JP2004162025A - Modified particle, catalyst component for addition polymerization, catalyst for addition polymerization and method for producing addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide modified particles capable of forming a catalyst for an addition polymerization exhibiting a high polymerization activity by using it as a co-catalyst for activation, a component of the catalyst for addition polymerization consisting of the modified particles, the addition polymerization catalyst exhibiting the high polymerization activity by using the modified particles and an efficient method for producing an addition polymer by using the catalyst for the addition polymerization. <P>SOLUTION: The modified particles are obtained by making the following component (a) in contact with components (b) and (c). The component (a) is BiL<SP>1</SP><SB>m</SB>, the component (b) is R<SP>1</SP><SB>t-n</SB>TH<SB>n</SB>and the component (c) is the particles [wherein (m) is a number corresponding to the atomic valence of Bi; L<SP>1</SP>is H, a halogen atom. a hydrocarbon or an oxyhydrocarbon; R<SP>1</SP>is a group containing an electron-withdrawing group or the electron-withdrawing group; T is a non-metal element of 15th or 16th group of the Periodic table; (t) is a number corresponding to the atomic valence of T: and (n) is 1 to (t) integer excluding 2]. <P>COPYRIGHT: (C)2004,JPO

Description

（式中、Ｒ³は水素原子、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、複数あるＲ³は互いに同じであっても異なっていてもよく、それら２つ以上が互いに結合していてもよく、環を形成していてもよい。）
【００７４】
前記一般式［５］におけるＲ³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。
【００７５】
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。
【００７６】
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。
【００７７】
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よく、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からなる群から選ばれる少なくとも１種の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Ｌ² 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Ｌ² 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Ｌ² 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Ｌ² 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。
【００７８】
一般式［３］におけるＸ¹ は、ハロゲン原子、炭化水素基またはＯＲ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。
【００７９】
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、イソアミル基、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イソアミル基である。
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。
【００８０】
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。
【００８１】
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。
【００８２】
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。
【００８３】
ＯＲのＲとしては炭化水素基であり、炭化水素基としてはアルキル基、アラルキル基やアリール基等が挙げられ、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のアラルキル基または炭素原子数６〜２０のアリール基が好ましい。これらの具体例は上記に記載されたものと同じものが挙げられる。
この場合のＲとして特に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、フェニル基、２，６−ジ（ｔｅｒｔ−ブチル）フェニル基またはベンジル基である。Ｒとして特に好ましくはメチル基、フェニル基、２，６−ジ（ｔｅｒｔ−ブチル）フェニル基またはベンジル基であり、最も好ましくはフェニル基である。
【００８４】
Ｘ¹ 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、ベンジル基、アリル基またはメタリル基である。
【００８５】
一般式［３］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の価数に応じて適宜選択される。
【００８６】
一般式［３］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、
【００８７】
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、
【００８８】
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、
【００８９】
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、
【００９０】
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、
【００９１】
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、
【００９２】
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、
【００９３】
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、
【００９４】
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、
【００９５】
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、
【００９６】
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、
【００９７】
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、
【００９８】
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、
【００９９】
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、
【０１００】
（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、
【０１０１】
（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、
【０１０２】
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、
【０１０３】
［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−ｎ−ブトキシド、ジイソブトキシド、ジ−ｔｅｒｔ−ブトキシド、ジフェノキシドまたはジ（２，６−ジ−ｔｅｒｔ−ブチルフェノキシド）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−ｎ−ブトキシド、トリイソブトキシド、トリ−ｔｅｒｔ−ブトキシド、トリフェノキシドまたはトリ（２，６−ジ−ｔｅｒｔ−ブチルフェノキシド）に変更した化合物などを例示することができる。
【０１０４】
一般式［３］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、
【０１０５】
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、
【０１０６】
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、
【０１０７】
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、
【０１０８】
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、
【０１０９】
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、
【０１１０】
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、
【０１１１】
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、
【０１１２】
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、
【０１１３】
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−ｎ−ブトキシド、ジイソブトキシド、ジ−ｔｅｒｔ−ブトキシド、ジフェノキシドまたはジ（２，６−ジ−ｔｅｒｔ−ブチルフェノキシド）に変更した化合物などを例示することができる。
【０１１４】
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、メタリル、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、ｎ−ブトキシド、イソブトキシド、ｔｅｒｔ−ブトキシド、フェノキシドまたは２，６−ジ−ｔｅｒｔ−ブチルフェノキシドに変更した化合物が挙げられる。
【０１１５】
また、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、Ｒ⁴ とＲ⁵ はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｒ⁶ およびＲ⁷ はそれぞれ水素原子またはメチル基あるいはＲ⁶ とＲ⁷ とがいっしょになってアセナフテン基であり、Ｘ² 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、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、イソブトキシ基、またはフェノキシ基であり、複数あるＸ²は互いに同じであっても異なっていてもよい。）
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。
【０１１６】
一般式［３］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、ジ−ｎ−プロポキシド、ジイソプロポキシド、ジ−ｎ−ブトキシド、ジイソブトキシド、ジ−ｔｅｒｔ−ブトキシド、ジフェノキシドまたはジ（２，６−ジ−ｔｅｒｔ−ブチルフェノキシド）に変更した化合物が挙げられる。
【０１１７】
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、エトキシド、ｎ−プロポキシド、イソプロポキシド、ｎ−ブトキシド、イソブトキシド、ｔｅｒｔ−ブトキシド、フェノキシド、または２，６−ジ−ｔｅｒｔ−ブチルフェノ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。
【０１１８】
また一般式［３］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、ｎ−ブトキシド、イソブトキシド、ｔｅｒｔ−ブトキシド、フェノキシドまたは２，６−ジ−ｔｅｒｔ−ブチル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。
【０１１９】
以上に例示した一般式［３］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。
【０１２０】
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。
【０１２１】
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。
【０１２２】
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［３］で表される遷移金属化合物である。中でも、上記一般式［３］におけるＭ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［３］におけるＬ² 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、いわゆるメタロセン系遷移金属化合物が好ましい。
【０１２３】
（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 ［６］で示される有機アルミニウム化合物である。
Ｒ⁸ _cＡｌＹ_3-c ［６］
（式中、Ｒ⁸ は炭化水素基を表し、Ｒ⁸が複数ある場合は、夫々のＲ⁸ 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、Ｙが複数ある場合は、夫々の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。）
【０１２４】
有機アルミニウム化合物を表す一般式［６］におけるＲ⁸ 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。
【０１２５】
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。
【０１２６】
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。
【０１２７】
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。
【０１２８】
一般式［６］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。
【０１２９】
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。
【０１３０】
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。
【０１３１】
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。
【０１３２】
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。
【０１３３】
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。
【０１３４】
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よい。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。
【０１３５】
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。
【０１３６】
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。
【０１３７】
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。
【０１３８】
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。
【０１３９】
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。
【０１４０】
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。
【０１４１】
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。
【０１４２】
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。
【０１４３】
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。
【０１４４】
予備重合を行う際のスラリー濃度は、０．１〜５０［ｇ−上記の改質された粒子］／［リットル−溶媒］が好ましく、特に０．５〜２０［ｇ−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。
【０１４５】
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よい。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よい。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。
【０１４６】
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。
【０１４７】
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。
【０１４８】
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。
【０１４９】
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。
【０１５０】
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。
【０１５１】
【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。
【０１５２】
（１）共重合体におけるα−オレフィン単位含有量：得られたポリマー中のα−オレフィン単位含有量は、赤外吸収スペクトルから求め、炭素原子１０００個当たりの短鎖分岐数（ＳＣＢ）として表した。尚、測定ならびに計算は、文献（Die Makromoleculare Chemie, 177, 449 (1976) McRae, M. A., Madams, W. F. ）記載の方法に従い、α−オレフィン由来の特性吸収を利用して実施した。赤外吸収スペクトルは、赤外分光光度計（日本分光工業社製 ＦＴ−ＩＲ７３００）を用いて測定した。
【０１５３】
（２）極限粘度［η］：ウベローデ型粘度計を用い、１３５℃でテトラリン溶液中で測定した。
【０１５４】
（３）¹³Ｃ−ＮＭＲの測定
¹³Ｃ−ＮＭＲの測定には、日本電子ＪＮＭ−ＥＸ２７０（６７．５ＭＨｚ，¹³Ｃ）を用いた。実施例に記載した重水素化溶媒を用い、室温にて測定を行った。
【０１５５】
（４）分子量および分子量分布
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、下記の条件で測定した。検量線は標準ポリスチレンを用いて作成した。分子量分布は重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）で評価した。
機種： ミリポアウオーターズ社製 １５０Ｃ型
カラム： ＴＳＫ−ＧＥＬ ＧＭＨ−ＨＴ（７．５×６００） ２本
測定温度：１４０℃
溶媒： オルトジクロロベンゼン、
測定濃度：５ｍｇ／５ｍｌ
（５）メルトフローレート（ＭＦＲ）
ＪＩＳ Ｋ７２１０−１９９５に規定された方法に従い、荷重２１．１８Ｎ、温度１９０℃の条件で、メルトフローレート（ＭＦＲ）を測定した。（単位：ｇ／１０分）
（６）メルトフローレートレシオ（ＭＦＲＲ）
ＪＩＳ Ｋ７２１０−１９９５に規定された方法に従い、荷重２１．１８Ｎ、温度１９０℃の条件でのメルトフローレート（ＭＦＲ）と、荷重２１１．８２Ｎ、温度１９０℃の条件でのメルトフローレート（ＭＦＲ２）とを測定し、ＭＦＲ２をＭＦＲで除した値（ＭＦＲ２／ＭＦＲ）を求め、メルトフローレートレシオ（ＭＦＲＲ）とした。
（７）スウェル比（ＳＲ）
ＪＩＳ Ｋ７２１０−１９９５に規定されたメルトフローレート測定装置を用いた荷重２１．１８Ｎ、温度１９０℃の条件でのメルトフローレート測定において、押し出したストランドの直径（ｄ（ｍｍ））を測定し、オリフィスの直径（ｄ₀（ｍｍ）＝２．０９５）で除した値（ｄ／ｄ₀）を求め、スウェル比（ＳＲ）とした。
（８）融点（ｍｐ）
示差走査熱量計（セイコー電子工業社製 ＳＳＣ−５２００）を用い以下の条件で測定した。
状態調整：４０℃から１５０℃まで１０℃／分で昇温後、１５０℃で５分間保持し、次に、１５０℃から４０℃まで５℃／分で降温後、４０℃で１０分間保持した。
融点測定：状態調整後、直ちに４０℃から１６０℃まで５℃／分で昇温した。
【０１５６】
［実施例１］
（１）中間体の合成
アルゴン置換した３００ｍｌ四つ口フラスコにトリフェニルビスマス ９．８８ｇ（２２．４ｍｍｏｌ）、トルエン １００ｍｌを入れ、室温で攪拌した。これにペンタフルオロフェノール １２．６ｇ（６８．５ｍｍｏｌ）のトルエン １００ｍｌ溶液を滴下した。滴下終了後、室温で１５．５時間攪拌を行った。その後、トルエン還流条件下で４時間、室温で１８時間、トルエン還流条件下で７時間、室温で１７時間順次反応を行った。生じた黄色針状結晶を濾別し、室温で減圧下乾燥を行うことにより、中間体 １２．６ｇを得た。
【０１５７】
（２）成分（Ａ）の合成
アルゴン置換した５０ｍｌ四つ口フラスコに実施例１（１）で合成した中間体１．５４ｇ、トルエン ４０ｍｌを入れ、室温で攪拌した。これに窒素流通下で３００℃において加熱処理したシリカ（デビソン社製 Ｓｙｌｏｐｏｌ９４８；メジアン径＝５５μｍ；細孔容量＝１．６６ｍｌ／ｇ；比表面積＝３０９ｍ²／ｇ）０．７３ｇを入れ、８０℃に昇温し２時間攪拌を行った。固体を濾別し、トルエン ２０ｍｌで４回、ヘキサン ２０ｍｌで１回洗浄を行い、減圧下、室温で乾燥を行うことにより成分（Ａ）を得た。元素分析の結果、Ｂｉ＝０．４８ｍｍｏｌ／ｇ、Ｆ＝４．０ ｍｍｏｌ／ｇであった。
【０１５８】
（３）重合
内容積３リットルの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、減圧し、水素 ０．４９ｖｏｌ％、溶媒としてブタン ７００ｇ、コモノマーとして１−ブテン ５０ｇを仕込み、反応器を７０℃まで昇温した。昇温後、エチレン圧を１．６ＭＰａに調整しながらフィードし、系内が安定した後、トリイソブチルアルミニウム ０．９ｍｍｏｌを投入し、続いてエチレンビス（インデニル）ジルコニウムジクロライド ０．５μｍｏｌを投入し、さらに上記（２）で得た成分（Ａ）１７．２ｍｇを投入して重合を開始した。６０分間重合を行った。
重合の結果、３５ｇのエチレン／１−ブテン共重合体が得られた。重合活性＝２０００（ｇ／ｇ-成分（Ａ）／ｈ）、ＳＣＢ＝１５．１５（１／１０００Ｃ）、ＭＦＲ＝０．９３（ｇ／１０分）、ＭＦＲＲ＝９１．４０、ＳＲ＝１．２５であった。
【０１５９】
［実施例２］
（１）重合
内容積０．４リットルの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、コモノマーとして１−ヘキセン １０ｍｌ、溶媒としてヘキサン １９０ｍｌを仕込み、反応器を７０℃まで昇温した。昇温後、エチレン圧を０．６ＭＰａに調整しながらフィードし、系内が安定した後、トリイソブチルアルミニウム ０．２５ｍｍｏｌを投入し、続いてエチレンビス（インデニル）ジルコニウムジクロライド １μｍｏｌを投入し、さらに上記実施例１（２）で得た成分（Ａ）３０．４ｍｇを投入して重合を開始した。３０分間重合を行った。
重合の結果、２２．４ｇのエチレン／１−ヘキセン共重合体が得られた。重合活性＝１５００（ｇ／ｇ-成分（Ａ）／ｈ）、４５（ｋｇ／ｍｍｏｌ-Ｚｒ／ｈ）、Ｍｗ＝５８０００、Ｍｗ／Ｍｎ＝１．９、ＳＣＢ＝３６．０（１／１０００Ｃ）であった。
【０１６０】
［実施例３］
（１）中間体の合成
アルゴン置換した２０００ｍｌ四つ口フラスコにトリフェニルビスマス １０１ｇ（２３０ｍｍｏｌ）、トルエン ５００ｍｌを入れ、室温で攪拌した。これにペンタフルオロフェノールのトルエン溶液（２ｍｍｏｌ／ｍｌ）３４５ｍｌ（６９０ｍｍｏｌ）を滴下した。滴下終了後、トルエン還流条件下で１１時間反応を行った。生じた黄色針状結晶を濾別し、室温で減圧下乾燥を行うことにより、中間体 １７１ｇを得た。元素分析より、Ｂｉ＝１．２ｍｍｏｌ／ｇ、Ｆ＝１５ｍｍｏｌ／ｇであった。
【０１６１】
（２）成分（Ａ）の合成
アルゴン置換した１０００ｍｌ四つ口フラスコに実施例３（１）で合成した中間体 １７．７ｇ（２３．４ｍｍｏｌ）、トルエン ３００ｍｌを入れ、室温で攪拌した。これに窒素流通下で３００℃において加熱処理したシリカ（デビソン社製 Ｓｙｌｏｐｏｌ９４８；メジアン径＝５５μｍ；細孔容量＝１．７ｍｌ／ｇ；比表面積＝３０６ｍ²／ｇ）２１．１ｇ、トルエン３０ｍｌを入れ、８０℃に昇温し２時間攪拌を行った。固体を濾別し、トルエン １００ｍｌで４回、ヘキサン １００ｍｌで１回洗浄を行い、減圧下、室温で乾燥を行うことにより成分（Ａ）２７．５ｇを得た。元素分析の結果、Ｂｉ＝０．４８ｍｍｏｌ／ｇ、Ｆ＝３．３ ｍｍｏｌ／ｇであった。
【０１６２】
（３）重合
内容積０．４リットルの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、コモノマーとして１−ヘキセン １０ｍｌ、溶媒としてヘキサン １９０ｍｌを仕込み、反応器を７０℃まで昇温した。昇温後、エチレン圧を０．６ＭＰａに調整しながらフィードし、系内が安定した後、トリイソブチルアルミニウム ０．２５ｍｍｏｌを投入し、続いてエチレンビス（インデニル）ジルコニウムジクロライド ０．３μｍｏｌを投入し、さらに上記実施例３（２）で得た成分（Ａ）９．１ｍｇを投入して重合を開始した。３０分間重合を行った。
重合の結果、１６．１ｇのエチレン／１−ヘキセン共重合体が得られた。重合活性＝３５００（ｇ／ｇ-成分（Ａ）／ｈ）、１１０（ｋｇ／ｍｍｏｌ-Ｚｒ／ｈ）、Ｍｗ＝１６００００、Ｍｗ／Ｍｎ＝３．８、η＝１．６５（ｄｌ／ｇ）、ＳＣＢ＝１８．８１（１／１０００Ｃ）であった。
【０１６３】
［比較例１］
（１）
実施例１（２）において、実施例１（１）で合成した中間体 １．５４ｇを用いる代わりにトリフェニルビスマス １．１６ｇを用い、シリカの量を１．１０ｇに変更した以外は実施例１（２）に従って合成を行った。その結果、白色固体０．７９ｇを得た。
【０１６４】
（２）重合
内容積０．４リットルの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、コモノマーとして１−ヘキセン １０ｍｌ、溶媒としてヘキサン １９０ｍｌを仕込み、反応器を７０℃まで昇温した。昇温後、エチレン圧を０．６ＭＰａに調整しながらフィードし、系内が安定した後、トリイソブチルアルミニウム ０．２５ｍｍｏｌを投入し、続いてエチレンビス（インデニル）ジルコニウムジクロライド １μｍｏｌを投入し、さらに上記比較例１（１）で得た白色固体 ２２．９ｍｇを投入して重合を開始した。３０分間重合を行った。
重合の結果、痕跡量のポリマーしか得られなかった。
【０１６５】
［実施例４］
（１）＜ジメチルシリレン（η⁵−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）チタニウムジメトキシドの合成＞
シュレンク管中、無水エーテル１０ｍｌにメタノール０．１３１ｇ（４．１ｍｍｏｌ）を溶解させ、−７８℃で濃度１．０５ｍｏｌ／Ｌのメチルリチウムのエーテル溶液（３．９ｍｌ、４．１ｍｍｏｌ）を滴下した。２０℃に昇温し、ガスの発生の終了を確認することにより、リチウムメトキシドの生成を確認し、再度−７８℃に冷却した。もう一つのシュレンク管に予め用意した、ジメチルシリレン（η⁵−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）チタニウムジクロライド０．９１９ｇ（２．０ｍｍｏｌ）の無水エーテル２０ｍｌ懸濁液を、先の反応液に移送し、その後、徐々に室温まで昇温させた。反応液を濃縮後、トルエン２０ｍｌを加え、不溶物をろ別した。ろ液を濃縮し、下記構造式のジメチルシリレン（η⁵−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）チタニウムジメトキシド（以下、化合物Ａと称する。）を黄色結晶として取得した。（０．８６ｇ、９５％）
¹Ｈ−ＮＭＲ（２７０ＭＨｚ，Ｃ₆Ｄ₆） δ７．２６（ｍ，２Ｈ），４．１３（ｓ，６Ｈ），２．３３（ｓ，３Ｈ），１．９７（ｓ，６Ｈ），１．８９（ｓ，６Ｈ），１．５９（ｓ，９Ｈ），０．５５（ｓ，６Ｈ）

【０１６６】
（２）重合
内容積０．４リットルの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、コモノマーとして１−ヘキセン ２ｍｌ、溶媒としてヘキサン １９８ｍｌを仕込み、反応器を７０℃まで昇温した。昇温後、エチレン圧を０．６ＭＰａに調整しながらフィードし、系内が安定した後、トリイソブチルアルミニウム０．２５ｍｍｏｌを投入し、続いて化合物Ａとトリイソブチルアルミニウムが混合されたトルエン溶液（化合物Ａの濃度は１μｍｏｌ／ｍｌ、トリイソブチルアルミニウムの濃度は５０μｍｏｌ／ｍｌで、Ａｌ原子とＴｉ原子のモル比を５０に調整した。）を１ｍｌ（即ち、化合物Ａを１μｍｏｌ、トリイソブチルアルミニウムを５０μｍｏｌ）投入し、さらに上記実施例１（２）で得た成分（Ａ）４３．０ｍｇを投入して重合を開始した。３０分間重合を行った。
重合の結果、１．７９ｇのエチレン／１−ヘキセン共重合体が得られた。重合活性＝８３（ｇ／ｇ-成分（Ａ）／ｈ）、３．６（ｋｇ／ｍｍｏｌ-Ｔｉ／ｈ）、Ｍｗ＝４４００００、Ｍｗ／Ｍｎ＝２．１、η＝４．５５（ｄｌ／ｇ）、ＳＣＢ＝１９．３４（１／１０００Ｃ）であった。
【０１６７】
［実施例５］
（１）中間体の合成
アルゴン置換した５００ｍｌ四つ口フラスコにトリフェニルビスマス １７．２ｇ（３９．１ｍｍｏｌ）、トルエン １７５ｍｌを入れ、室温で攪拌した。これにペンタフルオロフェノール２２．０ｇ（１１９ｍｍｏｌ）をトルエン５０ｍｌに溶解させた溶液を滴下した。滴下終了後、トルエン還流条件下で８時間、室温で１５時間、トルエン還流条件下で４時間反応を行った。生じた黄色針状結晶を濾別し、室温で減圧下乾燥を行うことにより、中間体 ２８．２ｇを得た。
【０１６８】
（２）成分（Ａ）の合成
アルゴン置換した１００ｍｌ四つ口フラスコに実施例５（１）で合成した中間体 ２．４８ｇ、トルエン ４０ｍｌを入れ、室温で攪拌した。これに窒素流通下で３００℃において加熱処理したシリカ（デビソン社製 Ｓｙｌｏｐｏｌ９４８；メジアン径＝５５μｍ；細孔容量＝１．６６ｍｌ／ｇ；比表面積＝３０９ｍ²／ｇ）３．１１ｇ、トルエン５ｍｌを入れ、８０℃に昇温し２時間攪拌を行った。固体を濾別し、トルエン ３０ｍｌで４回、ヘキサン ３０ｍｌで１回洗浄を行い、減圧下、室温で乾燥を行うことにより成分（Ａ）３．８４ｇを得た。元素分析の結果、Ｂｉ＝０．５３ｍｍｏｌ／ｇ、Ｆ＝３．２ ｍｍｏｌ／ｇであった。
【０１６９】
（３）重合
内容積０．４リットルの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、コモノマーとして１−ヘキセン １５ｍｌ、溶媒としてシクロヘキサン１８５ｍｌを仕込み、反応器を１８０℃まで昇温した。昇温後、エチレン圧を２．５ＭＰａに調整しながらフィードし、系内が安定した後、トリイソブチルアルミニウム ０．３ｍｍｏｌを投入し、続いて化合物Ａとトリイソブチルアルミニウムが混合されたトルエン溶液（化合物Ａの濃度は０．５μｍｏｌ／ｍｌ、トリイソブチルアルミニウムの濃度は２５μｍｏｌ／ｍｌで、Ａｌ原子とＴｉ原子のモル比を５０に調整した。）を１ｍｌ（即ち、化合物Ａを０．５μｍｏｌ、トリイソブチルアルミニウムを２５μｍｏｌ）投入し、さらに上記実施例５（２）で得た成分（Ａ）１２６ｍｇを投入して重合を開始した。２分間重合を行った。
重合の結果、１．４１ｇのエチレン／１−ヘキセン共重合体が得られた。重合活性＝３４０（ｇ／ｇ-成分（Ａ）／ｈ）、８５（ｋｇ／ｍｍｏｌ-Ｔｉ／ｈ）、Ｍｗ＝１０００００、Ｍｗ／Ｍｎ＝１．９、η＝１．４６（ｄｌ／ｇ）、融点＝８１．４（℃）であった。
【０１７０】
【発明の効果】
以上説明したように本発明によれば、活性化用助触媒成分として用いることにより高重合活性を示す付加重合用触媒を形成し得る改質された粒子、該改質された粒子よりなる付加重合用触媒成分、該改質された粒子を用いてなる高重合活性を示す付加重合用触媒、ならびに該付加重合用触媒を用いる効率的な付加重合体の製造方法が提供された。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a modified particle used as an addition polymerization catalyst component, an addition polymerization catalyst component comprising the same, an addition polymerization catalyst using the same, and an addition polymer using the addition polymerization catalyst. It relates to a manufacturing method.
[0002]
[Prior art]
Olefin 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 properties and economic efficiency. Conventionally, these olefin polymers are 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 polymerizing olefins using a conventional solid catalyst (multi-site catalyst).
[0003]
Production of an addition polymer in which a monomer capable of addition polymerization is polymerized using a so-called single-site catalyst in which a transition metal compound (for example, a metallocene complex) different from a solid catalyst component that has been used for a long time in recent years and an aluminoxane are combined. A method has been proposed. For example, a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane has been reported (for example, see Patent Document 1). It has also been reported to combine certain boron compounds with such transition metal compounds. For example, a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate has been reported (for example, see Patent Document 2). Olefin polymers obtained using these single-site catalysts have a narrower molecular weight distribution than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers, the comonomers are more uniformly copolymerized. Therefore, it is known that a more homogeneous olefin polymer can be obtained than when a conventional solid catalyst is used.
[0004]
Improvements in such addition polymerization catalysts have been studied diligently, and the types of metals used as main catalyst components have been widely studied in each group of the periodic table. It has been reported that a metallocene complex or a non-metallocene compound is effective as a main catalyst component (for example, see Non-Patent Document 1). On the other hand, as the co-catalyst component for activation to be combined with a metallocene complex or a non-metallocene compound, aluminoxane or a boron compound belonging to Group 13 compounds occupies the center of development. As the boron compound, a compound having an electron-withdrawing group on a boron atom is generally effective.
[0005]
[Patent Document 1]
JP-A-58-19309
[Patent Document 2]
Japanese Unexamined Patent Publication No. Hei 1-502036
[Non-patent document 1]
George JP Britovsek and 2 others, "The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes ”, Angewandte Chemie International Edition, (Germany), WILEY, 1999, Vol. 38, No. 4, p. 428-447
[0006]
[Problems to be solved by the invention]
In view of this situation, an object of the present invention is to provide a modified particle capable of forming an addition polymerization catalyst exhibiting high polymerization activity by using it as an activating co-catalyst component, and an addition polymerization comprising the modified particle. An object of the present invention is to provide a catalyst component, an addition polymerization catalyst having high polymerization activity using the modified particles, and a method for efficiently producing an addition polymer using the addition polymerization catalyst.
[0007]
[Means for Solving the Problems]
The present invention relates to modified particles obtained by contacting the following components (a), (b) and (c), and an addition polymerization catalyst component comprising the modified particles. A modified particle (A) and an addition polymerization catalyst obtained by bringing a group 3-11 or lanthanoid-based transition metal compound (B) into contact with the modified particle (A); The present invention relates to an addition polymerization catalyst obtained by bringing a group 11 or lanthanoid series transition metal compound (B) into contact with an organoaluminum compound (C), and to a method for producing an addition polymer using these addition polymerization catalysts. Such is the case.
(A): a compound represented by the general formula [1]
BiL¹ _m                        [1]
(B): a compound represented by the general formula [2]
R¹ _tnTH_n                      [2]
(C): particles
(In the above general formulas [1] and [2], m represents a number corresponding to the valence of Bi;¹Represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbonoxy group;¹When there are a plurality of groups, they may be the same or different from each other;¹Represents a group containing an electron-withdrawing group or an electron-withdrawing group;¹May be the same or different from each other, 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. And n represents an integer of 1 to t and a number excluding 2. )
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Component (a) is a compound represented by the following general formula [1].
BiL¹ _m                        [1]
In the general formula [1], m represents the valence of Bi and is 3 or 5.
[0009]
L in the above general formula [1]¹Represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbonoxy group;¹May 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. L¹Is preferably an alkyl group, an aryl group, or an aralkyl group. L¹Is preferably an alkoxy group or an aryloxy group.
[0010]
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.
[0011]
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.
[0012]
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.
Each of these aryl groups is 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]
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 are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. May be partially substituted.
[0014]
As the alkoxy group, an alkoxy group having 1 to 20 carbon atoms is preferable, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eico Examples thereof include a siloxy group, and more preferred are a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, and an isobutoxy 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.
[0015]
As the aryloxy group, an aryloxy group having 6 to 20 carbon atoms is preferable. For example, a phenoxy group, a 2-tolyloxy group, a 3-tolyloxy group, a 4-tolyloxy group, a 2,3-xylyloxy group, a 2,4-xylyloxy group Group, 2,5-xylyloxy group, 2,6-xylyloxy group, 3,4-xylyloxy group, 3,5-xylyloxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6 -Tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n- Ropylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, isobutylphenoxy group, n-pentylphenoxy group, neopentylphenoxy group, n-hexylphenoxy group, n- Examples include an octylphenoxy group, an n-decylphenoxy group, an n-dodecylphenoxy group, an n-tetradecylphenoxy group, a naphthyloxy group and an anthracenyloxy group, and more preferably a phenoxy group.
Each of these aryl groups is 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.
[0016]
L in the above general formula [1]¹Is preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, more preferably a halogen atom, an aryl group, an alkoxy group or an aryloxy group, and particularly preferably an aryl group.
[0017]
Component (b) is a compound represented by the general formula [2].
R¹ _tnTH_n                      [2]
T in the above general formula [2] 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 is preferably a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
[0018]
In the general formula [2], 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 2. n is an integer of 1 to t and represents a number excluding 2, and is preferably 1.
[0019]
R in the above general formula [2]¹ Represents a group containing an electron-withdrawing group or an electron-withdrawing group;¹May be the same or different from each other. 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.
[0020]
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.
[0021]
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-perchlor Butyl, 1H, 1H-perchloropentyl, 1H, 1H-perchlorohexyl, 1H, 1H-perchlorooctyl, 1H, 1H-perchlorododecyl, 1H, 1H-perchloropentadecyl, 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.
[0022]
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, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro- 4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, 2-chlorophenyl group, 3- Chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichloro Phenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, pentachlorophenyl group, 2,3,5,6-tetrachloro-4-trichloro Methylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, perchloro-2-naphthyl group, 2-bromophenyl group, 3-bromophenyl group, Bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenyl group, 2,4,6-tribromophenyl group, 2,3 , 5,6-tetrabromophenyl group, pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2, , 5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group, perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4 -Diiodophenyl group, 2,6-diiodophenyl group, 3,4-diiodophenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 2,3,5 6-tetraiodophenyl group, pentaiodophenyl group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, period- Examples thereof include a 1-naphthyl group and a period-2-naphthyl group.
[0023]
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.
[0024]
Specific examples of the cyanated aryl group include a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group.
[0025]
Specific examples of the nitrated aryl group include a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and the like.
[0026]
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.
[0027]
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.
[0028]
R¹ Is preferably a halogenated hydrocarbon group, and 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, 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)- A 2,2,2-trichloroethyl group, a 4-chlorophenyl group, a 2,6-dichlorophenyl group, a 3,5-dichlorophenyl group, a 2,4,6-trichlorophenyl group or a pentachlorophenyl group; An alkyl group or a fluoroaryl group, most preferably a trifluoromethyl group, a 2,2,2-trifluoro group; Oro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group Or a pentafluorophenyl group.
[0029]
Specific examples of the compound of the component (a) include bismuth (III) halides such as bismuth (III) fluoride, bismuth (III) chloride, bismuth (III) bromide, and bismuth (III) iodine; Triaryl bismuth such as alkyl bismuth and triphenyl bismuth; trialkoxy bismuth such as trimethoxy bismuth and triethoxy bismuth; triaryloxy bismuth such as triphenoxy bismuth; bismuth (V) fluoride, bismuth (V) chloride, bismuth (V ) Halogenated bismuth (V) such as bromide and bismuth (V) iodine; pentaalkylbismuth such as pentamethylbismuth; pentaarylbismuth such as pentaphenylbismuth; pentaalkoxy such as pentamethoxybismuth and pentaethoxybismuth Bismuth; penta aryloxy bismuth such as penta phenoxy bismuth and the like.
[0030]
The compound of component (a) is preferably bismuth (III) halide, trialkyl bismuth, triaryl bismuth, trialkoxy bismuth or triaryloxy bismuth, more preferably bismuth (III) halide, triaryl bismuth, Trialkoxy bismuth or triaryloxy bismuth, particularly preferably triaryl bismuth such as triphenyl bismuth.
[0031]
Specific examples of the compound of the component (b) include, as amines, di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine , Bis (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 -Triiodoethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2, , 3,3-pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2 , 2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethyl) Ethyl) 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-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-dibu Lomophenyl) 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 L) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) amine, bis (3 -Cyanophenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine, bis (1H, 1H-perfluoro) Butyl) 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. Can be 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.
[0032]
Examples of alcohols include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodmethanol, trifluoromethanol, trichloromethanol, tribromomethanol, triiodmethanol, -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-perfluoropentadecanol, 1H, H-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-per Bromooctanol, 1H, 1H-perbromododecanol, 1H, 1H-perbromopentadecanol, 1H, 1H-perbromoeicosanol and the like can be mentioned. 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.
[0033]
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, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, , 4-Dichlorophenol, 2,6-dichloropheno 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, 2-bromophenol , 3-bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4,6-tribromophenol, , 3,5,6-tetrabromophenol, pentabromophenol, 2,3,5 -Tetrabromo-4-tribromomethylphenol, 2,3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo-2-naphthol, 2-iodophenol, 3-iodophenol, -Iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol, 2,4,6-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, 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-nitrophenol, 4-nitrophenol and the like. 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.
[0034]
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.
[0035]
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, 3,4,5-trifluorophenol , Pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis ( (Trifluoromethyl) phenol or 2,4,6-tris (trifluoromethyl) phenol.
[0036]
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.
[0037]
As the particles of the component (c), 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. It is preferably used.
[0038]
From the viewpoint of the particle size distribution of the obtained polymer, the component (c) particles preferably have a volume-based geometric standard deviation of 2.5 or less, more preferably 2. 0 or less, more preferably 1.7 or less.
[0039]
Examples of inorganic substances that can be used as the particles of the component (c) include inorganic oxides and the like, and clay and clay minerals can also be used. These may be used as a mixture.
[0040]
Specific examples of the inorganic oxide include SiO 2_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, BaO, ThO_TwoAnd mixtures thereof, for example, SiO 2_Two-MgO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two−Cr_TwoO_Three, SiO_Two-TiO_Two-MgO and the like can be exemplified. Among these inorganic oxides, SiO 2_TwoAnd / or Al_TwoO_ThreeAre preferred, and especially SiO_Two(Ie, silica) is preferred. The inorganic oxide contains a small amount of Na_TwoCO_Three, K_TwoCO_Three, CaCO_Three, MgCO_Three, Na_TwoSO_Four, Al_Two(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)_Two, Al (NO_Three)_Three, Na_TwoO, K_TwoO, Li_TwoCarbonate such as O, sulfate, nitrate and oxide components may be contained.
[0041]
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.
[0042]
Among these inorganic substances, inorganic oxides are preferably used.
[0043]
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]
In addition, although a hydroxyl group is usually generated and present on the surface of the inorganic oxide, a modified inorganic oxide in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used as the inorganic oxide. Good. The substituent at this time is preferably a silyl group. Specific examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldichlorosilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as chlorosilane and methyltrichlorosilane, aryltrichlorosilanes such as phenyltrichlorosilane, trialkylalkoxysilanes such as trimethylmethoxysilane, triarylalkoxysilanes such as triphenylmethoxysilane, and dialkyldialkoxys such as dimethyldimethoxysilane Silanes, diaryldialkoxysilanes such as diphenyldimethoxysilane, alkyltrials such as methyltrimethoxysilane Contact treatment with aryl trialkoxysilanes such as coxysilane and phenyltrimethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, alkyldisilazanes such as 1,1,1,3,3,3-hexamethyldisilazane, and tetrachlorosilane Inorganic oxides.
[0045]
The median diameter of the inorganic substance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and further preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. Preferably, the specific surface area is 10 to 1000 m^Two/ G, more preferably 100-500 m^Two/ G.
[0046]
As the organic polymer that can be used as the particles of the component (c), 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.
[0047]
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.
[0048]
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.
[0049]
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.
[0050]
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.
[0051]
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.
[0052]
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.
[0053]
The median diameter of the organic polymer is preferably from 5 to 1000 μm, and 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 m^Two/ G, more preferably 50 to 500 m^Two/ G.
[0054]
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.
[0055]
The modified particles of the present invention are modified particles obtained by bringing the above components (a), (b) and (c) into contact. The order in which the component (a), the component (b) and the component (c) are brought into contact is not particularly limited, and includes the following order.
<1> A contact product of the component (a) and the component (b) is brought into contact with the component (c).
<2> A contact product of the component (a) and the component (c) is brought into contact with the component (b).
<3> The contact product of the component (b) and the component (c) is brought into contact with the component (a).
The order of contact is preferably <1> or <2> described above, and most preferably <1>.
[0056]
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.
[0057]
Examples of the solvent include non-polar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, and polar solvents such as halide solvents and ether solvents. Specific examples include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene, xylene and other aromatic hydrocarbon solvents; 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, tetra Ether solvents such as hydropyran like.
[0058]
The use amount of the component (b) with respect to the component (a) is not particularly limited, but the molar ratio of the component (b) / the component (a) is preferably 0.1 to 8, and is 1 to 6. More preferably, it is more preferably 2 to 4, and most preferably 2.5 to 3.5.
[0059]
In the preparation of the modified particles of the present invention, the amount of the component (c) to be used relative to the component (a) is determined based on the amount of the bismuth derived from the component (a) contained in the modified particles of the present invention. The amount of the atoms is preferably 0.1 mmol or more, more preferably 0.5 to 20 mmol, in terms of the amount of bismuth atoms contained per 1 g of the obtained particles. It may be determined appropriately so that
[0060]
In the modified particles of the present invention, as a result of such a contact treatment, the components (a), (b) and / or (c) as raw materials may remain as unreacted substances. However, when the present invention is applied to polymerization involving formation of addition polymer particles, it is preferable to perform 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 treatment temperature is usually -100 to 300C, preferably -80 to 200C. The processing time is usually from 1 minute to 200 hours, preferably from 10 minutes to 100 hours.
[0061]
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.
[0062]
Specific examples of the method for producing the modified particles of the present invention will be described in more detail in the case where component (a) is triphenylbismuth, component (b) is pentafluorophenol, and component (c) is silica. It is shown below.
Using toluene as a solvent, triphenylbismuth was added thereto, and a toluene solution of pentafluorophenol in an amount of 3 molar equivalents relative to triphenylbismuth was added dropwise thereto. The mixture was stirred at room temperature for 10 minutes to 24 hours, and then refluxed. Stir for 10 minutes to 24 hours below. Thereafter, the solvent is concentrated, and the precipitated solid component is separated by filtration and dried.
Toluene and silica are added to the solid component obtained by the above operation, and the mixture is stirred at 80 ° C. for 2 hours. After washing the solid component with toluene, drying is performed under reduced pressure. Thus, the modified particles of the present invention can be produced.
[0063]
The modified particles of the present invention described in detail above 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 the modified particles (A) of the present invention obtained by bringing the above-mentioned components (a), (b) and (c) into contact with each other; A catalyst for addition polymerization obtained by contacting a Group 11 or lanthanoid-based metal compound (B), and a modified product of the present invention obtained by contacting the above components (a), (b) and (c). Examples include an addition polymerization catalyst obtained by contacting particles (A), a Group 3 to 11 or lanthanoid-based metal compound (B), and an organoaluminum compound (C). The latter is more preferable because it has higher activity.
Hereinafter, the addition polymerization catalyst will be described in more detail.
[0064]
(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 a preparation method similar to that of a single-site catalyst in such a narrow sense, an addition polymer having a wide molecular weight distribution and a catalyst capable of obtaining an addition polymer having a wide composition distribution in the case of copolymerization are also included. .
[0065]
As the transition metal compound (B), a transition metal compound represented by the general formula [3] or a μ-oxo-type transition metal compound dimer thereof is preferable.
L^Two _aMX¹ _b                  [3]
(Wherein, M is a transition metal atom belonging to Groups 3 to 11 of the periodic table or a lanthanoid series. L^Two Is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom;^Two When there are a plurality of L, they may be the same or different from each other, and a plurality of L^Two May be directly connected or may be connected via a residue containing at least one atom selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. . X¹ Represents a halogen atom, a hydrocarbon group (however, excluding a group having a cyclopentadiene-type anion skeleton) or OR (where, R represents a hydrocarbon group or a halogenated hydrocarbon group, and when there are a plurality of R, they are mutually separated. May be the same or different), and X¹When there are two or more, they may be the same or different from each other. a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. )
[0066]
In the general formula [3], M is 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 the general formula [3] is 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, and particularly preferably a titanium atom, a zirconium atom or a hafnium atom. .
[0067]
In the general formula [3], L^Two Is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom;^Two May be the same or different. Also multiple L^Two May be directly connected or may be connected via a residue containing at least one atom selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. .
[0068]
L^Two Examples of the group having a cyclopentadiene-type anion skeleton include a (substituted) cyclopentadienyl group and η^Five -(Substituted) indenyl group, η^Five — (Substituted) fluorenyl group and the like. To give a concrete example, η^Five -Cyclopentadienyl group, η^Five -Methylcyclopentadienyl group, η^Five -Ethylcyclopentadienyl group, η^Five -N-butylcyclopentadienyl group, η^Five -Tert-butylcyclopentadienyl group, η^Five -1,2-dimethylcyclopentadienyl group, η^Five -1,3-dimethylcyclopentadienyl group, η^Five -1-methyl-2-ethylcyclopentadienyl group, η^Five -1-methyl-3-ethylcyclopentadienyl group, η^Five -1-tert-butyl-2-methylcyclopentadienyl group, η^Five -1-tert-butyl-3-methylcyclopentadienyl group, η^Five -1-methyl-2-isopropylcyclopentadienyl group, η^Five -1-methyl-3-isopropylcyclopentadienyl group, η^Five -1-methyl-2-n-butylcyclopentadienyl group, η^Five -1-methyl-3-n-butylcyclopentadienyl group, η^Five -1,2,3-trimethylcyclopentadienyl group, η^Five -1,2,4-trimethylcyclopentadienyl group, η^Five A tetramethylcyclopentadienyl group, η^Five -Pentamethylcyclopentadienyl group, η^Five -Indenyl group, η^Five -4,5,6,7-tetrahydroindenyl group, η^Five -2-methylindenyl group, η^Five -3-methylindenyl group, η^Five -4-methylindenyl group, η^Five -5-methylindenyl group, η^Five -6-methylindenyl group, η^Five -7-methylindenyl group, η^Five -2-tert-butylindenyl group, η^Five -3-tert-butylindenyl group, η^Five -4-tert-butylindenyl group, η^Five -5-tert-butylindenyl group, η^Five -6-tert-butylindenyl group, η^Five -7-tert-butylindenyl group, η^Five -2,3-dimethylindenyl group, η^Five -4,7-dimethylindenyl group, η^Five -2,4,7-trimethylindenyl group, η^Five -2-methyl-4-isopropylindenyl group, η^Five -4,5-benzindenyl group, η^Five -2-methyl-4,5-benzindenyl group, η^Five -4-phenylindenyl group, η^Five -2-methyl-5-phenylindenyl group, η^Five -2-methyl-4-phenylindenyl group, η^Five -2-methyl-4-naphthylindenyl group, η^Five A fluorenyl group, η^Five -2,7-dimethylfluorenyl group, η^Five -2,7-di-tert-butylfluorenyl group, and substituted products thereof.
In this specification, the name of the transition metal compound is "η^Five “-” May be omitted.
[0069]
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.
[0070]
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, catecholate group, 2-hydroxy Phenyl group, resorcinolate group, 3-hydroxyphenyl group, 4-isopropylcatecholate group, 4-isopropyl-2-hydroxyphenyl group, 3-methoxycatecholate group, 3-methoxy-2-hydroxyphenyl group, 1,8- Dihydroxynaphthyl group, 1,2-dihydroxyna Tyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol group, 2,2′-dihydroxy-6,6′-dimethylbiphenyl group, 4,4 ′, 6,6 ′ -Tetra-tert-butyl-2,2'methylenediphenoxy group, 4,4 ', 6,6'-tetramethyl-2,2'-isobutylidenediphenoxy group and the like.
[0071]
Further, examples of the group containing a hetero atom include a group represented by the following general formula [4].
R^Two _ThreeP = N- [4]
(Where R^Two Represents a hydrogen atom, a halogen atom or a hydrocarbon group;^Two May be the same or different from each other, and two or more of them may be bonded to each other or form a ring. )
[0072]
R in the general formula [4]^TwoSpecific 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.
[0073]
Further, examples of the group containing a hetero atom include a group represented by the following general formula [5].

(Where R^ThreeRepresents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbonoxy group, a silyl group or an amino group;^ThreeMay be the same or different from each other, and two or more of them may be bonded to each other or form a ring. )
[0074]
R in the general formula [5]^ThreeExamples 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.
[0075]
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.
[0076]
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.
[0077]
Groups having a cyclopentadiene-type anion skeleton, groups 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 or a silicon atom. They may be connected via a residue containing at least one atom selected from the group consisting of an atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. Preferably such residues are two L^Two Is a divalent residue in which a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably two L^Two Is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom;^Two A divalent residue having a minimum number of atoms of 3 or less between the atoms bonding to^Two Includes 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 A substituted silylene group such as a group, a tetramethyldisilylene group or a dimethoxysilylene group; or a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. (Isopropylidene group), diphenylmethylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group or dimethoxysilylene group.
[0078]
X in general formula [3]¹ Is a halogen atom, a hydrocarbon group or OR. 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.
[0079]
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, isoamyl 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 A tert-butyl group, an isobutyl group or an isoamyl 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.
[0080]
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 are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. May be partially substituted.
[0081]
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.
Each of these aryl groups is 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.
[0082]
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.
[0083]
R in OR is a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group, an aralkyl group, and an aryl group. Preferably, the alkyl group has 1 to 20 carbon atoms, and the aralkyl has 7 to 20 carbon atoms. Groups or aryl groups having 6 to 20 carbon atoms are preferred. Specific examples thereof include the same as those described above.
In this case, R is particularly preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a phenyl group, a 2,6-di (tert-butyl) phenyl group or a benzyl group. R is particularly preferably a methyl group, a phenyl group, a 2,6-di (tert-butyl) phenyl group or a benzyl group, and most preferably a phenyl group.
[0084]
X¹ Is more preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, benzyl group, allyl group or methallyl group.
[0085]
In the general formula [3], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M.
[0086]
Among the transition metal compounds represented by the general formula [3], 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,
[0087]
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,
[0088]
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,
[0089]
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,
[0090]
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,
[0091]
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,
[0092]
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,
[0093]
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,
[0094]
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,
[0095]
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,
[0096]
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,
[0097]
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,
[0098]
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,
[0099]
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,
[0100]
(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,
[0101]
(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,
[0102]
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,
[0103]
[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, Diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or di (2,6-di-tert. -Butylphenoxide), and trichloride as trifluoride, tribromide, triiodide, trimethyl, triethyl, triisopropyl, triphenyl, triben Jill, trimethoxide, triethoxide, tri-n-propoxide, triisopropoxide, tri-n-butoxide, triisobutoxide, tri-tert-butoxide, triphenoxide or tri (2,6-di-tert-butylphenoxide) And the like.
[0104]
Among the transition metal compounds represented by the general formula [3], 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,
[0105]
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,
[0106]
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,
[0107]
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,
[0108]
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,
[0109]
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,
[0110]
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,
[0111]
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,
[0112]
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,
[0113]
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, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or di (2,6-di-tert-butylphenoxide) Modified compounds and the like can be exemplified.
[0114]
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)]. Butylpyrazolyl) borate] Nickel chloride and chlorides of these compounds can be used as bromide, iodide, methyl, ethyl, allyl, methallyl, methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert- Compounds changed to butoxide, phenoxide or 2,6-di-tert-butylphenoxide are mentioned.
[0115]
Examples of the nickel compound include compounds represented by the following structural formula.

(Where R^Four And R^Five Each represents a 2,6-diisopropylphenyl group;⁶ And R⁷ Is a hydrogen atom or a methyl group or R⁶ And R⁷ Together with an acenaphthene group, X^Two Is 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 phenyl group, a benzyl group, a methoxy group, an ethoxy group, an n-propoxy group, A propoxy group, an n-butoxy group, an isobutoxy group, or a phenoxy group;^TwoMay be the same or different. )
Further, compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium in the above nickel compounds can also be exemplified.
[0116]
Among the transition metal compounds represented by the general formula [3], 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 Dichloride and the like, and dichlorides of these compounds, difluoride, dibromide, diiodide, dimethyl, diethyl, dimethoxide, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di- tert-butoxide, diphenoxide or di (2,6-di-tert-butylphenoxide) Further the compounds.
[0117]
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 chlorides of these compounds, such as fluoride, bromide, iodide, methyl, ethyl, allyl, methallyl, methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide , Tert-butoxide, phenoxide, or 2,6-di-tert-butylphenoxide.
In the above-mentioned iron compounds, compounds in which iron is replaced with cobalt or nickel can also be exemplified.
[0118]
Specific examples of the transition metal compound of the μ-oxo type represented by the general formula [3] 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. Further, chlorides of these compounds may be selected from fluoride, bromide, iodide, methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide, phenoxide or Compounds changed to 2,6-di-tert-butylphenoxide can be exemplified.
[0119]
In addition to the transition metal compound represented by the general formula [3] exemplified above and the compound used as the transition metal compound (B) in addition to the μ-oxo type transition metal compound, 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.
[0120]
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.
[0121]
These transition metal compounds may be used alone or in combination of two or more.
[0122]
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 [3]. Among them, a transition metal compound in which M in the general formula [3] is a Group 4 atom is preferable, and in particular, L in the general formula [3]^Two Is preferably a so-called metallocene transition metal compound having at least one group having a cyclopentadiene-type anion skeleton.
[0123]
(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 [6].
R⁸ _cAlY_3-c                    [6]
(Where R⁸ Represents a hydrocarbon group;⁸Is more than one, each R⁸ May be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, or an aryloxy group, and when there are a plurality of Y, each Y may be the same or different. c represents a number satisfying 0 <c ≦ 3. )
[0124]
R in general formula [6] representing an organoaluminum compound⁸ Is 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.
[0125]
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.
[0126]
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.
[0127]
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.
[0128]
Specific examples of the organoaluminum compound represented by the general formula [6] 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 and 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.
[0129]
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.
[0130]
The amount of component (B) used is usually 1 × 10^-6~ 1 × 10^-3mol, preferably 5 × 10^-6~ 5 × 10^-Fourmol. Component (C) is used in an amount of 0.01 to 0.01 as a molar ratio ((C) / (B)) of aluminum atom of component (C) organoaluminum compound to transition metal atom of component (B). It is preferably 10,000, more preferably 0.1 to 5,000, and most preferably 1 to 2,000.
[0131]
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.
[0132]
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.
[0133]
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.
[0134]
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.
[0135]
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.
[0136]
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.
[0137]
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).
[0138]
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.
[0139]
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.
[0140]
In the present invention, the preliminary polymerization described below may be performed before the polymerization (main polymerization) is performed.
[0141]
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.
[0142]
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.
[0143]
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.
[0144]
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], and particularly preferably from 0.5 to 20 [g-the above-mentioned modified particle]. [Particle] / [liter-solvent] is preferred. 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.
[0145]
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 the contact, any method such as the method of supplying the modified particles (A) described above may be used. 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.
[0146]
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).
[0147]
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.
[0148]
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.
[0149]
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.
[0150]
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.
[0151]
【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.
[0152]
(1) α-Olefin unit content in the copolymer: The α-olefin unit content in the obtained polymer is obtained from an infrared absorption spectrum, and is expressed as a number of short-chain branches per 1,000 carbon atoms (SCB). did. The measurement and the calculation were carried out by utilizing the characteristic absorption derived from α-olefin according to the method described in the literature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, M.A., Madams, W.F.). The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation).
[0153]
(2) Intrinsic viscosity [η]: Measured in a tetralin solution at 135 ° C. using an Ubbelohde viscometer.
[0154]
(3)¹³C-NMR measurement
¹³For the measurement of C-NMR, JEOL JNM-EX270 (67.5 MHz,¹³C) was used. The measurement was performed at room temperature using the deuterated solvent described in the examples.
[0155]
(4) Molecular weight and molecular weight distribution
The measurement was carried out by gel permeation chromatography (GPC) under the following conditions. A calibration curve was created using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model: 150C type manufactured by Millipore Waters
Column: Two TSK-GEL GMH-HT (7.5 × 600)
Measurement temperature: 140 ° C
Solvent: orthodichlorobenzene,
Measurement concentration: 5mg / 5ml
(5) Melt flow rate (MFR)
The melt flow rate (MFR) was measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. in accordance with the method specified in JIS K7210-1995. (Unit: g / 10 minutes)
(6) Melt flow rate ratio (MFRR)
According to the method specified in JIS K7210-1995, the melt flow rate (MFR) under the condition of a load of 21.18 N and a temperature of 190 ° C. and the melt flow rate (MFR2) under the condition of a load of 211.82 N and a temperature of 190 ° C. Was measured, and a value obtained by dividing MFR2 by MFR (MFR2 / MFR) was obtained and defined as a melt flow rate ratio (MFRR).
(7) Swell ratio (SR)
In a melt flow rate measurement under the conditions of a load of 21.18 N and a temperature of 190 ° C. using a melt flow rate measurement device specified in JIS K7210-1995, the diameter (d (mm)) of the extruded strand was measured, and the orifice was measured. Diameter (d₀(Mm) = 2.095) (d / d)₀) Was determined and defined as a swell ratio (SR).
(8) Melting point (mp)
The measurement was performed using a differential scanning calorimeter (SSC-5200 manufactured by Seiko Instruments Inc.) under the following conditions.
Conditioning: After raising the temperature from 40 ° C. to 150 ° C. at 10 ° C./min, holding at 150 ° C. for 5 minutes, then lowering the temperature from 150 ° C. to 40 ° C. at 5 ° C./min, and holding at 40 ° C. for 10 minutes. .
Melting point measurement: Immediately after condition adjustment, the temperature was raised from 40 ° C to 160 ° C at a rate of 5 ° C / min.
[0156]
[Example 1]
(1) Synthesis of intermediate
9.88 g (22.4 mmol) of triphenylbismuth and 100 ml of toluene were placed in a 300 ml four-necked flask purged with argon, and stirred at room temperature. To this was added dropwise a solution of 12.6 g (68.5 mmol) of pentafluorophenol in 100 ml of toluene. After completion of the dropwise addition, the mixture was stirred at room temperature for 15.5 hours. Thereafter, the reaction was carried out sequentially for 4 hours under refluxing conditions of toluene, 18 hours at room temperature, 7 hours under refluxing conditions of toluene, and 17 hours at room temperature. The resulting yellow needle-like crystals were separated by filtration and dried under reduced pressure at room temperature to obtain 12.6 g of an intermediate.
[0157]
(2) Synthesis of component (A)
1.54 g of the intermediate synthesized in Example 1 (1) and 40 ml of toluene were placed in a 50 ml four-necked flask purged with argon, and stirred at room temperature. Silica heat-treated at 300 ° C. under nitrogen flow (Sylopol 948, manufactured by Devison; median diameter = 55 μm; pore volume = 1.66 ml / g; specific surface area = 309 m)^Two/ G) 0.73 g was added, the temperature was raised to 80 ° C., and the mixture was stirred for 2 hours. The solid was separated by filtration, washed four times with 20 ml of toluene and once with 20 ml of hexane, and dried under reduced pressure at room temperature to obtain component (A). As a result of elemental analysis, Bi = 0.48 mmol / g and F = 4.0 mmol / g.
[0158]
(3) polymerization
An autoclave with a stirrer having an inner volume of 3 liters was vacuum-dried and purged with argon, and the pressure was reduced. Then, 0.49 vol% of hydrogen, 700 g of butane as a solvent, and 50 g of 1-butene as a comonomer were charged, and the reactor was heated to 70 ° C. did. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 1.6 MPa. After the system was stabilized, 0.9 mmol of triisobutylaluminum was added, followed by 0.5 μmol of ethylenebis (indenyl) zirconium dichloride. Further, 17.2 mg of the component (A) obtained in the above (2) was added to initiate polymerization. Polymerization was performed for 60 minutes.
As a result of the polymerization, 35 g of an ethylene / 1-butene copolymer was obtained. Polymerization activity = 2000 (g / g-component (A) / h), SCB = 15.15 (1 / 1000C), MFR = 0.93 (g / 10 min), MFRR = 91.40, SR = 1. 25.
[0159]
[Example 2]
(1) polymerization
An autoclave with an internal volume of 0.4 liter and equipped with a stirrer was vacuum-dried and purged with argon, 10 ml of 1-hexene as a comonomer and 190 ml of hexane as a solvent were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa. After the system was stabilized, 0.25 mmol of triisobutylaluminum was added, followed by 1 μmol of ethylenebis (indenyl) zirconium dichloride. 30.4 mg of the component (A) obtained in Example 1 (2) was added to initiate polymerization. Polymerization was performed for 30 minutes.
As a result of the polymerization, 22.4 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity = 1500 (g / g-component (A) / h), 45 (kg / mmol-Zr / h), Mw = 58000, Mw / Mn = 1.9, SCB = 36.0 (1 / 1000C) Met.
[0160]
[Example 3]
(1) Synthesis of intermediate
101 g (230 mmol) of triphenylbismuth and 500 ml of toluene were placed in a 2000 ml four-necked flask purged with argon, and stirred at room temperature. To this, 345 ml (690 mmol) of a toluene solution of pentafluorophenol (2 mmol / ml) was added dropwise. After the completion of the dropwise addition, the reaction was carried out under a reflux condition of toluene for 11 hours. The resulting yellow needle-like crystals were separated by filtration and dried at room temperature under reduced pressure to obtain 171 g of an intermediate. From elemental analysis, Bi = 1.2 mmol / g and F = 15 mmol / g.
[0161]
(2) Synthesis of component (A)
17.7 g (23.4 mmol) of the intermediate synthesized in Example 3 (1) and 300 ml of toluene were placed in a 1000 ml four-necked flask purged with argon, and stirred at room temperature. Silica heat-treated at 300 ° C. under a nitrogen flow (Syropol 948, manufactured by Devison; median diameter = 55 μm; pore volume = 1.7 ml / g; specific surface area = 306 m)^Two/ G) 21.1 g and 30 ml of toluene were added, the temperature was raised to 80 ° C., and the mixture was stirred for 2 hours. The solid was separated by filtration, washed four times with 100 ml of toluene and once with 100 ml of hexane, and dried at room temperature under reduced pressure to obtain 27.5 g of the component (A). As a result of elemental analysis, Bi = 0.48 mmol / g and F = 3.3 mmol / g.
[0162]
(3) polymerization
An autoclave with an internal volume of 0.4 liter and equipped with a stirrer was vacuum-dried and purged with argon, 10 ml of 1-hexene as a comonomer and 190 ml of hexane as a solvent were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa, and after the inside of the system was stabilized, 0.25 mmol of triisobutylaluminum was added, followed by 0.3 μmol of ethylenebis (indenyl) zirconium dichloride, Further, 9.1 mg of the component (A) obtained in Example 3 (2) was added to initiate polymerization. Polymerization was performed for 30 minutes.
As a result of the polymerization, 16.1 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity = 3500 (g / g-component (A) / h), 110 (kg / mmol-Zr / h), Mw = 160,000, Mw / Mn = 3.8, η = 1.65 (dl / g) , SCB = 18.81 (1 / 1000C).
[0163]
[Comparative Example 1]
(1)
Example 1 In Example 1 (2), except that 1.56 g of the intermediate synthesized in Example 1 (1) was used, 1.16 g of triphenylbismuth was used, and the amount of silica was changed to 1.10 g. Synthesis was performed according to (2). As a result, 0.79 g of a white solid was obtained.
[0164]
(2) polymerization
An autoclave with an internal volume of 0.4 liter and equipped with a stirrer was vacuum-dried and purged with argon, 10 ml of 1-hexene as a comonomer and 190 ml of hexane as a solvent were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa. After the system was stabilized, 0.25 mmol of triisobutylaluminum was added, followed by 1 μmol of ethylenebis (indenyl) zirconium dichloride. 22.9 mg of the white solid obtained in Comparative Example 1 (1) was added to initiate polymerization. Polymerization was performed for 30 minutes.
As a result of the polymerization, only a trace amount of the polymer was obtained.
[0165]
[Example 4]
(1) <dimethylsilylene (η^FiveSynthesis of -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide>
In a Schlenk tube, 0.131 g (4.1 mmol) of methanol was dissolved in 10 ml of anhydrous ether, and an ether solution of methyllithium (3.9 ml, 4.1 mmol) having a concentration of 1.05 mol / L was added dropwise at -78 ° C. The temperature was raised to 20 ° C., and the completion of gas generation was confirmed, whereby the formation of lithium methoxide was confirmed, and the mixture was cooled again to −78 ° C. Dimethylsilylene (η, previously prepared in another Schlenk tube^FiveA suspension of 0.919 g (2.0 mmol) of -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride in 20 ml of anhydrous ether was transferred to the above reaction solution, Thereafter, the temperature was gradually raised to room temperature. After concentrating the reaction solution, 20 ml of toluene was added, and insolubles were filtered off. The filtrate is concentrated, and dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (hereinafter, referred to as compound A) was obtained as yellow crystals. (0.86 g, 95%)
¹H-NMR (270 MHz, C₆D₆) 7.26 (m, 2H), 4.13 (s, 6H), 2.33 (s, 3H), 1.97 (s, 6H), 1.89 (s, 6H), 1.59 ( s, 9H), 0.55 (s, 6H)

[0166]
(2) polymerization
An autoclave with a stirrer having an inner volume of 0.4 liter was vacuum-dried and replaced with argon, 2 ml of 1-hexene as a comonomer and 198 ml of hexane as a solvent were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa. After the inside of the system was stabilized, 0.25 mmol of triisobutylaluminum was added, and then a toluene solution in which compound A and triisobutylaluminum were mixed (compound The concentration of A was 1 μmol / ml, the concentration of triisobutylaluminum was 50 μmol / ml, and the molar ratio between Al atoms and Ti atoms was adjusted to 50. Then, 43.0 mg of the component (A) obtained in Example 1 (2) was added to initiate polymerization. Polymerization was performed for 30 minutes.
As a result of the polymerization, 1.79 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity = 83 (g / g-component (A) / h), 3.6 (kg / mmol-Ti / h), Mw = 440000, Mw / Mn = 2.1, η = 4.55 (dl / g), SCB = 19.34 (1 / 1000C).
[0167]
[Example 5]
(1) Synthesis of intermediate
17.2 g (39.1 mmol) of triphenylbismuth and 175 ml of toluene were placed in a 500-ml four-necked flask purged with argon, and stirred at room temperature. A solution of 22.0 g (119 mmol) of pentafluorophenol dissolved in 50 ml of toluene was added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out for 8 hours under refluxing conditions of toluene, 15 hours at room temperature, and 4 hours under refluxing conditions of toluene. The resulting yellow needle-like crystals were separated by filtration and dried at room temperature under reduced pressure to obtain 28.2 g of an intermediate.
[0168]
(2) Synthesis of component (A)
2.48 g of the intermediate synthesized in Example 5 (1) and 40 ml of toluene were placed in a 100-ml four-necked flask purged with argon, and stirred at room temperature. Silica heat-treated at 300 ° C. under nitrogen flow (Sylopol 948, manufactured by Devison; median diameter = 55 μm; pore volume = 1.66 ml / g; specific surface area = 309 m)^Two/ G) 3.11 g and 5 ml of toluene were added, the temperature was raised to 80 ° C., and the mixture was stirred for 2 hours. The solid was separated by filtration, washed four times with 30 ml of toluene and once with 30 ml of hexane, and dried at room temperature under reduced pressure to obtain 3.84 g of the component (A). As a result of elemental analysis, Bi = 0.53 mmol / g and F = 3.2 mmol / g.
[0169]
(3) polymerization
A 0.4-liter autoclave with a stirrer was vacuum-dried and purged with argon, 15 ml of 1-hexene as a comonomer and 185 ml of cyclohexane as a solvent were charged, and the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.3 mmol of triisobutylaluminum was added, and then a toluene solution in which compound A and triisobutylaluminum were mixed (compound The concentration of A was 0.5 μmol / ml, the concentration of triisobutylaluminum was 25 μmol / ml, and the molar ratio between Al atoms and Ti atoms was adjusted to 50. 1 ml (that is, 0.5 μmol of compound A, triisobutyl Aluminum (25 μmol) was added, and further, 126 mg of the component (A) obtained in Example 5 (2) was added to initiate polymerization. Polymerization was performed for 2 minutes.
As a result of the polymerization, 1.41 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity = 340 (g / g-component (A) / h), 85 (kg / mmol-Ti / h), Mw = 100000, Mw / Mn = 1.9, η = 1.46 (dl / g) , Melting point = 81.4 (° C).
[0170]
【The invention's effect】
As described above, according to the present invention, modified particles capable of forming an addition polymerization catalyst having high polymerization activity by using as an activating co-catalyst component, addition polymerization comprising the modified particles The present invention provides a catalyst component for use, an addition polymerization catalyst having high polymerization activity using the modified particles, and a method for efficiently producing an addition polymer using the addition polymerization catalyst.

Claims (11)

Modified particles obtained by contacting the following components (a), (b) and (c).
(A): Compound BiL ¹ _m [1] represented by the general formula [1]
(B): Compound R ¹ _tn TH _n [2] represented by the general formula [2]
(C): particles (in the above general formulas [1] and [2], m represents a number corresponding to the valence of Bi, and L ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbonoxy group. represents, when L ¹ there are a plurality or different even they are identical to each other, R ¹ represents a group or an electron withdrawing group containing an electron withdrawing group, if R ¹ there are a plurality of May be the same as or different from each other, T represents a non-metallic atom of Group 15 or 16 of the periodic table, t represents a number corresponding to the valence of T, and n represents 1 Represents an integer other than 2 and an integer excluding 2) 2. The modified particle according to claim 1, wherein T is an oxygen atom. 3. The modified particles according to claim 1, wherein R ¹ is a halogenated hydrocarbon group. 4. The modified particle according to claim 1, wherein m is 3. An addition polymerization catalyst component comprising the modified particles according to claim 1. An addition polymerization catalyst comprising the modified particles (A) according to any one of claims 1 to 4 and a transition metal compound (B) belonging to a group 3 to 11 or a lanthanoid series. An addition polymerization obtained by contacting the modified particles (A) according to any one of claims 1 to 4, a group 3 to 11 or lanthanoid-based transition metal compound (B), and an organoaluminum compound (C). Catalyst. The addition polymerization catalyst according to claim 6 or 7, wherein the transition metal compound (B) of the group 3 to 11 or a lanthanoid series is a metallocene transition metal compound. 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.