JP4770044B2 - Olefin polymerization catalyst component, olefin polymerization catalyst, and process for producing olefin polymer - Google Patents

Description

（上記一般式［III］、［IV］または［Ｖ］においてそれぞれ、Ｍは元素の周期律表の第４族の遷移金属原子を示し、Ａは元素の周期律表の第１６族の原子を示し、Ｊは元素の周期律表の第１４族の原子を示す。Ｃｐはシクロペンタジエン形アニオン骨格を有する基を示す。Ｘ¹、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、置換シリル基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、２置換アミノ基、アルキルチオ基、アラルキルチオ基、アリールチオ基、アルキルセレノ基、アラルキルセレノ基、またはアリールセレノ基を示す。Ｘ²は元素の周期律表の第１６族の原子を示す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は任意に結合して環を形成しても良い。複数のＭ、Ａ、Ｊ、Ｃｐ、Ｘ¹、Ｘ²、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ同じであっても異なっていても良い。）
【００４４】
上記一般式［III］、［IV］または［Ｖ］におけるＭ、ＣｐおよびＸ²はそれぞれ、上記一般式［Ｉ］または［II］におけるそれらと同様である。また上記一般式［III］、［IV］または［Ｖ］におけるＸ¹、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に、上記一般式［Ｉ］または［II］におけるＸ¹と同様である。
【００４５】
但し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴として好ましくは、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、置換シリル基、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であり、中でもＲ¹としては、アルキル基、アラルキル基、アリール基または置換シリル基が特に好ましい。
【００４６】
また、上記一般式［III］、［IV］または［Ｖ］におけるＲ⁵、Ｒ⁶としては、それぞれ独立に、水素原子、アルキル基、アラルキル基、アリール基、置換シリル基、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が好ましい。
【００４７】
一般式［III］、［IV］または［Ｖ］において、Ａとして示される元素の周期律表の第１６族の原子としては、例えば酸素原子、硫黄原子、セレン原子などが挙げられる。好ましくは、酸素原子である。
【００４８】
一般式［III］、［IV］または［Ｖ］において、Ｊとして示される元素の周期律表の第１４族の原子としては、例えば炭素原子、ケイ素原子、ゲルマニウム原子などが挙げられる。好ましくは、炭素原子またはケイ素原子である。
【００４９】
かかる遷移金属化合物として、例えば、一般式［Ｉ］におけるｍが１で、架橋基がない遷移金属化合物の具体例として、（η⁵−シクロペンタジエニル）チタニウムトリクロライド、（η⁵−シクロペンタジエニル）チタニウムトリメチル、（η⁵−シクロペンタジエニル）（ジメチルアミノ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（ジエチルアミノ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（ジ−ｎ−ブチルアミノ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（ジ−ｎ−オクチルアミノ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（ジフェニルアミノ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（メトキシ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（エトキシ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（ｔｅｒｔ−ブトキシ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（フェノキシ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（２，６−ジ−ｔｅｒｔ−ブチルフェノキシ）チタニウムジクロライド、（η⁵−シクロペンタジエニル）（２−ｔｅｒｔ−ブチル−４−メチルフェノキシ）チタニウムジクロライドなどや、これらの化合物のη⁵−シクロペンタジエニルをη⁵−メチルシクロペンタジエニル、η⁵−ジメチルシクロペンタジエニル、η⁵−トリメチルシクロペンタジエニル、η⁵−テトラメチルシクロペンタジエニル、η⁵−ペンタメチルシクロペンタジエニル、η⁵−エチルシクロペンタジエニル、η⁵−ｎ−ブチルシクロペンタジエニル、η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル、η⁵−ジ−ｔｅｒｔ−ブチルシクロペンタジエニル、η⁵−トリメチルシリルシクロペンタジエニル、η⁵−ｔｅｒｔ−ブチルジメチルシリルシクロペンタジエニル、η⁵−フェニルシクロペンタジエニル、η⁵−インデニル、η⁵−メチルインデニル、η⁵−フェニルインデニルまたはη⁵−フルオレニルに変更した化合物、チタニウムをジルコニウムまたはハフニウムに変更した化合物、ジクロライドをジメチル、ジベンジル、ジメトキシド、ジフェノキシド、ビス（ジメチルアミノ）またはビス（ジエチルアミノ）に変更した化合物といった遷移金属化合物などを挙げることができる。
【００５０】
一般式［Ｉ］におけるｍが２で、架橋基がない遷移金属化合物の具体例として、ビス（η⁵−シクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−メチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−ジメチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−トリメチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−テトラメチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−ペンタメチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−エチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−ｎ−ブチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−トリメチルシリルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−ｔｅｒｔ−ブチルジメチルシリルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−フェニルシクロペンタジエニル）チタニウムジクロライド、ビス（η⁵−インデニル）チタニウムジクロライド、ビス（η⁵−フルオレニル）チタニウムジクロライドなどや、これらの化合物のチタニウムをジルコニウムまたはハフニウムに変更した化合物、ジクロライドをジメチル、ジベンジル、ジメトキシド、ジフェノキシド、ビス（ジメチルアミノ）またはビス（ジエチルアミノ）に変更した化合物といった遷移金属化合物などを挙げることができる。
【００５１】
一般式［Ｉ］におけるｍが１で、架橋基がある遷移金属化合物の具体例として、ジメチルシリレン（メチルアミノ）（η⁵−シクロペンタジエニル）チタニウムジクロライド、ジメチルシリレン（ｔｅｒｔ−ブチルアミノ）（η⁵−シクロペンタジエニル）チタニウムジクロライド、ジメチルシリレン（フェニルアミノ）（η⁵−シクロペンタジエニル）チタニウムジクロライド、ジメチルシリレン（シクロヘキシルアミノ）（η⁵−シクロペンタジエニル）チタニウムジクロライドなどや、これらの化合物のη⁵−シクロペンタジエニルをη⁵−メチルシクロペンタジエニル、η⁵−テトラメチルシクロペンタジエニル、η⁵−エチルシクロペンタジエニル、η⁵−ｎ−ブチルシクロペンタジエニル、η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル、η⁵−ジ−ｔｅｒｔ−ブチルシクロペンタジエニル、η⁵−トリメチルシリルシクロペンタジエニル、η⁵−ｔｅｒｔ−ブチルジメチルシリルシクロペンタジエニル、η⁵−フェニルシクロペンタジエニル、η⁵−インデニル、η⁵−メチルインデニル、η⁵−フェニルインデニルまたはη⁵−フルオレニルに変更した化合物、ジメチルシリレンをジエチルシリレン、ジフェニルシリレン、メチレン、エチレンまたはジメチルメチレン（イソプロピリデン）、ジフェニルメチレン、テトラメチルエチレン、テトラメチルジシリレンに変更した化合物、チタニウムをジルコニウムまたはハフニウムに変更した化合物、ジクロライドをジメチル、ジベンジル、ジメトキシド、ジフェノキシド、ビス（ジメチルアミノ）またはビス（ジエチルアミノ）に変更した化合物といった遷移金属化合物などが挙げられる。
【００５２】
一般式［Ｉ］におけるｍが２で、架橋基がある遷移金属化合物の具体例として、メチレンビス（η⁵−シクロペンタジエニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−シクロペンタジエニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−シクロペンタジエニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−シクロペンタジエニル）チタニウムジクロライド、メチレンビス（η⁵−メチルシクロペンタジエニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−メチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−メチルシクロペンタジエニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−メチルシクロペンタジエニル）チタニウムジクロライド、メチレンビス（η⁵−ジメチルシクロペンタジエニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−ジメチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−ジメチルシクロペンタジエニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−ジメチルシクロペンタジエニル）チタニウムジクロライド、メチレンビス（η⁵−テトラメチルシクロペンタジエニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−テトラメチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−テトラメチルシクロペンタジエニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−テトラメチルシクロペンタジエニル）チタニウムジクロライド、メチレンビス（η⁵−ｎ−ブチルシクロペンタジエニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−ｎ−ブチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−ｎ−ブチルシクロペンタジエニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−ｎ−ブチルシクロペンタジエニル）チタニウムジクロライド、メチレンビス（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）チタニウムジクロライド、
【００５３】
メチレンビス（η⁵−インデニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−インデニル）チタニウムジクロライド、エチレンビス（η⁵−インデニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−インデニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−インデニル）チタニウムジクロライド、メチレンビス（η⁵−メチルインデニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−メチルインデニル）チタニウムジクロライド、エチレンビス（η⁵−メチルインデニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−メチルインデニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−メチルインデニル）チタニウムジクロライド、メチレンビス（η⁵−テトラヒドロインデニル）チタニウムジクロライド、イソプロピリデンビス（η⁵−テトラヒドロインデニル）チタニウムジクロライド、エチレンビス（η⁵−テトラヒドロインデニル）チタニウムジクロライド、ジメチルシリレンビス（η⁵−テトラヒドロインデニル）チタニウムジクロライド、ジフェニルシリレンビス（η⁵−テトラヒドロインデニル）チタニウムジクロライド、メチレン（η⁵−シクロペンタジエニル）（η⁵−フルオレニル）チタニウムジクロライド、イソプロピリデン（η⁵−シクロペンタジエニル）（η⁵−フルオレニル）チタニウムジクロライド、ジメチルシリレン（η⁵−シクロペンタジエニル）（η⁵−フルオレニル）チタニウムジクロライド、ジフェニルシリレン（η⁵−シクロペンタジエニル）（η⁵−フルオレニル）チタニウムジクロライドなどや、これらの化合物のチタニウムをジルコニウムまたはハフニウムに変更した化合物、ジクロライドをジメチル、ジベンジル、ジメトキシド、ジフェノキシド、ビス（ジメチルアミノ）またはビス（ジエチルアミノ）に変更した化合物といった遷移金属化合物などが挙げられる。
【００５４】
一般式［II］で示される遷移金属化合物として、μ−オキソビス｛ビス（η⁵−シクロペンタジエニル）チタニウムクロライド｝、μ−オキソビス｛ビス（η⁵−メチルシクロペンタジエニル）チタニウムクロライド｝、μ−オキソビス｛ビス（η⁵−ペンタメチルシクロペンタジエニル）チタニウムクロライド｝、μ−オキソビス｛（η⁵−シクロペンタジエニル）チタニウムジクロライド｝、μ−オキソビス｛（η⁵−シクロペンタジエニル）（メトキシ）チタニウムクロライド｝、μ−オキソビス｛（η⁵−シクロペンタジエニル）（フェノキシ）チタニウムクロライド｝、μ−オキソビス｛（η⁵−シクロペンタジエニル）（ジメチルアミノ）チタニウムクロライド｝、μ−オキソビス｛（η⁵−シクロペンタジエニル）（ジエチルアミノ）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデンビス（η⁵−シクロペンタジエニル）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレンビス（η⁵−シクロペンタジエニル）チタニウムクロライド｝、μ−オキソビス｛エチレンビス（η⁵−シクロペンタジエニル）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレンビス（η⁵−インデニル）チタニウムクロライド｝、μ−オキソビス｛エチレンビス（η⁵−インデニル）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデン（η⁵−シクロペンタジエニル）（η⁵−フルオレニル）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレン（η⁵−シクロペンタジエニル）（ｔｅｒｔ−ブチルアミノ）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレン（η⁵−メチルシクロペンタジエニル）（ｔｅｒｔ−ブチルアミノ）チタニウムクロライド｝、μ−オキソビス｛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）（ｔｅｒｔ−ブチルアミノ）チタニウムクロライド｝などや、これらの化合物のチタニウムをジルコニウムまたはハフニウムに変更した化合物、クロライドをメチル、ベンジル、メトキシド、フェノキシド、ジメチルアミノまたはジエチルアミノに変更した化合物といった遷移金属化合物などが挙げられる。
【００５５】
さらに一般式［II］で示される遷移金属化合物として、例えば、ジ−μ−オキソビス｛ビス（η⁵−シクロペンタジエニル）チタニウム｝、ジ−μ−オキソビス｛ビス（η⁵−メチルシクロペンタジエニル）チタニウム｝、ジ−μ−オキソビス｛ビス（η⁵−ペンタメチルシクロペンタジエニル）チタニウム｝、ジ−μ−オキソビス｛（η⁵−シクロペンタジエニル）チタニウムクロライド｝、ジ−μ−オキソビス｛（η⁵−シクロペンタジエニル）（メトキシ）チタニウム｝、ジ−μ−オキソビス｛（η⁵−シクロペンタジエニル）（フェノキシ）チタニウム｝、ジ−μ−オキソビス｛（η⁵−シクロペンタジエニル）（ジメチルアミノ）チタニウム｝、ジ−μ−オキソビス｛（η⁵−シクロペンタジエニル）（ジエチルアミノ）チタニウム｝、ジ−μ−オキソビス｛イソプロピリデンビス（η⁵−シクロペンタジエニル）チタニウム｝、ジ−μ−オキソビス｛ジメチルシリレンビス（η⁵−シクロペンタジエニル）チタニウム｝、ジ−μ−オキソビス｛エチレンビス（η⁵−シクロペンタジエニル）チタニウム｝、ジ−μ−オキソビス｛ジメチルシリレンビス（η⁵−インデニル）チタニウム｝、ジ−μ−オキソビス｛エチレンビス（η⁵−インデニル）チタニウム｝、ジ−μ−オキソビス｛イソプロピリデン（η⁵−シクロペンタジエニル）（η⁵−フルオレニル）チタニウム｝、ジ−μ−オキソビス｛ジメチルシリレン（η⁵−シクロペンタジエニル）（ｔｅｒｔ−ブチルアミノ）チタニウム｝、ジ−μ−オキソビス｛ジメチルシリレン（η⁵−メチルシクロペンタジエニル）（ｔｅｒｔ−ブチルアミノ）チタニウム｝、ジ−μ−オキソビス｛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）（ｔｅｒｔ−ブチルアミノ）チタニウム｝などや、これらの化合物のチタニウムをジルコニウムまたはハフニウムに変更した化合物といった遷移金属化合物などが挙げられる。
【００５６】
一般式［III］で示される遷移金属化合物の具体例としては、メチレン（η⁵−シクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタニウムジクロライド、メチレン（η⁵−シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタニウムジクロライド、メチレン（η⁵−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、メチレン（η⁵−シクロペンタジエニル）（３−フェニル−２−フェノキシ）チタニウムジクロライド、メチレン（η⁵−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）チタニウムジクロライド、メチレン（η⁵−シクロペンタジエニル）（３−トリメチルシリル−５−メチル−２−フェノキシ）チタニウムジクロライド、メチレン（η⁵−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）チタニウムジクロライド、メチレン（η⁵−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）チタニウムジクロライド、メチレン（η⁵−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）チタニウムジクロライド、メチレン（η⁵−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）チタニウムジクロライド、メチレン（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、メチレン（η⁵−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）チタニウムジクロライド、メチレン（η⁵−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）チタニウムジクロライド、メチレン（η⁵−テトラメチルシクロペンタジエニル）（３−トリメチルシリル−５−メチル−２−フェノキシ）チタニウムジクロライド、メチレン（η⁵−テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタニウムジクロライド、メチレン（η⁵−テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタニウムジクロライド、
【００５７】
イソプロピリデン（η⁵−シクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタニウムジクロライド、イソプロピリデン（η⁵−シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタニウムジクロライド、イソプロピリデン（η⁵−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、イソプロピリデン（η⁵−シクロペンタジエニル）（３−フェニル−２−フェノキシ）チタニウムジクロライド、イソプロピリデン（η⁵−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）チタニウムジクロライド、イソプロピリデン（η⁵−シクロペンタジエニル）（３−トリメチルシリル−５−メチル−２−フェノキシ）チタニウムジクロライド、イソプロピリデン（η⁵−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）チタニウムジクロライド、イソプロピリデン（η⁵−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）チタニウムジクロライド、イソプロピリデン（η⁵−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）チタニウムジクロライド、イソプロピリデン（η⁵−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）チタニウムジクロライド、イソプロピリデン（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、イソプロピリデン（η⁵−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）チタニウムジクロライド、イソプロピリデン（η⁵−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）チタニウムジクロライド、イソプロピリデン（η⁵−テトラメチルシクロペンタジエニル）（３−トリメチルシリル−５−メチル−２−フェノキシ）チタニウムジクロライド、イソプロピリデン（η⁵−テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタニウムジクロライド、イソプロピリデン（η⁵−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）チタニウムジクロライド、
【００５８】
ジフェニルメチレン（η⁵−シクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタニウムジクロライド、ジフェニルメチレン（η⁵−シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタニウムジクロライド、ジフェニルメチレン（η⁵−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、ジフェニルメチレン（η⁵−シクロペンタジエニル）（３−フェニル−２−フェノキシ）チタニウムジクロライド、ジフェニルメチレン（η⁵−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）チタニウムジクロライド、ジフェニルメチレン（η⁵−シクロペンタジエニル）（３−トリメチルシリル−５−メチル−２−フェノキシ）チタニウムジクロライド、ジフェニルメチレン（η⁵−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）チタニウムジクロライド、ジフェニルメチレン（η⁵−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）チタニウムジクロライド、ジフェニルメチレン（η⁵−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）チタニウムジクロライド、ジフェニルメチレン（η⁵−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）チタニウムジクロライド、ジフェニルメチレン（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、ジフェニルメチレン（η⁵−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）チタニウムジクロライド、ジフェニルメチレン（η⁵−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）チタニウムジクロライド、ジフェニルメチレン（η⁵−テトラメチルシクロペンタジエニル）（３−トリメチルシリル−５−メチル−２−フェノキシ）チタニウムジクロライド、ジフェニルメチレン（η⁵−テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メトキシ−２−フェノキシ）チタニウムジクロライド、ジフェニルメチレン（η⁵−テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−クロロ−２−フェノキシ）チタニウムジクロライドなどや、これらの化合物のチタニウムをジルコニウムまたはハフニウムに変更した化合物、ジクロライドをジメチル、ジベンジル、ジメトキシド、ジフェノキシド、ビス（ジメチルアミノ）またはビス（ジエチルアミノ）に変更した化合物、（η⁵−シクロペンタジエニル）を（η⁵−メチルシクロペンタジエニル）、（η⁵−ジメチルシクロペンタジエニル）、（η⁵−トリメチルシクロペンタジエニル）、（η⁵−ｎ−ブチルシクロペンタジエニル）、（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）、（η⁵−トリメチルシリルシクロペンタジエニル）、（η⁵−ｔｅｒｔ−ブチルジメチルシリルシクロペンタジエニル）、（η⁵−インデニル）、（η⁵−メチルインデニル）、（η⁵−フェニルインデニル）または（η⁵−フルオレニル）に変更した化合物、（３，５−ジメチル−２−フェノキシ）を（２−フェノキシ）、（３−メチル−２−フェノキシ）、（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）、（３−フェニル−５−メチル−２−フェノキシ）、（３−ｔｅｒｔ−ブチルジメチルシリル−２−フェノキシ）、または（３−トリメチルシリル−２−フェノキシ）に変更した化合物といった遷移金属化合物、
【００５９】
ジメチルシリレン（η⁵−シクロペンタジエニル）（２−フェノキシ）チタニウムジクロライド、ジメチルシリレン（η⁵−シクロペンタジエニル）（３−メチル−２−フェノキシ）チタニウムジクロライド、ジメチルシレン（η⁵−シクロペンタジエニル）（３，５−ジメチル−２−フェノキシ）チタニウムジクロライド、ジメチルシリレン（η⁵−シクロペンタジエニル）（３−ｔｅｒｔ−ブチル−２−フェノキシ）チタニウムジクロライド、ジメチルシリレン（η⁵−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、ジメチルシリレン（η⁵−シクロペンタジエニル）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタニウムジクロライド、ジメチルシリレン（η⁵−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）チタニウムジクロライド、ジメチルシリレン（η⁵−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）チタニウムジクロライド、ジメチルシリレン（η⁵−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）チタニウムジクロライド、ジメチルシリレン（η⁵−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）チタニウムジクロライド、ジメチルシリレン（η⁵−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）チタニウムジクロライド、ジメチルシリレン（η⁵−シクロペンタジエニル）（３，５−ジアミル−２−フェノキシ）チタニウムジクロライド、ジメチルシリレン（η⁵−シクロペンタジエニル）（１−ナフトキシ−２−イル）チタニウムジクロライド、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）（２−フェノキシ）チタニウムジクロライド、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−メチル−２−フェノキシ）チタニウムジクロライド、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）（３，５−ジメチル−２−フェノキシ）チタニウムジクロライド、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−２−フェノキシ）チタニウムジクロライド、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、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）（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）チタニウムジクロライド、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）（５−メチル−３−フェニル−２−フェノキシ）チタニウムジクロライド、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−ブチルジメチルシリル−５−メチル−２−フェノキシ）チタニウムジクロライド、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）（５−メチル−３−トリメチルシリル−２−フェノキシ）チタニウムジクロライド、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−メトキシ−２−フェノキシ）チタニウムジクロライド、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−クロロ−２−フェノキシ）チタニウムジクロライド、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）（３，５−ジアミル−２−フェノキシ）チタニウムジクロライド、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）（１−ナフトキシ−２−イル）チタニウムジクロライドなどや、これらの化合物のη⁵−シクロペンタジエニルをη⁵−メチルシクロペンタジエニル、η⁵−ジメチルシクロペンタジエニル、η⁵−トリメチルシクロペンタジエニル、η⁵−エチルシクロペンタジエニル、η⁵−ｎ−プロピルシクロペンタジエニル、η⁵−イソプロピルシクロペンタジエニル、η⁵−ｎ−ブチルシクロペンタジエニル、η⁵−ｓｅｃ−ブチルシクロペンタジエニル、η⁵−イソブチルシクロペンタジエニル、η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル、η⁵−トリメチルシリルシクロペンタジエニル、η⁵−ｔｅｒｔ−ブチルジメチルシリルシクロペンタジエニル、η⁵−フェニルシクロペンタジエニル、η⁵−インデニル、η⁵−メチルインデニル、η⁵−フェニルインデニルまたはη⁵−フルオレニルに変更した化合物、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、チタニウムをジルコニウム、またはハフニウムに変更した化合物、ジクロリドをジメチル、ジベンジル、ジメトキシド、ジフェノキシド、ビス（ジメチルアミノ）またはビス（ジエチルアミノ）に変更した化合物といった遷移金属化合物などが挙げられる。
【００６０】
一般式［IV］で示される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（η⁵−シクロペンタジエニル）（２−フェノキシ）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデン（η⁵−シクロペンタジエニル）（２−フェノキシ）チタニウムメトキシド｝、μ−オキソビス｛イソプロピリデン（η⁵−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）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデン（η⁵−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）チタニウムメトキシド｝、μ−オキソビス｛イソプロピリデン（η⁵−メチルシクロペンタジエニル）（２−フェノキシ）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデン（η⁵−メチルシクロペンタジエニル）（２−フェノキシ）チタニウムメトキシド｝、μ−オキソビス｛イソプロピリデン（η⁵−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）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデン（η⁵−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）チタニウムメトキシド｝、μ−オキソビス｛イソプロピリデン（η⁵−テトラメチルシクロペンタジエニル）（２−フェノキシ）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデン（η⁵−テトラメチルシクロペンタジエニル）（２−フェノキシ）チタニウムメトキシド｝、μ−オキソビス｛イソプロピリデン（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）チタニウムクロライド｝、μ−オキソビス｛イソプロピリデン（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）チタニウムメトキシド｝、
【００６１】
μ−オキソビス｛ジメチルシリレン（η⁵−シクロペンタジエニル）（２−フェノキシ）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレン（η⁵−シクロペンタジエニル）（２−フェノキシ）チタニウムメトキシド｝、μ−オキソビス｛ジメチルシリレン（η⁵−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）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレン（η⁵−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）チタニウムメトキシド｝、μ−オキソビス｛ジメチルシリレン（η⁵−メチルシクロペンタジエニル）（２−フェノキシ）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレン（η⁵−メチルシクロペンタジエニル）（２−フェノキシ）チタニウムメトキシド｝、μ−オキソビス｛ジメチルシリレン（η⁵−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）チタニウムクロライド｝、μ−オキソビス｛ジメチルシリレン（η⁵−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）チタニウムメトキシド｝、μ−オキソビス｛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）（２−フェノキシ）チタニウムクロライド｝、μ−オキソビス｛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）（２−フェノキシ）チタニウムメトキシド｝、μ−オキソビス｛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）チタニウムクロライド｝、μ−オキソビス｛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）チタニウムメトキシド｝などや、これらの化合物のチタニウムをジルコニウムまたはハフニウムに変更した化合物、クロライドをメチル、ベンジル、フェノキシド、ジメチルアミノまたはジエチルアミノに変更した化合物、（η⁵−シクロペンタジエニル）を（η⁵−ジメチルシクロペンタジエニル）、（η⁵−トリメチルシクロペンタジエニル）、（η⁵−ｎ−ブチルシクロペンタジエニル）、（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）、（η⁵−トリメチルシリルシクロペンタジエニル）、（η⁵−ｔｅｒｔ−ブチルジメチルシリルシクロペンタジエニル）、（η⁵−インデニル）、（η⁵−メチルインデニル）、（η⁵−フェニルインデニル）または（η⁵−フルオレニル）に変更した化合物、（２−フェノキシ）を（３−メチル−２−フェノキシ）、（３，５−ジメチル−２−フェノキシ）、（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）、（３−フェニル−５−メチル−２−フェノキシ）または（３−トリメチルシリル−５−メチル−２−フェノキシ）に変更した化合物が挙げられる。
【００６２】
一般式［Ｖ］で示される遷移金属化合物の具体例としては、ジ−μ−オキソビス｛イソプロピリデン（η⁵−シクロペンタジエニル）（２−フェノキシ）チタニウム｝、ジ−μ−オキソビス｛イソプロピリデン（η⁵−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−μ−オキソビス｛イソプロピリデン（η⁵−メチルシクロペンタジエニル）（２−フェノキシ）チタニウム｝、ジ−μ−オキソビス｛イソプロピリデン（η⁵−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−μ−オキソビス｛イソプロピリデン（η⁵−テトラメチルシクロペンタジエニル）（２−フェノキシ）チタニウム｝、ジ−μ−オキソビス｛イソプロピリデン（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｝、
【００６３】
ジ−μ−オキソビス｛ジメチルシリレン（η⁵−シクロペンタジエニル）（２−フェノキシ）チタニウム｝、ジ−μ−オキソビス｛ジメチルシリレン（η⁵−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−μ−オキソビス｛ジメチルシリレン（η⁵−メチルシクロペンタジエニル）（２−フェノキシ）チタニウム｝、ジ−μ−オキソビス｛ジメチルシリレン（η⁵−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−μ−オキソビス｛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）（２−フェノキシ）チタニウム｝、ジ−μ−オキソビス｛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｝などや、これらの化合物のチタニウムをジルコニウムまたはハフニウムに変更した化合物、（η⁵−シクロペンタジエニル）を（η⁵−ジメチルシクロペンタジエニル）、（η⁵−トリメチルシクロペンタジエニル）、（η⁵−ｎ−ブチルシクロペンタジエニル）、（η⁵−ｔｅｒｔ−ブチルシクロペンタジエニル）、（η⁵−トリメチルシリルシクロペンタジエニル）、（η⁵−ｔｅｒｔ−ブチルジメチルシリルシクロペンタジエニル）、（η⁵−インデニル）、（η⁵−メチルインデニル）、（η⁵−フェニルインデニル）または（η⁵−フルオレニル）に変更した化合物、（２−フェノキシ）を（３−メチル−２−フェノキシ）、（３，５−ジメチル−２−フェノキシ）、（３，５−ジ−ｔｅｒｔ−ブチル−２−フェノキシ）、（３−フェニル−５−メチル−２−フェノキシ）または（３−トリメチルシリル−５−メチル−２−フェノキシ）に変更した化合物が挙げられる。
【００６４】
変性アルミニウムオキシ化合物、遷移金属化合物および有機アルミニウム化合物を組み合わせてオレフィン重合用触媒を調製する場合の、有機アルミニウム化合物としては通常、一般式 Ｅ_aＡｌＺ_3-a（但し、Ｅは炭化水素基であり、全てのＥは同じであっても異なっていても良い。Ｚは水素原子またはハロゲン原子を表し、全てのＺは同じであっても異なっていても良い。ａは０＜ａ≦３を満足する数を表す。）で示される有機アルミニウム化合物である。
Ｅにおける炭化水素基としては、炭素原子数１〜８の炭化水素基が好ましく、アルキル基がより好ましい。
【００６５】
一般式 Ｅ_aＡｌＺ_3-aで示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、トリプロピルアルミニウム、トリイソブチルアルミニウム、トリヘキシ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、ジプロピ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、プロピ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、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、ジプロピ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等を例示することができる。
より好ましくは、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、またはトリイソブチルアルミニウムである。
【００６６】
本発明のオレフィン重合用触媒は、上記の変性アルミニウムオキシ化合物および遷移金属化合物を接触させて得られるオレフィン重合用触媒、または、上記の変性アルミニウムオキシ化合物、遷移金属化合物および有機アルミニウム化合物を接触させて得られるオレフィン重合用触媒である。ここでいう接触とは、上記各成分が接触し、触媒が形成されるならどのような手段によってもよく、あらかじめ溶媒で希釈してもしくは希釈せずに上記各成分を混合して接触させる方法や、別々に重合反応器に供給して重合反応器の中で接触させる方法等を採用できる。本発明においては重合反応器に前記各成分を供給する際には、前記各成分を任意の順序で投入し使用することができるが、またそれらの任意の成分の組合わせを予め接触させて得られた反応物を用いても良い。
【００６７】
各成分の使用量は通常、［変性アルミニウムオキシ化合物に含まれるＡｌ原子］／［遷移金属化合物に含まれる遷移金属原子］のモル比が０．１〜１００００で、好ましくは５〜２０００、［有機アルミニウム化合物に含まれるＡｌ原子］／［遷移金属化合物に含まれる遷移金属原子］のモル比が０．１〜１００００で、好ましくは５〜２０００の範囲にあるように、各成分を用いることが望ましい。
【００６８】
各成分を溶液状態または溶媒に懸濁もしくはスラリー化した状態で用いる場合の濃度は、重合反応器に各成分を供給する装置の性能などの条件により、適宜選択されるが、一般に、遷移金属化合物がそれに含まれる遷移金属原子換算のモル数で通常０．００１〜２００ｍｍｏｌ／Ｌで、より好ましくは０．００１〜１００ｍｍｏｌ／Ｌ、さらに好ましくは０．０５〜５０ｍｍｏｌ／Ｌ、変性アルミニウムオキシ化合物はそれに含まれるＡｌ原子換算のモル数で通常１〜５０００ｍｍｏｌ／Ｌで使用されうるが、好ましくは１０〜２０００ｍｍｏｌ／Ｌ、さらに好ましくは１００〜１５００ｍｍｏｌ／Ｌ、有機アルミニウム化合物がそれに含まれるＡｌ原子換算のモル数で通常０．０１〜５０００ｍｍｏｌ／Ｌで、より好ましくは０．１〜２５００ｍｍｏｌ／Ｌ、さらに好ましくは０．１〜２０００ｍｍｏｌ／Ｌの範囲にあるように各成分を用いることが望ましい。
【００６９】
変性アルミニウムオキシ化合物を反応器に供給する方法としては通常、炭化水素溶媒に溶解させた溶液で供給する。遷移金属化合物および有機アルミニウム化合物を反応器に供給する方法としては、特に制限されるものではない。
【００７０】
本発明において重合に適用されるオレフィンとしては、炭素原子数２〜２０個からなるオレフィン類、特にエチレン、炭素原子数３〜２０のα−オレフィン、炭素原子数４〜２０のジオレフィン類等を用いることができ、同時に２種類以上のモノマーを用いることもできる。オレフィンの具体例としては、エチレン、プロピレン、ブテン−１、ペンテン−１、ヘキセン−１、ヘプテン−１、オクテン−１、ノネン−１、デセン−１等の直鎖状オレフィン類、３−メチルブテン−１、３−メチルペンテン−１、４−メチルペンテン−１、５−メチル−ヘキセン−１等の分岐オレフィン類、ビニルシクロヘキサン等が例示されるが、本発明は上記化合物に限定されるべきものではない。共重合を行う時のモノマーの組み合わせの具体例としては、エチレンとプロピレン、エチレンとブテン−１、エチレンとヘキセン−１、エチレンとオクテン−１、プロピレンとブテン−１等が例示されるが、本発明はこれらの組み合わせに限定されるべきものではない。
【００７１】
本発明は、特にエチレンとα−オレフィン、特にプロピレン、ブテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１等のα−オレフィンとの共重合体の製造に有効に適用できる。
【００７２】
重合方法も、特に限定されるべきものではないが、例えば、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、ベンゼン、トルエン等の芳香族炭化水素、もしくはメチレンジクロライド等のハロゲン化炭化水素を溶媒として用いる溶媒重合、またはスラリー重合、あるいは、高圧イオン重合法と呼ばれる方法であって、無溶媒で、高温高圧下で超臨界流体状態のオレフィンに生成したオレフィン重合体が溶融した状態で重合させる方法、さらには、ガス状のモノマー中での気相重合等が可能であり、また、連続重合、回分式重合のどちらでも可能である。
【００７３】
重合温度は通常−５０℃〜３５０℃、好ましくは−２０℃〜３００℃である。
重合圧力は通常０．１〜３５０ＭＰａ、好ましくは０．１〜３００ＭＰａ、より好ましくは０．１〜２００ＭＰａである。
【００７４】
重合時間は、一般的に、目的とするポリマーの種類、反応装置により適宜決定され、特に制限すべき条件はないが、３０秒間〜２０時間の範囲を取ることができる。また、本発明は共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できる。
【００７５】
本発明のオレフィン重合体の製造方法は、特に高圧イオン重合法で好適に実施される。具体的には、３０ＭＰａ以上の圧力および１００℃以上の温度で、好適に実施される。さらに好適には、圧力は３５〜３００ＭＰａ、温度は１３５〜３００℃で実施される。
この場合の重合形式としてはバッチ式または連続式のいずれでも可能であるが、連続式で実施するほうが好ましい。反応器は通常、攪拌式槽型反応器または管型反応器が使用できる。重合は単一反応域でも行われるが、１つの反応器を複数の反応帯域に区切って行うか、または複数個の反応器を直列もしくは並列に連結して行うこともできる。複数個の反応器を使用する場合には、槽型−槽型または槽型−管型のいずれの組合わせでもよい。複数反応帯域または複数反応器で重合させる方法では、各反応帯域ごとに温度、圧力、ガス組成を変えることにより、特性の異なるオレフィン重合体を生産することも可能である。
【００７６】
【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。実施例におけるオレフィン重合体の性質は下記の方法により測定した。
【００７７】
（１）共重合体の融点：セイコー電子工業社製ＳＳＣ５０００熱分析システムを用いて、以下の条件により求めた。
昇温：１５０℃まで昇温、５分間保持
冷却：１５０℃から１０℃（５℃／分）、１０分間保持
測定：１０℃から１６０℃（５℃／分）
【００７８】
（２）共重合体におけるα−オレフィンから誘導される繰り返し単位の含有量：赤外分光光度計（パーキネルマー社製 ＦＴＩＲ１６００シリーズ）を用いて、エチレンとα−オレフィンの特性吸収より求め、１０００炭素当たりの短鎖分岐数（ＳＣＢ）として表した。
【００７９】
（３）分子量および分子量分布：ゲル・パーミュエーション・クロマトグラフ（ウォーターズ社製 １５０，Ｃ）を用い、以下の条件により求めた。なお、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。
カラム：ＴＳＫ ｇｅｌ ＧＭＨ−ＨＴ
測定温度：１４５℃ 設定
測定濃度：１０ｍｇ／１０ｍｌ−オルトジクロルベンゼン
【００８０】
（４）極限粘度［η］：得られた共重合体１００ｍｇを、１３５℃のテトラリン５０ｍｌに溶解させ、１３５℃に保持された湯浴中にセットされた、ウベローデ型粘度計を用い、当該サンプルが溶解したテトラリン溶液の落下速度から求めた。
【００８１】
［参考例１（遷移金属化合物：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＜化合物▲１▼＞の合成例）］
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）チタニウムジクロリド ０．９１９ｇ（２．０ｍｍｏｌ）の無水エーテル ２０ｍｌへの懸濁液を、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、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）
【００８２】
［実施例１］（化合物Ａ液の調製）
５０ｍｌの３口フラスコに滴下ロートを取付け、窒素置換を行なった後、温度計を取付けた。ポリブチルアルミノキサンのヘキサン溶液（ＰＢＡＯ、東ソーアクゾ社製：Ａｌ原子換算濃度１．０８ｍｏｌ／ｌ）１０ｍｌをフラスコに仕込み、攪拌した。ペンタフルオロフェノールのトルエン溶液（２ｍｏｌ／ｌ）２．１６ｍｌを滴下ロートに仕込み、２５〜３０℃にて滴下した。引き続き、２−エチル−１−ヘキサノールのヘプタン溶液（１ｍｏｌ／ｌ）６．４８ｍｌを２５〜３０℃にて滴下し、ヘプタン ２．９６ｍｌで洗い流した。滴下終了後、２５〜３０℃にて２時間攪拌した。無色透明の反応溶液（以下「化合物Ａ液」と記載する。）を得た。（仕込み量より、Ａｌ原子換算濃度は０．５ｍｏｌ／ｌ）。
【００８３】
［実施例２］（重合）
内容積 ０．４リットルの攪拌翼付オートクレーブ型反応装置をアルゴン置換した後、溶媒としてシクロヘキサン １８５ｍｌを、α−オレフィンとしてヘキセン−１を１５ｍｌ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に調節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 ０．２ｍｍｏｌ、実施例１にて調製した化合物Ａ液を１ｍｌ（Ａｌ原子換算で０．５ｍｍｏｌ相当）および、化合物▲１▼とトリイソブチルアルミニウムが混合されたヘプタン溶液（化合物▲１▼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０．５ｍｌ（即ち、化合物▲１▼を０．５μｍｏｌ、トリイソブチルアルミニウムを２５μｍｏｌ）投入した。２分間重合を行った。重合の結果、［η］が１．４５ｄｌ／ｇ、ＳＣＢが３２．１、融点が７８．６℃、８６．１℃、Ｍｗが１００１００、Ｍｗ／Ｍｎが１．８であるエチレン−ヘキセン−１共重合体を４．５５ｇ得た。Ｔｉ原子１モル当たりの重合活性は２分間あたり、９．１×１０⁶ｇ／Ｔｉｍｏｌであった。
【００８４】
［比較例１］（化合物Ｂの調製）
１００ｍｌの４口フラスコに滴下ロートを取付け、窒素置換を行なった後、温度計を取付けた。ポリイソブチルアルミノキサンのヘキサン溶液（ＰＢＡＯ，東ソーアクゾ社製：Ａｌ原子換算濃度１．０８ｍｏｌ／ｌ）２０ｍｌをフラスコに仕込み、攪拌した。ペンタフルオロフェノールのトルエン溶液（２ｍｏｌ／ｌ）１０．８ｍｌを滴下ロートに仕込み、５℃〜１５℃にて滴下した。滴下終了後、５〜１５℃にて０．５時間、２５〜３０℃にて１時間攪拌した。白色のスラリーが得られた。減圧下で溶媒を除去し、白色固体を得た。（化合物Ｂ）。
【００８５】
［比較例２］（重合）
内容積 ０．４リットルの攪拌翼付オートクレーブ型反応装置をアルゴン置換した後、溶媒としてシクロヘキサン １８５ｍｌを、α−オレフィンとしてヘキセン−１を１５ｍｌ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に調節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 ０．２ｍｍｏｌ、比較例１にて調製した化合物Ｂを１２４．３ｍｇ（Ａｌ原子換算で０．５５ｍｍｏｌ相当）および、化合物▲１▼とトリイソブチルアルミニウムが混合されたヘプタン溶液（化合物▲１▼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０．５ｍｌ（即ち、化合物▲１▼を０．５μｍｏｌ、トリイソブチルアルミニウムを２５μｍｏｌ）投入した。２分間重合を行った。重合の結果、［η］が１．５６ｄｌ／ｇ、ＳＣＢが３０．３、融点が７７．４℃、８５．５℃、Ｍｗが９９３００、Ｍｗ／Ｍｎが１．８であるエチレン−ヘキセン−１共重合体を６．２８ｇ得た。Ｔｉ原子１モル当たりの重合活性は２分間あたり、１．３×１０⁷ｇ／Ｔｉｍｏｌであった。
【００８６】
【発明の効果】
以上詳述したとおり、本発明によれば、炭化水素溶媒に可溶なアルミニウムオキシ化合物、炭化水素溶媒に可溶な有機金属オレフィン重合養殖倍成分、それを用いて調製されるオレフィン重合用触媒、および、該オレフィン重合用触媒を用いるオレフィン重合体の製造方法が提供される。本発明によれば、炭化水素溶媒として飽和炭化水素溶媒を用いることにより、芳香族炭化水素溶媒を用いることなく（芳香族炭化水素溶媒の臭気が残存しない）オレフィン重合体を製造する方法も提供されるなど、産業上の利用価値はすこぶる大きい。
【図面の簡単な説明】
【図１】図１は、本発明の理解を助けるためのフローチャート図である。本フローチャート図は、本発明の実施態様の代表例であり、本発明は、何らこれに限定されるものではない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a modified aluminum oxy compound soluble in a hydrocarbon solvent, an olefin polymerization catalyst component comprising the same, an olefin polymerization catalyst prepared using the same, and a method for producing an olefin polymer using the olefin polymerization catalyst. .
[0002]
[Prior art]
Many reports have already been made on a method for producing an olefin polymer using a single site catalyst prepared by using a metallocene complex or the like. For example, JP-A-58-19306 reports a method for producing an olefin polymer using a metallocene complex and an aluminumoxy compound. This screw (η^FiveIn the method of producing an olefin polymer using cyclopentadienyl) zirconium dichloride and methylaluminoxane, the activity is insufficient from an industrial viewpoint, and the molecular weight of the resulting olefin polymer is low. Met.
[0003]
In order to solve these problems, many reports on the improvement of aluminum oxy compounds have been made so far. For example, JP-A-6-329714 and International Patent Application WO94 / 10180 disclose an olefin polymerization method using an electron-withdrawing group or a modified aluminumoxy compound having a group having an electron-withdrawing group and zirconocene. It has been reported. According to this method, a highly active catalyst can be obtained. However, the obtained modified aluminum oxy compound is usually insoluble in a solvent and has to be used for polymerization in a solid state. In order to handle the aluminum oxy compound in the solid state, a large-scale apparatus is required, and in order to use it in a slurry state, a special device for preventing sedimentation is required.
[0004]
[Problems to be solved by the invention]
In view of the present situation, the problem to be solved by the present invention, that is, the object of the present invention, is to use an aluminum oxy compound soluble in a hydrocarbon solvent, a catalyst component for organometallic olefin polymerization soluble in a hydrocarbon solvent, and using the same. It is an object of the present invention to provide an olefin polymerization catalyst and a method for producing an olefin polymer using the olefin polymerization catalyst.
[0005]
[Means for Solving the Problems]
  The present invention is soluble in a hydrocarbon solvent obtained by reacting the following (A), (B) and (C)NaoCatalyst component for olefin polymerization,Catalyst component for olefin polymerizationAnd an olefin polymerization catalyst obtained by contacting a transition metal compound,Catalyst component for olefin polymerizationThe olefin polymerization catalyst obtained by bringing a transition metal compound and an organoaluminum compound into contact with each other, and a method for producing an olefin polymer that homopolymerizes or copolymerizes olefins using these olefin polymerization catalysts. It is a solution.
(A) An aluminum oxy compound comprising the following (A1) and / or (A2)
(A1) General formula {-Al (E¹) -O-}_aCyclic aluminoxane having a structure represented by
(A2) General formula E²{-Al (E²) -O-}_bAlE² ₂A linear aluminoxane having a structure represented by
(However, E¹And E²EachAlkyl group having 1 to 8 carbon atomsAnd all E¹And all E²May be the same or different. a is 2~ 40Where b is 1~ 40Represents an integer. )
(B) General formula ROH (where R isHalogenated aryl group having 6 to 20 carbon atomsIt is. The compound represented by
(C) Compound represented by the general formula R'OH (wherein R 'is an alkyl group having 6 to 20 carbon atoms).
[0006]
DETAILED DESCRIPTION OF THE INVENTION
(A) Aluminum oxy compound
  The aluminum oxy compound (A) used for the preparation of the modified aluminum oxy compound of the present invention is an aluminum oxy compound comprising the following (A1) and / or (A2).
(A1) General formula {-Al (E¹) -O-}_aCyclic aluminoxane having a structure represented by
(A2) General formula E²{-Al (E²) -O-}_bAlE² ₂A linear aluminoxane having a structure represented by
(However, E¹And E²EachAlkyl group having 1 to 8 carbon atomsAnd all E¹And all E²May be the same or different. a is 2~ 40Where b is 1~ 40Represents an integer.)
[0007]
  General formula {-Al (E¹) -O-}_aA cyclic aluminoxane (A1) having the structure represented by the general formula E²{-Al (E²) -O-}_bAlE² ₂In the linear aluminoxane (A2) having the structure represented by¹, E²Specific examples thereof include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. a is 2~ 40And b is 1~ 40Is an integer. Preferably, E¹And E²Each independently represents a methyl group or an isobutyl groupis there.
[0008]
The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.
The aluminoxane obtained by such a method is usually considered to be a mixture of (A1) and (A2).
[0009]
(B) Compound represented by general formula ROH
  (B) used in the present invention has the general formula ROH (where R isHalogenated aryl group having 6 to 20 carbon atomsIt is. ). R may be a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a 3,5-bis (trifluoromethyl) phenyl group, a perfluoronaphthyl group, or the like. In which fluoro is changed to chloro or bromo.
  Examples of the compound represented by the general formula ROH include fluorophenol, difluorophenol, trifluorophenol, tetrafluorophenol, pentafluorophenol, 3,5-bis (trifluoromethyl) phenol, perfluoronaphthol, and these compounds. In which fluoro is changed to chloro or bromo.
[0010]
  R andAndMore preferably, it is a fluorinated aryl group having 6 to 20 carbon atoms.
  The compound represented by the general formula ROH is preferably pentafluorophenol, 3,5-bis (trifluoromethyl) phenol, or perfluoronaphthol, and particularly preferably pentafluorophenol.
[0011]
(C) Compound represented by general formula R'OH
(C) used in the present invention is a compound represented by the general formula R′OH (where R ′ is an alkyl group having 6 to 20 carbon atoms). Examples of R 'include hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, and eicosyl group.
[0012]
Examples of the compound represented by the general formula R′OH include n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol, n-dodecyl alcohol, n-tetradecyl alcohol, n-eicosyl alcohol and the like. Linear alcohol, 2-methyl-1-pentyl alcohol, 3-methyl-1-pentyl alcohol, 4-methyl-1-pentyl alcohol, 2-ethyl-1-butyl alcohol, 2-methyl-1-hexyl alcohol 3-methyl-1-hexyl alcohol, 2-ethyl-1-pentyl alcohol, 2-methyl-1-heptyl alcohol, 3-methyl-1-heptyl alcohol, 2-ethyl-1-hexyl alcohol, 2,2- Dimethyl-1-hexyl alcohol, 2-methyl-1-nonyla Examples include branched alcohols such as alcohol, 3-methyl-1-nonyl alcohol, and 2,2-dimethyl-1-octyl alcohol. Preferred is n-octyl alcohol, 2-methylheptyl alcohol, or 2-ethyl-1-hexyl alcohol.
[0013]
The modified aluminum oxy compound of the present invention comprises (A) an aluminum oxy compound, (B) a compound represented by the general formula ROH, and (C) a general formula R′OH.
It can be obtained by reacting a compound represented by the formula:
Such a reaction is preferably carried out in an inert gas atmosphere. The reaction temperature is not particularly limited, but is −80 ° C. to 200 ° C., preferably −50 to 120 ° C. The reaction time is usually 1 minute to 12 hours, preferably 2 minutes to 5 hours. Moreover, such a reaction may use a solvent, and may react these compounds directly, without using. Although the solvent used is not specifically limited, An aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, etc. are mentioned. Specific examples include hexane, heptane, benzene, toluene and the like.
[0014]
The use amount ratio (molar ratio) of each component in the present invention is such that the molar ratio of [(B)] / [Al atom contained in (A)] is 0.3 to 0.7, and [(C )] / [Al atom contained in (A)] is preferably 0.3 to 0.7, more preferably (B) and (C). Is substantially equal to or less than the number of moles of Al atoms contained in (A), and more preferably, the sum of the number of moles of (B) and the number of moles of (C) is substantially equal to Is a molar ratio in a range equal to the number of moles of Al atoms contained in (A).
[0015]
In the actual reaction between each component, even if you try to use each component at the intended ratio, the amount used may fluctuate slightly, and the amount of the component that remains unreacted is taken into account. Thus, it is usual to slightly increase or decrease the amount used as appropriate. Here, “the total is substantially the above (A)... Or less” and “the total is substantially the above (A)... Equal” are completely “the total is the above (A). .. Even if it is not “below” or “total is the above (A)... Equal”, “the total is the above (A)... Below” or “the total is the above (A). It is meant to include if each component is intended to react to be “equal”.
[0016]
The modified aluminum oxy compound thus obtained is used as a catalyst component for organometallic olefin polymerization that is soluble in a hydrocarbon solvent. After isolation and purification such as recrystallization, it can be dissolved in a hydrocarbon solvent and used as a catalyst component for olefin polymerization, but this reaction solution can also be used as it is as a catalyst component for olefin polymerization.
[0017]
The modified aluminum oxy compound of the present invention is soluble in a hydrocarbon solvent, and examples of the hydrocarbon solvent include a saturated hydrocarbon solvent and an aromatic hydrocarbon solvent. Examples of saturated hydrocarbon solvents include butane, pentane, hexane, heptane, octane, mixed alkanes, and liquid paraffin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like. These solvents may be a mixture. In the field of olefin polymerization, if an aromatic hydrocarbon solvent such as toluene remains in the olefin polymer, it often becomes a big quality problem in terms of its odor. Therefore, the modified aluminum oxy compound of the present invention is preferably one that is soluble in a saturated hydrocarbon solvent, and more preferably a butane, hexane, heptane, or mixed alkane as the saturated hydrocarbon solvent.
[0018]
As used herein, the degree of solubility means dissolution at a concentration of 0.01 mol / liter or more (in terms of Al atoms). The higher the soluble concentration, the better. The modified aluminum oxy compound of the present invention is preferably a modified aluminum oxy compound that is soluble in a hydrocarbon solvent at a concentration of 0.1 mol / liter or more (in terms of Al atom).
[0019]
The modified aluminum oxy compound of the present invention is used by preparing a catalyst for olefin polymerization by using in combination with a transition metal compound or in combination with a transition metal compound and an organoaluminum compound.
The transition metal compound is not particularly limited as long as it is a transition metal compound capable of forming a single site catalyst, but a Group 4 transition metal compound having a group having a cyclopentadiene type anion skeleton is preferable.
[0020]
The group 4 transition metal compound here is a group 4 transition metal compound in the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), for example, a titanium compound, a zirconium compound, and a hafnium compound. Etc. Titanium compounds or zirconium compounds are preferred.
The group having a cyclopentadiene-type anion skeleton here is the same as the group shown as the substituent Cp described later.
[0021]
The transition metal compound used in the present invention is preferably a transition metal compound represented by the following general formula [I] or [II].
Cp_mMX¹ _4-m              [I]
(Cp_pMX¹ _q)₂X² _r       [II]
(In the above general formula [I] or [II], M represents a group 4 transition metal atom in the periodic table of elements, and Cp represents a group having a cyclopentadiene-type anion skeleton. X¹Is a hydrogen atom, halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, alkoxy group, aralkyloxy group, aryloxy group, disubstituted amino group, alkylthio group, aralkylthio group, arylthio group, alkylseleno group, An aralkylseleno group or an arylseleno group is shown. X²Represents an atom of group 16 of the periodic table of elements. m is an integer that satisfies 1 ≦ m ≦ 4, p is a number that satisfies 1 ≦ p ≦ 3, q is a number that satisfies 0 ≦ q ≦ 2, and r is 1 or 2. It is an integer that satisfies p + q + r = 4. All Cp, all X¹, All X²May be the same or different. Also, multiple Cp's, multiple X's¹Or Cp and X¹And may be bonded directly or via a crosslinking group. )
[0022]
In the above general formula [I] or [II], the transition metal atom represented by M is a group 4 transition metal atom in the periodic table of elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), for example, titanium. An atom, a zirconium atom, a hafnium atom, etc. are mentioned. Preferably, it is a titanium atom or a zirconium atom.
[0023]
Examples of the group having a cyclopentadiene type anion skeleton represented by the substituent Cp include η^Five-(Substituted) cyclopentadienyl group, η^Five-(Substituted) indenyl group, η^Five-(Substituted) fluorenyl group and the like. For example, η^FiveA cyclopentadienyl group, η^Five-Methylcyclopentadienyl group, η^Five-Dimethylcyclopentadienyl group, η^Five-Trimethylcyclopentadienyl group, η^Five-Tetramethylcyclopentadienyl group, η^Five-Pentamethylcyclopentadienyl group, η^Five-Ethylcyclopentadienyl group, η^Five-N-propylcyclopentadienyl group, η^Five-Isopropylcyclopentadienyl group, η^Five-N-butylcyclopentadienyl group, η^Five-Sec-butylcyclopentadienyl group, η^Five-Tert-butylcyclopentadienyl group, η^Five-Phenylcyclopentadienyl group, η^Five-Trimethylsilylcyclopentadienyl group, η^Five-Tert-butyldimethylsilylcyclopentadienyl group, η^FiveAn indenyl group, η^FiveA methylindenyl group, η^Five-Dimethylindenyl group, η^Five-N-propylindenyl group, η^FiveAn isopropylindenyl group, η^Five-N-butylindenyl group, η^Five-Tert-butylindenyl group, η^Five-Phenylindenyl group, η^Five-Methylphenylindenyl group, η^FiveA naphthylindenyl group, η^Five-Trimethylsilylindenyl group, η^FiveA tetrahydroindenyl group, η^Five-Fluorenyl group, η^Five-Methylfluorenyl group, η^Five-Dimethylfluorenyl group, η^Five-Tert-butylfluorenyl group, η^Five-Di-tert-butylfluorenyl group, η^Five-Phenylfluorenyl group, η^Five-Diphenylfluorenyl group, η^Five-Trimethylsilylfluorenyl group, η^Five-Bistrimethylsilylfluorenyl group and the like, preferably η^Five-Cyclopentadienyl group, η^Five-Methylcyclopentadienyl group, η^Five-N-butylcyclopentadienyl group, η^Five-Tert-butylcyclopentadienyl group, η^Five-Tetramethylcyclopentadienyl group, η^Five-Pentamethylcyclopentadienyl group, η^FiveAn indenyl group, η^FiveA tetrahydroindenyl group, or η^Five-A fluorenyl group.
[0024]
Substituent X¹Examples of the halogen atom in are fluorine atom, chlorine atom, bromine atom and iodine atom, preferably chlorine atom or bromine atom, more preferably chlorine atom.
[0025]
Substituent X¹The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group. N-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, and the like, more preferably methyl. Group, ethyl group, isopropyl group, tert-butyl group, isobutyl group, or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or 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 thereof include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any 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.
[0026]
Substituent X¹As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable. For example, a 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-tetramethyl) Enyl) 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, and a benzyl group is more preferable.
These aralkyl groups are all 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. Etc. may be partially substituted.
[0027]
Substituent X¹As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, for example, a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 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- Tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butyl Enyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group , A naphthyl group, an anthracenyl group and the like, more preferably a phenyl group.
These aryl groups are all 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 or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.
[0028]
Substituent X¹The substituted silyl group in is a silyl group substituted with a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. Group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group and other alkyl groups having 1 to 10 carbon atoms, and aryl groups such as phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include monosubstituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, diethylsilyl group, and diphenylsilyl group. A disubstituted silyl group having 2 to 20 carbon atoms, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert 3 to 20 carbon atoms such as -butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group And trisubstituted silyl groups, preferably trimethylsilyl A tert- butyldimethylsilyl group or triphenylsilyl group.
All of these substituted silyl groups have a hydrocarbon group such as 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 a benzyloxy group. A part thereof may be substituted with an aralkyloxy group such as a group.
[0029]
Substituent X¹As the alkoxy group, an alkoxy group having 1 to 20 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, n -Pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadexoxy group, n-icosoxy group, etc., more preferably methoxy group, ethoxy group, isopropoxy group, or It is a tert-butoxy group.
These alkoxy groups are all 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. Etc. may be partially substituted.
[0030]
Substituent X¹The aralkyloxy group in is preferably an aralkyloxy group having 7 to 20 carbon atoms, such as benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, and (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-trimethylpheny ) Methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, 2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butyl) Phenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, A naphthylmethoxy group, an anthracenylmethoxy group, etc., more preferably a benzyloxy group That.
These aralkyloxy groups are all 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. A part thereof may be substituted with a group or the like.
[0031]
Substituent X¹As the aryloxy group, an aryloxy group having 6 to 20 carbon atoms is preferable, for example, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 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-tert-butyl-3-methylphenoxy Group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2, 3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethyl Phenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6 -Dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethyl Phenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2 3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, Ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, Examples thereof include an n-tetradecylphenoxy group, a naphthoxy group, and an anthracenoxy group.
These aryloxy groups are all 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. A part thereof may be substituted with a group or the like.
[0032]
Substituent X¹The disubstituted amino group in is an amino group substituted with two hydrocarbon groups or silyl groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- C1-C10 alkyl groups, such as a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group, 6-10 carbon atoms Aryl groups and aralkyl groups having 7 to 10 carbon atoms such as benzyl group, and the silyl groups include trimethylsilyl group and tert-butyldimethylsilyl group. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group. Group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, etc. And preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group, or a bistrimethylsilylamino group.
All of these disubstituted amino 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 aralkyl such as benzyloxy group. A part thereof may be substituted with an oxy group or the like.
[0033]
Substituent X¹The alkylthio group in is preferably an alkylthio group having 1 to 20 carbon atoms, for example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, n -Pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like, more preferably methylthio group, ethylthio group, isopropyl A thio group or a tert-butylthio group.
These alkylthio groups are all 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. Etc. may be partially substituted.
[0034]
Substituent X¹The aralkylthio group in is preferably an aralkylthio group having 7 to 20 carbon atoms, such as a benzylthio group, a (2-methylphenyl) methylthio group, a (3-methylphenyl) methylthio group, or a (4-methylphenyl) methylthio group. , (2,3-dimethylphenyl) methylthio group, (2,4-dimethylphenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4- (Dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, (2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6- Trimethylphenyl) methylthio group, (2,4,5-trimethylphenyl) methylthio group, (2,4,4) -Trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3,4,5-tetramethylphenyl) methylthio group, (2,3,4,6-tetramethylphenyl) methylthio Group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group, (n-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, ( n-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) methylthio group, (n-octylphenyl) methylthio group, (n-decylphenyl) Methylthio group, naphthylmethylthio group, anthracenylmethyl Such as O group, more preferably a benzylthio group.
These aralkylthio groups are all 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. A part thereof may be substituted with a group or the like.
[0035]
Substituent X¹As the arylthio group, an arylthio group having 6 to 20 carbon atoms is preferable. For example, a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, and a 2,3-dimethylphenylthio group. Group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-tert -Butyl-3-methylphenylthio group, 2-tert-butyl-4-methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2 , 3,4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethylpheny Thio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 2-tert-butyl-3,4-dimethylphenylthio group, 2-tert-butyl-3,5- Dimethylphenylthio group, 2-tert-butyl-3,6-dimethylphenylthio group, 2,6-di-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4,5-dimethylphenylthio Group, 2,6-di-tert-butyl-4-methylphenylthio group, 3,4,5-trimethylphenylthio group, 2,3,4,5-tetramethylphenylthio group, 2-tert-butyl- 3,4,5-trimethylphenylthio group, 2,3,4,6-tetramethylphenylthio group, 2-tert-butyl-3,4,6-trimethylphenylthio group, 2,6 Di-tert-butyl-3,4-dimethylphenylthio group, 2,3,5,6-tetramethylphenylthio group, 2-tert-butyl-3,5,6-trimethylphenylthio group, 2,6- Di-tert-butyl-3,5-dimethylphenylthio group, pentamethylphenylthio group, ethylphenylthio group, n-propylphenylthio group, isopropylphenylthio group, n-butylphenylthio group, sec-butylphenylthio group Group, tert-butylphenylthio group, n-hexylphenylthio group, n-octylphenylthio group, n-decylphenylthio group, n-tetradecylphenylthio group, naphthylthio group, anthracenylthio group and the like.
These arylthio groups are all 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. Etc. may be partially substituted.
[0036]
Substituent X¹The alkyl seleno group in is preferably an alkyl seleno group having 1 to 20 carbon atoms, for example, methyl seleno group, ethyl seleno group, n-propyl seleno group, isopropyl seleno group, n-butyl seleno group, sec-butyl seleno group, tert-butyl seleno group. Group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group, n-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n-eicosylseleno group and the like, more preferably A methylseleno group, an ethylseleno group, an isopropylseleno group, or a tert-butylseleno group.
These alkylseleno groups are all 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. A part thereof may be substituted with a group or the like.
[0037]
Substituent X¹The aralkylseleno group in is preferably an aralkylseleno group having 7 to 20 carbon atoms, such as benzylseleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) methylseleno group, (4-methylphenyl) methylseleno group. Group, (2,3-dimethylphenyl) methylseleno group, (2,4-dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6-dimethylphenyl) methylseleno group, (3,4) -Dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5-trimethylphenyl) methylseleno group, (2,3,6) -Trimethylphenyl) methylseleno group, (2,4,5-trimethylphene) (L) methylseleno group, (2,4,6-trimethylphenyl) methylseleno group, (3,4,5-trimethylphenyl) methylseleno group, (2,3,4,5-tetramethylphenyl) methylseleno group, (2, 3,4,6-tetramethylphenyl) methylseleno group, (2,3,5,6-tetramethylphenyl) methylseleno group, (pentamethylphenyl) methylseleno group, (ethylphenyl) methylseleno group, (n-propylphenyl) Methylseleno group, (isopropylphenyl) methylseleno group, (n-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group, (tert-butylphenyl) methylseleno group, (n-hexylphenyl) methylseleno group, (n-octyl) Phenyl) methylseleno group, (n-decylpheny) ) Methylseleno group, naphthylmethyl seleno group, anthracenylmethyl seleno group, more preferably a benzyl seleno group.
These aralkylseleno groups are all 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. A part thereof may be substituted with a group or the like.
[0038]
Substituent X¹As the arylseleno group, a C6-C20 arylseleno group is preferable. For example, a phenylseleno group, 2-methylphenylseleno group, 3-methylphenylseleno group, 4-methylphenylseleno group, 2,3- Dimethylphenylseleno group, 2,4-dimethylphenylseleno group, 2,5-dimethylphenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-dimethylphenylseleno group, 2-tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4-methylphenylseleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methylphenylseleno group Group, 2,3,4-trimethylphenylseleno group, 2,3,5-trimethylphenylse Group, 2,3,6-trimethylphenylseleno group, 2,4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2-tert-butyl-3,4-dimethylphenylseleno group 2-tert-butyl-3,5-dimethylphenylseleno group, 2-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di-tert-butyl-3-methylphenylseleno group, 2- tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4,5-trimethylphenylseleno group, 2,3,4,5-tetra Methylphenylseleno group, 2-tert-butyl-3,4,5-trimethylphenylseleno group, 2,3,4,6-tetramethylphenylseleno group, 2- ert-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno group, 2,3,5,6-tetramethylphenylseleno group, 2- tert-butyl-3,5,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,5-dimethylphenylseleno group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno Group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butylphenylseleno group, tert-butylphenylseleno group, n-hexylphenylseleno group, n-octylphenylseleno group, n-decylphenylseleno group, n -Tetradecylphenylseleno group, naphthylseleno group, anthracenylseleno group And the like.
These arylseleno groups are all 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. A part thereof may be substituted with a group or the like.
[0039]
Preferably X¹Are each independently a halogen atom, alkyl group, aralkyl group, alkoxy group, aryloxy group or disubstituted amino group, more preferably a halogen atom, alkyl group, alkoxy group or aryloxy group.
[0040]
X in the above general formula [II]²Represents an atom of group 16 of the periodic table of elements, and specific examples include an oxygen atom, a sulfur atom, and a selenium atom, preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. .
[0041]
In the general formula [I] or [II], a plurality of Cp, a plurality of X¹Or Cp and X¹And may be bonded directly or via a crosslinking group. Examples of the bridging group include a divalent bridging group containing an atom belonging to Group 14 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), preferably a divalent containing a carbon atom or a silicon atom. It is a crosslinking group. More preferably, Cp or X¹A divalent bridging group in which the atom bonded to the carbon atom is a carbon atom and / or a silicon atom, more preferably Cp or X¹Atoms bonded to carbon atoms and / or silicon atoms, Cp and X¹A divalent bridging group having a minimum number of atoms of 3 or less between the atoms bonded to (including Cp and X¹This includes the case where the atom bonded to is single. ). Specifically, methylene group, ethylene group, propylene group, dimethylmethylene group (isopropylidene group), diphenylmethylene group, tetramethylethylene group, silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, tetramethyldiethylene Examples thereof include a silylene group and a dimethoxysilylene group, and a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene group is particularly preferable.
The transition metal compound represented by the above general formula [I] or [II] is preferably Cp and X¹Is a transition metal compound bonded via a bridging group.
[0042]
In the above general formula [I], m is an integer satisfying 1 ≦ m ≦ 4. In the above general formula [II], p is a number satisfying 1 ≦ p ≦ 3, q is a number satisfying 0 ≦ q ≦ 2, r is 1 or 2, and p + q + r = 4 is satisfied Is an integer.
m and p represent the number of Cp bonded to the transition metal atom M. The transition metal compound used in the present invention is a transition in which a group having one cyclopentadiene-type anion skeleton is bonded to one transition metal atom. Metal compounds are preferred. That is, the transition metal compound used in the present invention is preferably a transition metal compound in which m in the general formula [I] is 1, or a transition metal compound in which p in the general formula [II] is 1.
[0043]
The transition metal compound used in the present invention is more preferably a transition metal compound represented by the following general formula [III], [IV] or [V].

(In the above general formula [III], [IV] or [V], M represents a transition metal atom of Group 4 of the periodic table of elements, and A represents an atom of Group 16 of the periodic table of elements. J represents an atom belonging to Group 14 of the periodic table of elements, and Cp represents a group having a cyclopentadiene-type anion skeleton.¹, R¹, R², R^Three, R^Four, R^FiveAnd R⁶Are each independently a hydrogen atom, halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, alkoxy group, aralkyloxy group, aryloxy group, disubstituted amino group, alkylthio group, aralkylthio group, arylthio group, An alkylseleno group, an aralkylseleno group, or an arylseleno group; X²Represents an atom of group 16 of the periodic table of elements. R¹, R², R^Three, R^Four, R^FiveAnd R⁶May be bonded together to form a ring. Multiple M, A, J, Cp, X¹, X², R¹, R², R^Three, R^Four, R^FiveAnd R⁶May be the same or different. )
[0044]
M, Cp and X in the above general formula [III], [IV] or [V]²Are the same as those in formula [I] or [II]. X in the above general formula [III], [IV] or [V]¹, R¹, R², R^Three, R^Four, R^FiveAnd R⁶Are each independently X in the above general formula [I] or [II].¹It is the same.
[0045]
However, R¹, R², R^Three, R^FourAnd preferably each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, or an aryloxy group, and in particular, R¹As an alkyl group, an aralkyl group, an aryl group or a substituted silyl group is particularly preferable.
[0046]
In the general formula [III], [IV] or [V], R^Five, R⁶As each independently, a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group is preferable.
[0047]
In the general formula [III], [IV] or [V], examples of the group 16 atom in the periodic table of the element represented by A include an oxygen atom, a sulfur atom, and a selenium atom. Preferably, it is an oxygen atom.
[0048]
In the general formula [III], [IV] or [V], examples of the group 14 atom in the periodic table of the element represented by J include a carbon atom, a silicon atom, and a germanium atom. Preferably, they are a carbon atom or a silicon atom.
[0049]
As such transition metal compounds, for example, (η^Five-Cyclopentadienyl) titanium trichloride, (η^Five-Cyclopentadienyl) titanium trimethyl, (η^Five-Cyclopentadienyl) (dimethylamino) titanium dichloride, (η^Five-Cyclopentadienyl) (diethylamino) titanium dichloride, (η^Five-Cyclopentadienyl) (di-n-butylamino) titanium dichloride, (η^Five-Cyclopentadienyl) (di-n-octylamino) titanium dichloride, (η^Five-Cyclopentadienyl) (diphenylamino) titanium dichloride, (η^Five-Cyclopentadienyl) (methoxy) titanium dichloride, (η^Five-Cyclopentadienyl) (ethoxy) titanium dichloride, (η^Five-Cyclopentadienyl) (tert-butoxy) titanium dichloride, (η^Five-Cyclopentadienyl) (phenoxy) titanium dichloride, (η^Five-Cyclopentadienyl) (2,6-di-tert-butylphenoxy) titanium dichloride, (η^Five-Cyclopentadienyl) (2-tert-butyl-4-methylphenoxy) titanium dichloride and the like, and η of these compounds^Five-Cyclopentadienyl to η^Five-Methylcyclopentadienyl, η^Five-Dimethylcyclopentadienyl, η^Five-Trimethylcyclopentadienyl, η^Five-Tetramethylcyclopentadienyl, η^Five-Pentamethylcyclopentadienyl, η^Five-Ethylcyclopentadienyl, η^Five-N-butylcyclopentadienyl, η^Five-Tert-butylcyclopentadienyl, η^Five-Di-tert-butylcyclopentadienyl, η^Five-Trimethylsilylcyclopentadienyl, η^Five-Tert-butyldimethylsilylcyclopentadienyl, η^Five-Phenylcyclopentadienyl, η^FiveIndenyl, η^Five-Methylindenyl, η^Five-Phenylindenyl or η^Five-Transition metal compounds such as compounds changed to fluorenyl, titanium changed to zirconium or hafnium, dichloride changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino) Can do.
[0050]
As a specific example of the transition metal compound in which m in the general formula [I] is 2 and has no crosslinking group, bis (η^Five-Cyclopentadienyl) titanium dichloride, bis (η^Five-Methylcyclopentadienyl) titanium dichloride, bis (η^Five-Dimethylcyclopentadienyl) titanium dichloride, bis (η^Five-Trimethylcyclopentadienyl) titanium dichloride, bis (η^Five-Tetramethylcyclopentadienyl) titanium dichloride, bis (η^Five-Pentamethylcyclopentadienyl) titanium dichloride, bis (η^Five-Ethylcyclopentadienyl) titanium dichloride, bis (η^Five-N-butylcyclopentadienyl) titanium dichloride, bis (η^Five-Tert-butylcyclopentadienyl) titanium dichloride, bis (η^Five-Trimethylsilylcyclopentadienyl) titanium dichloride, bis (η^Five-Tert-butyldimethylsilylcyclopentadienyl) titanium dichloride, bis (η^Five-Phenylcyclopentadienyl) titanium dichloride, bis (η^Five-Indenyl) titanium dichloride, bis (η^FiveTransition metals such as -fluorenyl) titanium dichloride, compounds in which the titanium of these compounds is changed to zirconium or hafnium, and compounds in which the dichloride is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino) A compound etc. can be mentioned.
[0051]
As a specific example of the transition metal compound in which m in the general formula [I] is 1 and has a crosslinking group, dimethylsilylene (methylamino) (η^Five-Cyclopentadienyl) titanium dichloride, dimethylsilylene (tert-butylamino) (η^Five-Cyclopentadienyl) titanium dichloride, dimethylsilylene (phenylamino) (η^Five-Cyclopentadienyl) titanium dichloride, dimethylsilylene (cyclohexylamino) (η^Five-Cyclopentadienyl) titanium dichloride, etc., and η of these compounds^Five-Cyclopentadienyl to η^Five-Methylcyclopentadienyl, η^Five-Tetramethylcyclopentadienyl, η^Five-Ethylcyclopentadienyl, η^Five-N-butylcyclopentadienyl, η^Five-Tert-butylcyclopentadienyl, η^Five-Di-tert-butylcyclopentadienyl, η^Five-Trimethylsilylcyclopentadienyl, η^Five-Tert-butyldimethylsilylcyclopentadienyl, η^Five-Phenylcyclopentadienyl, η^FiveIndenyl, η^Five-Methylindenyl, η^Five-Phenylindenyl or η^Five-Compounds changed to fluorenyl, dimethylsilylene changed to diethylsilylene, diphenylsilylene, methylene, ethylene or dimethylmethylene (isopropylidene), diphenylmethylene, tetramethylethylene, tetramethyldisilene, titanium changed to zirconium or hafnium And transition metal compounds such as compounds in which dichloride is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino).
[0052]
As a specific example of the transition metal compound in which m in the general formula [I] is 2 and has a bridging group, methylene bis (η^Five-Cyclopentadienyl) titanium dichloride, isopropylidenebis (η^Five-Cyclopentadienyl) titanium dichloride, dimethylsilylene bis (η^Five-Cyclopentadienyl) titanium dichloride, diphenylsilylene bis (η^Five-Cyclopentadienyl) titanium dichloride, methylenebis (η^Five-Methylcyclopentadienyl) titanium dichloride, isopropylidenebis (η^Five-Methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (η^Five-Methylcyclopentadienyl) titanium dichloride, diphenylsilylene bis (η^Five-Methylcyclopentadienyl) titanium dichloride, methylenebis (η^Five-Dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (η^Five-Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (η^Five-Dimethylcyclopentadienyl) titanium dichloride, diphenylsilylene bis (η^Five-Dimethylcyclopentadienyl) titanium dichloride, methylenebis (η^Five-Tetramethylcyclopentadienyl) titanium dichloride, isopropylidenebis (η^Five-Tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (η^Five-Tetramethylcyclopentadienyl) titanium dichloride, diphenylsilylene bis (η^Five-Tetramethylcyclopentadienyl) titanium dichloride, methylenebis (η^Five-N-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (η^Five-N-butylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (η^Five-N-butylcyclopentadienyl) titanium dichloride, diphenylsilylene bis (η^Five-N-butylcyclopentadienyl) titanium dichloride, methylenebis (η^Five-Tert-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (η^Five-Tert-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (η^Five-Tert-butylcyclopentadienyl) titanium dichloride, diphenylsilylenebis (η^Five-Tert-butylcyclopentadienyl) titanium dichloride,
[0053]
Methylenebis (η^Five-Indenyl) titanium dichloride, isopropylidenebis (η^Five-Indenyl) titanium dichloride, ethylene bis (η^Five-Indenyl) titanium dichloride, dimethylsilylene bis (η^Five-Indenyl) titanium dichloride, diphenylsilylene bis (η^Five-Indenyl) titanium dichloride, methylenebis (η^Five-Methylindenyl) titanium dichloride, isopropylidenebis (η^Five-Methylindenyl) titanium dichloride, ethylene bis (η^Five-Methylindenyl) titanium dichloride, dimethylsilylene bis (η^Five-Methylindenyl) titanium dichloride, diphenylsilylene bis (η^Five-Methylindenyl) titanium dichloride, methylenebis (η^Five-Tetrahydroindenyl) titanium dichloride, isopropylidenebis (η^Five-Tetrahydroindenyl) titanium dichloride, ethylenebis (η^Five-Tetrahydroindenyl) titanium dichloride, dimethylsilylene bis (η^Five-Tetrahydroindenyl) titanium dichloride, diphenylsilylene bis (η^Five-Tetrahydroindenyl) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (η^Five-Fluorenyl) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (η^Five-Fluorenyl) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (η^Five-Fluorenyl) titanium dichloride, diphenylsilylene (η^Five-Cyclopentadienyl) (η^FiveTransition metals such as -fluorenyl) titanium dichloride, compounds in which the titanium of these compounds is changed to zirconium or hafnium, and compounds in which the dichloride is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino) Compound etc. are mentioned.
[0054]
As the transition metal compound represented by the general formula [II], μ-oxobis {bis (η^Five-Cyclopentadienyl) titanium chloride}, μ-oxobis {bis (η^Five-Methylcyclopentadienyl) titanium chloride}, μ-oxobis {bis (η^Five-Pentamethylcyclopentadienyl) titanium chloride}, μ-oxobis {(η^Five-Cyclopentadienyl) titanium dichloride}, μ-oxobis {(η^Five-Cyclopentadienyl) (methoxy) titanium chloride}, μ-oxobis {(η^Five-Cyclopentadienyl) (phenoxy) titanium chloride}, μ-oxobis {(η^Five-Cyclopentadienyl) (dimethylamino) titanium chloride}, μ-oxobis {(η^Five-Cyclopentadienyl) (diethylamino) titanium chloride}, μ-oxobis {isopropylidenebis (η^Five-Cyclopentadienyl) titanium chloride}, μ-oxobis {dimethylsilylenebis (η^Five-Cyclopentadienyl) titanium chloride}, μ-oxobis {ethylenebis (η^Five-Cyclopentadienyl) titanium chloride}, μ-oxobis {dimethylsilylenebis (η^Five-Indenyl) titanium chloride}, μ-oxobis {ethylenebis (η^Five-Indenyl) titanium chloride}, μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (η^Five-Fluorenyl) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (tert-butylamino) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (tert-butylamino) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (tert-butylamino) titanium chloride}, compounds in which the titanium of these compounds is changed to zirconium or hafnium, chlorides are changed to methyl, benzyl, methoxide, phenoxide, dimethylamino or diethylamino Transition metal compounds such as the above compounds.
[0055]
Further, as the transition metal compound represented by the general formula [II], for example, di-μ-oxobis {bis (η^Five-Cyclopentadienyl) titanium}, di-μ-oxobis {bis (η^Five-Methylcyclopentadienyl) titanium}, di-μ-oxobis {bis (η^Five-Pentamethylcyclopentadienyl) titanium}, di-μ-oxobis {(η^Five-Cyclopentadienyl) titanium chloride}, di-μ-oxobis {(η^Five-Cyclopentadienyl) (methoxy) titanium}, di-μ-oxobis {(η^Five-Cyclopentadienyl) (phenoxy) titanium}, di-μ-oxobis {(η^Five-Cyclopentadienyl) (dimethylamino) titanium}, di-μ-oxobis {(η^Five-Cyclopentadienyl) (diethylamino) titanium}, di-μ-oxobis {isopropylidenebis (η^Five-Cyclopentadienyl) titanium}, di-μ-oxobis {dimethylsilylenebis (η^Five-Cyclopentadienyl) titanium}, di-μ-oxobis {ethylenebis (η^Five-Cyclopentadienyl) titanium}, di-μ-oxobis {dimethylsilylenebis (η^Five-Indenyl) titanium}, di-μ-oxobis {ethylenebis (η^Five-Indenyl) titanium}, di-μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (η^Five-Fluorenyl) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (tert-butylamino) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (tert-butylamino) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (tert-butylamino) titanium} and the like, and transition metal compounds such as compounds in which titanium of these compounds is changed to zirconium or hafnium.
[0056]
Specific examples of the transition metal compound represented by the general formula [III] include methylene (η^Five-Cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
[0057]
Isopropylidene (η^Five-Cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
[0058]
Diphenylmethylene (η^Five-Cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, compounds obtained by changing titanium of these compounds to zirconium or hafnium, dichloride being dimethyl, dibenzyl, dimethoxide, Compound changed to diphenoxide, bis (dimethylamino) or bis (diethylamino), (η^Five-Cyclopentadienyl) to (η^Five-Methylcyclopentadienyl), (η^Five-Dimethylcyclopentadienyl), (η^Five-Trimethylcyclopentadienyl), (η^Five-N-butylcyclopentadienyl), (η^Five-Tert-butylcyclopentadienyl), (η^Five-Trimethylsilylcyclopentadienyl), (η^Five-Tert-butyldimethylsilylcyclopentadienyl), (η^Five-Indenyl), (η^Five-Methylindenyl), (η^Five-Phenylindenyl) or (η^Five-Fluorenyl), (3,5-dimethyl-2-phenoxy) to (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy) ), (3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy), or a transition metal compound such as (3-trimethylsilyl-2-phenoxy)
[0059]
Dimethylsilylene (η^Five-Cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilene (η^Five-Cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like, and η of these compounds^Five-Cyclopentadienyl to η^Five-Methylcyclopentadienyl, η^Five-Dimethylcyclopentadienyl, η^Five-Trimethylcyclopentadienyl, η^Five-Ethylcyclopentadienyl, η^Five-N-propylcyclopentadienyl, η^Five-Isopropylcyclopentadienyl, η^Five-N-butylcyclopentadienyl, η^Five-Sec-butylcyclopentadienyl, η^Five-Isobutylcyclopentadienyl, η^Five-Tert-butylcyclopentadienyl, η^Five-Trimethylsilylcyclopentadienyl, η^Five-Tert-butyldimethylsilylcyclopentadienyl, η^Five-Phenylcyclopentadienyl, η^FiveIndenyl, η^Five-Methylindenyl, η^Five-Phenylindenyl or η^FiveA compound changed to fluorenyl, a compound changed from 2-phenoxy to 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy, or 3-tert-butyldimethylsilyl-2-phenoxy, dimethylsilylene to diethylsilylene, Transition metals such as diphenylsilylene or dimethoxysilylene compound, titanium changed to zirconium or hafnium, dichloride changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino) Compound etc. are mentioned.
[0060]
Specific examples of the transition metal compound represented by the general formula [IV] include μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η^Five-Methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η^Five-Methylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η^Five-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η^Five-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η^Five-Tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η^Five-Tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide},
[0061]
μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide} and the like, compounds in which titanium of these compounds is changed to zirconium or hafnium, chlorides of methyl, benzyl, Compound changed to phenoxide, dimethylamino or diethylamino, (η^Five-Cyclopentadienyl) to (η^Five-Dimethylcyclopentadienyl), (η^Five-Trimethylcyclopentadienyl), (η^Five-N-butylcyclopentadienyl), (η^Five-Tert-butylcyclopentadienyl), (η^Five-Trimethylsilylcyclopentadienyl), (η^Five-Tert-butyldimethylsilylcyclopentadienyl), (η^Five-Indenyl), (η^Five-Methylindenyl), (η^Five-Phenylindenyl) or (η^Five-Fluorenyl), (2-phenoxy) was changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy) ), (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy).
[0062]
Specific examples of the transition metal compound represented by the general formula [V] include di-μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η^Five-Methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η^Five-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η^Five-Tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium},
[0063]
Di-μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium} and the like, and compounds obtained by changing titanium of these compounds to zirconium or hafnium, (η^Five-Cyclopentadienyl) to (η^Five-Dimethylcyclopentadienyl), (η^Five-Trimethylcyclopentadienyl), (η^Five-N-butylcyclopentadienyl), (η^Five-Tert-butylcyclopentadienyl), (η^Five-Trimethylsilylcyclopentadienyl), (η^Five-Tert-butyldimethylsilylcyclopentadienyl), (η^Five-Indenyl), (η^Five-Methylindenyl), (η^Five-Phenylindenyl) or (η^Five-Fluorenyl), (2-phenoxy) was changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy) ), (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy).
[0064]
In the case of preparing an olefin polymerization catalyst by combining a modified aluminum oxy compound, a transition metal compound and an organoaluminum compound, the organoaluminum compound is usually represented by the general formula E_aAlZ_3-a(However, E is a hydrocarbon group, all E may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. A represents an organic aluminum compound represented by 0 <a ≦ 3.
As a hydrocarbon group in E, a C1-C8 hydrocarbon group is preferable and an alkyl group is more preferable.
[0065]
Formula E_aAlZ_3-aSpecific examples of the organoaluminum compound represented by are trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum. Dialkylaluminum chlorides such as chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride; dimethylaluminum hydride and diethylaluminium Hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
More preferred is trialkylaluminum, and further preferred is trimethylaluminum, triethylaluminum, or triisobutylaluminum.
[0066]
The catalyst for olefin polymerization of the present invention is a catalyst for olefin polymerization obtained by contacting the modified aluminum oxy compound and the transition metal compound, or by contacting the modified aluminum oxy compound, transition metal compound and organoaluminum compound. The resulting catalyst for olefin polymerization. The contact here may be any means as long as the above-mentioned components come into contact with each other to form a catalyst. A method in which the above-mentioned components are mixed and contacted with dilution in a solvent in advance or without dilution. Alternatively, a method of separately supplying to the polymerization reactor and contacting in the polymerization reactor can be employed. In the present invention, when the respective components are supplied to the polymerization reactor, the respective components can be charged and used in an arbitrary order. Alternatively, a combination of these arbitrary components is obtained by contacting them in advance. The reaction product obtained may be used.
[0067]
The amount of each component used is usually a molar ratio of [Al atom contained in the modified aluminum oxy compound] / [Transition metal atom contained in the transition metal compound] of 0.1 to 10,000, preferably 5 to 2,000, It is desirable to use each component so that the molar ratio of [Al atom contained in aluminum compound] / [transition metal atom contained in transition metal compound] is 0.1 to 10,000, preferably 5 to 2,000. .
[0068]
The concentration in the case of using each component in a solution state or in a state suspended or slurried in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. Is usually 0.001 to 200 mmol / L, more preferably 0.001 to 100 mmol / L, still more preferably 0.05 to 50 mmol / L, and the modified aluminum oxy compound is Although it can be normally used at 1 to 5000 mmol / L in terms of moles of Al atoms contained, it is preferably 10 to 2000 mmol / L, more preferably 100 to 1500 mmol / L, and moles of Al atoms contained in the organoaluminum compound. The number is usually 0.01 to 5000 mmol / L, more preferably 0.1 to 25 0 mmol / L, more preferably it is desirable to use each component to be in the range of 0.1~2000mmol / L.
[0069]
As a method for supplying the modified aluminum oxy compound to the reactor, it is usually supplied as a solution dissolved in a hydrocarbon solvent. The method for supplying the transition metal compound and the organoaluminum compound to the reactor is not particularly limited.
[0070]
Examples of the olefin applied to the polymerization in the present invention include olefins having 2 to 20 carbon atoms, particularly ethylene, α-olefins having 3 to 20 carbon atoms, diolefins having 4 to 20 carbon atoms, and the like. It is possible to use two or more monomers at the same time. Specific examples of olefins include linear olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1, 3-methylbutene- Examples thereof include branched olefins such as 1,3-methylpentene-1,4-methylpentene-1,5-methyl-hexene-1, vinylcyclohexane and the like, but the present invention should not be limited to the above compounds. Absent. Specific examples of the combination of monomers when copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, propylene and butene-1, etc. The invention should not be limited to these combinations.
[0071]
The present invention is particularly applicable to the production of copolymers of ethylene and α-olefins, particularly α-olefins such as propylene, butene-1,4-methylpentene-1, hexene-1, octene-1.
[0072]
The polymerization method is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene and toluene, or halogenated carbonization such as methylene dichloride. Solvent polymerization using hydrogen as a solvent, slurry polymerization, or high-pressure ion polymerization method, in the state where no olefin polymer formed in a supercritical fluid olefin is melted without solvent at high temperature and high pressure. A polymerization method, gas phase polymerization in a gaseous monomer, and the like are possible, and either continuous polymerization or batch polymerization is possible.
[0073]
The polymerization temperature is usually −50 ° C. to 350 ° C., preferably −20 ° C. to 300 ° C.
The polymerization pressure is usually 0.1 to 350 MPa, preferably 0.1 to 300 MPa, more preferably 0.1 to 200 MPa.
[0074]
In general, the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, and there is no particular condition to be limited, but it can be in the range of 30 seconds to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.
[0075]
The method for producing an olefin polymer of the present invention is particularly preferably carried out by a high pressure ionic polymerization method. Specifically, it is preferably carried out at a pressure of 30 MPa or more and a temperature of 100 ° C. or more. More preferably, the pressure is 35 to 300 MPa and the temperature is 135 to 300 ° C.
In this case, the polymerization can be performed either batchwise or continuously, but it is preferable to carry out the polymerization in a continuous manner. Generally, a stirred tank reactor or a tube reactor can be used as the reactor. The polymerization is also carried out in a single reaction zone, but it can also be carried out by dividing one reactor into a plurality of reaction zones, or by connecting a plurality of reactors in series or in parallel. When a plurality of reactors are used, any combination of tank type-tank type or tank type-tube type may be used. In the method of polymerizing in a plurality of reaction zones or reactors, it is possible to produce olefin polymers having different characteristics by changing the temperature, pressure and gas composition for each reaction zone.
[0076]
【Example】
Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these. The properties of the olefin polymer in the examples were measured by the following methods.
[0077]
(1) Melting | fusing point of a copolymer: It calculated | required on condition of the following using the SSC5000 thermal analysis system by Seiko Denshi Kogyo.
Temperature rise: Temperature rise to 150 ° C, hold for 5 minutes
Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes
Measurement: 10 ° C to 160 ° C (5 ° C / min)
[0078]
(2) Content of repeating unit derived from α-olefin in copolymer: Using infrared spectrophotometer (FTIR1600 series, manufactured by Perkinelmer), obtained from characteristic absorption of ethylene and α-olefin, per 1000 carbons Expressed as the number of short chain branches (SCB).
[0079]
(3) Molecular weight and molecular weight distribution: It was determined under the following conditions using a gel permeation chromatograph (150, C manufactured by Waters). The molecular weight distribution was evaluated by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Column: TSK gel GMH-HT
Measurement temperature: 145 ° C setting
Measurement concentration: 10 mg / 10 ml-orthodichlorobenzene
[0080]
(4) Intrinsic viscosity [η]: 100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at 135 ° C., and the sample was prepared using an Ubbelohde viscometer set in a hot water bath maintained at 135 ° C. It was determined from the falling speed of the tetralin solution in which the solution was dissolved.
[0081]
[Reference Example 1 (transition metal compound: dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide <Synthesis Example of Compound (1)>]]
In a Schlenk tube, 0.131 g (4.1 mmol) of methanol was dissolved in 10 ml of anhydrous ether, and an ether solution (3.9 ml, 4.1 mmol) of methyllithium having a concentration of 1.05 mol / L was added dropwise at −78 ° C. By raising the temperature to 20 ° C. and confirming the end of gas generation, the formation of lithium methoxide was confirmed, and the mixture was cooled again to −78 ° C. Dimethylsilylene (η prepared in advance in another Schlenk tube^Five-A suspension of 0.919 g (2.0 mmol) of 0.919 g (2.0 mmol) in anhydrous ether in 20 ml of anhydrous ether was transferred to the previous reaction liquid. -Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride Then, the temperature was gradually raised to room temperature. After concentration of the reaction solution, 20 ml of toluene was added, and insoluble matters were filtered off. The filtrate was concentrated and dimethylsilylene (η^Five-Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide was obtained as yellow crystals. (0.86g, 95%)

¹H-NMR (270 MHz, C₆D₆) Δ 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)
[0082]
[Example 1] (Preparation of Compound A solution)
A dropping funnel was attached to a 50 ml three-necked flask, and after replacing with nitrogen, a thermometer was attached. 10 ml of a hexane solution of polybutylaluminoxane (PBAO, manufactured by Tosoh Akzo Co., Ltd .: Al atom conversion concentration: 1.08 mol / l) was charged into a flask and stirred. 2.16 ml of a toluene solution of pentafluorophenol (2 mol / l) was charged into a dropping funnel and dropped at 25 to 30 ° C. Subsequently, 6.48 ml of a heptane solution of 2-ethyl-1-hexanol (1 mol / l) was added dropwise at 25 to 30 ° C., followed by washing with 2.96 ml of heptane. After completion of dropping, the mixture was stirred at 25 to 30 ° C. for 2 hours. A colorless and transparent reaction solution (hereinafter referred to as “compound A solution”) was obtained. (From the amount charged, the concentration in terms of Al atom is 0.5 mol / l).
[0083]
[Example 2] (Polymerization)
The autoclave reactor with a stirring blade having an internal volume of 0.4 liter was purged with argon, and then 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 180 ° C. After the temperature increase, the ethylene pressure was fed while adjusting the pressure to 2.5 Mpa, and after the system was stabilized, 0.2 ml of triisobutylaluminum and 1 ml of the compound A solution prepared in Example 1 (0.00% in terms of Al atom). 5 mmol) and a heptane solution in which compound (1) and triisobutylaluminum are mixed (compound (1) has a concentration of 1 μmol / ml, triisobutylaluminum has a concentration of 50 μmol / ml, and the molar ratio of Al atom to Ti atom) Was adjusted to 50.) (0.5 μmol of compound (1) and 25 μmol of triisobutylaluminum) was added. Polymerization was carried out for 2 minutes. As a result of the polymerization, ethylene-hexene-1 having [η] of 1.45 dl / g, SCB of 32.1, melting points of 78.6 ° C., 86.1 ° C., Mw of 100100, and Mw / Mn of 1.8. 4.55 g of copolymer was obtained. The polymerization activity per mole of Ti atom is 9.1 × 10 2 minutes.⁶g / Timol.
[0084]
[Comparative Example 1] (Preparation of Compound B)
A dropping funnel was attached to a 100 ml four-necked flask, and after nitrogen substitution, a thermometer was attached. A flask was charged with 20 ml of a polyisobutylaluminoxane hexane solution (PBAO, manufactured by Tosoh Akzo Co., Ltd .: Al atom equivalent concentration 1.08 mol / l) and stirred. 10.8 ml of a toluene solution of pentafluorophenol (2 mol / l) was charged into a dropping funnel and dropped at 5 to 15 ° C. After completion of dropping, the mixture was stirred at 5 to 15 ° C for 0.5 hour and at 25 to 30 ° C for 1 hour. A white slurry was obtained. The solvent was removed under reduced pressure to give a white solid. (Compound B).
[0085]
[Comparative Example 2] (Polymerization)
The autoclave reactor with a stirring blade having an internal volume of 0.4 liter was purged with argon, and then 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 180 ° C. After the temperature increase, the ethylene pressure was fed while adjusting the pressure to 2.5 Mpa. After the system was stabilized, 0.2 mmol of triisobutylaluminum and 124.3 mg of Compound B prepared in Comparative Example 1 (0 in terms of Al atom) .55 mmol) and a heptane solution in which compound (1) and triisobutylaluminum are mixed (compound (1) has a concentration of 1 μmol / ml, triisobutylaluminum has a concentration of 50 μmol / ml) The ratio was adjusted to 50.) (0.5 μmol of compound (1) and 25 μmol of triisobutylaluminum) was added. Polymerization was carried out for 2 minutes. As a result of the polymerization, ethylene-hexene-1 having [η] of 1.56 dl / g, SCB of 30.3, melting points of 77.4 ° C., 85.5 ° C., Mw of 99300, and Mw / Mn of 1.8 6.28 g of copolymer was obtained. The polymerization activity per mole of Ti atom is 1.3 × 10 2 per 2 minutes.⁷g / Timol.
[0086]
【The invention's effect】
As described above in detail, according to the present invention, an aluminum oxy compound soluble in a hydrocarbon solvent, an organometallic olefin polymerization culture double component soluble in a hydrocarbon solvent, an olefin polymerization catalyst prepared using the same, And the manufacturing method of the olefin polymer using this olefin polymerization catalyst is provided. According to the present invention, there is also provided a method for producing an olefin polymer by using a saturated hydrocarbon solvent as a hydrocarbon solvent without using an aromatic hydrocarbon solvent (the odor of the aromatic hydrocarbon solvent does not remain). The industrial utility value is extremely large.
[Brief description of the drawings]
FIG. 1 is a flowchart for helping understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (12)

A catalyst component for olefin polymerization which is soluble in a hydrocarbon solvent obtained by reacting the following (A), (B) and (C).
(A) Aluminum oxy compound (A1) composed of the following (A1) and / or (A2) (A1) General formula {-Al (E ¹ ) -O-} _a cyclic aluminoxane (A2) having the structure represented by a ² {-Al (E ² ) -O—} _b Linear aluminoxane having a structure represented by AlE ² ₂ (where E ¹ and E ² are each an alkyl group having 1 to 8 carbon atoms , E ¹ and all E ² may be the same or different, a represents an integer of 2 to 40 , and b represents an integer of 1 to 40. )
(B) Compound represented by general formula ROH (where R is a halogenated aryl group having 6 to 20 carbon atoms ) (C) General formula R'OH (where R 'is 6 to 20 carbon atoms) A compound represented by the following formula: The molar ratio of [(B)] / [Al atom contained in (A)] is 0.3 to 0.7, and [(C)] / [Al atom contained in (A)]. The olefin polymerization catalyst component according to claim 1, wherein the molar ratio of the olefin polymerization is 0.3 to 0.7. The sum of the number of moles of (B) and the number of moles of (C) is substantially equal to or less than the number of moles of Al atoms contained in (A). Catalyst component for olefin polymerization . The olefin according to claim 1 or 2, wherein the total number of moles of (B) and moles of (C) is substantially equal to the number of moles of Al atoms contained in (A). Polymerization catalyst component . The catalyst component for olefin polymerization according to any one of claims 1 to 4, wherein the hydrocarbon solvent is a saturated hydrocarbon solvent. An olefin polymerization catalyst obtained by contacting the catalyst component for olefin polymerization according to any one of claims 1 to 5 and a transition metal compound represented by the following general formula [I] or [II].
Cp _m MX ¹ _4-m            [I]
(Cp _p MX ¹ _q ) ₂ X ² _r     [II]
(In the above general formula [I] or [II], M represents a group 4 transition metal atom in the periodic table of elements, and Cp represents a group having a cyclopentadiene-type anion skeleton. X ¹ Is a hydrogen atom, halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, alkoxy group, aralkyloxy group, aryloxy group, disubstituted amino group, alkylthio group, aralkylthio group, arylthio group, alkylseleno group, An aralkylseleno group or an arylseleno group is shown. X ² Represents an atom of group 16 of the periodic table of elements. m is an integer that satisfies 1 ≦ m ≦ 4, p is a number that satisfies 1 ≦ p ≦ 3, q is a number that satisfies 0 ≦ q ≦ 2, and r is 1 or 2. It is an integer that satisfies p + q + r = 4. All Cp, all X ¹ , All X ² May be the same or different. Also, multiple Cp's, multiple X's ¹ Or Cp and X ¹ And may be bonded directly or via a crosslinking group. ) The catalyst for olefin polymerization according to claim 6, wherein the molar ratio of [Al atom contained in catalyst component for olefin polymerization] / [transition metal atom contained in transition metal compound] is 0.1 to 10,000. . An olefin polymerization characterized by being obtained by contacting the catalyst component for olefin polymerization according to any one of claims 1 to 5, a transition metal compound represented by the following general formula [I] or [II] and an organoaluminum compound: Catalyst.
Cp _m MX ¹ _4-m            [I]
(Cp _p MX ¹ _q ) ₂ X ² _r     [II]
(In the above general formula [I] or [II], M represents a group 4 transition metal atom in the periodic table of elements, and Cp represents a group having a cyclopentadiene-type anion skeleton. X ¹ Is a hydrogen atom, halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, alkoxy group, aralkyloxy group, aryloxy group, disubstituted amino group, alkylthio group, aralkylthio group, arylthio group, alkylseleno group, An aralkylseleno group or an arylseleno group is shown. X ² Represents an atom of group 16 of the periodic table of elements. m is an integer that satisfies 1 ≦ m ≦ 4, p is a number that satisfies 1 ≦ p ≦ 3, q is a number that satisfies 0 ≦ q ≦ 2, and r is 1 or 2. It is an integer that satisfies p + q + r = 4. All Cp, all X ¹ , All X ² May be the same or different. Also, multiple Cp's, multiple X's ¹ Or Cp and X ¹ And may be bonded directly or via a crosslinking group. ) Organoaluminum compounds are represented by the general formula E _a AlZ _3-a (However, E is an alkyl group having 1 to 8 carbon atoms, and all E may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z are the same. 9. The olefin polymerization catalyst according to claim 8, wherein a is an organoaluminum compound represented by the formula: a represents a number satisfying 0 <a ≦ 3. The molar ratio of [Al atom contained in catalyst component for olefin polymerization] / [Transition metal atom contained in transition metal compound] is 0.1 to 10,000, and [Al atom contained in organoaluminum compound] / [Transition metal] 10. The olefin polymerization catalyst according to claim 8, wherein the molar ratio of the transition metal atom contained in the compound is 0.1 to 10,000. A method for producing an olefin polymer, wherein the olefin is homopolymerized or copolymerized using the olefin polymerization catalyst according to any one of claims 6 to 10 . The method for producing an olefin polymer according to claim 11 , wherein the olefin polymer is a copolymer of ethylene and α-olefin .

Images