min. The melting point was 130.1 ° C., the heat of fusion was 187 mJ / mg, the density was 945 kg / m ³ , the Vicat softening temperature was 123 ° C., the durometer D hardness was 65, and the haze was 31.6%.

Example 4
[Production of olefin polymer]

Hexane (3,000 mL) and component (D): diethylzinc hexane solution (1.06 M, 3.8 mL, 4 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the catalyst component for olefin polymerization (0.20 mL) described in Example 1 was added, and an ethylene / hydrogen mixed gas (containing 3000 ppm of hydrogen) and 1-butene (18.0 g) were introduced to initiate polymerization. did. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of the ethylene / hydrogen mixed gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 203 g, Mn = 15,300, Mw / Mn = 4.02, MFR = 7.74 g / 10 min. The melting point was 122.2 ° C., the heat of fusion was 171 mJ / mg, the density was 934 kg / m ³ , the Vicat softening temperature was 110 ° C., the durometer D hardness was 61, and the haze was 17.1%.

Example 5
[Production of olefin polymer]

Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.30 mL) described in Example 1 was added, and ethylene gas and 1-butene (18.0 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 201g, Mn = 28,100, Mw / Mn = 5.13, MFR = 0.34g / 10min. The melting point was 128.2 ° C., the heat of fusion was 170 mJ / mg, the density was 938 kg / m ³ , the Vicat softening temperature was 119 ° C., the durometer D hardness was 64, and the haze was 17.1%.

Example 6
[Production of olefin polymer]

Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.30 mL) described in Example 1 was added, and ethylene gas and 1-butene (30.1 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 215 g, Mn = 28,200, Mw / Mn = 4.40, MFR = 0.50 g / 10 min. Melting points were 124.1 ° C. and 112.0 ° C., heat of fusion was 159 mJ / mg, density was 932 kg / m ³ , Vicat softening temperature was 111 ° C., durometer D hardness was 62, and haze was 17.2%.

Example 7
[Production of olefin polymer]

Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.30 mL) described in Example 1 was added, and ethylene gas and 1-butene (60.2 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 230 g, Mn = 27,900, Mw / Mn = 3.86, MFR = 0.82 g / 10 min. The melting points were 119.4 ° C. and 96.7 ° C., the heat of fusion was 127 mJ / mg, the density was 919 kg / m ³ , the Vicat softening temperature was 96 ° C., the durometer D hardness was 56, and the haze was 15.7%.

Example 8
[Production of olefin polymer]

Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.30 mL) described in Example 1 was added, and ethylene gas and 1-butene (90.3 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 264 g, Mn = 26,500, Mw / Mn = 3.53, MFR = 1.46 g / 10 min. Melting points were 118.5 ° C. and 82.2 ° C., heat of fusion was 99 mJ / mg, density was 910 kg / m ³ , Vicat softening temperature was 77 ° C., durometer D hardness was 50, and haze was 16.9%.

Example 8
[Production of olefin polymer]

Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.30 mL) described in Example 1 was added, and ethylene gas and 1-butene (90.3 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 264 g, Mn = 26,500, Mw / Mn = 3.53, MFR = 1.46 g / 10 min. Melting points were 118.5 ° C. and 82.2 ° C., heat of fusion was 99 mJ / mg, density was 910 kg / m ³ , Vicat softening temperature was 77 ° C., durometer D hardness was 50, and haze was 16.9%.

Example 9
[Preparation of catalyst component for olefin polymerization]
Component (A): (Dimethylsilylene) (1-cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride (complex A-2, 26.4 mg, 60 μmol) suspended in hexane (7 mL) Component (E): Triethylaluminum in hexane (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (A) and component (E). Component (B): (diphenylmethylene) (4-phenyl-indenyl) (2,7-ditertiarybutylfluorenyl) zirconium dichloride (complex B-1, 47.7 mg, 60 μmol) is suspended in hexane (7 mL). The mixture was made turbid, and a hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (B) and component (E). These contact products were added to a hexane suspension of the modified hectorite (3.0 g) of component (C) described in Example 1 and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (30 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Hexane was added to adjust the slurry concentration (100 g of the solid catalyst component per liter), and an olefin polymerization catalyst component containing component (A), component (B), component (C), and component (E) was obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc hexane solution (1.06 M, 3.8 mL, 4 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the above olefin polymerization catalyst component (0.30 mL) was added, and ethylene gas and 1-butene (12.0 g) were introduced to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 208 g and MFR = 2.71 g / 10 min. The melting point was 127.2 ° C., the density was 943 kg / m ³ , the Vicat softening temperature was 115 ° C., the durometer D hardness was 62, and the haze was 25.5%.

Example 10
[Preparation of catalyst component for olefin polymerization]
Component (A): (Dimethylsilylene) (1-cyclopentadienyl) (2,3,4,7-tetramethylindenyl) zirconium dichloride (complex A-3, 27.3 mg, 60 μmol) in hexane (7 mL) Into the mixture, component (E): a solution of triethylaluminum in hexane (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (A) and component (E). Component (B): (diphenylmethylene) (4-phenyl-indenyl) (2,7-ditertiarybutylfluorenyl) zirconium dichloride (complex B-1, 47.7 mg, 60 μmol) is suspended in hexane (7 mL). The mixture was made turbid, and a hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (B) and component (E). These contact products were added to a hexane suspension of the modified hectorite (3.0 g) of component (C) described in Example 1 and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (30 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Hexane was added to adjust the slurry concentration (100 g of the solid catalyst component per liter), and an olefin polymerization catalyst component containing component (A), component (B), component (C), and component (E) was obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc hexane solution (1.06 M, 3.8 mL, 4 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the above olefin polymerization catalyst component (0.30 mL) was added, and ethylene gas and 1-butene (12.0 g) were introduced to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 165 g and MFR = 2.57 g / 10 min. The melting point was 128.9 ° C., the density was 945 kg / m ³ , the Vicat softening temperature was 116 ° C., the durometer D hardness was 64, and the haze was 32.8%.

Example 11
[Preparation of catalyst component for olefin polymerization]
Component (A): bis (indenyl) zirconium dichloride (complex A-4, 23.5 mg, 60 μmol) is suspended in hexane (7 mL), and component (E): hexane solution of triethylaluminum (E-1, 1.. 20M, 5 mL) was added to obtain a contact product of component (A) and component (E). Component (B): (diphenylmethylene) (4-phenyl-indenyl) (2,7-ditertiarybutylfluorenyl) zirconium dichloride (complex B-1, 47.7 mg, 60 μmol) is suspended in hexane (7 mL). The mixture was made turbid, and a hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (B) and component (E). These contact products were added to a hexane suspension of the modified hectorite (3.0 g) of component (C) described in Example 1 and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (30 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Hexane was added to adjust the slurry concentration (100 g of the solid catalyst component per liter), and an olefin polymerization catalyst component containing component (A), component (B), component (C), and component (E) was obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc hexane solution (1.06 M, 3.8 mL, 4 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, the above olefin polymerization catalyst component (0.20 mL) was added, and ethylene gas and 1-butene (12.0 g) were introduced to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 135 g and MFR = 1.59 g / 10 min. The melting point was 128.9 ° C., the density was 945 kg / m ³ , the Vicat softening temperature was 118 ° C., the durometer D hardness was 65, and the haze was 31.0%.

Example 12
[Preparation of catalyst component for olefin polymerization]
Component (A): (1,3-propanediyl) bis (1-cyclopentadienyl) zirconium dichloride (complex A-5, 20.0 mg, 60 μmol) was suspended in hexane (7 mL), and component (E) : A hexane solution of triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (A) and component (E). Component (B): (diphenylmethylene) (4-phenyl-indenyl) (2,7-ditertiarybutylfluorenyl) zirconium dichloride (complex B-1, 47.7 mg, 60 μmol) is suspended in hexane (7 mL). The mixture was made turbid, and a hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (B) and component (E). These contact products were added to a hexane suspension of the modified hectorite (3.0 g) of component (C) described in Example 1 and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (30 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Hexane was added to adjust the slurry concentration (100 g of the solid catalyst component per liter), and an olefin polymerization catalyst component containing component (A), component (B), component (C), and component (E) was obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc hexane solution (1.06 M, 3.8 mL, 4 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, the above olefin polymerization catalyst component (0.20 mL) was added, and ethylene gas and 1-butene (30.0 g) were introduced to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 175 g and MFR = 0.69 g / 10 min. The melting point was 127.5 ° C., the density was 945 kg / m ³ , the Vicat softening temperature was 120 ° C., the durometer D hardness was 65, and the haze was 32.2%.

Example 13
[Preparation of catalyst component for olefin polymerization]
Component (A): (1,1,3,3-tetramethyldisiloxane-1,3-diyl) bis (1-cyclopentadienyl) zirconium dichloride (complex A-1, 25.3 mg, 60 μmol) in hexane Suspended in (7 mL), hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (A) and component (E). Component (B): (Dimethylmethylene) (1-cyclopentadienyl) (2,7-ditertiarybutylfluorenyl) zirconium dichloride (complex B-2, 32.7 mg, 60 μmol) is suspended in hexane (7 mL). The mixture was made turbid, and a hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 5 mL) was added to obtain a contact product of component (B) and component (E). These contact products were added to a hexane suspension of the modified hectorite (3.0 g) of the above component (C) and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (30 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Hexane was added to adjust the slurry concentration (100 g of the solid catalyst component per liter), and an olefin polymerization catalyst component containing component (A), component (B), component (C), and component (E) was obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 5.7 mL, 6 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the above olefin polymerization catalyst component (0.30 mL) was added, and ethylene gas and 1-butene (12.0 g) were introduced to initiate polymerization. During the polymerization, an ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 144 g and MFR = 12.6 g / 10 min. The melting point was 128.5 ° C., the density was 942 kg / m ³ , the Vicat softening temperature was 115 ° C., the durometer D hardness was 61, and the haze was 17.9%. A list of polymerization results is shown in Table 1.

Example 14
[Preparation of Contact Product of Component (H) and Component (C)]
Silica (10 g, Grace, sypol 952, component (H)) calcined at 150 ° C. for 8 hours under a nitrogen atmosphere was suspended in toluene (100 mL). While maintaining at 0 ° C., a toluene solution of methylaluminoxane (TMAO-211, 8.9 wt%, 45.5 g, component (C) manufactured by Tosoh Finechem) was added and reacted at 100 ° C. for 4 hours. After cooling the reaction solution to room temperature, the supernatant is removed. Washing was performed twice with hexane (100 mL), and drying was performed at room temperature under reduced pressure to obtain a contact organism of component (H) and component (C).
[Preparation of catalyst component for olefin polymerization]
Component (A): (1,1,3,3-tetramethyldisiloxane-1,3-diyl) bis (1-cyclopentadienyl) zirconium dichloride (complex A-1, 84.3 mg, 200 μmol) in hexane (23.4 mL), component (E): triethylaluminum in hexane solution (E-1, 1.20 M, 16.6 mL) is added, and contact product of component (A) and component (E) Got. Component (B): (diphenylmethylene) (4-phenyl-indenyl) (2,7-ditertiarybutylfluorenyl) zirconium dichloride (complex B-1, 159 mg, 200 μmol) suspended in hexane (23.4 mL). The mixture was made turbid, and a hexane solution of component (E): triethylaluminum (E-1, 1.20 M, 16.6 mL) was added to obtain a contact product of component (B) and component (E). These contact products were added to a hexane (100) suspension of the contact product (10.0 g) of the above component (H) and component (C), and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (100 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Add hexane to adjust slurry concentration (100 g of solid catalyst component per liter), and catalyst for olefin polymerization comprising component (A), component (B), component (C), component (E), and component (H) Ingredients were obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and component (D): diethylzinc in hexane (1.06 M, 4.2 mL, 4.5 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the above-mentioned catalyst component for olefin polymerization (9 mL) was added, and ethylene gas and 1-butene (90.3 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 264 g, Mn = 25,600, Mw / Mn = 2.48, MFR = 0.78 g / 10 min. Melting points were 114.4 ° C. and 73.5 ° C., heat of fusion was 87 mJ / mg, density was 906 kg / m ³ , Vicat softening temperature was 66 ° C., hardness was 48, and haze was 16.5%.

Comparative Example 1
[Production of olefin polymer]
Hexane (3,000 mL) and triisobutylaluminum hexane solution (0.70 M, 1.0 mL, 0.7 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.15 mL) described in Example 1 was added, and an ethylene / hydrogen mixed gas (containing 1.0% hydrogen) and 1-butene (12.0 g) were introduced. Polymerization was started. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of the ethylene / hydrogen mixed gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 132 g, Mn = 4,200, Mw / Mn = 17.58, and MFR = 2.91 g / 10 minutes. The melting point was 125.0 ° C., the heat of fusion was 197 mJ / mg, the density was 946 kg / m ³ , the Vicat softening temperature was 116 ° C., the durometer D hardness was 66, and the haze was 66.9%.

Comparative Example 2
[Production of olefin polymer]
Hexane (3,000 mL) and triisobutylaluminum hexane solution (0.70 M, 1.0 mL, 0.7 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the catalyst component for olefin polymerization (0.15 mL) described in Example 1 was added, and an ethylene / hydrogen mixed gas (containing 0.8% hydrogen) and 1-butene (18.0 g) were introduced. Polymerization was started. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of the ethylene / hydrogen mixed gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 171 g, Mn = 4,800, Mw / Mn = 19.07, and MFR = 1.50 g / 10 min. Melting point was 123.5 ° C., heat of fusion was 182 mJ / mg, density was 938 kg / m ³ , Vicat softening temperature was 113 ° C., durometer D hardness was 64, and haze was 57.7%.

Comparative Example 3
[Production of olefin polymer]
Hexane (3,000 mL) and triisobutylaluminum hexane solution (0.70 M, 1.0 mL, 0.7 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the catalyst component for olefin polymerization (0.15 mL) described in Example 1 was added, and an ethylene / hydrogen mixed gas (containing 0.8% hydrogen) and 1-butene (60.1 g) were introduced. Polymerization was started. During the polymerization, the ethylene / hydrogen mixed gas was continuously introduced so that the partial pressure of the ethylene / hydrogen mixed gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 60 minutes, the internal temperature of the autoclave was cooled to 40 ° C., the internal pressure of the autoclave was depressurized, and then the contents were suction filtered and dried. The obtained olefin polymer was 264 g, MFR = 0.60 g / 10 min. Melting points were 109.2 ° C., 88.5 ° C., heat of fusion was 81 mJ / mg, density was 909 kg / m ³ , Vicat softening temperature was 81 ° C., durometer D hardness was 51, and haze was 28.9%.

Comparative Example 4
[Preparation of catalyst component for olefin polymerization]
Bisindenylzirconium dichloride (47.1 mg, 120 μmol) was suspended in hexane (7 mL), and a hexane solution of triethylaluminum (E-1, 1.20 M, 5 mL) was added thereto. Hectorite (3.0 g) was added to a hexane suspension and reacted at 60 ° C. for 3 hours. After cooling to room temperature and allowing to stand, the supernatant is removed, hexane (30 mL) is added, the mixture is stirred and allowed to stand, and then the supernatant is removed to wash the solid components. Hexane was added to adjust the slurry concentration (100 g of the solid catalyst component per liter), and an olefin polymerization catalyst component having one transition metal compound as a constituent component was obtained.
[Production of olefin polymer]
Hexane (3,000 mL) and triisobutylaluminum hexane solution (0.70 M, 1.0 mL, 0.7 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, the above olefin polymerization catalyst component (0.15 mL) was added, and an ethylene / hydrogen mixed gas (containing 0.1% hydrogen) was introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 90 minutes, the internal temperature of the autoclave was cooled to 40 ° C., and the internal pressure of the autoclave was depressurized. Then, the contents were suction filtered and dried. The obtained olefin polymer was 184 g and MFR = 1.0 g / 10 min. The melting point was 136.6 ° C., the density was 953 kg / m ³ , the Vicat softening temperature was 128 ° C., the durometer D hardness was 65, and the haze was 73.2%.

Comparative Example 5
[Production of olefin polymer]
Hexane (3,000 mL) and triisobutylaluminum hexane solution (0.70 M, 1.0 mL, 0.7 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the catalyst component for olefin polymerization (0.15 mL) described in Comparative Example 4 was added, and an ethylene / hydrogen mixed gas (containing 0.1% hydrogen) and 1-butene (60 g) were introduced for polymerization. Started. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 90 minutes, the internal temperature of the autoclave was cooled to 40 ° C., and the internal pressure of the autoclave was depressurized. Then, the contents were suction filtered and dried. The obtained olefin polymer was 238 g and MFR = 3.8 g / 10 min. The melting point was 119.8 ° C., the density was 924 kg / m ³ , the Vicat softening temperature was 106 ° C., the durometer D hardness was 55, and the haze was 43.2%.

Comparative Example 6
[Production of olefin polymer]
Hexane (3,000 mL) and triisobutylaluminum hexane solution (0.70 M, 1.0 mL, 0.7 mmol) were introduced into a 5 L autoclave, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, the olefin polymerization catalyst component (0.15 mL) described in Comparative Example 4 was added, and ethylene gas and 1-butene (120 g) were introduced to initiate polymerization. During the polymerization, ethylene gas was continuously introduced so that the partial pressure of ethylene gas was maintained at 0.9 MPa, and the internal temperature of the autoclave was controlled at 85 ° C. After reacting for 90 minutes, the internal temperature of the autoclave was cooled to 40 ° C., and the internal pressure of the autoclave was depressurized. Then, the contents were suction filtered and dried. The obtained olefin polymer was 170 g and MFR = 1.1 g / 10 min. The melting point was 107.8 ° C., the density was 916 kg / m ³ , the Vicat softening temperature was 95 ° C., the durometer D hardness was 51, and the haze was 17.4%.

Comparative Example 7
The polyethylene obtained in Comparative Example 4 and the polyethylene obtained in Comparative Example 5 were melt kneaded at a weight ratio of 1/3. The MFR of the obtained blend was 2.7 g / 10 minutes. Melting points were 127.3 ° C., 113.7 ° C., density was 932 kg / m ³ , Vicat softening temperature was 112 ° C., durometer D hardness was 58, and haze was 52.8%.

Comparative Example 8
The polyethylene obtained in Comparative Example 4 and the polyethylene obtained in Comparative Example 6 were melt kneaded at a weight ratio of 1/1. The MFR of the obtained blend was 1.1 g / 10 minutes. Melting points were 126.4 ° C., 101.5 ° C., density was 924 kg / m ³ , Vicat softening temperature was 98 ° C., durometer D hardness was 58, and haze was 58.4%.

From FIG. 1, the olefin weight produced using the olefin polymerization catalyst comprising the component (A), the component (B), the component (C), the component (D), and the component (E) shown in the examples of the present invention. The coalescence is an olefin polymer produced using an olefin polymerization catalyst comprising the component (A), component (B), component (C) and component (E) shown in the comparative example, a blend of HDPE and LLDPE, and LLDPE. In comparison, it can be seen that transparency at the same density is high (has low haze).
From FIG. 2, the olefin weight produced using the olefin polymerization catalyst comprising the component (A), the component (B), the component (C), the component (D), and the component (E) shown in the examples of the present invention as components. The coalescence is an olefin polymer produced using an olefin polymerization catalyst comprising the component (A), component (B), component (C) and component (E) shown in the comparative example, a blend of HDPE and LLDPE, and LLDPE. By comparison, it can be seen that the same density has the same heat resistance.

  From FIG. 3, the olefin weight produced using the olefin polymerization catalyst comprising the component (A), the component (B), the component (C), the component (D), and the component (E) shown in the examples of the present invention as components. The coalescence is an olefin polymer produced using an olefin polymerization catalyst comprising the component (A), component (B), component (C) and component (E) shown in the comparative example, a blend of HDPE and LLDPE, and LLDPE. In comparison, it can be seen that the same density has the same strength.

  From FIG. 4, the olefin weight produced using the olefin polymerization catalyst comprising the component (A), the component (B), the component (C), the component (D), and the component (E) shown in the examples of the present invention. Compared to an olefin polymer produced using an olefin polymerization catalyst comprising the component (A), component (B), component (C), and component (E) shown in the comparative example, the combined heat resistance is equivalent. It turns out that transparency is high.

Claims (8)

Component (A), (B) two different group 4 metallocene compounds of the periodic table,
Component (C) activation promoter,
Component (D) The following general formula Zn (R ′) ₂ (d)
(In general formula (d), each R ′ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. And may be the same or different from each other)
Component (E) The following general formula (e)
Al (R ″) ₃ (e)
(Wherein R ″ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other. A catalyst for olefin polymerization comprising an organoaluminum compound represented by the formula: Further component (H) according to claim 1, wherein the olefin polymerization catalyst and a solid carrier component. The catalyst for olefin polymerization according to claim 1 or 2, wherein the component (C) is a modified clay mineral treated with an organic compound. Component (C) is represented by the following general formula (c-1)
[R ²¹ R ²² _x-1 GH] _y [J] _z (c-1)
(In the formula, [R ²¹ R ²² _x-1 GH] is a cation, G is an element selected from Group 15 or Group 16 of the periodic table, and R ²¹ is a hydrocarbon group having 1 to 30 carbon atoms. And each R ²² independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, x = 3 when G is a Group 15 element, and x = 2 when G is a Group 16 element. Wherein [J] is an anion, and y and z are integers selected so that the electric charges are balanced, and a modified clay mineral treated with an organic compound represented by the formula: 3. The catalyst for olefin polymerization according to 3. Ethylene and one or more components in the copolymerization of the comonomers (B) an olefin polymerization catalyst according to any one of claims 1 to 4 comonomer uptake ability are different from each other than the component (A) of 6. The comonomer uptake capacity of component (B) in the copolymerization of ethylene and one or more types of comonomer is at least twice the comonomer uptake capacity of component (A). The catalyst for olefin polymerization as described The contact product of component (A) and component (E) and the contact product of component (B) and component (E) are contacted with component (C) and then contacted with component (D) olefin polymerization catalyst according to any one of claims 1 to 6. Process for producing an olefin polymer characterized by polymerizing ethylene and one or more comonomers with a catalyst for olefin polymerization according to any one of claims 1 to 7.

Images