JP2004027099A - Modified particle, method for producing the same, carrier, catalytic component for addition polymerization, catalyst for addition polymerization, and method for producing addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a particle, a carrier and a catalytic component for addition polymerization, for producing a high-molecular weight addition polymer by the addition polymerization by using them in combination with a transition metal compound forming a single-site catalyst; to provide a method for producing the particle; to provide a catalyst for the addition polymerization using the particle; and to provide a method for producing the addition polymer by using the catalyst for the addition polymerization. <P>SOLUTION: The modified particle is obtained by bringing (a) M<SP>1</SP>L<SP>1</SP><SB>m</SB>, (b) R<SP>1</SP><SB>t-1</SB>TH and (c) R<SP>2</SP><SB>t-2</SB>TH<SB>2</SB>into contact with (d') a particle obtained by a contact treatment of (d) a particle with (a') R<SP>3</SP><SB>t-1</SB>TH. (In the formulas, M<SP>1</SP>is a group 1, 2, 12, 14 or 15 typical metal atom; m is a valence of M<SP>1</SP>; L<SP>1</SP>is a hydrogen atom, a halogen atom or a hydrocarbon group; R<SP>1</SP>is an electron attracting group or a group containing the electron attracting group; R<SP>2</SP>is a hydrocarbon group or a halogenated hydrocarbon group; R<SP>3</SP>is a hydrocarbon group; T is a group 15 or 16 nonmetallic atom; and t is a valence of T). <P>COPYRIGHT: (C)2004,JPO

Description

（式中、Ｒ^５　はそれぞれの場合に水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、それらは互いに同じであっても異なっていても良く、それら２つ以上が互いに結合していても良く、環を形成していても良い。）
【００９７】
前記一般式［７］におけるＲ^５　の具体例としては、水素原子、フッ素原子、塩素原子、臭素原子、よう素原子、フェニル基、１−ナフチル基、２−ナフチル基、ｔｅｒｔ−ブチル基、２，６−ジメチルフェニル基、２−フルオレニル基、２−メチルフェニル基、４−トリフルオロメチルフェニル基、４−メトキシフェニル基、４−ピリジル基、シクロヘキシル基、２−イソプロピルフェニル基、ベンジル基、メチル基、トリエチルシリル基、ジフェニルメチルシリル基、１−メチル−１−フェニルエチル基、１，１−ジメチルプロピル基、２−クロロフェニル基、ペンタフルオロフェニル基等が挙げられるが、これらに限定されるものではない。
【００９８】
前記キレート性配位子とは複数の配位部位を有する配位子を指し、具体的に例示すれば、アセチルアセトナート、ジイミン、オキサゾリン、ビスオキサゾリン、テルピリジン、アシルヒドラゾン、ジエチレントリアミン、トリエチレンテトラミン、ポルフィリン、クラウンエーテル、クリプタートなどが挙げられる。
【００９９】
前記複素環基の具体例としては、ピリジル基、Ｎ−置換イミダゾリル基、Ｎ−置換インダゾリル基であり、好ましくはピリジル基である。
【０１００】
シクロペンタジエン形アニオン骨格を有する基同士、シクロペンタジエン形アニオン骨格を有する基とヘテロ原子を含有する基、またはヘテロ原子を含有する基同士は、それぞれ、直接連結されていても良く、炭素原子、ケイ素原子、窒素原子、酸素原子、硫黄原子もしくはリン原子を含有する残基を介して連結されていてもよい。かかる残基として好ましくは、２つのＬ^２　と結合する原子が炭素原子、ケイ素原子、窒素原子、酸素原子、硫黄原子および／またはリン原子である２価の残基であり、さらに好ましくは、２つのＬ^２　と結合する原子が炭素原子、ケイ素原子、窒素原子、酸素原子、硫黄原子および／またはリン原子であり、２つのＬ^２　と結合する原子間の最小原子数が３以下の２価の残基（これには２つのＬ^２　と結合する原子が単一の場合を含む。）である。具体的には、メチレン基、エチレン基、プロピレン基等のアルキレン基、ジメチルメチレン基（イソプロピリデン基）、ジフェニルメチレン基などの置換アルキレン基、またはシリレン基、ジメチルシリレン基、ジエチルシリレン基、ジフェニルシリレン基、テトラメチルジシリレン基、ジメトキシシリレン基などの置換シリレン基、または窒素原子、酸素原子、硫黄原子、リン原子などのヘテロ原子などが挙げられ、特に好ましくはメチレン基、エチレン基、ジメチルメチレン基（イソプロピリデン基）、ジフェニルメチレン基、ジメチルシリレン基、ジエチルシリレン基、ジフェニルシリレン基またはジメトキシシリレン基である。
【０１０１】
一般式［５］におけるＸ^１　は、ハロゲン原子、炭化水素基（但し、シクロペンタジエン形アニオン骨格を有する基を除く）、または炭化水素オキシ基である。ハロゲン原子の具体例としてフッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。ここでいう炭化水素基としてはシクロペンタジエン形アニオン骨格を有する基を含まない。ここでいう炭化水素基としてはアルキル基、アラルキル基、アリール基、アルケニル基等が挙げられ、好ましくは、炭素原子数１〜２０のアルキル基、炭素原子数７〜２０のアラルキル基、炭素原子数６〜２０のアリール基または炭素原子数３〜２０のアルケニル基が好ましい。
【０１０２】
炭素原子数１〜２０のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、イソブチル基、ｎ−ペンチル基、ネオペンチル基、アミル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−デシル基、ｎ−ドデシル基、ｎ−ペンタデシル基、ｎ−エイコシル基などが挙げられ、より好ましくはメチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基、イソブチル基またはアミル基である。
これらのアルキル基はいずれも、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子で置換されていてもよい。ハロゲン原子で置換された炭素原子数１〜１０のアルキル基としては、例えばフルオロメチル基、トリフルオロメチル基、クロロメチル基、トリクロロメチル基、フルオロエチル基、ペンタフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基、パークロロプロピル基、パークロロブチル基、パーブロモプロピル基などが挙げられる。
またこれらのアルキル基はいずれも、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基などのアリールオキシ基またはベンジルオキシ基などのアラルキルオキシ基などで一部が置換されていてもよい。
【０１０３】
炭素原子数７〜２０のアラルキル基としては、例えばベンジル基、（２−メチルフェニル）メチル基、（３−メチルフェニル）メチル基、（４−メチルフェニル）メチル基、（２，３−ジメチルフェニル）メチル基、（２，４−ジメチルフェニル）メチル基、（２，５−ジメチルフェニル）メチル基、（２，６−ジメチルフェニル）メチル基、（３，４−ジメチルフェニル）メチル基、（３，５−ジメチルフェニル）メチル基、（２，３，４−トリメチルフェニル）メチル基、（２，３，５−トリメチルフェニル）メチル基、（２，３，６−トリメチルフェニル）メチル基、（３，４，５−トリメチルフェニル）メチル基、（２，４，６−トリメチルフェニル）メチル基、（２，３，４，５−テトラメチルフェニル）メチル基、（２，３，４，６−テトラメチルフェニル）メチル基、（２，３，５，６−テトラメチルフェニル）メチル基、（ペンタメチルフェニル）メチル基、（エチルフェニル）メチル基、（ｎ−プロピルフェニル）メチル基、（イソプロピルフェニル）メチル基、（ｎ−ブチルフェニル）メチル基、（ｓｅｃ−ブチルフェニル）メチル基、（ｔｅｒｔ−ブチルフェニル）メチル基、（ｎ−ペンチルフェニル）メチル基、（ネオペンチルフェニル）メチル基、（ｎ−ヘキシルフェニル）メチル基、（ｎ−オクチルフェニル）メチル基、（ｎ−デシルフェニル）メチル基、（ｎ−ドデシルフェニル）メチル基、ナフチルメチル基、アントラセニルメチル基などが挙げられ、より好ましくはベンジル基である。
これらのアラルキル基はいずれも、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基などのアリールオキシ基またはベンジルオキシ基などのアラルキルオキシ基などで一部が置換されていてもよい。
【０１０４】
炭素原子数６〜２０のアリール基としては、例えばフェニル基、２−トリル基、３−トリル基、４−トリル基、２，３−キシリル基、２，４−キシリル基、２，５−キシリル基、２，６−キシリル基、３，４−キシリル基、３，５−キシリル基、２，３，４−トリメチルフェニル基、２，３，５−トリメチルフェニル基、２，３，６−トリメチルフェニル基、２，４，６−トリメチルフェニル基、３，４，５−トリメチルフェニル基、２，３，４，５−テトラメチルフェニル基、２，３，４，６−テトラメチルフェニル基、２，３，５，６−テトラメチルフェニル基、ペンタメチルフェニル基、エチルフェニル基、ｎ−プロピルフェニル基、イソプロピルフェニル基、ｎ−ブチルフェニル基、ｓｅｃ−ブチルフェニル基、ｔｅｒｔ−ブチルフェニル基、ｎ−ペンチルフェニル基、ネオペンチルフェニル基、ｎ−ヘキシルフェニル基、ｎ−オクチルフェニル基、ｎ−デシルフェニル基、ｎ−ドデシルフェニル基、ｎ−テトラデシルフェニル基、ナフチル基、アントラセニル基などが挙げられ、より好ましくはフェニル基である。
これらのアリール基はいずれも、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基などのアリールオキシ基またはベンジルオキシ基などのアラルキルオキシ基などで一部が置換されていてもよい。
【０１０５】
炭素原子数３〜２０のアルケニル基としては、例えばアリル基、メタリル基、クロチル基、１，３−ジフェニル−２−プロペニル基などが挙げられ、より好ましくはアリル基またはメタリル基である。
【０１０６】
またここでいう炭化水素オキシ基としてはアルコキシ基、アラルキルオキシ基やアリールオキシ基等が挙げられ、好ましくは、炭素原子数１〜２０のアルコキシ基、炭素原子数７〜２０のアラルキルオキシ基または炭素原子数６〜２０のアリールオキシ基が好ましい。
【０１０７】
炭素原子数１〜２０のアルコキシ基としては、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペントキシ基、ネオペントキシ基、ｎ−ヘキソキシ基、ｎ−オクトキシ基、ｎ−ドデソキシ基、ｎ−ペンタデソキシ基、ｎ−イコソキシ基などが挙げられ、より好ましくはメトキシ基、エトキシ基、イソプロポキシ基、またはｔｅｒｔ−ブトキシ基である。
これらのアルコキシ基はいずれも、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基などのアリールオキシ基またはベンジルオキシ基などのアラルキルオキシ基などで一部が置換されていてもよい。
【０１０８】
炭素原子数７〜２０のアラルキルオキシ基としては、例えばベンジルオキシ基、（２−メチルフェニル）メトキシ基、（３−メチルフェニル）メトキシ基、（４−メチルフェニル）メトキシ基、（２、３−ジメチルフェニル）メトキシ基、（２、４−ジメチルフェニル）メトキシ基、（２、５−ジメチルフェニル）メトキシ基、（２、６−ジメチルフェニル）メトキシ基、（３，４−ジメチルフェニル）メトキシ基、（３，５−ジメチルフェニル）メトキシ基、（２，３，４−トリメチルフェニル）メトキシ基、（２，３，５−トリメチルフェニル）メトキシ基、（２，３，６−トリメチルフェニル）メトキシ基、（２，４，５−トリメチルフェニル）メトキシ基、（２，４，６−トリメチルフェニル）メトキシ基、（３，４，５−トリメチルフェニル）メトキシ基、（２，３，４，５−テトラメチルフェニル）メトキシ基、（２，３，４，６−テトラメチルフェニル）メトキシ基、（２，３，５，６−テトラメチルフェニル）メトキシ基、（ペンタメチルフェニル）メトキシ基、（エチルフェニル）メトキシ基、（ｎ−プロピルフェニル）メトキシ基、（イソプロピルフェニル）メトキシ基、（ｎ−ブチルフェニル）メトキシ基、（ｓｅｃ−ブチルフェニル）メトキシ基、（ｔｅｒｔ−ブチルフェニル）メトキシ基、（ｎ−ヘキシルフェニル）メトキシ基、（ｎ−オクチルフェニル）メトキシ基、（ｎ−デシルフェニル）メトキシ基、ナフチルメトキシ基、アントラセニルメトキシ基などが挙げられ、より好ましくはベンジルオキシ基である。
これらのアラルキルオキシ基はいずれも、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基などのアリールオキシ基またはベンジルオキシ基などのアラルキルオキシ基などで一部が置換されていてもよい。
【０１０９】
炭素原子数６〜２０のアリールオキシ基としては、例えばフェノキシ基、２−メチルフェノキシ基、３−メチルフェノキシ基、４−メチルフェノキシ基、２、３−ジメチルフェノキシ基、２、４−ジメチルフェノキシ基、２、５−ジメチルフェノキシ基、２、６−ジメチルフェノキシ基、３，４−ジメチルフェノキシ基、３，５−ジメチルフェノキシ基、２−ｔｅｒｔ−ブチル−３−メチルフェノキシ基、２−ｔｅｒｔ−ブチル−４−メチルフェノキシ基、２−ｔｅｒｔ−ブチル−５−メチルフェノキシ基、２−ｔｅｒｔ−ブチル−６−メチルフェノキシ基、２，３，４−トリメチルフェノキシ基、２，３，５−トリメチルフェノキシ基、２，３，６−トリメチルフェノキシ基、２，４，５−トリメチルフェノキシ基、２，４，６−トリメチルフェノキシ基、２−ｔｅｒｔ−ブチル−３，４−ジメチルフェノキシ基、２−ｔｅｒｔ−ブチル−３，５−ジメチルフェノキシ基、２−ｔｅｒｔ−ブチル−３，６−ジメチルフェノキシ基、２，６−ジ−ｔｅｒｔ−ブチル−３−メチルフェノキシ基、２−ｔｅｒｔ−ブチル−４，５−ジメチルフェノキシ基、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ基、３，４，５−トリメチルフェノキシ基、２，３，４，５−テトラメチルフェノキシ基、２−ｔｅｒｔ−ブチル−３，４，５−トリメチルフェノキシ基、２，３，４，６−テトラメチルフェノキシ基、２−ｔｅｒｔ−ブチル−３，４，６−トリメチルフェノキシ基、２，６−ジ−ｔｅｒｔ−ブチル−３，４−ジメチルフェノキシ基、２，３，５，６−テトラメチルフェノキシ基、２−ｔｅｒｔ−ブチル−３，５，６−トリメチルフェノキシ基、２，６−ジ−ｔｅｒｔ−ブチル−３，５−ジメチルフェノキシ基、ペンタメチルフェノキシ基、エチルフェノキシ基、ｎ−プロピルフェノキシ基、イソプロピルフェノキシ基、ｎ−ブチルフェノキシ基、ｓｅｃ−ブチルフェノキシ基、ｔｅｒｔ−ブチルフェノキシ基、ｎ−ヘキシルフェノキシ基、ｎ−オクチルフェノキシ基、ｎ−デシルフェノキシ基、ｎ−テトラデシルフェノキシ基、ナフトキシ基、アントラセノキシ基などが挙げられる。
これらのアリールオキシ基はいずれも、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、メトキシ基、エトキシ基等のアルコキシ基、フェノキシ基などのアリールオキシ基またはベンジルオキシ基などのアラルキルオキシ基などで一部が置換されていてもよい。
【０１１０】
Ｘ^１　としてより好ましくは塩素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、トリフルオロメトキシ基、フェニル基、フェノキシ基、２，６−ジ−ｔｅｒｔ−ブチルフェノキシ基、３，４，５−トリフルオロフェノキシ基、ペンタフルオロフェノキシ基、２，３，５，６−テトラフルオロ−４−ペンタフルオロフェニルフェノキシ基またはベンジル基である。
【０１１１】
一般式［５］におけるａは０＜ａ≦８を満足する数を、ｂは０＜ｂ≦８を満足する数を表し、Ｍ^２　の価数に応じて適宜選択される。Ｍ^２　がチタン原子、ジルコニウム原子またはハフニウム原子である場合、ａは２であることが好ましく、ｂも２であることが好ましい。
【０１１２】
一般式［５］で表される遷移金属化合物の内、遷移金属原子がチタン原子、ジルコニウム原子またはハフニウム原子である化合物の具体例としては、ビス（シクロペンタジエニル）チタンジクロライド、ビス（メチルシクロペンタジエニル）チタンジクロライド、ビス（エチルシクロペンタジエニル）チタンジクロライド、ビス（ｎ−ブチルシクロペンタジエニル）チタンジクロライド、ビス（ｔｅｒｔ−ブチルシクロペンタジエニル）チタンジクロライド、ビス（１，２−ジメチルシクロペンタジエニル）チタンジクロライド、ビス（１，３−ジメチルシクロペンタジエニル）チタンジクロライド、ビス（１−メチル−２−エチルシクロペンタジエニル）チタンジクロライド、ビス（１−メチル−３−エチルシクロペンタジエニル）チタンジクロライド、ビス（１−メチル−２−ｎ−ブチルシクロペンタジエニル）チタンジクロライド、ビス（１−メチル−３−ｎ−ブチルシクロペンタジエニル）チタンジクロライド、ビス（１−メチル−２−イソプロピルシクロペンタジエニル）チタンジクロライド、ビス（１−メチル−３−イソプロピルシクロペンタジエニル）チタンジクロライド、ビス（１−ｔｅｒｔ−ブチル−２−メチルシクロペンタジエニル）チタンジクロライド、ビス（１−ｔｅｒｔ−ブチル−３−メチルシクロペンタジエニル）チタンジクロライド、ビス（１，２，３−トリメチルシクロペンタジエニル）チタンジクロライド、ビス（１，２，４−トリメチルシクロペンタジエニル）チタンジクロライド、ビス（テトラメチルシクロペンタジエニル）チタンジクロライド、ビス（ペンタメチルシクロペンタジエニル）チタンジクロライド、ビス（インデニル）チタンジクロライド、ビス（４，５，６，７−テトラヒドロインデニル）チタンジクロライド、ビス（フルオレニル）チタンジクロライド、ビス（２−フェニルインデニル）チタンジクロライド、
【０１１３】
ビス［２−（ビス−３，５−トリフルオロメチルフェニル）インデニル］チタンジクロライド、ビス［２−（４−ｔｅｒｔ−ブチルフェニル）インデニル］チタンジクロライド、ビス［２−（４−トリフルオロメチルフェニル）インデニル］チタンジクロライド、ビス［２−（４−メチルフェニル）インデニル］チタンジクロライド、ビス［２−（３，５−ジメチルフェニル）インデニル］チタンジクロライド、ビス［２−（ペンタフルオロフェニル）インデニル］チタンジクロライド、シクロペンタジエニル（ペンタメチルシクロペンタジエニル）チタンジクロライド、シクロペンタジエニル（インデニル）チタンジクロライド、シクロペンタジエニル（フルオレニル）チタンジクロライド、インデニル（フルオレニル）チタンジクロライド、ペンタメチルシクロペンタジエニル（インデニル）チタンジクロライド、ペンタメチルシクロペンタジエニル（フルオレニル）チタンジクロライド、シクロペンタジエニル（２−フェニルインデニル）チタンジクロライド、ペンタメチルシクロペンタジエニル（２−フェニルインデニル）チタンジクロライド、
【０１１４】
ジメチルシリレンビス（シクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２−メチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（３−メチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２−ｎ−ブチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（３−ｎ−ブチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，３−ジメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，４−ジメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，５−ジメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（３，４−ジメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，３−エチルメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，４−エチルメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，５−エチルメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（３，５−エチルメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，３，４−トリメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（２，３，５−トリメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレンビス（テトラメチルシクロペンタジエニル）チタンジクロライド、
【０１１５】
ジメチルシリレンビス（インデニル）チタンジクロライド、ジメチルシリレンビス（２−メチルインデニル）チタンジクロライド、ジメチルシリレンビス（２−ｔｅｒｔ−ブチルインデニル）チタンジクロライド、ジメチルシリレンビス（２，３−ジメチルインデニル）チタンジクロライド、ジメチルシリレンビス（２，４，７−トリメチルインデニル）チタンジクロライド、ジメチルシリレンビス（２−メチル−４−イソプロピルインデニル）チタンジクロライド、ジメチルシリレンビス（４，５−ベンズインデニル）チタンジクロライド、ジメチルシリレンビス（２−メチル−４，５−ベンズインデニル）チタンジクロライド、ジメチルシリレンビス（２−フェニルインデニル）チタンジクロライド、ジメチルシリレンビス（４−フェニルインデニル）チタンジクロライド、ジメチルシリレンビス（２−メチル−４−フェニルインデニル）チタンジクロライド、ジメチルシリレンビス（２−メチル−５−フェニルインデニル）チタンジクロライド、ジメチルシリレンビス（２−メチル−４−ナフチルインデニル）チタンジクロライド、ジメチルシリレンビス（４，５，６，７−テトラヒドロインデニル）チタンジクロライド、
【０１１６】
ジメチルシリレン（シクロペンタジエニル）（インデニル）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（インデニル）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（インデニル）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（インデニル）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（フルオレニル）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（フルオレニル）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（フルオレニル）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（インデニル）チタンジクロライド、ジメチルシリレン（インデニル）（フルオレニル）チタンジクロライド、ジメチルシリレンビス（フルオレニル）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（テトラメチルシクロペンタジエニル）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（フルオレニル）チタンジクロライド、
【０１１７】
シクロペンタジエニルチタントリクロライド、ペンタメチルシクロペンタジエニルチタントリクロライド、シクロペンタジエニル（ジメチルアミド）チタンジクロライド、シクロペンタジエニル（フェノキシ）チタンジクロライド、シクロペンタジエニル（２，６−ジメチルフェニル）チタンジクロライド、シクロペンタジエニル（２，６−ジイソプロピルフェニル）チタンジクロライド、シクロペンタジエニル（２，６−ジ−ｔｅｒｔ−ブチルフェニル）チタンジクロライド、ペンタメチルシクロペンタジエニル（２，６−ジメチルフェニル）チタンジクロライド、ペンタメチルシクロペンタジエニル（２，６−ジイソプロピルフェニル）チタンジクロライド、ペンタメチルシクロペンタジエニル（２，６−ｔｅｒｔ−ブチルフェニル）チタンジクロライド、インデニル（２，６−ジイソプロピルフェニル）チタンジクロライド、フルオレニル（２，６−ジイソプロピルフェニル）チタンジクロライド、
【０１１８】
ジメチルシリレン（シクロペンタジエニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（シクロペンタジエニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１１９】
ジメチルシリレン（メチルシクロペンタジエニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（メチルシクロペンタジエニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１２０】
ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｎ−ブチルシクロペンタジエニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１２１】
ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルシクロペンタジエニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１２２】
ジメチルシリレン（テトラメチルシクロペンタジエニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（テトラメチルシクロペンタジエニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１２３】
ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（トリメチルシリルシクロペンタジエニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１２４】
ジメチルシリレン（インデニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（インデニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１２５】
ジメチルシリレン（フルオレニル）（２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３，５−ジメチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（５−メチル−３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３−ｔｅｒｔ−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３，５−ジアミル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（３−フェニル−２−フェノキシ）チタンジクロライド、ジメチルシリレン（フルオレニル）（１−ナフトキシ−２−イル）チタンジクロライド、
【０１２６】
（ｔｅｒｔ−ブチルアミド）テトラメチルシクロペンタジエニル−１，２−エタンジイルチタンジクロライド、（メチルアミド）テトラメチルシクロペンタジエニル−１，２−エタンジイルチタンジクロライド、（エチルアミド）テトラメチルシクロペンタジエニル−１，２−エタンジイルチタンジクロライド、
（ｔｅｒｔ−ブチルアミド）テトラメチルシクロペンタジエニルジメチルシランチタンジクロライド、（ベンジルアミド）テトラメチルシクロペンタジエニルジメチルシランチタンジクロライド、（フェニルフォスファイド）テトラメチルシクロペンタジエニルジメチルシランチタンジクロライド、（ｔｅｒｔ−ブチルアミド）インデニル−１，２−エタンジイルチタンジクロライド、（ｔｅｒｔ−ブチルアミド）テトラヒドロインデニル−１，２−エタンジイルチタンジクロライド、（ｔｅｒｔ−ブチルアミド）フルオレニル−１，２−エタンジイルチタンジクロライド、（ｔｅｒｔ−ブチルアミド）インデニルジメチルシランチタンジクロライド、（ｔｅｒｔ−ブチルアミド）テトラヒドロインデニルジメチルシランチタンジクロライド、（ｔｅｒｔ−ブチルアミド）フルオレニルジメチルシランチタンジクロライド、
【０１２７】
（ジメチルアミノメチル）テトラメチルシクロペンタジエニルチタン（ＩＩＩ）ジクロライド、（ジメチルアミノエチル）テトラメチルシクロペンタジエニルチタン（ＩＩＩ）ジクロライド、（ジメチルアミノプロピル）テトラメチルシクロペンタジエニルチタン（ＩＩＩ）ジクロライド、（Ｎ−ピロリジニルエチル）テトラメチルシクロペンタジエニルチタンジクロライド、（Ｂ−ジメチルアミノボラベンゼン）シクロペンタジエニルチタンジクロライド、シクロペンタジエニル（９−メシチルボラアントラセニル）チタンジクロライド、
【０１２８】
２，２’−チオビス［４−メチル−６−ｔｅｒｔ−ブチルフェノキシ］チタンジクロライド、２，２’−チオビス［４−メチル−６−（１−メチルエチル）フェノキシ］チタンジクロライド、２，２’−チオビス（４，６−ジメチルフェノキシ）チタンジクロライド、２，２’−チオビス（４−メチル−６−ｔｅｒｔ−ブチルフェノキシ）チタンジクロライド、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノキシ）チタンジクロライド、２，２’−エチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノキシ）チタンジクロライド、２，２’−スルフィニルビス（４−メチル−６−ｔｅｒｔ−ブチルフェノキシ）チタンジクロライド、２，２’−（４，４’，６，６’−テトラ−ｔｅｒｔ−ブチル−１，１’ビフェノキシ）チタンジクロライド、（ジ−ｔｅｒｔ−ブチル−１，３−プロパンジアミド）チタンジクロライド、（ジシクロヘキシル−１，３−プロパンジアミド）チタンジクロライド、
【０１２９】
［ビス（トリメチルシリル）−１，３−プロパンジジアミド］チタンジクロライド、［ビス（ｔｅｒｔ−ブチルジメチルシリル）−１，３−プロパンジアミド］チタンジクロライド、［ビス（２，６−ジメチルフェニル）−１，３−プロパンジアミド］チタンジクロライド、［ビス（２，６−ジイソプロピルフェニル）−１，３−プロパンジアミド］チタンジクロライド、［ビス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−１，３−プロパンジアミド］チタンジクロライド、［ビス（トリイソプロピルシリル）ナフタレンジアミド］チタンジクロライド、［ビス（トリメチルシリル）ナフタレンジアミド］チタンジクロライド、［ビス（ｔｅｒｔ−ブチルジメチルシリル）ナフタレンジアミド］チタンジクロライド、［ヒドロトリス（３，５−ジメチルピラゾリル）ボレート］チタントリクロライド、［ヒドロトリス（３，５−ジエチルピラゾリル）ボレート］チタントリクロライド、［ヒドロトリス（３，５−ジ−ｔｅｒｔ−ブチルピラゾリル）ボレート］チタントリクロライド、［トリス（３，５−ジメチルピラゾリル）メチル］チタントリクロライド、［トリス（３，５−ジエチルピラゾリル）メチル］チタントリクロライド、［トリス（３，５−ジ−ｔｅｒｔ−ブチルピラゾリル）メチル］チタントリクロライド、などや、これらの化合物のチタンをジルコニウムまたはハフニウムに変更した化合物、（２−フェノキシ）を（３−フェニル−２−フェノキシ）、（３−トリメチルシリル−２−フェノキシ）、または（３−ｔｅｒｔ−ブチルジメチルシリル−２−フェノキシ）に変更した化合物、ジメチルシリレンをメチレン、エチレン、ジメチルメチレン（イソプロピリデン）、ジフェニルメチレン、ジエチルシリレン、ジフェニルシリレン、またはジメトキシシリレンに変更した化合物、ジクロライドをジフルオライド、ジブロマイド、ジアイオダイド、ジメチル、ジエチル、ジイソプロピル、ジフェニル、ジベンジル、ジメトキシド、ジエトキシド、ジ（ｎ−プロポキシド）、ジ（イソプロポキシド）、ジフェノキシド、またはジ（ペンタフルオロフェノキシド）に変更した化合物、トリクロライドをトリフルオライド、トリブロマイド、トリアイオダイド、トリメチル、トリエチル、トリイソプロピル、トリフェニル、トリベンジル、トリメトキシド、トリエトキシド、トリ（ｎ−プロポキシド）、トリ（イソプロポキシド）、トリフェノキシド、またはトリ（ペンタフルオロフェノキシド）に変更した化合物などを例示することができる。
【０１３０】
一般式［５］で表される遷移金属化合物のうち、遷移金属原子がニッケル原子である化合物の具体例としては、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジメチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジエチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジ−ｎ−プロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジイソプロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジシクロヘキシルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジメトキシオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジエトキシオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５’−ジフェニルオキサゾリン］ニッケルジブロマイド、
【０１３１】
２，２’−メチレンビス［（４Ｒ）−４−メチル−５，５−ジ−（２−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−メチル−５，５−ジ−（３−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−メチル−５，５−ジ−（４−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−メチル−５，５−ジ−（２−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−メチル−５，５−ジ−（３−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−メチル−５，５−ジ−（４−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−メチルオキサゾリン−５，１’−シクロブタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−メチルオキサゾリン−５，１’−シクロペンタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−メチルオキサゾリン−５，１’−シクロヘキサン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−メチルオキサゾリン−５，１’−シクロヘプタン｝］ニッケルジブロマイド、
【０１３２】
２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジメチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジエチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジ−ｎ−プロピルオキサゾリン］、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジイソプロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジシクロヘキシルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジフェニルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジ−（２−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジ−（３−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジ−（４−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジ−（２−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジ−（３−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソプロピル−５，５−ジ−（４−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、
【０１３３】
２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソプロピルオキサゾリン−５，１’−シクロブタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソプロピルオキサゾリン−５，１’−シクロペンタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソプロピルオキサゾリン−５，１’−シクロヘキサン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソプロピルオキサゾリン−５，１’−シクロヘプタン｝］ニッケルジブロマイド、２，２−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジメチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジエチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−ｎ−プロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−イソプロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジシクロヘキシルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジフェニルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−（２−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−（３−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−（４−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−（２−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−（３−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−イソブチル−５，５−ジ−（４−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、
【０１３４】
２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソブチルオキサゾリン−５，１’−シクロブタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソブチルオキサゾリン−５，１’−シクロペンタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソブチルオキサゾリン−５，１’−シクロヘキサン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−イソブチルオキサゾリン−５，１’−シクロヘプタン｝］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジメチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジエチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−４−ｔｅｒｔ−ブチル−５，５−ジ−ｎ−プロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジ−イソプロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジフェニルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジシクロヘキシルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジ−（２−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジ−（３−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジ−（４−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジ−（２−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジ−（３−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ｔｅｒｔ−ブチル−５，５−ジ−（４−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、
【０１３５】
２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ｔｅｒｔ−ブチルオキサゾリン−５，１’−シクロブタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ｔｅｒｔ−ブチルオキサゾリン−５，１’−シクロペンタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ｔｅｒｔ−ブチルオキサゾリン−５，１’−シクロヘキサン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ｔｅｒｔ−ブチルオキサゾリン−５，１’−シクロヘプタン｝］ニッケルジブロマイド、
【０１３６】
２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジメチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジエチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−ｎ−プロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−イソプロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジシクロヘキシルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジフェニルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−（２−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−（３−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−（４−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−（２−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−（３−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−フェニル−５，５−ジ−（４−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、
【０１３７】
２，２’−メチレンビス［スピロ｛（４Ｒ）−４−フェニルオキサゾリン−５，１’−シクロブタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−フェニルオキサゾリン−５，１’−シクロペンタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−フェニルオキサゾリン−５，１’−シクロヘキサン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−フェニルオキサゾリン−５，１’−シクロヘプタン｝］ニッケルジブロマイド、
【０１３８】
２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジメチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジエチルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−ｎ−プロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−イソプロピルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジシクロヘキシルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジフェニルオキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−（２−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−（３−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−（４−メチルフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−（２−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−（３−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、２，２’−メチレンビス［（４Ｒ）−４−ベンジル−５，５−ジ−（４−メトキシフェニル）オキサゾリン］ニッケルジブロマイド、
【０１３９】
２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ベンジルオキサゾリン−５，１’−シクロブタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ベンジルオキサゾリン−５，１’−シクロペンタン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ベンジルオキサゾリン−５，１’−シクロヘキサン｝］ニッケルジブロマイド、２，２’−メチレンビス［スピロ｛（４Ｒ）−４−ベンジルオキサゾリン−５，１’−シクロヘプタン｝］ニッケルジブロマイド、および上記各化合物の対掌体などが挙げられる。また、上記ビスオキサゾリン型化合物の一方のオキサゾリン環の不斉炭素の立体配置を逆の配置にした化合物や、これらの化合物のジブロマイドをジフルオライド、ジクロライド、ジアイオダイド、ジメチル、ジエチル、ジイソプロピル、ジフェニル、ジベンジル、ジメトキシド、ジエトキシド、ジ（ｎ−プロポキシド）、ジ（イソプロポキシド）、ジフェノキシド、またはジ（ペンタフルオロフェノキシド）に変更した化合物などを例示することができる。
【０１４０】
さらにニッケル化合物の具体例としては、［ヒドロトリス（３，５−ジメチルピラゾリル）ボレート］ニッケルクロライド、［ヒドロトリス（３，５−ジエチルピラゾリル）ボレート］ニッケルクロライド、［ヒドロトリス（３，５−ジ−ｔｅｒｔ−ブチルピラゾリル）ボレート］ニッケルクロライドや、これらの化合物のクロライドを、ブロマイド、アイオダイド、メチル、エチル、アリル、またはメタリルに変更した化合物が挙げられる。
【０１４１】
そしてニッケル化合物として、下記構造式にて示される化合物などが挙げられる。

（式中、Ｒ^６　とＲ^７　はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｒ^８　およびＲ^９　はそれぞれ水素原子またはメチル基あるいはＲ^８　とＲ^９　とがいっしょになってアセナフテン基であり、Ｘ^２　はフッ素原子、塩素原子、臭素原子、よう素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基である。）
また、上記のニッケル化合物において、ニッケルをパラジウム、コバルト、ロジウム、またはルテニウムに置き換えた化合物も同様に例示することができる。
【０１４２】
一般式［５］で表される遷移金属化合物のうち、遷移金属原子が鉄である化合物の具体例としては、２，６−ビス−［１−（２，６−ジメチルフェニルイミノ）エチル］ピリジン鉄ジクロライド、２，６−ビス−［１−（２，６−ジイソプロピルフェニルイミノ）エチル］ピリジン鉄ジクロライド、２，６−ビス−［１−（２−ｔｅｒｔ−ブチル−フェニルイミノ）エチル］ピリジン鉄ジクロライドなどや、これらの化合物のジクロライドを、ジフルオライド、ジブロマイド、ジアイオダイド、ジメチル、ジエチル、ジメトキシド、ジエトキシド、またはジフェノキシドに変更した化合物が挙げられる。
【０１４３】
さらに鉄化合物の具体例としては、［ヒドロトリス（３，５−ジメチルピラゾリル）ボレート］鉄クロライド、［ヒドロトリス（３，５−ジエチルピラゾリル）ボレート］鉄クロライド、［ヒドロトリス（３，５−ジ−ｔｅｒｔ−ブチルピラゾリル）ボレート］鉄クロライドなどや、これらの化合物のクロライドを、フルオライド、ブロマイド、アイオダイド、メチル、エチル、アリル、メタリル、メトキシド、またはエトキシドに変更した化合物が挙げられる。
また、上記の鉄化合物において、鉄をコバルトまたはニッケルに置き換えた化合物も同様に例示することができる。
【０１４４】
また一般式［５］で表される遷移金属化合物のμ−オキソタイプの遷移金属化合物の具体例としては、μ−オキソビス［イソプロピリデン（シクロペンタジエニル）（２−フェノキシ）チタンクロライド］、μ−オキソビス［イソプロピリデン（シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンクロライド］、μ−オキソビス［イソプロピリデン（メチルシクロペンタジエニル）（２−フェノキシ）チタンクロライド］、μ−オキソビス［イソプロピリデン（メチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンクロライド］、μ−オキソビス［イソプロピリデン（テトラメチルシクロペンタジエニル）（２−フェノキシ）チタンクロライド］、μ−オキソビス［イソプロピリデン（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンクロライド］、μ−オキソビス［ジメチルシリレン（シクロペンタジエニル）（２−フェノキシ）チタンクロライド］、μ−オキソビス［ジメチルシリレン（シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンクロライド］、μ−オキソビス［ジメチルシリレン（メチルシクロペンタジエニル）（２−フェノキシ）チタンクロライド］、μ−オキソビス［ジメチルシリレン（メチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンクロライド］、μ−オキソビス［ジメチルシリレン（テトラメチルシクロペンタジエニル）（２−フェノキシ）チタンクロライド］、μ−オキソビス［ジメチルシリレン（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタンクロライド］などが挙げられる。また、これらの化合物のクロライドをフルオライド、ブロマイド、アイオダイド、メチル、エチル、イソプロピル、フェニル、ベンジル、メトキシド、エトキシド、ｎ−プロポキシド、イソプロポキシド、フェノキシド、またはペンタフルオロフェノキシドに変更した化合物などを例示することができる。
【０１４５】
以上に例示した一般式［５］で表される遷移金属化合物やそのμ−オキソタイプの遷移金属化合物の他に、遷移金属化合物（Ｂ）として用いられる化合物を例示すると、遷移金属原子がニッケル原子である化合物として塩化ニッケル、臭化ニッケル、よう化ニッケル、硫酸ニッケル、硝酸ニッケル、過塩素酸ニッケル、酢酸ニッケル、トリフルオロ酢酸ニッケル、シアン化ニッケル、蓚酸ニッケル、ニッケルアセチルアセトナート、ビス（アリル）ニッケル、ビス（１，５−シクロオクタジエン）ニッケル、ジクロロ（１，５−シクロオクタジエン）ニッケル、ジクロロビス（アセトニトリル）ニッケル、ジクロロビス（ベンゾニトリル）ニッケル、カルボニルトリス（トリフェニルホスフィン）ニッケル、ジクロロビス（トリエチルホスフィン）ニッケル、ジアセトビス（トリフェニルホスフィン）ニッケル、テトラキス（トリフェニルホスフィン）ニッケル、ジクロロ［１，２−ビス（ジフェニルホスフィノ）エタン］ニッケル、ビス［１，２−ビス（ジフェニルホスフィノ）エタン］ニッケル、ジクロロ［１，３−ビス（ジフェニルホスフィノ）プロパン］ニッケル、ビス［１，３−ビス（ジフェニルホスフィノ）プロパン］ニッケル、テトラアミンニッケルナイトレート、テトラキス（アセトニトリル）ニッケルテトラフルオロボレート、ニッケルフタロシアニンなどが挙げられる。
【０１４６】
同様に、遷移金属原子がバナジウム原子である化合物の具体例としてはバナジウムアセチルアセトナート、バナジウムテトラクロライド、バナジウムオキシトリクロライドなどが挙げられる。
また、遷移金属原子がサマリウム原子である化合物の具体例としてはビス（ペンタメチルシクロペンタジエニル）サマリウムメチルテトラヒドロフランなどが挙げられる。
遷移金属原子がイッテルビウム原子である化合物の具体例としてはビス（ペンタメチルシクロペンタジエニル）イッテルビウムメチルテトラヒドロフランなどが挙げられる。
【０１４７】
これらの遷移金属化合物は一種類のみを用いても、二種類以上を組み合わせて用いてもよい。
【０１４８】
以上に例示した遷移金属化合物のうち、本発明で用いる遷移金属化合物（Ｂ）として好ましくは上記の一般式［５］で表される遷移金属化合物である。中でも、上記一般式［５］におけるＭ^２　が第４族原子である遷移金属化合物が好ましく、特に一般式［５］におけるＬ^２　としてシクロペンタジエン形アニオン骨格を有する基を少なくとも一つ持つ遷移金属化合物が好ましい。
【０１４９】
（Ｃ）有機アルミニウム化合物
本発明の付加重合用触媒に使用される成分（Ｃ）有機アルミニウム化合物としては、公知の有機アルミニウム化合物が使用できる。好ましくは、下記一般式　［８］で示される有機アルミニウム化合物である。
Ｒ^１０ _ｃＡｌＹ_３−ｃ　　　　　　　　　　［８］
（式中、Ｒ^１０は炭化水素基を表し、全てのＲ^１０は同一であっても異なっていてもよい。Ｙは水素原子、ハロゲン原子、アルコキシ基、アラルキルオキシ基、またはアリールオキシ基を表し、全てのＹは同一であっても異なっていてもよい。ｃは０＜ｃ≦３を満足する数を表す。）
【０１５０】
有機アルミニウム化合物を表す一般式［８］におけるＲ^１０として好ましくは炭素原子数１〜２４の炭化水素基であり、より好ましくは炭素原子数１〜２４のアルキル基である。具体例としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、イソブチル基、ｎ−ヘキシル基、２−メチルヘキシル基、ｎ−オクチル基等が挙げられ、好ましくはエチル基、ｎ−ブチル基、イソブチル基、ｎ−ヘキシル基またはｎ−オクチル基である。
【０１５１】
また、Ｙがハロゲン原子である場合の具体例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、好ましくは塩素原子である。
Ｙにおけるアルコキシ基としては炭素原子数１〜２４のアルコキシ基が好ましく、具体例としては、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペントキシ基、ネオペントキシ基、ｎ−ヘキソキシ基、ｎ−オクトキシ基、ｎ−ドデソキシ基、ｎ−ペンタデソキシ基、ｎ−イコソキシ基などが挙げられ、好ましくはメトキシ基、エトキシ基またはｔｅｒｔ−ブトキシ基である。
【０１５２】
Ｙにおけるアリールオキシ基としては炭素原子数６〜２４のアリールオキシ基が好ましく、具体例としては、例えばフェノキシ基、２−メチルフェノキシ基、３−メチルフェノキシ基、４−メチルフェノキシ基、２，３−ジメチルフェノキシ基、２，４−ジメチルフェノキシ基、２，５−ジメチルフェノキシ基、２，６−ジメチルフェノキシ基、３，４−ジメチルフェノキシ基、３，５−ジメチルフェノキシ基、２，３，４−トリメチルフェノキシ基、２，３，５−トリメチルフェノキシ基、２，３，６−トリメチルフェノキシ基、２，４，５−トリメチルフェノキシ基、２，４，６−トリメチルフェノキシ基、３，４，５−トリメチルフェノキシ基、２，３，４，５−テトラメチルフェノキシ基、２，３，４，６−テトラメチルフェノキシ基、２，３，５，６−テトラメチルフェノキシ基、ペンタメチルフェノキシ基、エチルフェノキシ基、ｎ−プロピルフェノキシ基、イソプロピルフェノキシ基、ｎ−ブチルフェノキシ基、ｓｅｃ−ブチルフェノキシ基、ｔｅｒｔ−ブチルフェノキシ基、ｎ−ヘキシルフェノキシ基、ｎ−オクチルフェノキシ基、ｎ−デシルフェノキシ基、ｎ−テトラデシルフェノキシ基、ナフトキシ基、アントラセノキシ基などが挙げられる。
【０１５３】
Ｙにおけるアラルキルオキシ基としては炭素原子数７〜２４のアラルキルオキシ基が好ましく、具体例としては、例えばベンジルオキシ基、（２−メチルフェニル）メトキシ基、（３−メチルフェニル）メトキシ基、（４−メチルフェニル）メトキシ基、（２，３−ジメチルフェニル）メトキシ基、（２，４−ジメチルフェニル）メトキシ基、（２，５−ジメチルフェニル）メトキシ基、（２，６−ジメチルフェニル）メトキシ基、（３，４−ジメチルフェニル）メトキシ基、（３，５−ジメチルフェニル）メトキシ基、（２，３，４−トリメチルフェニル）メトキシ基、（２，３，５−トリメチルフェニル）メトキシ基、（２，３，６−トリメチルフェニル）メトキシ基、（２，４，５−トリメチルフェニル）メトキシ基、（２，４，６−トリメチルフェニル）メトキシ基、（３，４，５−トリメチルフェニル）メトキシ基、（２，３，４，５−テトラメチルフェニル）メトキシ基、（２，３，５，６−テトラメチルフェニル）メトキシ基、（ペンタメチルフェニル）メトキシ基、（エチルフェニル）メトキシ基、（ｎ−プロピルフェニル）メトキシ基、（イソプロピルフェニル）メトキシ基、（ｎ−ブチルフェニル）メトキシ基、（ｓｅｃ−ブチルフェニル）メトキシ基、（ｔｅｒｔ−ブチルフェニル）メトキシ基、（ｎ−ヘキシルフェニル）メトキシ基、（ｎ−オクチルフェニル）メトキシ基、（ｎ−デシルフェニル）メトキシ基、（ｎ−テトラデシルフェニル）メトキシ基、ナフチルメトキシ基、アントラセニルメトキシ基などが挙げられ、好ましくはベンジルオキシ基である。
【０１５４】
一般式［８］で表される有機アルミニウム化合物の具体例としては、トリメチルアルミニウム、トリエチルアルミニウム、トリ−ｎ−プロピルアルミニウム、トリ−ｎ−ブチルアルミニウム、トリイソブチルアルミニウム、トリ−ｎ−ヘキシルアルミニウム、トリ−ｎ−オクチルアルミニウム等のトリアルキルアルミニウム；ジメチルアルミニウムクロライド、ジエチルアルミニウムクロライド、ジ−ｎ−プロピルアルミニウムクロライド、ジ−ｎ−ブチルアルミニウムクロライド、ジイソブチルアルミニウムクロライド、ジ−ｎ−ヘキシルアルミニウムクロライド等のジアルキルアルミニウムクロライド；メチルアルミニウムジクロライド、エチルアルミニウムジクロライド、ｎ−プロピルアルミニウムジクロライド、ｎ−ブチルアルミニウムジクロライド、イソブチルアルミニウムジクロライド、ｎ−ヘキシルアルミニウムジクロライド等のアルキルアルミニウムジクロライド；ジメチルアルミニウムハイドライド、ジエチルアルミニウムハイドライド、ジ−ｎ−プロピルアルミニウムハイドライド、ジ−ｎ−ブチルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライド、ジ−ｎ−ヘキシルアルミニウムハイドライド等のジアルキルアルミニウムハイドライド；メチル（ジメトキシ）アルミニウム、メチル（ジエトキシ）アルミニウム、メチル（ジ−ｔｅｒｔ−ブトキシ）アルミニウム等のアルキル（ジアルコキシ）アルミニウム；ジメチル（メトキシ）アルミニウム、ジメチル（エトキシ）アルミニウム、ジメチル（ｔｅｒｔ−ブトキシ）アルミニウム等のジアルキル（アルコキシ）アルミニウム；メチル（ジフェノキシ）アルミニウム、メチルビス（２，６−ジイソプロピルフェノキシ）アルミニウム、メチルビス（２，６−ジフェニルフェノキシ）アルミニウム等のアルキル（ジアリールオキシ）アルミニウム；ジメチル（フェノキシ）アルミニウム、ジメチル（２，６−ジイソプロピルフェノキシ）アルミニウム、ジメチル（２，６−ジフェニルフェノキシ）アルミニウム等のジアルキル（アリールオキシ）アルミニウム等を例示することができる。
【０１５５】
これらの内、好ましくはトリアルキルアルミニウムであり、さらに好ましくはトリメチルアルミニウム、トリエチルアルミニウム、トリ−ｎ−ブチルアルミニウム、トリイソブチルアルミニウム、トリ−ｎ−ヘキシルアルミニウムまたはトリ−ｎ−オクチルアルミニウムであり、特に好ましくはトリイソブチルアルミニウムまたはトリ−ｎ−オクチルアルミニウムである。
これらの有機アルミニウム化合物は一種類のみを用いても、二種類以上を組み合わせて用いてもよい。
【０１５６】
成分（Ｂ）の使用量は、成分（Ａ）１ｇに対し通常１×１０^−６〜１×１０^−３ｍｏｌであり、好ましくは５×１０^−６〜５×１０^−４ｍｏｌである。また成分（Ｃ）の使用量は、成分（Ｂ）遷移金属化合物の遷移金属原子に対する成分（Ｃ）有機アルミニウム化合物のアルミニウム原子のモル比（Ｃ）／（Ｂ）として、０．０１〜１０，０００であることが好ましく、０．１〜５，０００であることがより好ましく、１〜２，０００であることが最も好ましい。
【０１５７】
本発明の付加重合用触媒としては、成分（Ａ）および成分（Ｂ）、場合によってはさらに成分（Ｃ）を予め接触させて得られた反応物を用いてもよく、重合反応装置中に別々に投入して用いてもよい。成分（Ａ）、（Ｂ）および（Ｃ）を用いる場合には、それらの内の任意の２つの成分を予め接触させて、その後もう一つの成分を接触させてもよい。
【０１５８】
各触媒成分を触媒調製用反応器もしくは重合用反応器に供給する方法も、特に制限されるものではない。各成分を固体状態で供給する方法、水分や酸素等の触媒成分を失活させる成分を十分に取り除いた炭化水素溶媒に溶解させた溶液状態、または懸濁もしくはスラリー化させた状態で供給する方法等が挙げられる。このときの溶媒としては、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素溶媒、ベンゼン、トルエン等の芳香族炭化水素溶媒、またはメチレンクロライド等のハロゲン化炭化水素が挙げられ、脂肪族炭化水素または芳香族炭化水素が好ましい。
【０１５９】
各触媒成分を溶液状態、または懸濁もしくはスラリー化させた状態で供給する場合、成分（Ａ）の濃度は、通常０．０１〜１０００ｇ／リットル、好ましくは０．１〜５００ｇ／リットルである。成分（Ｃ）の濃度は、Ａｌ原子換算で通常０．０００１〜１００モル／リットル、好ましくは０．０１〜１０モル／リットルである。成分（Ｂ）の濃度は、遷移金属原子換算で通常０．０００１〜１０００ミリモル／リットル、好ましくは０．０１〜５０ミリモル／リットルである。
【０１６０】
重合方法も特に限定されるものではなく、ガス状のモノマー中での気相重合、溶媒を使用する溶液重合、スラリー重合等が可能である。溶液重合、またはスラリー重合に用いる溶媒としては、ブタン、ヘキサン、ペンタン、ヘプタン、オクタン等の脂肪族炭化水素溶媒、ベンゼン、トルエン等の芳香族炭化水素溶媒、またはメチレンクロライド等のハロゲン化炭化水素溶媒が挙げられ、あるいはオレフィン自身を溶媒に用いる（バルク重合）ことも可能である。重合方法は、回分式重合、連続式重合のいずれでも可能であり、さらに重合を反応条件の異なる２段階以上に分けて行っても良い。重合時間は、一般に、目的とするオレフィン重合体の種類、反応装置により適宜決定されるが、１分間〜２０時間の範囲を取ることができる。
【０１６１】
本発明は、付加重合体粒子の形成を伴う重合（例えばスラリー重合、気相重合、バルク重合等）に特に好適に適用される。
スラリー重合は、公知のスラリー重合方法、重合条件に従って行えばよいが、それらに限定される事はない。スラリー法における好ましい重合方法として、モノマー（およびコモノマー）、供給物、稀釈剤などを必要に応じて連続的に添加し、かつ、ポリマー生成物を連続的または少なくとも周期的に取出す連続式反応器が含まれる。反応器としては、ループ反応器を使用する方法や攪拌反応器を使用する方法を挙げることが出来る。また、反応器が異なったり、反応条件が異なる複数の攪拌反応器を直列または並列またはこれらの組合せなどが挙げられる。
【０１６２】
稀釈剤としては、例えばパラフィン、シクロパラフィンまたは芳香族炭化水素のような不活性稀釈剤（媒質）を用いることができる。重合反応器または反応帯域の温度は、通常約０℃〜約１５０℃、好ましくは３０℃〜１００℃の範囲をとることができる。圧力は通常約０．１ＭＰａ〜約１０ＭＰａに変化させることができ、好ましくは０．５ＭＰａ〜５ＭＰａである。触媒を懸濁状態に保持し、媒質および少なくとも一部のモノマーおよびコモノマーを液相に維持し、モノマーおよびコモノマーを接触させることができる圧力をとることができる。従って、媒質、温度、および圧力は、付加重合体が固体粒子として生成され、その形態で回収されるように選択すればよい。
【０１６３】
付加重合体の分子量は反応帯域の温度の調節、水素の導入等、公知の各種の手段によって制御することができる。
各触媒成分、モノマー（およびコモノマー）は、公知の任意の方法によって、任意の順序で反応器、または反応帯域に添加できる。例えば、各触媒成分、モノマー（およびコモノマー）を反応帯域に同時に添加する方法、逐次に添加する方法等を用いることができる。所望ならば、各触媒成分はモノマー（およびコモノマー）と接触させる前に、不活性雰囲気中において予備接触させることができる。
【０１６４】
気相重合は、公知の気相重合方法、重合条件に従って行えばよいが、それらに限定されることはない。気相重合反応装置としては、流動層型反応槽、好ましくは、拡大部を有する流動層型反応槽が用いられる。反応槽内に攪拌翼が設置された反応装置でも何ら問題はない。
各成分を重合槽に供給する方法としては通常、窒素、アルゴン等の不活性ガス、水素、エチレン等を用いて、水分のない状態で供給する、あるいは溶媒に溶解または稀釈して、溶液またはスラリー状態で供給する等の方法を用いることができる。各触媒成分は個別に供給してもよいし、任意の成分を任意の順序にあらかじめ接触させて供給してもよい。
【０１６５】
重合条件として、温度は重合体が溶融する温度未満、好ましくは０℃〜１５０℃、特に好ましくは３０℃〜１００℃の範囲である。さらに最終製品の溶融流動性を調節する目的で、水素を分子量調節剤として添加しても構わない。また、重合に際して、混合ガス中に不活性ガスを共存させてもよい。
【０１６６】
本発明においては、このような重合（本重合）の実施前に以下に述べる予備重合を行ってもかまわない。
【０１６７】
予備重合は、上記の改質された粒子（Ａ）および遷移金属化合物（Ｂ）の存在下、あるいはさらに有機アルミニウム化合物（Ｃ）の存在下、少量のオレフィンを供給して実施され、スラリー状態で行うのが好ましい。スラリー化するのに用いる溶媒としては、プロパン、ブタン、イソブタン、ペンタン、イソペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエンのような不活性炭化水素を挙げることができる。また、スラリー化に際し、不活性炭化水素溶媒の一部または全部に変えて液状のオレフィンを用いることができる。
【０１６８】
予備重合時の有機アルミニウム化合物（Ｃ）の使用量は、遷移金属化合物（Ｂ）１モル当たり、０．５〜７００モルのごとく広範囲に選ぶことができるが、０．８〜５００モルが好ましく、１〜２００モルが特に好ましい。
【０１６９】
また、予備重合されるオレフィンの量は、上記の改質された粒子１ｇ当たり通常０．０１〜１０００ｇ、好ましくは０．０５〜５００ｇ、特に好ましくは０．１〜２００ｇである。
【０１７０】
予備重合を行う際のスラリー濃度は、０．１〜５０ｇ−上記の改質された粒子／リットル−溶媒が好ましく、特に０．５〜２０ｇ−上記の改質された粒子／リットル−溶媒が好ましい。予備重合温度は、−２０℃〜１００℃が好ましく、特に０℃〜８０℃が好ましい。また、予備重合中の気相部でのオレフィンの分圧は、０．００１ＭＰａ〜２ＭＰａが好ましく、特に０．０１ＭＰａ〜１ＭＰａが好ましいが、予備重合の圧力、温度において液状であるオレフィンについては、この限りではない。さらに、予備重合時間に特に制限はないが、通常２分間から１５時間が好適である。
【０１７１】
予備重合を実施する際、上記の改質された粒子（Ａ）、遷移金属化合物（Ｂ）、有機アルミニウム化合物（Ｃ）、オレフィンを供給する方法としては、上記の改質された粒子（Ａ）と、遷移金属化合物（Ｂ）とを接触させておいた後、あるいは必要に応じて有機アルミニウム化合物（Ｃ）をも接触させておいた後オレフィンを供給する方法、上記の改質された粒子（Ａ）と、遷移金属化合物（Ｂ）およびオレフィンとを接触させておいた後、有機アルミニウム化合物（Ｃ）を供給する方法、オレフィン存在下、有機アルミニウム化合物（Ｃ）および遷移金属化合物（Ｂ）を接触させた後、上記の改質された粒子（Ａ）を供給する方法などのいずれの方法を用いても良いが、上記の改質された粒子（Ａ）と有機アルミニウム化合物（Ｃ）とを接触させる際にはオレフィンが予め存在している方が好ましい。また、オレフィンの供給方法としては、重合槽内が所定の圧力になるように保持しながら順次オレフィンを供給する方法、或いは所定のオレフィン量を最初にすべて供給する方法のいずれの方法を用いても良い。また、得られる重合体の分子量を調節するために水素等の連鎖移動剤を添加することも可能である。
【０１７２】
本発明においては、このようにして予備重合して得られたものについて、触媒成分として、あるいは触媒として使用する。本発明に係る予備重合済の触媒成分は、上記の改質された粒子（Ａ）、並びに第３〜１１族もしくはランタノイド系列の遷移金属化合物（Ｂ）を接触させて得られる一次触媒の存在下に、オレフィンを予備重合して得られる予備重合済付加重合用触媒成分、あるいは、上記の改質された粒子（Ａ）、第３〜１１族もしくはランタノイド系列の遷移金属化合物（Ｂ）、並びに有機アルミニウム化合物（Ｃ）を接触させて得られる一次触媒の存在下に、オレフィンを予備重合して得られる予備重合済付加重合用触媒成分である。また本発明に係る予備重合済の触媒は、上記の改質された粒子（Ａ）、並びに第３〜１１族もしくはランタノイド系列の遷移金属化合物（Ｂ）を接触させて得られる一次触媒の存在下に、オレフィンを予備重合して得られる付加重合用触媒、あるいは、上記の改質された粒子（Ａ）、第３〜１１族もしくはランタノイド系列の遷移金属化合物（Ｂ）、並びに有機アルミニウム化合物（Ｃ）を接触させて得られる一次触媒の存在下に、オレフィンを予備重合して得られる付加重合用触媒である。本発明に係る該予備重合済付加重合用触媒成分を用いる触媒は、該予備重合済付加重合用触媒成分、並びに有機アルミニウム化合物（Ｃ）を接触させて得られる付加重合用触媒である。
【０１７３】
本発明の付加重合体の製造方法は、前記の本発明の付加重合用触媒の存在下、付加重合可能なモノマーを付加重合させる付加重合体の製造方法である。
重合に使用するモノマーとしては、炭素原子数２〜２０のオレフィン、ジオレフィン、環状オレフィン、アルケニル芳香族炭化水素、極性モノマー等を挙げることができ、同時に２種以上のモノマーを用いることもできる。
【０１７４】
これらの具体例としては、エチレン、プロピレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、５−メチル−１−ヘキセン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン等のオレフィン；１，５−ヘキサジエン、１，４−ヘキサジエン、１，４−ペンタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン、４−メチル−１，４−ヘキサジエン、５−メチル−１，４−ヘキサジエン、７−メチル−１，６−オクタジエン、５−エチリデン−２−ノルボルネン、ジシクロペンタジエン、５−ビニル−２−ノルボルネン、ノルボルナジエン、５−メチレン−２−ノルボルネン、１，５−シクロオクタジエン、５，８−エンドメチレンヘキサヒドロナフタレン、１，３−ブタジエン、イソプレン、１，３−ヘキサジエン、１，３−オクタジエン、１，３−シクロオクタジエン、１，３−シクロヘキサジエン等のジオレフィン；ノルボルネン、５−メチル−２−ノルボルネン、５−エチル−２−ノルボルネン、５−ブチル−２−ノルボルネン、５−フェニル−２−ノルボルネン、５−ベンジル−２−ノルボルネン、テトラシクロドデセン、トリシクロデセン、トリシクロウンデセン、ペンタシクロペンタデセン、ペンタシクロヘキサデセン、８−メチルテトラシクロドデセン、８−エチルテトラシクロドデセン、５−アセチル−２−ノルボルネン、５−アセチルオキシ−２−ノルボルネン、５−メトキシカルボニル−２−ノルボルネン、５−エトキシカルボニル−２−ノルボルネン、５−メチル−５−メトキシカルボニル−２−ノルボルネン、５−シアノ−２−ノルボルネン、８−メトキシカルボニルテトラシクロドデセン、８−メチル−８−テトラシクロドデセン、８−シアノテトラシクロドデセン等の環状オレフィン；スチレン、２−フェニルプロピレン、２−フェニルブテン、３−フェニルプロピレン等のアルケニルベンゼン、ｐ−メチルスチレン、ｍ−メチルスチレン、ｏ−メチルスチレン、ｐ−エチルスチレン、ｍ−エチルスチレン、ｏ−エチルスチレン、α−メチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、３，４−ジメチルスチレン、３，５−ジメチルスチレン、３−メチル−５−エチルスチレン、１，１−ジフェニルエチレン、ｐ−第３級ブチルスチレン、ｐ−第２級ブチルスチレンなどのアルキルスチレン、ジビニルベンゼン等のビスアルケニルベンゼン、１−ビニルナフタレン等のアルケニルナフタレン等のアルケニル芳香族炭化水素；アクリル酸、メタクリル酸、フマル酸、無水マレイン酸、イタコン酸、無水イタコン酸、ビシクロ（２，２，１）−５−ヘプテン−２，３−ジカルボン酸等のα，β−不飽和カルボン酸、およびそのナトリウム、カリウム、リチウム、亜鉛、マグネシウム、カルシウム等の金属塩、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル、アクリル酸ｔｅｒｔ−ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル等のα，β−不飽和カルボン酸エステル、マレイン酸、イタコン酸等の不飽和ジカルボン酸、酢酸ビニル、プロピオン酸ビニル、カプロン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、トリフルオロ酢酸ビニル等のビニルエステル、アクリル酸グリシジル、メタクリル酸グリシジル、イタコン酸モノグリシジルエステル等の不飽和カルボン酸グリシジルエステル等の極性モノマーなどが挙げられる。
【０１７５】
本発明は、これらのモノマーの単独重合または共重合に適用される。共重合体を構成するモノマーの具体例としては、エチレンとプロピレン、エチレンと１−ブテン、エチレンと１−ヘキセン、エチレンと１−オクテン、プロピレンと１−ブテン、エチレンとプロピレンとブテン、エチレンとプロピレンと１−ヘキセン等が例示されるが、本発明はこれらに限定されるべきものではない。
【０１７６】
本発明の付加重合用触媒はオレフィン重合用触媒として特に好適であり、オレフィン重合体の製造方法に好適に用いられる。かかるオレフィン重合体として特に好ましくはエチレンとα−オレフィンとの共重合体であり、中でもポリエチレン結晶構造を有するエチレンとα−オレフィンとの共重合体が好ましい。ここでいうα−オレフィンとして好ましくは、炭素原子数３〜８のα−オレフィンであり、具体的には１−ブテン、１−ヘキセン、１−オクテンなどが挙げられる。
【０１７７】
【実施例】
以下、実施例および比較例によって本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。実施例中の各項目の測定値は、下記の方法で測定した。
【０１７８】
（１）共重合体におけるα−オレフィンから誘導される繰り返し単位の含有量は、赤外分光光度計（日本分光工業社製　ＦＴ−ＩＲ７３００）を用い、エチレンとα−オレフィンの特性吸収より検量線を用いて求め、炭素原子１０００個当たりの短鎖分岐数（ＳＣＢ）として表した。
【０１７９】
（２）メルトフローレート＝ＭＦＲ：ＪＩＳ　Ｋ７２１０−１９９５に規定された方法に従い、１９０℃にて荷重２１．１８Ｎ（２．１６ｋｇ）で測定したメルトフローレート値である（単位：ｇ／１０分）。
【０１８０】
（３）スウェル比＝ＳＲ：ＭＦＲ測定時に得られたストランド径をダイの内径である２．０９５ｍｍで除した値である。
【０１８１】
（４）メルトフローレート比＝ＭＦＲＲ：ＪＩＳ　Ｋ７２１０−１９９５に規定された方法に従い、１９０℃、荷重２１１．８２Ｎ（２１．６０ｋｇ）で測定されたメルトフローレート値を、荷重２１．１８Ｎ（２．１６ｋｇ）で測定されたメルトフローレート値（ＭＦＲ）で除した値である。
上記メルトフローレート測定についてはすべて、予め酸化防止剤を１０００ｐｐｍ配合した重合体を用いた。
【０１８２】
（５）元素分析：
Ａｌ、Ｚｎ：試料を硫酸水溶液（１ｍｏｌ／リットル）に投じたのち超音波をあてて金属成分を抽出した。得られた液体部分についてＩＣＰ発光分析法により定量した。
Ｆ：酸素を充填させたフラスコ中で試料を燃焼させて生じた燃焼ガスを水酸化ナトリウム水溶液（１０％）に吸収させ、得られた当該水溶液についてイオン電極法を用いて定量した。
【０１８３】
［実施例１］
（１）化合物（ａ’）と粒子（ｄ）との事前接触
窒素置換した２００ｍｌの四つ口フラスコに、窒素流通下でエタノール　５．９ｍｌ（０．１ｍｏｌ）、トリエチルアミン　１３．９ｍｌ（０．１ｍｏｌ）、およびトルエン　７０ｍｌを入れ、これに、３００℃において加熱処理したシリカ（デビソン社製　Ｓｙｌｏｐｏｌ９４８；平均粒子径＝６１μｍ；細孔容量＝１．７０ｍｌ／ｇ；比表面積＝２９１ｍ^２／ｇ）５．５９ｇを室温下で加えた。シリカ添加後、加熱還流下で８時間攪拌した。その後、室温でトルエン　２０ｍｌにて３回、ヘキサン　２０ｍｌにて３回、フィルターを用いた洗浄を行った。その後、固体成分を減圧下、１２０℃で４時間乾燥を行うことにより、固体成分４．２２ｇを得た。
【０１８４】
（２）成分（Ａ）の合成
窒素置換した１００ｍｌの四つ口フラスコに、トルエン　３２．１ｍｌ、ジエチル亜鉛のヘキサン溶液（２．０ｍｏｌ／リットル）５．７　ｍｌ（１１ｍｍｏｌ）を入れ５℃に冷却した。これに、濃度を２．０ｍｍｏｌ／ｍｌに調整したペンタフルオロフェノールのトルエン溶液　２．８３ｍｌを１５分間で滴下した。滴下終了後、４０℃で０．５時間攪拌した。その後、氷浴で５℃にした後、上記実施例１（１）で得られた固体成分　３．７８ｇを入れ、次いでトルエン　５ｍｌを入れてフラスコ壁面に付着した固体成分を洗い流した。５分間攪拌後、Ｈ_２Ｏ　０．１５ｍｌ（８．５ｍｍｏｌ）を２０分間で滴下した。滴下終了後、５℃で１時間、８０℃で２時間攪拌した。その後、静置し、固体成分を沈降させ、沈降した固体成分の層と上層のスラリー部分との界面が見えた時点で上層のスラリー部分を取り除き、次いで残りの液成分をフィルターにて除去した後、トルエン５０ｍｌを加えた。その後、９５℃で２時間攪拌した。その後、９５℃でトルエン　５０ｍｌにて４回、室温でヘキサン　５０ｍｌにて２回、静置し、固体成分を沈降させ、沈降した固体成分の層と上層のスラリー部分との界面が見えた時点で上層のスラリー部分を取り除き、次いで残りの液成分をフィルターにて除去した。その後、固体成分を減圧下、１２０℃で２時間乾燥を行うことにより、成分（Ａ）５．３７ｇを得た。
【０１８５】
（３）重合
減圧乾燥後、アルゴンで置換した内容積３リットルの撹拌機付きオートクレーブ内を真空にし、水素をその分圧が０．０１７ＭＰａになるように加え、ブタンを６９５ｇ、１−ブテンを５５ｇ仕込み、７０℃まで昇温した。その後、エチレンを、その分圧が１．６ＭＰａになるように加え系内を安定させた。ガスクロマトグラフィー分析の結果、系内のガス組成は、水素＝１．０６ｍｏｌ％、１−ブテン＝２．８９ｍｏｌ％であった。これに、濃度を１ｍｍｏｌ／ｍｌに調整したトリイソブチルアルミニウムのヘプタン溶液　０．９ｍｌを投入した。次に、濃度を２μｍｏｌ／ｍｌに調整したラセミ−エチレンビス（１−インデニル）ジルコニウムジクロライドのトルエン溶液　０．５ｍｌを投入し、続いて上記実施例１（２）で得られた成分（Ａ）９．４ｍｇを固体触媒成分として投入した。
全圧を一定に保つように水素を０．３５ｍｏｌ％含有したエチレンと水素の混合ガスをフィードしながら７０℃で、６０分間重合を行った。その結果、粒子性状の良好なオレフィン重合体　２４ｇが得られた。ジルコニウム原子当たりの重合活性は２．４×１０^７　ｇ／ｍｏｌＺｒ／時間で、固体触媒成分当りの重合活性は２５００ｇ／ｇ固体触媒成分／時間であった。また、得られたオレフィン重合体はＳＣＢ＝１５．３、ＭＦＲ＝０．１１、ＭＦＲＲ＝１５７、ＳＲ＝１．１１であった。
【０１８６】
［実施例２］
（１）化合物（ａ’）と粒子（ｄ）との事前接触
窒素置換した２００ｍｌの四つ口フラスコに、窒素流通下でフェノール　５．０４ｇ（５３．５ｍｍｏｌ）、トリエチルアミン　７．５ｍｌ（５４ｍｍｏｌ）、およびトルエン　７０ｍｌを入れ、これに、３００℃において加熱処理したシリカ（デビソン社製　Ｓｙｌｏｐｏｌ９４８；平均粒子径＝６１μｍ；細孔容量＝１．７０ｍｌ／ｇ；比表面積＝２９１ｍ^２／ｇ）５．７８ｇを室温下で加えた。シリカ添加後、加熱還流下で８時間攪拌した。その後、室温でトルエン　２０ｍｌにて３回、ヘキサン　２０ｍｌにて３回、フィルターを用いた洗浄を行った。その後、固体成分を減圧下、１２０℃で４時間乾燥を行うことにより、成分（Ｄ）５．２０ｇを得た。
【０１８７】
（２）成分（Ａ）の合成
窒素置換した１００ｍｌの四つ口フラスコに、トルエン　３９．４ｍｌ、ジエチル亜鉛のヘキサン溶液（２．０ｍｏｌ／リットル）７．０ｍｌ（１４ｍｍｏｌ）を入れ５℃に冷却した。これに、濃度を２．０ｍｍｏｌ／ｍｌに調整したペンタフルオロフェノールのトルエン溶液　３．４８ｍｌを１５分間で滴下した。滴下終了後、４０℃で０．５時間攪拌した。その後、氷浴で５℃にした後、上記実施例１（１）で得られた固体成分　４．６４ｇを入れ、次いでトルエン　５ｍｌを入れてフラスコ壁面に付着した固体成分を洗い流した。５分間攪拌後、Ｈ_２Ｏ０．１９ｍｌ（１０．４ｍｍｏｌ）を２０分間で滴下した。滴下終了後、５℃で１時間、８０℃で２時間攪拌した。その後、静置し、固体成分を沈降させ、沈降した固体成分の層と上層のスラリー部分との界面が見えた時点で上層のスラリー部分を取り除き、次いで残りの液成分をフィルターにて除去した後、トルエン５０ｍｌを加えた。その後、９５℃で２時間攪拌した。その後、９５℃でトルエン　５０ｍｌにて４回、室温でヘキサン　５０ｍｌにて２回、静置し、固体成分を沈降させ、沈降した固体成分の層と上層のスラリー部分との界面が見えた時点で上層のスラリー部分を取り除き、次いで残りの液成分をフィルターにて除去した。その後、固体成分を減圧下、１２０℃で２時間乾燥を行うことにより、成分（Ａ）６．３７ｇを得た。
【０１８８】
（３）重合
減圧乾燥後、アルゴンで置換した内容積３リットルの撹拌機付きオートクレーブ内を真空にし、水素をその分圧が０．０１７ＭＰａになるように加え、ブタンを６９５ｇ、１−ブテンを５５ｇ仕込み、７０℃まで昇温した。その後、エチレンを、その分圧が１．６ＭＰａになるように加え系内を安定させた。ガスクロマトグラフィー分析の結果、系内のガス組成は、水素＝１．２０ｍｏｌ％、１−ブテン＝２．７６ｍｏｌ％であった。これに、濃度を１ｍｍｏｌ／ｍｌに調整したトリイソブチルアルミニウムのヘプタン溶液　０．９ｍｌを投入した。次に、濃度を２μｍｏｌ／ｍｌに調整したラセミ−エチレンビス（１−インデニル）ジルコニウムジクロライドのトルエン溶液　０．５ｍｌを投入し、続いて上記実施例１（２）で得られた成分（Ａ）８．８ｍｇを固体触媒成分として投入した。
全圧を一定に保つように水素を０．３５ｍｏｌ％含有したエチレンと水素の混合ガスをフィードしながら７０℃で、６０分間重合を行った。その結果、粒子性状の良好なオレフィン重合体　４１ｇが得られた。ジルコニウム原子当たりの重合活性は４．１×１０^７　ｇ／ｍｏｌＺｒ／時間で、固体触媒成分当りの重合活性は４６３０ｇ／ｇ固体触媒成分／時間であった。また、得られたオレフィン重合体はＳＣＢ＝１４．９、ＭＦＲ＝０．０６、ＭＦＲＲ＝２１２、ＳＲ＝１．０３であった。
【０１８９】
［参考例１］
（１）成分（Ａ）の合成
窒素置換した５リットルの四つ口フラスコに、トルエン　３．０リットル、ジエチル亜鉛のヘキサン溶液（２．００ｍｏｌ／リットル）０．５２５リットル（１．０５ｍｏｌ）を入れ５℃に冷却した。これに、ペンタフルオロフェノール　９８．６ｇ（０．５４ｍｏｌ）をトルエン　１６０ｍｌに溶解させた溶液を６０分間で滴下した。滴下終了後、５℃で１時間攪拌した。その後、４０℃に加熱し、１時間攪拌した。氷浴で５℃にした後、窒素流通下で３００℃において加熱処理したシリカ（デビソン社製　Ｓｙｌｏｐｏｌ９４８；平均粒子径＝５９μｍ；細孔容量＝１．６６ｍｌ／ｇ；比表面積＝２９６ｍ^２／ｇ）３５１ｇを入れ、次いでトルエン　０．１リットルを入れてフラスコ壁面に付着したシリカを洗い流した。５分間攪拌後、Ｈ_２Ｏ　１４．０ｇ（０．７８ｍｏｌ）を１．５時間で滴下した。滴下終了後、５℃で１．５時間、４０℃で２時間攪拌した。その後、室温にて一晩静置した。その後８０℃で２時間攪拌した。その後、静置し、固体成分を沈降させ、沈降した固体成分の層と上層のスラリー部分との界面が見えた時点で上層のスラリー部分を取り除き、次いで残りの液成分をフィルターにてろ過した後、トルエン　３．５リットルを加え９５℃で２時間攪拌した。その後、９５℃でトルエン　３．５リットルにて４回、室温でヘキサン　３．５リットルにて２回、攪拌した後、静置し、固体成分を沈降させ、沈降した固体成分の層と上層のスラリー部分との界面が見えた時点で上層のスラリー部分を取り除き、次いで残りの液成分をフィルターにてろ過する洗浄を行った。その後、固体成分を減圧下、１２０℃で４時間乾燥を行うことにより、成分（Ａ）５２４ｇを得た。元素分析の結果、Ｚｎ＝２．１ｍｍｏｌ／ｇ、Ｆ＝５．１ｍｍｏｌ／ｇであった。
【０１９０】
（２）重合
固体触媒成分として、上記参考例１（１）で得られた成分（Ａ）７．８ｍｇを用いたことと、ガスクロマトグラフィー分析による系内のガス組成が、水素＝０．７１ｍｏｌ％、１−ブテン＝２．５９ｍｏｌ％であったことと、フィードしたエチレンと水素の混合ガスにおける水素の含有率が０．２６ｍｏｌ％であったこと以外は、実施例１（３）と同様にして重合を行った。
その結果、粒子性状の良好なオレフィン重合体　６７ｇが得られた。ジルコニウム原子当たりの重合活性は６．７×１０^７　ｇ／ｍｏｌＺｒ／時間で、固体触媒成分当りの重合活性は８６００ｇ／ｇ固体触媒成分／時間であった。また、得られたオレフィン重合体はＳＣＢ＝１７．４１、ＭＦＲ＝０．９４、ＭＦＲＲ＝５７．８、ＳＲ＝１．２１であった。
【０１９１】
［比較例１］
（１）
窒素置換した５リットルの４つ口フラスコに撹拌機、滴下ロートおよび温度計を取り付けた。そのフラスコへ、窒素流通下で３００℃において加熱処理したシリカ（デビソン社製　Ｓｙｌｏｐｏｌ９４８；平均粒子径＝６４μｍ；細孔容量＝１．６２ｍｌ／ｇ；比表面積＝３１２ｍ^２　／ｇ）３８２ｇを採取した。そこへトルエン　３．３リットルを加えてスラリーとし、氷浴を用いて５℃に冷却した後、濃度を２．１ｍｍｏｌ／ｍｌに調整したトリメチルアルミニウムのトルエン溶液　３７５ｍｌを徐々に滴下した。その際、ガスの発生が見られた。５℃で３０分間、８０℃で２時間撹拌した後、上澄み液を除去し、残存の固体生成物をトルエン　３．３リットルで４回洗浄した。その後、再びトルエンを３．３リットル加えてスラリーとした。
【０１９２】
（２）
上記比較例１（１）にて得られたスラリーを氷浴を用いて５℃に冷却した後、濃度を２ｍｍｏｌ／ｍｌに調整したペンタフルオロフェノールのトルエン溶液　４２０ｍｌをゆっくりと加えた。その際、ガスの発生が見られた。５℃で３０分、８０℃で２時間撹袢した後、上澄み液を濾過し、残存の固体生成物をトルエン３．３リットルで４回、ヘキサン　３．３リットルで２回洗浄した。その後、固体生成物を減圧乾燥して、流動性のある固体生成物　４３４ｇを得た。元素分析の結果、Ａｌ＝１．２ｍｍｏｌ／ｇ、Ｆ＝４．６ｍｍｏｌ／ｇであった。
【０１９３】
（３）重合
減圧乾燥後、アルゴンで置換した内容積５リットルの撹拌機付きオートクレーブ内を真空にし、水素をその分圧が０．００７ＭＰａになるように加え、ブタンを１１４５ｇ、１−ブテンを５５ｇ仕込み、７０℃まで昇温した。その後、エチレンを、その分圧が１．６ＭＰａになるように加え系内を安定させた。ガスクロマトグラフィー分析の結果、系内のガス組成は、水素＝０．３７ｍｏｌ％、１−ブテン＝１．５５ｍｏｌ％であった。これに、濃度を１ｍｍｏｌ／ｍｌに調整したトリイソブチルアルミニウムのヘプタン溶液　１．５ｍｌを投入した。次に、濃度を２μｍｏｌ／ｍｌに調整したラセミ−エチレンビス（１−インデニル）ジルコニウムジクロライドのトルエン溶液　０．５ｍｌを投入し、続いて上記比較例１（２）で得られた固体生成物　３６ｍｇを固体触媒成分として投入した。全圧を一定に保つようにエチレン／水素混合ガス（水素０．２２ｍｏｌ％）をフィードしながら７０℃で、６０分間重合を行った。その結果、オレフィン重合体　１３５ｇが得られた。ジルコニウム原子当たりの重合活性は１．４×１０^８　ｇ／ｍｏｌＺｒ／時間で、固体触媒成分当りの重合活性は３７２０ｇ／ｇ固体触媒成分／時間であった。また、得られたオレフィン重合体はＳＣＢ＝１２．４、ＭＦＲ＝２．５５、ＭＦＲＲ＝４８、ＳＲ＝１．３５であった。
【０１９４】
【発明の効果】
以上詳述したように本発明によれば、シングルサイト触媒の分野で、付加重合体粒子の形成を伴う重合（例えばスラリー重合、気相重合、バルク重合等）に好適に使用される高分子量の付加重合体を製造し得る粒子、担体、および付加重合用触媒成分、該粒子の製造、該粒子を用いてなる付加重合用触媒、ならびに該付加重合用触媒を用いる高分子量の付加重合体の製造方法が提供される。また本発明によれば、付加重合体粒子の形成を伴う重合（例えばスラリー重合、気相重合、バルク重合等）に適用した場合に、形状、粒子性状に優れた付加重合体を与える付加重合用触媒の調整に有用な粒子、担体および付加重合用触媒成分、該粒子の製造方法、該粒子を用いてなる付加重合用触媒、ならびに該付加重合用触媒を用いる付加重合体粒子の形成を伴う重合（例えばスラリー重合、気相重合、バルク重合等）に適用した場合に、粒子性状に優れた付加重合体の製造方法も提供される。さらにいえば、本発明においては高活性な付加重合用触媒、および効率的な付加重合体の製造方法も提供される。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a modified particle useful as a carrier and a catalyst component for addition polymerization, a method for producing the same, a use thereof, an addition polymerization catalyst obtained using the same, and a method for producing an addition polymer.
[0002]
2. Description of the Related Art
Addition polymers such as polypropylene and polyethylene are widely used in various molding fields because of their excellent mechanical properties, chemical resistance and the like, and their excellent balance between their properties and economic efficiency.
These addition polymers have conventionally been obtained by combining a solid catalyst component mainly obtained using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride with a Group 13 metal compound represented by an organoaluminum compound. It has been produced by multi-site polymerization in which an olefin or the like is polymerized using a conventional solid catalyst (multi-site catalyst).
[0003]
In recent years, a so-called single-site catalyst that combines a transition metal compound (for example, a metallocene complex or a non-metallocene compound) different from a solid catalyst component that has been used for a long time and an aluminoxane has been used. Manufacturing methods have been proposed. For example, JP-A-58-19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. It has also been reported to combine certain boron compounds with such transition metal compounds. For example, Japanese Patent Application Laid-Open Publication No. 1-502036 discloses a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Addition polymers obtained using these single-site catalysts generally have narrower molecular weight distributions than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers, the comonomers are copolymerized more uniformly. Therefore, it is known that a more homogeneous addition polymer can be obtained than when a conventional solid catalyst is used.
[0004]
However, since these known single-site catalysts are soluble in the reaction system, when applied to polymerization involving formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), the generated addition polymer Irregularly shaped, resulting in the formation of coarse addition polymer particles, bulk addition polymer, fine powder addition polymer, etc., decrease in bulk density of the addition polymer, adhesion of the addition polymer to the polymerization reactor wall, etc. Maybe. These factors contribute to poor heat transfer and poor heat removal in the reactor, leading to a problem that stable operation is difficult and productivity is reduced. Japanese Patent Application Laid-Open No. H11-193306 discloses a solution to such a problem, but the solution described in the publication is still insufficient in terms of polymerization activity per solid catalyst component. Accordingly, the present applicant has proposed a novel method in Japanese Patent Application No. 2000-395776, but has further studied thereafter, and has attempted to obtain an addition polymer having a higher molecular weight by the novel method.
An object of the present invention is to provide particles capable of producing a high-molecular-weight addition polymer by addition polymerization using a transition metal compound that forms a single-site catalyst, a carrier and a catalyst component for addition polymerization, a method for producing the particles, An object of the present invention is to provide an addition polymerization catalyst using the particles and a method for producing an addition polymer using the addition polymerization catalyst.
[0005]
[Means for Solving the Problems]
The present invention relates to modified particles obtained by bringing the following (a), the following (b), the following (c) and the following (d ') into contact with each other, and the following (a), the following (b), the following ( c) and the following method (d ′) for producing a modified particle. (A): a compound represented by the following general formula [1]
M¹L¹ _m[1]
(B): a compound represented by the following general formula [2]
R¹ _t-1TH [2]
(C): a compound represented by the following general formula [3]
R² _t-2TH₂[3]
(D '): Particles obtained by contacting particles (d) with a compound (a') represented by the following general formula [4]
(A '): a compound represented by the following general formula [4]
R³ _t-1TH [4]
(In the above general formulas [1] to [4], M¹Represents a typical metal atom of Groups 1, 2, 12, 14 or 15 of the periodic table, and m is M¹Represents the number corresponding to the valence of 価L¹Represents a hydrogen atom, a halogen atom or a hydrocarbon group;¹When there are a plurality of, they may be the same or different from each other. R¹Represents an electron-withdrawing group or a group containing an electron-withdrawing group;¹When there are a plurality of, they may be the same or different. R²Represents a hydrocarbon group or a halogenated hydrocarbon group;³Represents a hydrocarbon group. T independently represents a non-metallic atom of Group 15 or Group 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound. )
[0006]
The present invention also relates to a carrier comprising the modified particles and a catalyst component for addition polymerization comprising the modified particles.
The present invention further relates to an addition polymerization catalyst obtained by bringing the modified particles (A) into contact with a Group 3-11 or lanthanoid-based transition metal compound (B). The present invention relates to an addition polymerization catalyst obtained by contacting a modified particle (A), a Group 3-11 or lanthanoid series transition metal compound (B), and an organoaluminum compound (C).
The present invention also relates to a method for producing an addition polymer using any one of the above addition polymerization catalysts.
Hereinafter, the present invention will be described in more detail.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Compound (a) is a compound represented by the following general formula [1].
M¹L¹ _m[1]
M in the above general formula [1]¹Represents a typical metal atom belonging to Groups 1, 2, 12, 14 or 15 of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989). Specific examples include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, germanium, and tin atoms. , A lead atom, an antimony atom, a bismuth atom and the like. M¹Are preferably a magnesium atom, a calcium atom, a strontium atom, a barium atom, a zinc atom, a germanium atom, a tin atom or a bismuth atom, particularly preferably a magnesium atom, a zinc atom, a tin atom or a bismuth atom, and most preferably zinc. Is an atom.
In the general formula [1], m is M¹Represents a number corresponding to the valence of, for example, M¹M is 2 when is a zinc atom.
[0008]
L in the above general formula [1]¹Represents a hydrogen atom, a halogen atom or a hydrocarbon group;¹When there are a plurality of, they may be the same or different from each other. L¹Specific examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. L¹As the hydrocarbon group in, an alkyl group, an aryl group, or an aralkyl group is preferable.
[0009]
The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, and the like, More preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group.
[0010]
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, -Fluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, Bromopentadecyl group, perbromoeicosyl group, 1H, 1H-perfluoropropyl group, 1H, 1H-perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H -Perfluorooctyl group, 1H 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group, 1H, 1H-perfluoroeicosyl group, 1H, 1H-perchloropropyl group, 1H, 1H-perchlorobutyl group, 1H, 1H-per Chloropentyl group, 1H, 1H-perchlorohexyl group, 1H, 1H-perchlorooctyl group, 1H, 1H-perchlorododecyl group, 1H, 1H-perchloropentadecyl group, 1H, 1H-perchloroeicosyl group 1H, 1H-perbromopropyl group, 1H, 1H-perbromobutyl group, 1H, 1H-perbromopentyl group, 1H, 1H-perbromohexyl group, 1H, 1H-perbromooctyl group, 1H, 1H- Perbromododecyl group, 1H, 1H-perbromopentadecyl group, 1H, 1H-perbromoeicosyl group and the like. Can be
All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.
[0011]
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable. For example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2, 3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetra Methylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl Tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl Examples include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable.
All of these aryl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.
[0012]
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, for example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2 , 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) Methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) Methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl Methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (N-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) methyl group, (N-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthracene A benzyl group; and more preferably a benzyl group.
All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.
[0013]
L in the above general formula [1]¹Is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.
[0014]
Compound (b) is a compound represented by the following general formula [2].
R¹ _t-1TH [2]
The compound (c) is a compound represented by the following general formula [3].
R² _t-2TH₂[3]
T in the above general formula [2] or [3] each independently represents a non-metallic atom of Group 15 or Group 16 of the Periodic Table of the Elements (Revised Edition of IUPAC Inorganic Chemical Nomenclature 1989). T in the general formula [2] or [3] may be the same or different. Specific examples of the Group 15 non-metallic atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 non-metallic atom include an oxygen atom and a sulfur atom. T is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
In the general formula [2] or [3], t represents a number corresponding to the valence of each T. When T is a Group 15 non-metal atom, t is 3, and T is Group 16 non-metal. In the case of an atom, t is 2.
[0015]
R in the above general formula [2]¹Represents an electron-withdrawing group or a group containing an electron-withdrawing group;¹When there are a plurality of, they may be the same or different. As an index of electron withdrawing property, a Hammett's rule substituent constant σ and the like are known, and a functional group having a positive Hammett's substituent constant σ is mentioned as an electron withdrawing group.
[0016]
Specific examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an aralkyloxycarbonyl group, Aryloxycarbonyl group), an acyl group, an acyl halide group and the like.
[0017]
Specific examples of the halogenated alkyl group include fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl, dibromomethyl, diiodomethyl, trifluoromethyl, trichloromethyl, and tribromomethyl. Methyl group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2 3,3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1-trichloromethyl group Ethyl group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2,2 2-trifluoroethyl group {1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group}, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group {1, , 1-bis (triiodomethyl) -2,2,2-triiodoethyl, 1H, 1H-perfluorobutyl, 1H, 1H-perfluoropentyl, 1H, 1H-perfluorohexyl, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group, 1H, 1H-perfluoroeicosyl group, 1H, 1H-pa Chlorobutyl group, 1H, 1H-perchloropentyl group, 1H, 1H-perchlorohexyl group, 1H, 1H-perchlorooctyl group, 1H, 1H-perchlorododecyl group, 1H, 1H-perchloropentadecyl group, 1H , 1H-perchloroeicosyl, 1H, 1H-perbromobutyl, 1H, 1H-perbromopentyl, 1H, 1H-perbromohexyl, 1H, 1H-perbromooctyl, 1H, 1H-per Bromodecyl, 1H, 1H-perbromopentadecyl, 1H, 1H-perbromoeicosyl and the like can be mentioned.
[0018]
Specific examples of the halogenated aryl group include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, and a 3,4-difluorophenyl Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 4,5,6,7,8-pentafluoro-2-naphthyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4- Lorophenyl group, 2,4-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group 2,3,5,6-tetrachlorophenyl group, pentachlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenyl Phenyl group, perchloro-1-naphthyl group, perchloro-2-naphthyl group, 4,5,6,7,8-pentachloro-2-naphthyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl Group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenyl group 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6-tetrabromophenyl group, pentabromophenyl group, 2,3,5,6 -Tetrabromo-4-tribromomethylphenyl group, 2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group, perbromo-2-naphthyl group, 4,5,6,7 , 8-Pentabromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenyl group, 3,4- Diiodophenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentayo Phenyl group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, period-1-naphthyl group, period-2- Examples include a naphthyl group and a 4,5,6,7,8-pentaiodo-2-naphthyl group.
[0019]
Specific examples of the (halogenated alkyl) aryl group include a 2- (trifluoromethyl) phenyl group, a 3- (trifluoromethyl) phenyl group, a 4- (trifluoromethyl) phenyl group, and a 2,6-bis (tri A fluoromethyl) phenyl group, a 3,5-bis (trifluoromethyl) phenyl group, and a 2,4,6-tris (trifluoromethyl) phenyl group.
[0020]
Specific examples of the cyanated aryl group include a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group.
[0021]
Specific examples of the nitrated aryl group include a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and the like.
[0022]
Specific examples of the ester group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, a phenoxycarbonyl group, a trifluoromethoxycarbonyl group, and a pentafluorophenoxycarbonyl group.
[0023]
Specific examples of the acyl group include formyl, ethanoyl, propanoyl, butanoyl, trifluoroethanoyl, benzoyl, pentafluorobenzoyl, perfluoroethanoyl, perfluoropropanoyl, and perfluorobutanoyl. Group, perfluoropentanoyl group, perfluorohexanoyl group, perfluoroheptanoyl group, perfluorooctanoyl group, perfluorononanoyl group, perfluorodecanoyl group, perfluoroundecanoyl group, perfluorododecanoyl group And the like.
[0024]
R¹Is preferably a halogenated hydrocarbon group, more preferably a halogenated alkyl group or a halogenated aryl group. More preferably, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,2-triethyl group Fluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-triphenyl Fluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoro Tylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, 4,5,6,7,8-pentafluoro -2-naphthyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro -1-trichloromethylethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4 , 6-trichlorophenyl group, 3,4,5-trichlorophenyl group or pentachlorophenyl group, particularly preferably a fluoroalkyl group. Is a fluoroaryl group, most preferably a trifluoromethyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group, a 1,1-bis (trifluoromethyl) -2,2,2- A trifluoroethyl group, a 3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group or a pentafluorophenyl group.
[0025]
R in the above general formula [3]²Represents a halogenated hydrocarbon group or a hydrocarbon group. R²Examples of the halogenated hydrocarbon group in include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group.¹The same halogenated alkyl group, halogenated aryl group, and (halogenated alkyl) aryl group as those mentioned as specific examples of the electron-withdrawing group in are used. As the hydrocarbon group, an alkyl group, an aryl group or an aralkyl group is preferable, and L in the general formula [1] is preferable.¹The same hydrocarbon groups as those described as are used.
[0026]
R in the above general formula [3]²Is preferably a halogenated hydrocarbon group, and more preferably a fluorinated hydrocarbon group.
[0027]
Specific examples of the compound (a) include M¹Is a zinc atom, specific examples include dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc; diphenyl zinc, dinaphthyl zinc, bis (pentane Diaryl zinc such as fluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, isobutyl zinc chloride, n-hexyl zinc, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl zinc bromide, methyl zinc iodide, ethyl zinc iodide Propyl zinc iodide, n-butyl zinc iodide, isobutyl zinc iodide, n-hexyl iodide Halogenated alkyl zinc such as lead, zinc fluoride, zinc chloride, zinc bromide, and halogenated zinc such as zinc iodide.
[0028]
The compound (a) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, or di-n-hexyl zinc, and particularly preferably dimethyl zinc. Zinc or diethyl zinc.
[0029]
When the compound (b) is specifically exemplified, as the amines, di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, bis (difluoromethyl) amine (Dichloromethyl) amine, bis (dibromomethyl) amine, bis (diiodomethyl) amine, bis (trifluoromethyl) amine, bis (trichloromethyl) amine, bis (tribromomethyl) amine, bis (triiodomethyl) amine, Bis (2,2,2-trifluoroethyl) amine, bis (2,2,2-trichloroethyl) amine, bis (2,2,2-tribromoethyl) amine, bis (2,2,2-triethyl) amine Iodoethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,3,3 3-pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2 2-trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethylethyl) amine , Bis (2,2,2-triiodo-1-triiodomethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, bis (1,1 -Bis (trichloromethyl) -2,2,2-trichloroethyl) amine, bis (1,1-bis (tribromomethyl) -2,2,2-tribromoethyl) amine, bis (1,1 Bis (triiodomethyl) -2,2,2-triiodoethyl) amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2- Chlorophenyl) amine, bis (3-chlorophenyl) amine, bis (4-chlorophenyl) amine, bis (2-bromophenyl) amine, bis (3-bromophenyl) amine, bis (4-bromophenyl) amine, bis (2 -Iodophenyl) amine, bis (3-iodophenyl) amine, bis (4-iodophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2 6-dichlorophenyl) amine, bis (3,5-dichlorophenyl) amine, bis (2,6-dibromophenyl) amine Enyl) amine, bis (3,5-dibromophenyl) amine, bis (2,6-diiodophenyl) amine, bis (3,5-diiodophenyl) amine, bis (2,4,6-trifluorophenyl) ) Amine, bis (2,4,6-trichlorophenyl) amine, bis (2,4,6-tribromophenyl) amine, bis (2,4,6-triiodophenyl) amine, bis (pentafluorophenyl) Amine, bis (pentachlorophenyl) amine, bis (pentabromophenyl) amine, bis (pentaiodophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine , Bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di (trifluoromethyl) phenyl) Min, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) amine, (3-cyanophenyl ) Amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine, bis (1H, 1H-perfluorobutyl) amine , Bis (1H, 1H-perfluoropentyl) amine, bis (1H, 1H-perfluorohexyl) amine, bis (1H, 1H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoropentadecyl) amine, bis (1H, 1H-perfluoroeicosyl) amine, Bis (1H, 1H-perchlorobutyl) amine, bis (1H, 1H-perchloropentyl) amine, bis (1H, 1H-perchlorohexyl) amine, bis (1H, 1H-perchlorooctyl) amine, bis ( 1H, 1H-perchlorododecyl) amine, bis (1H, 1H-perchloropentadecyl) amine, bis (1H, 1H-perchloroeicosyl) amine, bis (1H, 1H-perbromobutyl) amine, bis ( 1H, 1H-perbromopentyl) amine, bis (1H, 1H-perbromohexyl) amine, bis (1H, 1H-perbromooctyl) amine, bis (1H, 1H-perbromododecyl) amine, bis (1H, 1H-perbromopentadecyl) amine, bis (1H, 1H-perbromoeicosyl) amine and the like. A phosphine compound in which a nitrogen atom is substituted by a phosphorus atom can also be exemplified. These phosphine compounds are compounds represented by rewriting the amine in the above specific examples with phosphine.
[0030]
Examples of alcohols include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodmethanol, trifluoromethanol, trichloromethanol, tribromomethanol, triiodmethanol, 2,2,2 -Trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3,3-pentafluoropropanol, 2, 2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol, 2,2,3,3,3-pentaiodopropanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, 2,2,2-to Chloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1-bis (trifluoromethyl) -2 1,2,2-trifluoroethanol, 1,1-bis (trichloromethyl) -2,2,2-trichloroethanol, 1,1-bis (tribromomethyl) -2,2,2-tribromoethanol, , 1-bis (triiodomethyl) -2,2,2-triiodoethanol, 1H, 1H-perfluorobutanol, 1H, 1H-perfluoropentanol, 1H, 1H-perfluorohexanol, 1H, 1H-per Fluorooctanol, 1H, 1H-perfluorododecanol, 1H, 1H-perfluoropentanol, 1H, 1H Perfluoroeicosanol, 1H, 1H-perchlorobutanol, 1H, 1H-perchloropentanol, 1H, 1H-perchlorohexanol, 1H, 1H-perchlorooctanol, 1H, 1H-perchlorododecanol, 1H, 1H-perchloropentadecanol, 1H, 1H-perchloroeicosanol, 1H, 1H-perbromobutanol, 1H, 1H-perbromopentanol, 1H, 1H-perbromohexanol, 1H, 1H-perbromooctanol And 1H, 1H-perbromododecanol, 1H, 1H-perbromopentadecanol, 1H, 1H-perbromoeicosanol and the like. A thiol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiol compounds are, for example, methanol to methanethiol, ethanol to ethanethiol, propanol to propanethiol, butanol to butanethiol, pentanol to pentanethiol, hexanol to hexanethiol, and octanol to hexanethiol of the above specific examples. Compounds represented by rewriting thiol, dodecanol to dodecanethiol, pentadecanol to pentadecanethiol, and eicosanol to eicosanthiol.
[0031]
Examples of phenols include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethyl Phenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7,8-pentafluoro-2-naphthol , 2-chlorophenol, 3-chlorophenol, 4-chlorophenol 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3 5,6-tetrachlorophenol, pentachlorophenol, 2,3,5,6-tetrachloro-4-trichloromethylphenol, 2,3,5,6-tetrachloro-4-pentachlorophenylphenol, perchloro-1- Naphthol, perchloro-2-naphthol, 4,5,6,7,8-pentachloro-2-naphthol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6- Dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4 -Tribromophenol, 3,4,5-tribromophenol, 2,3,5,6-tetrabromophenol, pentabromophenol, 2,3,5,6-tetrabromo-4-tribromomethylphenol, 2, 3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo-2-naphthol, 4,5,6,7,8-pentabromo-2-naphthol, 2-iodophenol, 3- Iodophenol, 4-iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol, 2,4,6-triiodophenol, 3,4,5-triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3,5,6-tetraiodo-4-triiodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol, period-1-naphthol, period-2-naphthol, 4,5 6,7,8-pentaiodo-2-naphthol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol , 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitro Phenol and 4-nitrophenol are exemplified. A thiophenol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiophenol compounds are compounds represented by rewriting phenol in the above specific examples with thiophenol (in the case of naphthol, compounds represented by rewriting naphthol with naphthylthiol) and the like.
[0032]
Examples of the halogenated carboxylic acid include pentafluorobenzoic acid, perfluoroethanolic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, and perfluorohexanoic acid. Examples thereof include noic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid.
[0033]
As the compound (b), preferably, the amines include bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) ) Amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine or bis Examples of (pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, and 2,2,2-trifluoro-1. -As trifluoromethylethanol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol and phenols Is 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 2- (trifluoro Methyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol or 2,4 6-Tris (trifluoromethyl) phenol.
[0034]
More preferably, compound (b) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1-bis (Trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6 -Trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, or 2,4,6-tris (trifluoro Fluoromethyl) phenol, and more preferably 3,5- Fluoro phenol, 3,4,5-fluorophenol, pentafluorophenol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol.
[0035]
Specific examples of the compound (c) include water, hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, and (halogenated alkyl) arylamine, and more preferably, Water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, n-hexylamine , N-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3-tolylamine, 4-tolylamine 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3 , 5-Trimethylaniline, 2,3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4 , 6-Tetramethylaniline, 2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, tert-butylaniline, n -Pentylaniline, neopentylaniline, n-hexylaniline, n-octylaniline, n Decyl aniline, n- dodecyl aniline, n- tetradecyl aniline, naphthylamine, anthracenyl amine,
[0036]
Benzylamine, (2-methylphenyl) methylamine, (3-methylphenyl) methylamine, (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methyl Amine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) methylamine, (3,4-dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3 , 4-trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) methylamine, (2,3,6-trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2 , 4,6-trimethylphenyl) methylamine, (2,3,4,5-tetramethylphenyl) methylamido (2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n -Propylphenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (sec-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (Neopentylphenyl) methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methylamine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthra Cenylmethylamine, fluorome Ruamine, chloromethylamine, bromomethylamine, iodomethylamine, difluoromethylamine, dichloromethylamine, dibromomethylamine, diiodomethylamine, trifluoromethylamine, trichloromethylamine, tribromomethylamine, triiodomethylamine, 2,2,2-trifluoroethylamine, 2,2,2-trichloroethylamine, 2,2,2-tribromoethylamine, 2,2,2-triiodoethylamine, 2,2,3,3,3-pentane Fluoropropylamine, 2,2,3,3,3-pentachloropropylamine, 2,2,3,3,3-pentabromopropylamine, 2,2,3,3,3-pentaiodopropylamine, 2 , 2,2-trifluoro-1-trifluoromethylethylamine, 2,2 , 2-Trichloro-1-trichloromethylethylamine, 2,2,2-tribromo-1-tribromomethylethylamine, 2,2,2-triiodo-1-triiodomethylethylamine, 1,1-bis (trifluoromethyl ) -2,2,2-trifluoroethylamine, 1,1-bis (trichloromethyl) -2,2,2-trichloroethylamine, 1,1-bis (tribromomethyl) -2,2,2-tribromo Ethylamine, 1,1-bis (triiodomethyl) -2,2,2-triiodoethylamine,
[0037]
Perfluoropropylamine, perchloropropylamine, perbromopropylamine, periodopropylamine, perfluorobutylamine, perchlorobutylamine, perbromobutylamine, periodobutylamine, perfluoropentylamine, perchloropentylamine, perbromopentylamine , Periodopentylamine, perfluorohexylamine, perchlorohexylamine, perbromohexylamine, periodohexylamine, perfluorooctylamine, perchlorooctylamine, perbromooctylamine, periodooctylamine, perfluorododecylamine , Perchlorododecylamine, perbromododecylamine, periododododecylamine, perfluoropentadecylamine, perchlor Pentadecyl amine, perbromododecyl amine, perfluoro-iodo pentadecyl amine, perfluoro eicosyl amine, perchlorethylene eicosyl amine, perfluoro-bromo eicosyl amine, perfluoro-iodo eicosyl amine,
[0038]
2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,6-dibromoaniline, 3,5-dibromo Aniline, 2,6-diiodoaniline, 3,5-diiodoaniline, 2,4,6-trifluoroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2,4 , 6-Triiodoaniline, 3,4,5-trifluoroaniline, 3,4,5-trichloroaniline, 3,4,5- Libromoaniline, 3,4,5-triiodaniline, pentafluoroaniline, pentachloroaniline, pentabromoaniline, pentaiodaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (Trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, and 2,4,6-tri (trifluoromethyl) aniline.
[0039]
Compound (c) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2, 6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, Perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4-f Oroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, -(Trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline or 2,4,6-tris (tri Fluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 6-difluoroaniline, 3,5-difluoroa Phosphorus, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl ) Aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline or 2,4,6-tris (trifluoromethyl) aniline, most preferably water or pentane It is fluoroaniline.
[0040]
Particle (d ') is a particle obtained by subjecting particle (d) to contact treatment with compound (a').
As the particles (d), those generally used as a carrier are preferably used, a porous substance having a uniform particle size is preferable, an inorganic substance or an organic polymer is suitably used, and an inorganic substance is more preferably used. Is done.
From the viewpoint of the particle size distribution of the obtained polymer, the particle (d) preferably has a volume-based geometric standard deviation of the particle diameter of the particle (d) of 2.5 or less, more preferably 2.0 or less, and still more preferably. Is 1.7 or less.
[0041]
Examples of inorganic substances that can be used as the particles (d) include inorganic oxides and the like, and clay and clay minerals can also be used. These may be used as a mixture.
Specific examples of the inorganic oxide include SiO 2₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂And mixtures thereof, for example, SiO 2₂-MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂−Cr₂O₃, SiO₂-TiO₂-MgO and the like can be exemplified. Among these inorganic oxides, SiO 2₂And / or Al₂O₃Are preferred, and especially SiO₂(Ie, silica) is preferred. The inorganic oxide contains a small amount of Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg (NO₃)₂, Al (NO₃)₃, Na₂O, K₂O, Li₂Carbonate such as O, sulfate, nitrate and oxide components may be contained.
[0042]
As clay or clay minerals, kaolin, bentonite, Kibushi clay, gairome clay, allophane, hissingelite, bilophilite, talc, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, Halloy site and the like.
Among these, smectite, montmorillonite, hectorite, laponite and saponite are preferred, and montmorillonite and hectorite are more preferred.
[0043]
Among these inorganic substances, inorganic oxides are preferably used.
These inorganic substances are preferably dried and substantially free of moisture, and are preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., and more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during the heating, for example, a method of flowing a dried inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure may be used, but the method is not limited thereto.
[0044]
The average particle diameter of the inorganic substance is preferably from 5 to 1,000 μm, more preferably from 10 to 500 μm, and still more preferably from 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. Preferably, the specific surface area is 10 to 1000 m²/ G, more preferably 100-500 m²/ G.
[0045]
As the organic polymer that can be used as the particles (d), any organic polymer may be used, and a plurality of types of organic polymers may be used as a mixture. As the organic polymer, a polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group is preferable.
[0046]
The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Specific examples include a primary amino group, a secondary amino group, an imino group, an amide group, a hydrazide group, an amidino group, and a hydroxy group. , A hydroperoxy group, a carboxyl group, a formyl group, a carbamoyl group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiol group, a thioformyl group, a pyrrolyl group, an imidazolyl group, a piperidyl group, an indazolyl group, and a carbazolyl group. . Preferably, they are a primary amino group, a secondary amino group, an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group. Particularly preferred are a primary amino group, a secondary amino group, an amide group and a hydroxy group. In addition, these groups may be substituted by a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
[0047]
The non-proton donating Lewis basic functional group is not particularly limited as long as it has a Lewis base moiety having no active hydrogen atom, and specific examples thereof include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted group. Indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group , A furyl group, a carbonyl group, a thiocarbonyl group, an alkoxy group, an alkyloxycarbonyl group, an N, N-substituted carbamoyl group, a thioalkoxy group, a substituted sulfinyl group, a substituted sulfonyl group, and a substituted sulfonic acid group. It is preferably a heterocyclic group, and more preferably an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group, and most preferred is a pyridyl group. In addition, these groups may be substituted by a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
[0048]
The amount of the functional group having an active hydrogen or the non-proton-donating Lewis basic functional group is not particularly limited, but is preferably 0.01 to 50 mmol / g as a molar amount of the functional group per unit gram of the polymer. And more preferably 0.1 to 20 mmol / g.
[0049]
The polymer having such a functional group is obtained, for example, by homopolymerizing a monomer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups, or It can be obtained by copolymerizing this with another monomer having a polymerizable unsaturated group. At this time, it is preferable to further copolymerize together a crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups.
[0050]
Examples of such a monomer having an active hydrogen-containing functional group or an aprotic donating Lewis basic functional group and one or more polymerizable unsaturated groups include the active hydrogen-containing functional group and one or more polymerizable unsaturated groups. Examples of the monomer include a monomer having a saturated group, or a monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups. Examples of such a polymerizable unsaturated group include an alkenyl group such as a vinyl group and an allyl group, and an alkynyl group such as an ethyne group.
Examples of the monomer having an active hydrogen-containing functional group and one or more polymerizable unsaturated groups include a vinyl group-containing primary amine, a vinyl group-containing secondary amine, a vinyl group-containing amide compound, and a vinyl group-containing hydroxy compound. Can be mentioned. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine, -Ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol and the like No.
Specific examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, vinyl (N-substituted) indazole Can be mentioned.
[0051]
Examples of the other monomer having a polymerizable unsaturated group include ethylene, α-olefin, and aromatic vinyl compound. Specific examples include ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1. -Pentene, styrene and the like. Preferably it is ethylene or styrene. Two or more of these monomers may be used.
Further, specific examples of the crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.
[0052]
The average particle size of the organic polymer is preferably from 5 to 1000 μm, more preferably from 10 to 500 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. Preferably, the specific surface area is 10 to 1000 m²/ G, more preferably 50 to 500 m²/ G.
[0053]
These organic polymers are preferably dried and substantially free of moisture, and are preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 30 to 400 ° C, preferably 50 to 200 ° C, and more preferably 70 to 150 ° C for an organic polymer whose water content cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during the heating, for example, a method of flowing a dried inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure may be used, but the method is not limited thereto.
[0054]
Compound (a ') is a compound represented by the following general formula [4].
R³ _t-1TH [4]
T in the above general formula [4] independently represents a non-metallic atom of Group 15 or Group 16 of the Periodic Table of the Elements (IUPAC revised edition of inorganic chemical nomenclature 1989). Specific examples of the Group 15 non-metallic atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 non-metallic atom include an oxygen atom and a sulfur atom. T in the above general formula [4] is preferably a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
In the general formula [4], t represents a number corresponding to the valence of T. When T is a Group 15 non-metallic atom, t is 3. When T is a Group 16 non-metallic atom, t is t. 2.
[0055]
R in the above general formula [4]³Represents a hydrocarbon group. R³As the hydrocarbon group in, an alkyl group, an aryl group or an aralkyl group having no electron-withdrawing group is preferable.
[0056]
The alkyl group referred to herein is preferably an alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, and the like, More preferably, they are a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a tert-butyl group or an isobutyl group.
[0057]
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable. For example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2, 3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetra Methylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl Tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl Examples include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable.
[0058]
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, for example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2 , 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) Methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) Methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl Methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (N-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) methyl group, (N-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthracene A benzyl group; and more preferably a benzyl group.
[0059]
R in the above general formula [4]³Is preferably an alkyl group or an aryl group.
[0060]
When the compound (a ′) is specifically exemplified, the amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, di-n-hexylamine , Diphenylamine, bis (2-methylphenyl) amine, bis (3-methylphenyl) amine, bis (4-methylphenyl) amine, bis (2,6-dimethylphenyl) amine, bis (3,5-dimethylphenyl) Amine, bis (2,4,6-trimethylphenyl) amine, bis (3,4,5-trimethylphenyl) amine, bis (pentamethylphenyl) amine, (2-methoxyphenyl) amine, (3-methoxyphenyl) Amine, bis (4-methoxyphenyl) amine, bis (2-ethoxyphenyl) ) Amine, bis (3-ethoxyphenyl) amine, bis (4-ethoxyphenyl) amine. A phosphine compound in which a nitrogen atom is substituted by a phosphorus atom can also be exemplified. These phosphine compounds are compounds represented by rewriting the amine in the above specific examples with phosphine.
[0061]
Examples of alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, octanol, dodecanol, pentadecanol, eicosanol and the like. A thiol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiol compounds are compounds represented by rewriting the above-mentioned specific examples of knol with thiol.
[0062]
As phenols, phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4,6-trimethylphenol, 3,4,5-trimethylphenol, 2,3,5,6-tetramethylphenol, pentamethylphenol, 2, 6-di-t-bryl-4-methylphenol, 1-naphthol, 2-naphthol, 4,5,6,7,8-pentamethyl-2-naphthol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxy Phenol, 2,3-dimethoxyphenol, 2,4-dimethoxyphenol, 2,5 Dimethoxyphenol, 2,6-dimethoxyphenol, 3,4-dimethoxyphenol, 3,5-dimethoxyphenol, 2,4,6-trimethoxyphenol, 3,4,5-trimethoxyphenol, 2,3,5 6-tetramethoxyphenol, pentamethoxyphenol, 4,5,6,7,8-pentamethoxy-2-naphthol and the like can be mentioned. A thiophenol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiophenol compounds are compounds represented by rewriting phenol in the above specific examples with thiophenol (in the case of naphthol, compounds represented by rewriting naphthol with naphthylthiol) and the like.
[0063]
As the compound (a ′), preferably, the amines are dimethylamine, diethylamine, dipropylamine, diphenylamine, bis (4-methylphenyl) amine, or bis (4-methoxyphenyl) amine, and the alcohols are methanol , Ethanol, propanol, n-butanol, isobutanol, t-butanol, or hexanol; phenols such as phenol, 4-methylphenol, 2,6-dimethylphenol, 3,5-dimethylphenol, 2,4,6 -Trimethylphenol, pentamethylphenol or 2,6-di-t-butyl-4-methylphenol is used.
[0064]
More preferably, the compound (a ') is dimethylamine, diethylamine, diphenylamine, methanol, ethanol, n-butanol, t-butanol, phenol, 2,6-dimethylphenol, or 2,6-di-t-butyl-4. -Methylphenol is used, more preferably, diethylamine, diphenylamine, methanol, ethanol, phenol, or 2,6-di-t-butyl-4-methylphenol is used, and particularly preferably, methanol, ethanol, or phenol is used. Can be
[0065]
When the particles (d) are contact-treated with (a '), an accelerator for improving the reactivity of (a') may be used. As the accelerator used at this time, a compound having no nitrogen and having no active hydrogen is preferable. Specific examples of the accelerator include trialkylamines such as trimethylamine and triethylamine, and heterocyclic compounds having a nitrogen atom in the ring such as pyridine and lutidine, and one or more of these are preferably used.
[0066]
The modified particles of the present invention are modified particles obtained by contacting the above (a), (b), (c) and (d ').
The order in which (a), (b), (c) and (d ') are brought into contact is not particularly limited, and the following order and the like can be mentioned.
<1> A contact product obtained by bringing a contact product of (a) and (b) into contact with (c) and (d ').
<2> A contact product obtained by bringing (a) and (b) into contact with (d ') and (c) into contact with (c).
<3> (d ') is brought into contact with a contact product obtained by bringing (a) and (c) into contact with (b).
<4> (b) is brought into contact with a contact product obtained by bringing a contact product between (a) and (c) into contact with (d ').
<5> A contact substance obtained by contacting a contact substance between (a) and (d ') with (b) is brought into contact with (c).
<6> (b) is brought into contact with a contact substance obtained by bringing a contact substance between (a) and (d ') into contact with (c).
<7> A contact substance obtained by bringing (a) into contact with a contact substance between (b) and (c) and (d ').
<8> A contact substance obtained by contacting a contact substance between (b) and (c) with (d ′) and (a) are brought into contact with (a).
<9> A contact product obtained by contacting a contact product between (b) and (d ') with (a) and (c).
<10> A contact substance obtained by contacting a contact substance between (b) and (d ') with (c) is brought into contact with (a).
<11> A contact product obtained by bringing (a) into contact with a contact product between (c) and (d ') and (b).
<12> (a) is brought into contact with a contact product obtained by bringing a contact product of (c) and (d ') into contact with (b).
The contact order is preferably <1>, <2>, <3>, <5>, <11> or <12>, and particularly preferably <2> or <5>.
[0067]
Such a contact treatment is preferably performed in an inert gas atmosphere. The processing temperature is usually -100 to 300C, preferably -80 to 200C. The processing time is generally 1 minute to 200 hours, preferably 10 minutes to 100 hours.
In such a treatment, a solvent may be used, or these compounds may be directly treated without using a solvent.
[0068]
As the solvent, a solvent that does not react with each of the components to be brought into contact when the solvent is used or a contact product obtained by the contact is usually used. As described above, when the components are contacted in a stepwise manner, for example, even if the solvent reacts with the above (a), the contact obtained by contacting the above (a) with other components is obtained. The substance may no longer react with the solvent, and in such a case, the solvent can be used as a solvent in a contact operation using the contact substance as one component. Examples of the solvent are shown below, and the solvent may be appropriately used as described above. Examples of solvents that can be used include aliphatic hydrocarbon solvents, non-polar solvents such as aromatic hydrocarbon solvents, or halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, Examples include polar solvents such as nitrile solvents, nitro compounds, amine solvents, and sulfur compounds. Specific examples include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, aliphatic hydrocarbon solvents such as cyclohexane, benzene, toluene, aromatic hydrocarbon solvents such as xylene, dichloromethane, difluoromethane, Halide solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, Dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl-ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran, Ether solvents such as trahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol Alcohol solvents such as ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol and glycerin, phenol solvents such as phenol and p-cresol, acetone, ethyl methyl ketone, cyclohexanone and anhydrous Carbonyl solvents such as acetic acid, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; Samethylphosphoric acid triamide, phosphoric acid derivatives such as triethyl phosphate, acetonitrile, propionitrile, succinonitrile, nitrile solvents such as benzonitrile, nitro compounds such as nitromethane, nitrobenzene, amine solvents such as pyridine, piperidine and morpholine, Sulfur compounds such as dimethyl sulfoxide and sulfolane.
[0069]
(A) When the contact object (e) obtained by bringing (b) and (c) into contact with (d '), that is, in the case of the above <1>, <3>, and <7> In the above, the solvent (s1) for producing the contact product (e) is preferably the above-mentioned aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether-based solvent.
[0070]
On the other hand, a polar solvent is preferable as the solvent (s2) for bringing the contact product (e) into contact with (d '). As an index indicating the polarity of the solvent, E_T ^NValues (C. Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988)), etc., and 0.8 ≧ E_T ^NSolvents satisfying ≧ 0.1 are particularly preferred. Examples of such polar solvents include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, and bromobenzene. , O-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, Tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cycle Hexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, ethylenediamine , Pyridine, piperidine, morpholine, dimethylsulfoxide, sulfolane and the like. More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, ethylene Glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol or triethylene glycol, particularly preferably di-n-butyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or cyclohexanol And most preferably tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.
[0071]
Further, as the solvent (s2), a mixed solvent of these polar solvents and a hydrocarbon solvent can also be used. As the hydrocarbon solvent, the aliphatic hydrocarbon solvents and the aromatic hydrocarbon solvents exemplified above are used. Specific examples of a mixed solvent of a polar solvent and a hydrocarbon solvent include a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a hexane / 1-propanol mixed solvent, a hexane / 2-propanol mixed solvent, and a heptane / methanol mixed solvent. Mixed solvent, heptane / ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent , A xylene / methanol mixed solvent, a xylene / ethanol mixed solvent, a xylene / 1-propanol mixed solvent, a xylene / 2-propanol mixed solvent, and the like. Preferably, hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent is there. More preferred are hexane / methanol mixed solvents, hexane / ethanol mixed solvents, toluene / methanol mixed solvents or toluene / ethanol mixed solvents. Most preferred is a mixed solvent of toluene / ethanol.
The preferred range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, more preferably 15 to 30% by volume.
[0072]
A method of contacting a contact object (e) obtained by bringing (a), (b) and (c) into contact with (d ′), that is, in the case of the above <1>, <3>, and <7> In the above, a hydrocarbon solvent can be used as both the solvent (s1) and the solvent (s2). In this case, after the (a), (b) and (c) are brought into contact with each other, the resulting contact product (e) ) And (d ') are preferably short in time interval until they come into contact with each other. The time interval is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Moreover, the temperature at the time of making contact object (e) and (d ') contact is usually -100 to 40 degreeC, Preferably it is -20 to 20 degreeC, Most preferably, it is -10 to 10 degreeC. ° C.
[0073]
In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, and <12>, any of the above nonpolar solvents and polar solvents may be used. Although possible, non-polar solvents are more preferred. This is because a contact product of (a) and (c) or a contact product of (a) and (b) and a contact product of (c) generally have solubility in a nonpolar solvent. When (d ') is present in the reaction system when these contacts are formed, it is more stable to deposit the formed contacts on the (d') surface than in the nonpolar solvent. Therefore, it is considered that it is more likely to be fixed, which is preferable.
[0074]
As the solvent when the particles (d) are brought into contact with (a '), the above-mentioned aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents or ether solvents are preferable.
[0075]
The amount of the compound (a ') used should be at least one mole of the functional group having active hydrogen or the non-proton donating Lewis basic functional group contained in (d). Is preferably 1.25 to 100 times the molar number, and more preferably 5 to 50 times the molar number, and the amount may be appropriately determined so as to fall within the above range. When the accelerator is used, the amount thereof is preferably 0.5 times or more, and more preferably 0.75 to 5 times the amount of (a '). More preferably, it is particularly preferably 0.9 to 1.5 times the molar number.
[0076]
The contact between the compound (a ') and the particles (d) is preferably carried out under an inert atmosphere. The temperature and time for contacting may be appropriately selected as long as the reaction proceeds sufficiently, and the temperature is preferably from -20 ° C to 150 ° C, more preferably from 0 ° C to 130 ° C. The time is preferably 30 minutes or more, more preferably 1 hour to 8 hours.
[0077]
After the particles (d) are brought into contact with the compound (a '), a washing operation is preferably performed to remove unreacted (a'). In this case, any solvent can be used, but the solvent used as the reaction solvent is more preferable.
[0078]
For simplicity, the particles (d ') thus obtained can be subjected to a contact treatment with other components in a slurry state or a wet cake state without completely removing the solvent.
[0079]
The amount of each compound used in (a), (b) and (c) is not particularly limited, but the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: y: z In this case, it is preferable that y and z substantially satisfy the following formula (1).
| My−2z | ≦ 1 (1)
(In the above formula (1), m is M¹Represents the number corresponding to the valence of 価)
Y in the above formula (1) is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and even more preferably a number of 0.20 to 1.50. Yes, most preferably a number from 0.30 to 1.00, and a similar preferred range of z in the above formula (1) is determined by m, y and the above formula (1).
[0080]
In actual contact treatment of each compound, even if the use of each compound is intended so as to completely satisfy the above formula (1), the use amount may fluctuate slightly, and unreacted residual It is common practice to slightly increase or decrease the amount of use as appropriate in consideration of the amount of the compound to be converted. Here, "substantially satisfying the formula (1)" means that each compound is obtained by bringing each compound into contact with each other at a molar ratio satisfying the formula (1) without completely satisfying the formula (1). It is meant to include when it is intended to obtain such an object.
[0081]
In the preparation of the modified particles of the present invention, the amount of (d ′) used for (a) is included in the particles obtained by contacting (a) with (d ′). It is preferable that the amount of the typical metal atom derived from is, in terms of the number of moles of the typical metal atom contained in 1 g of the obtained particles, 0.1 mmol or more, more preferably 0.5 to 20 mmol. Since it is preferable, it may be appropriately determined so as to fall within the range.
[0082]
After the contact treatment as described above, heating is also preferably performed to further promote the reaction. At the time of heating, it is preferable to use a solvent having a higher boiling point in order to raise the temperature, and the solvent used for the contact treatment may be replaced with another solvent having a higher boiling point.
[0083]
As the modified particles of the present invention, even if the raw materials (a), (b), (c) and / or (d ') remain as unreacted substances as a result of such contact treatment, Good. However, when the present invention is applied to polymerization involving the formation of addition polymer particles, it is preferable to carry out a washing treatment for removing unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such a cleaning treatment is preferably performed in an inert gas atmosphere. The processing temperature is usually -100 to 300C, preferably -80 to 200C. The processing time is generally 1 minute to 200 hours, preferably 10 minutes to 100 hours.
[0084]
Further, after such a contact treatment or a washing treatment, it is preferable that the solvent is distilled off from the product, and then drying is performed at a temperature of 25 ° C. or more under reduced pressure for 1 hour to 24 hours. More preferably 1 hour to 24 hours at a temperature of 40 ° C to 200 ° C, further preferably 1 hour to 24 hours at a temperature of 60 ° C to 200 ° C, particularly preferably 2 hours to 18 hours at a temperature of 60 ° C to 160 ° C. It is most preferable to carry out drying at a temperature of 80C to 160C for 4 hours to 18 hours.
[0085]
Specific examples of the method for producing the modified particles of the present invention¹Is a zinc atom, compound (a ′) is phenol, compound (b) is pentafluorophenol, compound (c) is water, and particles (d) are silica. Shown in Toluene was used as a solvent, a hexane solution of diethylzinc was added thereto, and the mixture was cooled to 5 ° C., and pentafluorophenol was added thereto in a 0.5-fold molar amount with respect to diethylzinc and stirred at room temperature for 10 minutes to 24 hours. After that, silica previously contacted with phenol using toluene as a solvent is added thereto, and 0.75 times the molar amount of water with respect to diethylzinc is added dropwise, followed by stirring at room temperature for 10 minutes to 24 hours. Thereafter, the solvent is distilled off, and drying is performed at 120 ° C. under reduced pressure for 4 hours. Thus, the modified particles of the present invention can be produced.
[0086]
The modified particles of the present invention can be used as a carrier for supporting a catalyst component for addition polymerization comprising a transition metal compound forming a single-site catalyst, and are suitably used for polymerization accompanied by the formation of addition polymer particles. Further, the modified particles of the present invention are useful as a catalyst component for addition polymerization (among others, a catalyst component for olefin polymerization). Specific examples of the addition polymerization catalyst of the present invention include an addition polymerization catalyst obtained by contacting the above-mentioned modified particles (A) with a Group 3-11 or lanthanoid-based transition metal compound (B). A catalyst; and addition polymerization obtained by contacting the above-mentioned modified particles (A), a group 3-11 or lanthanoid-based transition metal compound (B), and an organoaluminum compound (C). Catalysts, the latter being more active and preferred.
Hereinafter, the addition polymerization catalyst will be described in more detail.
[0087]
(B) Group 3-11 or lanthanoid series transition metal compounds
As the transition metal compound (B) of Group 3 to 11 or a lanthanoid series used for the addition polymerization catalyst of the present invention, a transition metal compound forming a single-site catalyst is used, and the modified particles (A) ( Alternatively, there is no particular limitation as long as it is a Group 3-11 or lanthanoid-based transition metal compound that exhibits addition polymerization activity by using an organoaluminum compound (C)) as an activating co-catalyst component. The single-site catalyst referred to here is a concept distinguished from a conventional solid catalyst, and has a narrow molecular weight distribution and, in the case of copolymerization, not only a narrow-sense single-site catalyst in which an addition polymer having a narrow composition distribution is obtained. As long as the catalyst is obtained by an adjustment method similar to that of a single-site catalyst in such a narrow sense, an addition polymer having a wide molecular weight distribution or a catalyst capable of obtaining an addition polymer having a wide composition distribution in the case of copolymerization is also included. .
[0088]
As the transition metal compound (B), a transition metal compound represented by the following general formula [5] or a μ-oxo type transition metal compound dimer thereof is preferable.
L² _aM²X¹ _b[5]
(Where M²Is a transition metal atom belonging to Groups 3 to 11 of the periodic table or a lanthanoid series. L²Is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L²May be directly connected to each other or may be connected via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. X¹Represents a halogen atom, a hydrocarbon group (however, excluding a group having a cyclopentadiene-type anion skeleton) or a hydrocarbon oxy group. a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8.
[0089]
In general formula [5], M²Is a transition metal atom belonging to Groups 3 to 11 of the periodic table (IUPAC 1989) or a lanthanoid series. Specific examples thereof include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel, and palladium atoms. , Samarium atom, ytterbium atom and the like. M in general formula [5]³Are preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a chromium atom, an iron atom, a cobalt atom or a nickel atom, particularly preferably a titanium atom, a zirconium atom or a hafnium atom, and most preferably a zirconium atom. is there.
[0090]
In the general formula [5], L²Is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and²May be the same or different. Also multiple L²May be directly connected to each other or may be connected via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
[0091]
L²The group having a cyclopentadiene-type anion skeleton in is η⁵-(Substituted) cyclopentadienyl group, η⁵-(Substituted) indenyl group, η⁵-(Substituted) fluorenyl group and the like. To give a concrete example, η⁵-Cyclopentadienyl group, η⁵-Methylcyclopentadienyl group, η⁵-Ethylcyclopentadienyl group, η⁵-N-butylcyclopentadienyl group, η⁵-Tert-butylcyclopentadienyl group, η⁵-1,2-dimethylcyclopentadienyl group, η⁵-1,3-dimethylcyclopentadienyl group, η⁵-1-methyl-2-ethylcyclopentadienyl group, η⁵-1-methyl-3-ethylcyclopentadienyl group, η⁵-1-tert-butyl-2-methylcyclopentadienyl group, η⁵-1-tert-butyl-3-methylcyclopentadienyl group, η⁵-1-methyl-2-isopropylcyclopentadienyl group, η⁵-1-methyl-3-isopropylcyclopentadienyl group, η⁵-1-methyl-2-n-butylcyclopentadienyl group, η⁵-1-methyl-3-n-butylcyclopentadienyl group, η⁵-1,2,3-trimethylcyclopentadienyl group, η⁵-1,2,4-trimethylcyclopentadienyl group, η⁵-Tetramethylcyclopentadienyl group, η⁵-Pentamethylcyclopentadienyl group, η⁵-Indenyl group, η⁵-4,5,6,7-tetrahydroindenyl group, η⁵-2-methylindenyl group, η⁵-3-methylindenyl group, η⁵-4-methylindenyl group, η⁵-5-methylindenyl group, η⁵-6-methylindenyl group, η⁵-7-methylindenyl group, η⁵-2-tert-butylindenyl group, η⁵-3-tert-butylindenyl group, η⁵-4-tert-butylindenyl group, η⁵-5-tert-butylindenyl group, η⁵-6-tert-butylindenyl group, η⁵-7-tert-butylindenyl group, η⁵-2,3-dimethylindenyl group, η⁵-4,7-dimethylindenyl group, η⁵-2,4,7-trimethylindenyl group, η⁵-2-methyl-4-isopropylindenyl group, η⁵-4,5-benzindenyl group, η⁵-2-methyl-4,5-benzindenyl group, η⁵-4-phenylindenyl group, η⁵-2-methyl-5-phenylindenyl group, η⁵-2-methyl-4-phenylindenyl group, η⁵-2-methyl-4-naphthylindenyl group, η⁵-Fluorenyl group, η⁵-2,7-dimethylfluorenyl group, η⁵-2,7-di-tert-butylfluorenyl group and substituted products thereof. In this specification, the name of the transition metal compound is "η⁵"-" May be omitted.
[0092]
Examples of the hetero atom in the group containing a hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom, and such a group includes an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, and an alkyl group. Amino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, or aromatic or aliphatic heterocyclic group having an oxygen, sulfur, nitrogen, and / or phosphorus atom in the ring Is preferred.
[0093]
Specific examples of the group containing a hetero atom include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a 2-methylphenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethyl group. Phenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,6 -Di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,5 -Dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitrophen A xy group, a 2-aminophenoxy group, a 3-aminophenoxy group, a 4-aminothiophenoxy group, a 2,3,6-trichlorophenoxy group, a 2,4,6-trifluorophenoxy group, a thiomethoxy group, a dimethylamino group, Diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, resorcinol, 4- Isopropyl catechol, 3-methoxy catechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol group, 2,2 ′ -Dihydroxy-6,6'-dimethylbiphenyl group, 4,4 ', 6,6'-te La -tert- butyl 2,2 'methylenedianiline phenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group and the like.
[0094]
Examples of the group containing a hetero atom include a group represented by the following general formula [6].
R⁴ ₃P = N- [6]
(Where R⁴Represents a hydrogen atom, a halogen atom or a hydrocarbon group in each case, which may be the same as or different from each other, two or more of which may be bonded to each other, forming a ring, Is also good. )
[0095]
R in the general formula [6]⁴Specific examples of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a cyclopropyl group, Examples include, but are not limited to, cyclobutyl, cycloheptyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, benzyl and the like.
[0096]
Examples of the group containing a hetero atom include a group represented by the following general formula [7].

(Where R⁵Represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbonoxy group, a silyl group or an amino group in each case, which may be the same or different from each other; Two or more of them may be bonded to each other or form a ring. )
[0097]
R in the general formula [7]⁵Examples of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tert-butyl group, a 2,6-dimethylphenyl group, Fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group, triethylsilyl group, diphenylmethylsilyl Groups, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, pentafluorophenyl group, and the like, but are not limited thereto.
[0098]
The chelating ligand refers to a ligand having a plurality of coordination sites, specifically, acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, triethylenetetramine, Porphyrin, crown ether, cryptate and the like.
[0099]
Specific examples of the heterocyclic group include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and are preferably a pyridyl group.
[0100]
Groups having a cyclopentadiene-type anion skeleton, a group having a cyclopentadiene-type anion skeleton and a group containing a hetero atom, or groups containing a hetero atom may be directly connected to each other, and may be a carbon atom, a silicon atom, It may be connected via a residue containing an atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Preferably such residues are two L²原子 is a divalent residue having a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably two L²The atom bonded to is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom;²A divalent residue having a minimum number of atoms of 3 or less between atoms bonding to (this includes two L²Includes the case where the atom bonded to is single. ). Specifically, alkylene groups such as methylene group, ethylene group and propylene group, substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group, or silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group Group, a substituted silylene group such as a tetramethyldisilylene group, a dimethoxysilylene group, or a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Particularly preferred are a methylene group, an ethylene group, and a dimethylmethylene group. (Isopropylidene group), diphenylmethylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group or dimethoxysilylene group.
[0101]
X in general formula [5]¹Represents a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton), or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Here, the hydrocarbon group does not include a group having a cyclopentadiene-type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Preferably, the hydrocarbon group is an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon atom. An aryl group having 6 to 20 or an alkenyl group having 3 to 20 carbon atoms is preferable.
[0102]
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl Group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, Examples include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, a perbromopropyl group, and the like.
All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.
[0103]
Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl, and (2,3-dimethylphenyl). ) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3 , 5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3 , 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, and the like, More preferably, it is a benzyl group.
All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.
[0104]
Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, and 2,5-xylyl. Group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethyl Phenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, , 3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl Nyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, anthracenyl And more preferably a phenyl group.
All of these aryl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.
[0105]
Examples of the alkenyl group having 3 to 20 carbon atoms include an allyl group, a methallyl group, a crotyl group, a 1,3-diphenyl-2-propenyl group, and more preferably an allyl group or a methallyl group.
[0106]
Examples of the hydrocarbon oxy group herein include an alkoxy group, an aralkyloxy group and an aryloxy group, preferably an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms or carbon atom. An aryloxy group having 6 to 20 atoms is preferred.
[0107]
Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and a neopentoxy group. , N-hexoxy group, n-octoxy group, n-dodecoxy group, n-pentadesoxy group, n-icosoxy group and the like, and more preferably methoxy group, ethoxy group, isopropoxy group, or tert-butoxy group. .
Each of these alkoxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. May be partially substituted.
[0108]
Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group, a (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl Phenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like. And more preferably a benzyloxy group.
All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.
[0109]
Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, and a 2,4-dimethylphenoxy group 2,2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl -4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethyl Phenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di -Tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3 2,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, Isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, And an anthracenoxy group.
All of these aryloxy groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.
[0110]
X¹More preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, trifluoromethoxy group Phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4-pentafluoro It is a phenylphenoxy group or a benzyl group.
[0111]
In the general formula [5], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and M²It is appropriately selected according to the valence of. M²When is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.
[0112]
Among the transition metal compounds represented by the general formula [5], specific examples of the compound in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclohexane). (Pentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2- Dimethylcyclopentadienyl) titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethyl) Cyclopentadienyl) titanium Chloride, bis (1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclo) Pentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl) -3-methylcyclopentadienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethyl Cyclopentadienyl) titanium dichloro Id, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenyl) Indenyl) titanium dichloride,
[0113]
Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindenyl) Nil) titanium dichloride,
[0114]
Dimethylsilylenebis (cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (tetramethylcyclopentadienyl) titanium dichloride,
[0115]
Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylenebis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylenebis (2-phenylindenyl) titanium dichloride, dimethylsilylenebis (4-phenyl Indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,
[0116]
Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra) Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (Indenyl) (fluorenyl) titanium dichloride, dimethylsilylenebis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) ) Titanium dichloride,
[0117]
Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) ) Titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thio Njikuroraido, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,
[0118]
Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl) -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2 -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,
[0119]
Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentane) Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl Down (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,
[0120]
Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentane) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5- (Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) ( 3,5-diamil- -Phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride,
[0121]
Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentane) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dime Rusilylene (tert-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,
[0122]
Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-) Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1- Naphthoxy-2-yl) titanium dichloride,
[0123]
Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, Rusilylene (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadiene) Enyl) (1-naphthoxy-2-yl) titanium dichloride,
[0124]
Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl Dimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride Dimethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (1-naphthoxy-2-yl) titanium dichloride,
[0125]
Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) ( -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,
[0126]
(Tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyl titanium dichloride,
(Tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert-butylamido) (Butylamido) indenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) Butylamido) indenyldimethylsilanetitanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilanetitanium dichloride (Tert- butylamido) fluorenyl dimethylsilane titanium dichloride,
[0127]
(Dimethylaminomethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyltitanium (III) dichloride (N-pyrrolidinylethyl) tetramethylcyclopentadienyltitanium dichloride, (B-dimethylaminoborabenzene) cyclopentadienyltitanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) titanium dichloride,
[0128]
2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2′-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2′-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2′-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2′-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2 '-(4,4', 6,6'-tetra-tert-butyl-1,1'bipheno Shi) titanium dichloride, (di -tert- butyl-1,3-propane diamide) titanium dichloride, (dicyclohexyl-1,3-propane diamide) titanium dichloride,
[0129]
[Bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1, 3-propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide ] Titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [hydrotris (3 -Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [tris (3 , 5-Dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride and the like A compound in which titanium of these compounds is changed to zirconium or hafnium, (2-phenoxy) is (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl) -2-phenoki ), Methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene or a compound changed to dimethoxysilylene, dichloride to difluoride, dibromide, diiodide, dimethyl, diethyl, Compounds obtained by changing diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), diphenoxide, or di (pentafluorophenoxide), and trichloride to trifluoride, tribromide, and tria Iodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, triethoxide, tri (n-propoxide), tri ( Compounds changed to isopropoxide), triphenoxide, or tri (pentafluorophenoxide) can be exemplified.
[0130]
Among the transition metal compounds represented by the general formula [5], specific examples of the compound in which the transition metal atom is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′- Dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5 , 5'-Di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dibromide, 2,2'-methylenebis [( 4R) -4-phenyl-5,5'-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- -Phenyl-5,5'-dimethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [ (4R) -4-phenyl-5,5'-diphenyloxazoline] nickel dibromide,
[0131]
2,2′-methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5 5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, , 2'-methylenebis [(4R) -4-methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-methyl-5,5 -Di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-methyl-5,5-di- (4-methoxyphenyl) Xazoline] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4 -Methyloxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel dibromide,
[0132]
2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline], 2,2'-methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5- Diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4- Sopropyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) Oxazoline] nickel dibromide,
[0133]
2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] Nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl- 5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-isobutyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2'-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxa Phosphorus] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methoxyphenyl) oxazoline Nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide,
[0134]
2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-diethyloxazo ] Nickel dibromide, 2,2'-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2′-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- ( 2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl 5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) oxazoline Nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4 -Methoxyphenyl) oxazoline] nickel dibromide,
[0135]
2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyl] Oxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1'-cycloheptane}] nickel dibromide,
[0136]
2,2′-methylenebis [(4R) -4-phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-f Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibro Ido,
[0137]
2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4-phenyloxazoline-5,1′-cycloheptane}] nickel dibromide,
[0138]
2,2′-methylenebis [(4R) -4-benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-b Jill-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibro Ido,
[0139]
2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4-benzyloxazoline-5,1′-cycloheptane}] nickel dibromide and enantiomers of the above compounds. Compounds in which the asymmetric carbon of one of the oxazoline rings of the bisoxazoline-type compound has the opposite configuration, or dibromide of these compounds is difluoride, dichloride, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl , Dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), diphenoxide, or a compound changed to di (pentafluorophenoxide).
[0140]
Further, specific examples of the nickel compound include [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, and [hydrotris (3,5-di-tert-borate)]. [Butyl pyrazolyl) borate] nickel chloride and compounds obtained by changing chlorides of these compounds to bromide, iodide, methyl, ethyl, allyl, or methallyl.
[0141]
Examples of the nickel compound include a compound represented by the following structural formula.

(Where R⁶And R⁷Each represents a 2,6-diisopropylphenyl group;⁸And R⁹Represents a hydrogen atom or a methyl group or R⁸And R⁹And together form an acenaphthene group, and X²Is a fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methoxy, ethoxy, or phenoxy group . )
Further, compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium in the above nickel compounds can also be exemplified.
[0142]
Among the transition metal compounds represented by the general formula [5], specific examples of the compound in which the transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine Iron dichloride, 2,6-bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridineiron dichloride, 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron Examples include dichloride and compounds obtained by changing dichloride of these compounds to difluoride, dibromide, diiodide, dimethyl, diethyl, dimethoxide, diethoxide, or diphenoxide.
[0143]
Further, specific examples of iron compounds include [hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, and [hydrotris (3,5-di-tert-borate)]. [Butyl pyrazolyl) borate] iron chloride and the like, and compounds obtained by changing the chloride of these compounds to fluoride, bromide, iodide, methyl, ethyl, allyl, methallyl, methoxide, or ethoxide.
In the above-mentioned iron compounds, compounds in which iron is replaced with cobalt or nickel can also be exemplified.
[0144]
Specific examples of the transition metal compound of the μ-oxo type represented by the general formula [5] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chloride], μ-oxobis [ Sopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) tita Chloride], .mu. Okisobisu [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and the like. Examples of the compounds in which chloride of these compounds is changed to fluoride, bromide, iodide, methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, phenoxide, or pentafluorophenoxide can do.
[0145]
When the compound used as the transition metal compound (B) is exemplified in addition to the transition metal compound represented by the general formula [5] and the μ-oxo type transition metal compound thereof, the transition metal atom is a nickel atom. Compounds that are nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate, nickel trifluoroacetate, nickel cyanide, nickel oxalate, nickel acetylacetonate, bis (allyl) Nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dichlorobis (acetonitrile) nickel, dichlorobis (benzonitrile) nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis ( Triethylphosph Nickel), diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] Nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis (diphenylphosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, nickel Phthalocyanine and the like.
[0146]
Similarly, specific examples of the compound in which the transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, vanadium oxytrichloride, and the like.
Further, specific examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran.
Specific examples of the compound in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.
[0147]
These transition metal compounds may be used alone or in combination of two or more.
[0148]
Of the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above general formula [5]. Among them, M in the above general formula [5]²A transition metal compound in which is a Group 4 atom is preferable, and in particular, L in the general formula [5]²As, a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton is preferable.
[0149]
(C) Organoaluminum compound
As the component (C) organoaluminum compound used in the addition polymerization catalyst of the present invention, a known organoaluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula [8].
R¹⁰ _cAlY_3-c[8]
(Where R¹⁰Represents a hydrocarbon group, and all R¹⁰May be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, or an aryloxy group, and all Y may be the same or different. c represents a number satisfying 0 <c ≦ 3. )
[0150]
R in the general formula [8] representing an organoaluminum compound¹⁰Is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-hexyl group, a 2-methylhexyl group, and an n-octyl group. -Butyl, isobutyl, n-hexyl or n-octyl.
[0151]
Specific examples of the case where Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
The alkoxy group in Y is preferably an alkoxy group having 1 to 24 carbon atoms, and specific examples include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert -Butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, preferably methoxy group, ethoxy group or tert group. -A butoxy group.
[0152]
The aryloxy group for Y is preferably an aryloxy group having 6 to 24 carbon atoms, and specific examples thereof include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, and 2,3. -Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4 -Trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5 -Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group , 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy , N-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.
[0153]
The aralkyloxy group for Y is preferably an aralkyloxy group having 7 to 24 carbon atoms, and specific examples include, for example, a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, and a (4) -Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group , (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6- (Methylmethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy Group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group , (Tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group , Anthracenyl methoxy group and the like, and preferably a benzyloxy group. That.
[0154]
Specific examples of the organoaluminum compound represented by the general formula [8] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-aluminum. Trialkylaluminums such as -n-octylaluminum; dialkylaluminums such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminumchloride Chloride; methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum Alkyl aluminum dichlorides such as mudichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n- Dialkyl aluminum hydride such as hexyl aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum and methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum And dimethyl (tert-butoxy) aluminum Alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methyl bis (2, 6-diisopropylphenoxy) aluminum, methyl bis (2, 6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl ( Examples thereof include dialkyl (aryloxy) aluminums such as 2,6-diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum.
[0155]
Of these, trialkylaluminum is preferable, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum is particularly preferable. Is triisobutylaluminum or tri-n-octylaluminum.
These organoaluminum compounds may be used alone or in combination of two or more.
[0156]
The amount of component (B) used is usually 1 × 10^-6~ 1 × 10^-3mol, preferably 5 × 10^-6~ 5 × 10^-4mol. The amount of the component (C) used is 0.01 to 10 as a molar ratio (C) / (B) of the component (C) aluminum atom to the transition metal atom of the component (B) transition metal compound. 000, more preferably 0.1 to 5,000, and most preferably 1 to 2,000.
[0157]
As the catalyst for addition polymerization of the present invention, a reaction product obtained by previously contacting component (A) and component (B), and optionally component (C) may be used. May be used. When components (A), (B) and (C) are used, any two of them may be brought into contact beforehand and then the other component is brought into contact.
[0158]
The method for supplying each catalyst component to the catalyst preparation reactor or the polymerization reactor is not particularly limited. A method in which each component is supplied in a solid state, a method in which a solution is dissolved in a hydrocarbon solvent from which components for deactivating catalyst components such as moisture and oxygen have been sufficiently removed, or a method in which the components are suspended or slurryed And the like. Examples of the solvent at this time include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane; aromatic hydrocarbon solvents such as benzene and toluene; and halogenated hydrocarbons such as methylene chloride. Hydrocarbons or aromatic hydrocarbons are preferred.
[0159]
When each catalyst component is supplied in the form of a solution, or a suspension or slurry, the concentration of the component (A) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. The concentration of the component (C) is usually 0.0001 to 100 mol / l, preferably 0.01 to 10 mol / l in terms of Al atom. The concentration of the component (B) is usually 0.0001 to 1000 mmol / L, preferably 0.01 to 50 mmol / L in terms of transition metal atoms.
[0160]
The polymerization method is not particularly limited, and gas-phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible. Solvents used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, hexane, pentane, heptane, and octane; aromatic hydrocarbon solvents such as benzene and toluene; and halogenated hydrocarbon solvents such as methylene chloride. Or olefin itself can be used as a solvent (bulk polymerization). The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages under different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can range from 1 minute to 20 hours.
[0161]
The present invention is particularly suitably applied to polymerization involving formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, and the like).
Slurry polymerization may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. As a preferred polymerization method in the slurry method, a continuous reactor in which a monomer (and a comonomer), a feed, a diluent, and the like are continuously added as necessary, and a polymer product is continuously or at least periodically removed. included. Examples of the reactor include a method using a loop reactor and a method using a stirring reactor. Further, a plurality of stirred reactors having different reactors or different reaction conditions may be used in series or in parallel, or a combination thereof.
[0162]
As diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature of the polymerization reactor or reaction zone can usually range from about 0C to about 150C, preferably from 30C to 100C. The pressure can usually be varied from about 0.1 MPa to about 10 MPa, preferably from 0.5 MPa to 5 MPa. The catalyst can be kept in suspension, the medium and at least some of the monomers and comonomers can be maintained in a liquid phase, and pressure can be applied to bring the monomers and comonomers into contact. Thus, the medium, temperature, and pressure may be selected so that the addition polymer is produced as solid particles and recovered in that form.
[0163]
The molecular weight of the addition polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen.
Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and a monomer (and a comonomer) to the reaction zone, a method of sequentially adding the components, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere before contacting with the monomer (and comonomer).
[0164]
The gas phase polymerization may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto. As the gas phase polymerization reactor, a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion is used. There is no problem even with a reactor in which a stirring blade is installed in the reaction tank.
As a method of supplying each component to the polymerization tank, usually, an inert gas such as nitrogen or argon, hydrogen, ethylene or the like is used to supply the components in a water-free state, or dissolved or diluted in a solvent to prepare a solution or slurry. A method such as supplying in a state can be used. Each catalyst component may be supplied individually, or any components may be contacted in any order in advance and supplied.
[0165]
As the polymerization conditions, the temperature is lower than the temperature at which the polymer melts, preferably from 0 ° C to 150 ° C, particularly preferably from 30 ° C to 100 ° C. Further, hydrogen may be added as a molecular weight regulator for the purpose of controlling the melt fluidity of the final product. In addition, at the time of polymerization, an inert gas may be allowed to coexist in the mixed gas.
[0166]
In the present invention, the preliminary polymerization described below may be performed before the polymerization (main polymerization) is performed.
[0167]
The prepolymerization is carried out by supplying a small amount of olefin in the presence of the modified particles (A) and the transition metal compound (B) or in the presence of the organoaluminum compound (C). It is preferred to do so. Examples of the solvent used for slurrying include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, at the time of slurrying, a liquid olefin can be used instead of part or all of the inert hydrocarbon solvent.
[0168]
The amount of the organoaluminum compound (C) used in the prepolymerization can be selected from a wide range such as 0.5 to 700 mol per mol of the transition metal compound (B), but is preferably 0.8 to 500 mol. Particularly preferred is 1 to 200 mol.
[0169]
The amount of the olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g per 1 g of the modified particles.
[0170]
The slurry concentration at the time of performing the prepolymerization is preferably from 0.1 to 50 g-the above-mentioned modified particles / liter-solvent, particularly preferably from 0.5 to 20 g-the above-mentioned modified particles / liter-solvent. . The pre-polymerization temperature is preferably from -20C to 100C, particularly preferably from 0C to 80C. Further, the partial pressure of the olefin in the gas phase during the prepolymerization is preferably from 0.001 MPa to 2 MPa, particularly preferably from 0.01 MPa to 1 MPa. Not as long. Further, the prepolymerization time is not particularly limited, but is usually preferably from 2 minutes to 15 hours.
[0171]
When performing the prepolymerization, the modified particles (A), the transition metal compound (B), the organoaluminum compound (C), and the method for supplying the olefin include the modified particles (A). And after contacting the transition metal compound (B) with the transition metal compound (B) or, if necessary, the organoaluminum compound (C). A), a method of supplying an organoaluminum compound (C) after contacting a transition metal compound (B) and an olefin, and a method of supplying an organoaluminum compound (C) and a transition metal compound (B) in the presence of an olefin. After contacting, any method such as a method of supplying the above-mentioned modified particles (A) may be used, but the above-mentioned modified particles (A) and the organoaluminum compound (C) may be used. Contact It is preferable that the olefin is present in advance when to. As a method for supplying the olefin, either a method of sequentially supplying the olefin while maintaining the inside of the polymerization tank at a predetermined pressure or a method of initially supplying a predetermined amount of the olefin at all is used. good. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the obtained polymer.
[0172]
In the present invention, the product obtained by the prepolymerization in this manner is used as a catalyst component or as a catalyst. The pre-polymerized catalyst component according to the present invention is prepared in the presence of a primary catalyst obtained by bringing the above-mentioned modified particles (A) into contact with a group 3-11 or lanthanoid-based transition metal compound (B). A prepolymerized addition polymerization catalyst component obtained by prepolymerizing an olefin, or the above-mentioned modified particles (A), a Group 3-11 or lanthanoid-based transition metal compound (B), and an organic compound. A prepolymerized addition polymerization catalyst component obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting an aluminum compound (C). The pre-polymerized catalyst according to the present invention can be obtained by contacting the modified particles (A) with a group 3-11 or lanthanoid-based transition metal compound (B) in the presence of a primary catalyst. A catalyst for addition polymerization obtained by prepolymerizing an olefin, or the above-mentioned modified particles (A), a transition metal compound of group 3 to 11 or a lanthanoid series (B), and an organoaluminum compound (C) ) Is an addition polymerization catalyst obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting the olefin. The catalyst using the prepolymerized addition polymerization catalyst component according to the present invention is the prepolymerized addition polymerization catalyst component and the addition polymerization catalyst obtained by contacting the organoaluminum compound (C).
[0173]
The method for producing an addition polymer of the present invention is a method for producing an addition polymer in which an addition-polymerizable monomer is subjected to addition polymerization in the presence of the above-mentioned catalyst for addition polymerization of the present invention.
Examples of the monomers used for the polymerization include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers, and the like, and two or more monomers can be used at the same time.
[0174]
Specific examples of these include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. And olefins such as 1-decene; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, 5-methylene- 2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, i Diolefins such as prene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, and 1,3-cyclohexadiene; norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene , 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8- Methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl-2-norbornene, 5 -Methyl-5-methoxycarbonyl-2- Cyclic olefins such as rubornene, 5-cyano-2-norbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2-phenylpropylene, Alkenylbenzenes such as -phenylbutene and 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, α-methylstyrene, 2, 4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, 1,1-diphenylethylene, p-tertiary butylstyrene, p-Alkylstyrenes such as secondary butylstyrene, divinylbenzene Alkenyl aromatic hydrocarbons such as bisalkenylbenzene such as alkenylnaphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo (2,2,1) Α, β-unsaturated carboxylic acids such as -5-heptene-2,3-dicarboxylic acid and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium and calcium, methyl acrylate, ethyl acrylate and acrylic acid α such as n-propyl, isopropyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate , Β-unsaturated carboxylic acid ester , Maleic acid, unsaturated dicarboxylic acids such as itaconic acid, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate and other vinyl esters, glycidyl acrylate, Examples include polar monomers such as glycidyl carboxylate such as glycidyl methacrylate and monoglycidyl itaconate.
[0175]
The invention applies to the homopolymerization or copolymerization of these monomers. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, propylene and 1-butene, ethylene and propylene and butene, and ethylene and propylene. And 1-hexene, but the present invention should not be limited to these.
[0176]
The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is suitably used in a method for producing an olefin polymer. As such an olefin polymer, a copolymer of ethylene and an α-olefin is particularly preferred, and a copolymer of ethylene and an α-olefin having a polyethylene crystal structure is particularly preferred. The α-olefin referred to herein is preferably an α-olefin having 3 to 8 carbon atoms, and specifically includes 1-butene, 1-hexene, 1-octene and the like.
[0177]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The measured value of each item in the examples was measured by the following method.
[0178]
(1) The content of the repeating unit derived from the α-olefin in the copolymer was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation) based on the characteristic absorption of ethylene and α-olefin. And expressed as the number of short-chain branches per 1000 carbon atoms (SCB).
[0179]
(2) Melt flow rate = MFR: It is a melt flow rate value measured at 190 ° C. under a load of 21.18 N (2.16 kg) in accordance with the method specified in JIS K7210-1995 (unit: g / 10 minutes). .
[0180]
(3) Swell ratio = SR: a value obtained by dividing the strand diameter obtained at the time of MFR measurement by the internal diameter of the die, 2.095 mm.
[0181]
(4) Melt flow rate ratio = MFRR: The melt flow rate value measured at 190 ° C. and a load of 211.82 N (21.60 kg) was calculated according to the method specified in JIS K7210-1995 by a load of 21.18 N (2. 16 kg) divided by the measured melt flow rate (MFR).
In all of the above melt flow rate measurements, a polymer in which an antioxidant was previously blended at 1000 ppm was used.
[0182]
(5) Elemental analysis:
Al, Zn: The sample was poured into a sulfuric acid aqueous solution (1 mol / L), and then subjected to ultrasonic waves to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry.
F: Combustion gas generated by burning a sample in a flask filled with oxygen was absorbed by an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified by an ion electrode method.
[0183]
[Example 1]
(1) Pre-contact between compound (a ') and particles (d)
In a 200-ml four-necked flask purged with nitrogen, ethanol 5.9 ml (0.1 mol), triethylamine 13.9 ml (0.1 mol), and toluene 70 ml were placed under a nitrogen stream, and heated at 300 ° C. Silica (Sylpol 948, manufactured by Davison); average particle diameter = 61 μm; pore volume = 1.70 ml / g; specific surface area = 291 m²/ G) at room temperature. After the addition of silica, the mixture was stirred for 8 hours under reflux with heating. Thereafter, washing with a filter was performed at room temperature three times with toluene 20 ml and three times with hexane 20 ml. Thereafter, the solid component was dried under reduced pressure at 120 ° C. for 4 hours to obtain 4.22 g of the solid component.
[0184]
(2) Synthesis of component (A)
In a 100 ml four-necked flask purged with nitrogen, 32.1 ml of toluene and 5.7 ml (11 mmol) of a hexane solution of diethylzinc (2.0 mol / l) were placed and cooled to 5 ° C. To this, 2.83 ml of a toluene solution of pentafluorophenol adjusted to a concentration of 2.0 mmol / ml was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred at 40 ° C. for 0.5 hour. Then, after the temperature was raised to 5 ° C. in an ice bath, 3.78 g of the solid component obtained in Example 1 (1) was added, and then 5 ml of toluene was added to wash off the solid component attached to the wall of the flask. After stirring for 5 minutes, H₂O 0.15 ml (8.5 mmol) was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C for 1 hour and at 80 ° C for 2 hours. Thereafter, the mixture was allowed to stand, the solid component was allowed to settle, and when the interface between the settled solid component layer and the upper slurry portion was seen, the upper slurry portion was removed, and then the remaining liquid component was removed with a filter. And 50 ml of toluene. Then, it stirred at 95 degreeC for 2 hours. Thereafter, the mixture was allowed to stand at 95 ° C. four times with toluene 50 ml, and at room temperature twice with hexane 50 ml, to settle the solid component, and when the interface between the settled solid component layer and the upper slurry portion was visible. The upper portion of the slurry was removed, and the remaining liquid components were removed with a filter. Thereafter, the solid component was dried under reduced pressure at 120 ° C. for 2 hours to obtain 5.37 g of the component (A).
[0185]
(3) polymerization
After drying under reduced pressure, the inside of a 3-liter autoclave equipped with a stirrer and purged with argon was evacuated, hydrogen was added so that the partial pressure became 0.017 MPa, 695 g of butane and 55 g of 1-butene were charged, and 70 ° C. Temperature. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.06 mol% and 1-butene = 2.89 mol%. To this was added 0.9 ml of a heptane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml. Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml (0.5 ml) was added thereto, followed by the component (A) 9 obtained in Example 1 (2) above. 0.4 mg was charged as a solid catalyst component.
Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.35 mol% of hydrogen so as to keep the total pressure constant. As a result, # 24 g of an olefin polymer having good particle properties was obtained. The polymerization activity per zirconium atom is 2.4 × 10⁷At g / mol Zr / hour, the polymerization activity per solid catalyst component was 2500 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 15.3, MFR = 0.11, MFRR = 157, SR = 1.11.
[0186]
[Example 2]
(1) Pre-contact between compound (a ') and particles (d)
Phenol (5.04 g, 53.5 mmol), triethylamine (7.5 ml, 54 mmol), and toluene (70 ml) were placed in a 200-ml four-necked flask purged with nitrogen under a nitrogen stream, and silica (heat-treated at 300 ° C.) was added thereto. Sypolpol 948, manufactured by Devison Co .; average particle diameter = 61 μm; pore volume = 1.70 ml / g; specific surface area = 291 m²/ G) at room temperature. After the addition of silica, the mixture was stirred for 8 hours under reflux with heating. Thereafter, washing with a filter was performed at room temperature three times with toluene 20 ml and three times with hexane 20 ml. Thereafter, the solid component was dried at 120 ° C. for 4 hours under reduced pressure to obtain 5.20 g of the component (D).
[0187]
(2) Synthesis of component (A)
In a 100-ml four-necked flask purged with nitrogen, 39.4 ml of toluene and 7.0 ml (14 mmol) of a hexane solution of diethylzinc (2.0 mol / l) were placed and cooled to 5 ° C. To this, 3.48 ml of a toluene solution of pentafluorophenol adjusted to a concentration of 2.0 mmol / ml was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred at 40 ° C. for 0.5 hour. Then, after the temperature was raised to 5 ° C. in an ice bath, 4.64 g of the solid component obtained in Example 1 (1) was added, and then 5 ml of toluene was added to wash off the solid component adhered to the flask wall. After stirring for 5 minutes, H₂0.19 ml (10.4 mmol) of O was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C for 1 hour and at 80 ° C for 2 hours. Thereafter, the mixture was allowed to stand, the solid component was allowed to settle, and when the interface between the settled solid component layer and the upper slurry portion was seen, the upper slurry portion was removed, and then the remaining liquid component was removed with a filter. And 50 ml of toluene. Then, it stirred at 95 degreeC for 2 hours. Thereafter, the mixture was allowed to stand at 95 ° C. four times with toluene 50 ml, and at room temperature twice with hexane 50 ml, to settle the solid component, and when the interface between the settled solid component layer and the upper slurry portion was visible. The upper portion of the slurry was removed, and the remaining liquid components were removed with a filter. Thereafter, the solid component was dried under reduced pressure at 120 ° C. for 2 hours to obtain 6.37 g of the component (A).
[0188]
(3) polymerization
After drying under reduced pressure, the inside of a 3-liter autoclave equipped with a stirrer and purged with argon was evacuated, hydrogen was added so that the partial pressure became 0.017 MPa, 695 g of butane and 55 g of 1-butene were charged, and 70 ° C. Temperature. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.20 mol%, 1-butene = 2.76 mol%. To this was added 0.9 ml of a heptane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml. Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml (0.5 ml) was added, and then the component (A) 8 obtained in Example 1 (2) above was added. 0.8 mg was charged as a solid catalyst component.
Polymerization was carried out at 70 ° C. for 60 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.35 mol% of hydrogen so as to keep the total pressure constant. As a result, 41 g of an olefin polymer having good particle properties was obtained. The polymerization activity per zirconium atom is 4.1 × 10⁷At 活性 g / mol Zr / hour, the polymerization activity per solid catalyst component was 4630 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 14.9, MFR = 0.06, MFRR = 212, SR = 1.03.
[0189]
[Reference Example 1]
(1) Synthesis of component (A)
A 5-liter four-necked flask purged with nitrogen was charged with 3.0 liters of toluene and 0.525 liters (1.05 mol) of a hexane solution of diethyl zinc (2.00 mol / liter), and cooled to 5 ° C. To this, a solution in which 98.6 g (0.54 mol) of pentafluorophenol was dissolved in 160 ml of toluene was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour. Then, it heated at 40 degreeC and stirred for 1 hour. After heating to 5 ° C. in an ice bath and heating at 300 ° C. under a nitrogen stream, silica (@Sylopol 948, manufactured by Devison; average particle diameter = 59 μm; pore volume = 1.66 ml / g; specific surface area = 296 m)²/ G) 351 g was added, and then toluene (0.1 liter) was added to wash away silica adhering to the wall of the flask. After stirring for 5 minutes, H₂O 14.0 g (0.78 mol) was added dropwise over 1.5 hours. After completion of the dropwise addition, the mixture was stirred at 5 ° C for 1.5 hours and at 40 ° C for 2 hours. Then, it left still at room temperature overnight. Thereafter, the mixture was stirred at 80 ° C. for 2 hours. Thereafter, the mixture was allowed to stand, the solid component was allowed to settle, and when the interface between the settled solid component layer and the upper slurry portion was seen, the upper slurry portion was removed, and then the remaining liquid component was filtered with a filter. Then, 3.5 L of toluene was added, and the mixture was stirred at 95 ° C. for 2 hours. Thereafter, the mixture was stirred at 95 ° C. four times with toluene 3.5 liters, and at room temperature twice with hexane 3.5 liters, and allowed to stand. When the interface with the slurry portion was seen, the upper layer slurry portion was removed, and then the remaining liquid component was washed with a filter. Thereafter, the solid component was dried at 120 ° C. for 4 hours under reduced pressure to obtain 524 g of the component (A). As a result of elemental analysis, Zn = 2.1 mmol / g and F = 5.1 mmol / g.
[0190]
(2) polymerization
As the solid catalyst component, 7.8 mg of the component (A) obtained in Reference Example 1 (1) was used, and the gas composition in the system was determined by gas chromatography analysis to be hydrogen = 0.71 mol%, 1- Polymerization was carried out in the same manner as in Example 1 (3) except that butene was 2.59 mol% and the hydrogen content in the mixed gas of ethylene and hydrogen fed was 0.26 mol%. Was.
As a result, 67 g of an olefin polymer having a good particle property was obtained. The polymerization activity per zirconium atom is 6.7 × 10⁷At 活性 g / mol Zr / hour, the polymerization activity per solid catalyst component was 8600 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 17.41, MFR = 0.94, MFRR = 57.8, and SR = 1.21.
[0191]
[Comparative Example 1]
(1)
A 5-liter four-necked flask purged with nitrogen was equipped with a stirrer, a dropping funnel and a thermometer. The flask was heated at 300 ° C. under a stream of nitrogen and heated at 300 ° C. (Sypolpol 948, manufactured by Devison; average particle diameter = 64 μm; pore volume = 1.62 ml / g; specific surface area = 312 m)²(/ G) 382 g was collected. Thereto was added 3.3 mL of toluene to form a slurry, which was cooled to 5 ° C. using an ice bath, and then 375 mL of a toluene solution of trimethylaluminum adjusted to a concentration of 2.1 mmol / mL was gradually added dropwise. At that time, gas generation was observed. After stirring at 5 ° C. for 30 minutes and at 80 ° C. for 2 hours, the supernatant was removed and the remaining solid product was washed four times with 3.3 liters of toluene. Thereafter, 3.3 liters of toluene were added again to form a slurry.
[0192]
(2)
The slurry obtained in Comparative Example 1 (1) was cooled to 5 ° C. using an ice bath, and then フ ル オ ロ 420 ml of a toluene solution of pentafluorophenol adjusted to a concentration of 2 mmol / ml was slowly added. At that time, gas generation was observed. After stirring at 5 ° C. for 30 minutes and at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid product was washed four times with 3.3 liters of toluene and twice with 3.3 liters of hexane. Thereafter, the solid product was dried under reduced pressure to obtain 434 g of a fluid solid product. As a result of elemental analysis, Al was 1.2 mmol / g and F was 4.6 mmol / g.
[0193]
(3) polymerization
After drying under reduced pressure, the inside of a 5-liter autoclave equipped with a stirrer replaced with argon was evacuated, hydrogen was added so that the partial pressure became 0.007 MPa, 1145 g of butane and 55 g of 1-butene were charged, and 70 ° C. Temperature. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.37 mol% and 1-butene = 1.55 mol%. To this was added 1.5 ml of a heptane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml. Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was charged, followed by 36 mg of the solid product obtained in Comparative Example 1 (2). Charged as a solid catalyst component. Polymerization was performed at 70 ° C. for 60 minutes while feeding an ethylene / hydrogen mixed gas (hydrogen 0.22 mol%) so as to keep the total pressure constant. As a result, 135 g of an olefin polymer was obtained. The polymerization activity per zirconium atom is 1.4 × 10⁸At g / mol Zr / hour, the polymerization activity per solid catalyst component was 3720 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 12.4, MFR = 2.55, MFRR = 48, and SR = 1.35.
[0194]
【The invention's effect】
As described in detail above, according to the present invention, in the field of single-site catalysts, a high molecular weight polymer preferably used for polymerization involving formation of addition polymer particles (eg, slurry polymerization, gas phase polymerization, bulk polymerization, etc.) Particles capable of producing an addition polymer, carrier, and catalyst component for addition polymerization, production of the particles, addition polymerization catalyst using the particles, and production of high molecular weight addition polymer using the addition polymerization catalyst A method is provided. Further, according to the present invention, when applied to polymerization accompanied by the formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), the addition polymerization gives an addition polymer excellent in shape and particle properties. Particles, carrier and catalyst component for addition polymerization useful for catalyst preparation, method for producing the particles, catalyst for addition polymerization using the particles, and polymerization involving formation of addition polymer particles using the catalyst for addition polymerization (For example, when applied to slurry polymerization, gas phase polymerization, bulk polymerization, etc.), a method for producing an addition polymer having excellent particle properties is also provided. Furthermore, the present invention also provides a highly active addition polymerization catalyst and a method for efficiently producing an addition polymer.

Claims (11)

Modified particles obtained by contacting the following (a), (b), (c) and (d ').
(A): Compound M ¹ L ¹ _m [1] represented by the following general formula [1]
(B): Compound R ¹ _t-1 TH [2] represented by the following general formula [2]
(C): a compound R ² _t-2 TH ₂ [3] represented by the following general formula [3]
(D '): Particle (a') obtained by contacting particle (d) with compound (a ') represented by the following general formula [4]: Compound represented by the following general formula [4] R ³ _t-1 TH [4]
(In the above general formulas [1] to [4], M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table, and m is a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when a plurality of L ¹ are present, they may be the same or different from each other, and R ¹ is an electron-withdrawing group or an electron-withdrawing property. It represents a group containing a group, when R ¹ existing in plural numbers may be different even they mutually identical .R ² represents a hydrocarbon group or a halogenated hydrocarbon group, R ³ is a hydrocarbon T represents a non-metallic atom of Group 15 or 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound.) The modified particles according to claim 1, wherein R ³ is an alkyl group or an aryl group having no electron-withdrawing group. A method for producing modified particles in which the following (a), the following (b), the following (c) and the following (d ′) are brought into contact:
(A): Compound M ¹ L ¹ _m [1] represented by the following general formula [1]
(B): Compound R ¹ _t-1 TH [2] represented by the following general formula [2]
(C): a compound R ² _t-2 TH ₂ [3] represented by the following general formula [3]
(D '): Particle (a') obtained by contacting particle (d) with compound (a ') represented by the following general formula [4]: Compound represented by the following general formula [4] R ³ _t-1 TH [4]
(In the above general formulas [1] to [4], M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table, and m is a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when a plurality of L ¹ are present, they may be the same or different from each other, and R ¹ is an electron-withdrawing group or an electron-withdrawing property. It represents a group containing a group, when R ¹ existing in plural numbers may be different even they mutually identical .R ² represents a hydrocarbon group or a halogenated hydrocarbon group, R ³ is a hydrocarbon T represents a non-metallic atom of Group 15 or 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound.) A carrier comprising the modified particles according to claim 1. A catalyst component for addition polymerization comprising the modified particles according to claim 1. An addition polymerization catalyst obtained by bringing the modified particles (A) according to claim 1 or 2 into contact with a Group 3-11 or lanthanoid-based transition metal compound (B). An addition polymerization catalyst obtained by bringing the modified particles (A) according to claim 1 or 2 into contact with a group 3-11 or lanthanoid-based transition metal compound (B) and an organoaluminum compound (C). The catalyst for addition polymerization according to claim 6 or 7, wherein the transition metal compound (B) of the group 3 to 11 or a lanthanoid series is a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton. A method for producing an addition polymer using the addition polymerization catalyst according to claim 6. The method for producing an addition polymer according to claim 9, wherein the addition polymer is an olefin polymer. The method for producing an addition polymer according to claim 9, wherein the addition polymer is a copolymer of ethylene and an α-olefin.