JP3975489B2 - Process for producing ethylene / α-olefin copolymer - Google Patents

Description

【００２５】
【化２】

【００２６】
［式中、Ｍ１はチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｙは各々独立して水素原子、ハロゲン原子、炭素数１〜２０のアルキル基、または炭素数６〜２０のアリール基、アリールアルキル基若しくはアルキルアリール基であり、Ｒ１，Ｒ２は各々独立して下記一般式（３）、（４）、（５）または （６）
【００２７】
【化３】

【００２８】
（式中、Ｒ６は各々独立して水素原子、炭素数１〜２０のアルキル基、または炭素数６〜２０のアリール基、アリールアルキル基若しくはアルキルアリール基である。）
で表される配位子であり、該配位子はＭ１と一緒にサンドイッチ構造を形成し、Ｒ４，Ｒ５は各々独立して下記一般式（７）、（８）、（９）または（１０）
【００２９】
【化４】

【００３０】
（式中、Ｒ７は各々独立して水素原子、炭素数１〜２０のアルキル基、または炭素数６〜２０のアリール基、アリールアルキル基若しくはアルキルアリール基である。）
で表される配位子であり、該配位子はＭ１と一緒にサンドイッチ構造を形成し、Ｒ３は下記一般式（１１）
【００３１】
【化５】

【００３２】
（式中、Ｒ８は各々独立して水素原子、炭素数１〜２０のアルキル基、または炭素数６〜２０のアリール基、アリールアルキル基若しくはアルキルアリール基であり、Ｍ２は炭素原子、珪素原子、ゲルマニウム原子または錫原子である。）
で表され、Ｒ４およびＲ５を架橋するように作用しており、ｐは１〜５の整数である。］
で表される。
【００３３】
前記一般式（１）または（２）で表される化合物としては、例えば、ビス（シクロペンタジエニル）チタニウムジクロライド、ビス（シクロペンタジエニル）ジルコニウムジクロライド、ビス（シクロペンタジエニル）ハフニウムジクロライド、ビス（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（メチルシクロペンタジエニル）ジルコニウムジクロライド、ビス（メチルシクロペンタジエニル）ハフニウムジクロライド、ビス（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（ブチルシクロペンタジエニル）ジルコニウムジクロライド、ビス（ブチルシクロペンタジエニル）ハフニウムジクロライド、ビス（ペンタメチルシクロペンタジエニル）チタニウムジクロライド、ビス（ペンタメチルシクロペンタジエニル）ジルコニウムジクロライド、ビス（ペンタメチルシクロペンタジエニル）ハフニウムジクロライド、ビス（インデニル）チタニウムジクロライド、ビス（インデニル）ジルコニウムジクロライド、ビス（インデニル）ハフニウムジクロライド、メチレンビス（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（シクロペンタジエニル）ジルコニウムジクロライド、メチレンビス（シクロペンタジエニル）ハフニウムジクロライド、メチレンビス（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（メチルシクロペンタジエニル）ジルコニウムジクロライド、メチレンビス（メチルシクロペンタジエニル）ハフニウムジクロライド、メチレンビス（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（ブチルシクロペンタジエニル）ジルコニウムジクロライド、メチレンビス（ブチルシクロペンタジエニル）ハフニウムジクロライド、メチレンビス（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（テトラメチルシクロペンタジエニル）ジルコニウムジクロライド、メチレンビス（テトラメチルシクロペンタジエニル）ハフニウムジクロライド、エチレンビス（インデニル）チタニウムジクロライド、エチレンビス（インデニル）ジルコニウムジクロライド、エチレンビス（インデニル）ハフニウムジクロライド、エチレンビス（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（テトラヒドロインデニル）ジルコニウムジクロライド、エチレンビス（テトラヒドロインデニル）ハフニウムジクロライド、エチレンビス（２−メチル−１−インデニル）チタニウムジクロライド、エチレンビス（２−メチル−１−インデニル）ジルコニウムジクロライド、エチレンビス（２−メチル−１−インデニル）ハフニウムジクロライド、イソプロピリデン（シクロペンタジエニル−９−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（シクロペンタジエニル−９−フルオレニル）ジルコニウムジクロライド、イソプロピリデン（シクロペンタジエニル−９−フルオレニル）ハフニウムジクロライド、イソプロピリデン（シクロペンタジエニル−２，７−ジメチル−９−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（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ジルコニウムジクロライド、イソプロピリデン（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ハフニウムジクロライド、イソプロピリデン（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−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（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロライド、イソプロピリデン（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ハフニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−９−フルオレニル）チタニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−９−フルオレニル）ジルコニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−９−フルオレニル）ハフニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）チタニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ジルコニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ハフニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）チタニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロライド、ジフェニルメチレン（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ハフニウムジクロライド、ジメチルシランジイルビス（シクロペンタジエニル）チタニウムジクロライド、ジメチルシランジイルビス（シクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（シクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（メチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシランジイルビス（メチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（メチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（ブチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシランジイルビス（ブチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（ブチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（２，４，５−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、ジメチルシランジイルビス（２，４−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、ジメチルシランジイルビス（３−メチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）チタニウムジクロライド、ジメチルシランジイルビス（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、ジメチルシランジイルビス（インデニル）チタニウムジクロライド、ジメチルシランジイルビス（２−メチル−インデニル）チタニウムジクロライド、ジメチルシランジイルビス（テトラヒドロインデニル）チタニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−９−フルオレニル）チタニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）チタニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）チタニウムジクロライド、ジメチルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（２，４−ジメチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（３−メチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（テトラメチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（インデニル）ジルコニウムジクロライド、ジメチルシランジイルビス（２−メチル−インデニル）ジルコニウムジクロライド、ジメチルシランジイルビス（テトラヒドロインデニル）ジルコニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−９−フルオレニル）ジルコニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ジルコニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロライド、ジメチルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（２，４−ジメチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（３−メチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（テトラメチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（インデニル）ハフニウムジクロライド、ジメチルシランジイルビス（２−メチル−インデニル）ハフニウムジクロライド、ジメチルシランジイルビス（テトラヒドロインデニル）ハフニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−９−フルオレニル）ハフニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ハフニウムジクロライド、ジメチルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ハフニウムジクロライド、ジエチルシランジイルビス（２，４，５−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、ジエチルシランジイルビス（２，４−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、ジエチルシランジイルビス（３−メチルシクロペンタジエニル）チタニウムジクロライド、ジエチルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）チタニウムジクロライド、ジエチルシランジイルビス（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、ジエチルシランジイルビス（インデニル）チタニウムジクロライド、ジエチルシランジイルビス（２−メチル−インデニル）チタニウムジクロライド、ジエチルシランジイルビス（テトラヒドロインデニル）チタニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−９−フルオレニル）チタニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）チタニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）チタニウムジクロライド、ジエチルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ジルコニウムジクロライド、ジエチルシランジイルビス（２，４−ジメチルシクロペンタジエニル）ジルコニウムジクロライド、ジエチルシランジイルビス（３−メチルシクロペンタジエニル）ジルコニウムジクロライド、ジエチルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）ジルコニウムジクロライド、ジエチルシランジイルビス（テトラメチルシクロペンタジエニル）ジルコニウムジクロライド、ジエチルシランジイルビス（インデニル）ジルコニウムジクロライド、ジエチルシランジイルビス （２−メチル−インデニル）ジルコニウムジクロライド、ジエチルシランジイルビス（テトラヒドロインデニル）ジルコニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−９−フルオレニル）ジルコニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ジルコニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロライド、ジエチルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ハフニウムジクロライド、ジエチルシランジイルビス（３−メチルシクロペンタジエニル）ハフニウムジクロライド、ジエチルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）ハフニウムジクロライド、ジエチルシランジイルビス（テトラメチルシクロペンタジエニル）ハフニウムジクロライド、ジエチルシランジイルビス（インデニル）ハフニウムジクロライド、ジエチルシランジイルビス（２−メチル−インデニル）ハフニウムジクロライド、ジエチルシランジイルビス（テトラヒドロインデニル）ハフニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−９−フルオレニル）ハフニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ハフニウムジクロライド、ジエチルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ハフニウムジクロライド、ジフェニルシランジイルビス（２，４，５−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、ジフェニルシランジイルビス（２，４−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、ジフェニルシランジイルビス（３−メチルシクロペンタジエニル）チタニウムジクロライド、ジフェニルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）チタニウムジクロライド、ジフェニルシランジイルビス（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、ジフェニルシランジイルビス（インデニル）チタニウムジクロライド、ジフェニルシランジイルビス（２−メチル−インデニル）チタニウムジクロライド、ジフェニルシランジイルビス（テトラヒドロインデニル）チタニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−９−フルオレニル）チタニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）チタニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）チタニウムジクロライド、ジフェニルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（２，４−ジメチルシクロペンタジエニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（３−メチルシクロペンタジエニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（テトラメチルシクロペンタジエニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（インデニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（２−メチル−インデニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（テトラヒドロインデニル）ジルコニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−９−フルオレニル）ジルコニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ジルコニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロライド、ジフェニルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ハフニウムジクロライド、ジフェニルシランジイルビス（３−メチルシクロペンタジエニル）ハフニウムジクロライド、ジフェニルシランジイルビス（４−ｔ−ブチル−２−メチルシクロペンタジエニル）ハフニウムジクロライド、ジフェニルシランジイルビス（テトラメチルシクロペンタジエニル）ハフニウムジクロライド、ジフェニルシランジイルビス（インデニル）ハフニウムジクロライド、ジフェニルシランジイルビス（２−メチル−インデニル）ハフニウムジクロライド、ジフェニルシランジイルビス（テトラヒドロインデニル）ハフニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−９−フルオレニル）ハフニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ハフニウムジクロライド、ジフェニルシランジイル（シクロペンタジエニル−２，７−ジ−ｔ−ブチル−９−フルオレニル）ハフニウムジクロライド等のジクロル体および上記４族遷移金属化合物のジメチル体、ジエチル体、ジヒドロ体、ジフェニル体、ジベンジル体等を例示することができる。
【００３４】
本発明に用いられるプロトン酸は、下記一般式（１２）
［ＨＬ１_l］［Ｍ２Ｒ５₄］ （１２）
（式中、Ｈはプロトンであり、Ｌ１は各々独立してルイス塩基であり、ｌは０＜ｌ≦２であり、Ｍ２はホウ素原子、アルミニウム原子またはガリウム原子であり、Ｒ５は各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表される化合物である。
【００３５】
ルイス酸は、下記一般式（１３）
［Ｃ］［Ｍ２Ｒ５₄］ （１３）
（式中、Ｃはカルボニウムカチオンまたはトロピリウムカチオンであり、Ｍ２はホウ素原子、アルミニウム原子またはガリウム原子であり、Ｒ５は各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表される化合物である。
【００３６】
イオン化イオン性化合物は、下記一般式（１４）
［Ｍ３Ｌ２_m］［Ｍ２Ｒ５₄］ （１４）
（式中、Ｍ３は周期表の２族、８族、９族、１０族、１１族または１２族から選ばれる金属の陽イオンであり、Ｌ２はルイス塩基またはシクロペンタジエニル基であり、ｍは０≦ｍ≦２であり、Ｍ２はホウ素原子、アルミニウム原子またはガリウム原子であり、Ｒ５は各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表される化合物である。
【００３７】
ルイス酸性化合物は、下記一般式（１５）
［Ｍ２Ｒ５₃］ （１５）
（式中、Ｍ２はホウ素原子、アルミニウム原子またはガリウム原子であり、Ｒ５は各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表される化合物である。
【００３８】
本発明の触媒の構成成分として用いられる一般式（１２）で表されるプロトン酸、一般式（１３）で表されるルイス酸、一般式（１４）で表されるイオン化イオン性化合物または一般式（１５）で表されるルイス酸性化合物は、上記の遷移金属化合物をカチオン性化合物にしうる化合物であり、生成したカチオン性化合物に対して弱く配位および／または相互作用するが、反応しない対アニオンを提供する化合物である。
【００３９】
一般式（１２）で表されるプロトン酸の具体例として、ジエチルオキソニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルオキソニウムテトラキス（ペンタフルオロフェニル）ボレート、テトラメチレンオキソニウムテトラキス（ペンタフルオロフェニル）ボレート、ヒドロニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ−ジメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリ−ｎ−ブチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジエチルオキソニウムテトラキス（ペンタフルオロフェニル）アルミネート、ジメチルオキソニウムテトラキス（ペンタフルオロフェニル）アルミネート、テトラメチレンオキソニウムテトラキス（ペンタフルオロフェニル）アルミネート、ヒドロニウムテトラキス（ペンタフルオロフェニル）アルミネート、Ｎ，Ｎ−ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）アルミネート、トリ−ｎ−ブチルアンモニウムテトラキス（ペンタフルオロフェニル）アルミネート等を挙げることができるが、これらに限定されるものではない。
【００４０】
一般式（１３）で表されるルイス酸としては、具体的にはトリチルテトラキス（ペンタフルオロフェニル）ボレート、トリチルテトラキス（ペンタフルオロフェニル）アルミネート、トロピリウムテトラキス（ペンタフルオロフェニル）ボレート、トロピリウムテトラキス（ペンタフルオロフェニル）アルミネート等を挙げることができるが、これらに限定されるものではない。
【００４１】
そして、一般式（１４）で表されるイオン化イオン性化合物としては、具体的にはリチウムテトラキス（ペンタフルオロフェニル）ボレート、リチウムテトラキス（ペンタフルオロフェニル）アルミネート等のリチウム塩、またはそのエーテル錯体、フェロセニウムテトラキス（ペンタフルオロフェニル）ボレート、フェロセニウムテトラキス（ペンタフルオロフェニル）アルミネート等のフェロセニウム塩、シルバーテトラキス（ペンタフルオロフェニル）ボレート、シルバーテトラキス（ペンタフルオロフェニル）アルミネート等の銀塩等を挙げることができるが、これらに限定されるものではない。
【００４２】
一般式（１５）で表されるルイス酸性化合物の具体的な例として、トリス（ペンタフルオロフェニル）ボラン、トリス（２，３，５，６−テトラフルオロフェニル）ボラン、トリス（２，３，４，５−テトラフェニルフェニル）ボラン、トリス（３，４，５−トリフルオロフェニル）ボラン、フェニルビス（パーフルオロフェニル）ボラン、トリス（３，４，５−トリフルオロフェニル）アルミニウム等が挙げられるが、これらに限定されるものではない。
【００４３】
本発明において用いられる周期表１族、２族、１３族、ＳｎまたはＺｎを含む有機金属化合物は、下記一般式（１６）
Ｍ５Ｒ１６_n （１６）
［式中、Ｍ５は周期表１族、２族、１３族、ＳｎまたはＺｎの元素である。Ｒ１６は各々独立して水素原子、炭素数１〜２０のアルキル基若しくはアルコキシ基、または炭素数６〜２０のアリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アルキルアリール基若しくはアルキルアリールオキシ基であり、少なくとも１つのＲ１６は水素原子、炭素数１〜２０のアルキル基、または炭素数６〜２０のアリール基、アリールアルキル基若しくはアルキルアリール基である。ｎはＭ５の酸化数に等しい。］
で表される化合物である。
【００４４】
前記一般式（１６）で表される化合物としては、例えば、トリメチルアルミニウム、トリエチルアルミニウム、トリイソプロピルアルミニウム、トリ−ｎ−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−ｎ−ブチルアルミニウム、トリアミルアルミニウム、ジメチルアルミニウムエトキサイド、ジエチルアルミニウムエトキサイド、ジイソプロピルアルミニウムエトキサイド，ジ−ｎ−プロピルアルミニウムエトキサイド、ジイソブチルアルミニウムエトキサイド、ジ−ｎ−ブチルアルミニウムエトキサイド、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、ジイソプロピルアルミニウムハイドライド、ジ−ｎ−プロピルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライド、ジ−ｎ−ブチルアルミニウムハイドライド等を例示することができる。
【００４５】
上記のａ）周期表４族の遷移金属を含む遷移金属化合物、ｂ）プロトン酸、ルイス酸、イオン化イオン性化合物またはルイス酸性化合物、およびｃ）周期表１族、２族、１３族、ＳｎまたはＺｎのいずれかを含む有機金属化合物から触媒を調製する方法としては、例えば、これらの化合物を不活性な溶媒下で混合する方法が挙げられるが、これに限定されるものではない。また、触媒においてプロトン酸、ルイス酸、イオン化イオン性化合物またはルイス酸性化合物の量は、遷移金属化合物に対して０．１〜１００倍ｍｏｌとするのが好ましく、特に０．５〜３０倍ｍｏｌとすることが好ましい。さらに、有機金属化合物の量は特に限定されないが、好ましくは遷移金属化合物に対して１〜１００００倍ｍｏｌである。
【００４６】
本発明において共重合する炭素数３以上のα−オレフィンとしてはプロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、スチレン等を挙げることができ、これらの１種を用いても２種以上混合してもよい。また、α−オレフィンは上記のものに限定されるものではない。
【００４７】
【実施例】
本発明を実施例、比較例により詳細に説明するが、本発明はこれら実施例に制限されるものではない。
【００４８】
実施例１
１０リットルの撹拌付き反応器を有する高温高圧法エチレン／α−オレフィン共重合体の製造プロセスにおいて、低密度飽和炭化水素としてエタンを用い、圧縮機（４）直前の（Ａ）より、エチレンとα−オレフィンの総循環量３６０ｋｇ／ｈに対してエタンを注入量１．４ｋｇ／ｈで注入した。反応器への該単量体の供給温度は４０℃で、反応圧力は９００ｋｇｆ／ｃｍ²、反応温度は１６０℃、１５００ｒｐｍで撹拌しながら１７０時間の連続運転を実施した。得られた共重合体の生産速度は３２ｋｇ／ｈであった。メタロセン触媒には、ジフェニルメチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライド、Ｎ，Ｎ−ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、トリイソブチルアルミニウムをホウ素／ジルコニウムのモル比が１．２、アルミニウム／ジルコニウムのモル比が２５０で、ジルコニウム濃度６５０μｍｏｌ／ｌに調製したトルエン溶液を用いた。
【００４９】
実施例２
低密度飽和炭化水素にプロパンを用い、エチレンの供給ライン（１）の（Ｂ）より、エチレンとα−オレフィンの総循環量３５０ｋｇ／ｈに対してプロパンを注入量１０．７ｋｇ／ｈで注入し、反応温度を２００℃、メタロセン触媒のジフェニルメチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライドの代わりにジフェニルメチレン（シクロペンタジエニル）（２，７−ジメチルフルオレニル）ジルコニウムジクロライドを用いて、ジルコニウム濃度を３００μｍｏｌ／ｌにした以外は実施例１と同様に行った。得られた共重合体の生産速度は４１ｋｇ／ｈであった。
【００５０】
実施例３
高圧分離器（８）の入口（Ｄ）より、エチレンとα−オレフィンの総循環量３００ｋｇ／ｈに対してエタンを注入量５．７ｋｇ／ｈで、温度１８０℃まで加熱して注入し、反応器入口のα−オレフィン／エチレンのモル比を２．３３、反応圧力を１５００ｋｇｆ／ｃｍ²にした以外は実施例１と同様に行った。得られた共重合体の生産速度は３２ｋｇ／ｈであった。
【００５１】
実施例４
α−オレフィンに１−ブテンを用い、エチレンの供給ライン（１）の（Ｂ）より、エチレンとα−オレフィンの総循環量３００ｋｇ／ｈに対してエタンを注入量６．０ｋｇ／ｈで注入し、反応器入口のα−オレフィン／エチレンのモル比を１．３０、反応温度を１８０℃にした以外は実施例１と同様に行った。得られた共重合体の生産速度は３５ｋｇ／ｈであった。
【００５２】
実施例５
α−オレフィンに１−ブテンを用い、α−オレフィンの供給ライン（２）の （Ｃ）より、エチレンとα−オレフィンの総循環量３１０ｋｇ／ｈに対してエタンを注入量２．８ｋｇ／ｈで注入し、反応器入口のα−オレフィン／エチレンのモル比を２．３３、反応温度を１４０℃にした以外は実施例１と同様に行った。得られた共重合体の生産速度は２６ｋｇ／ｈであった。
【００５３】
実施例６
分離器（１０）の入口（Ｅ）より、未反応単量体混合物量３６０ｋｇ／ｈに対してエタンを注入量０．６ｋｇ／ｈで注入し、反応器入口のα−オレフィン／エチレンのモル比を０．４３にした以外は実施例１と同様に行った。得られた共重合体の生産速度は３９ｋｇ／ｈであった。
【００５４】
実施例７
低密度飽和炭化水素にプロパンを用い、分離器（１０）の入口（Ｅ）より、未反応単量体混合物量３６０ｋｇ／ｈに対してプロパンを注入量２．６ｋｇ／ｈで注入し、反応器入口のα−オレフィン／エチレンのモル比を０．４４にし、メタロセン触媒のジフェニルメチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロライドの代わりにジフェニルメチレン（シクロペンタジエニル）（２，７−ジメチルフルオレニル）ジルコニウムジクロライドを用いて、ジルコニウム濃度を３００μｍｏｌ／ｌにした以外は実施例１と同様に行った。得られた共重合体の生産速度は３９ｋｇ／ｈであった。
【００５５】
実施例８
分離器（１０）の入口（Ｅ）より、未反応単量体混合物量３６０ｋｇ／ｈに対してエタンを注入量１．６ｋｇ／ｈで注入し、反応器入口のα−オレフィン／エチレンのモル比を１．００にし、反応圧力を１５００ｋｇｆ／ｃｍ²にした以外は実施例１と同様に行った。得られた共重合体の生産速度は３９ｋｇ／ｈであった。
【００５６】
実施例９
熱交換器（９）が設けられておらず、分離器（１０）の入口（Ｅ）より、未反応単量体混合物量３６０ｋｇ／ｈに対してエタンを注入量０．６ｋｇ／ｈで注入し、反応器入口のα−オレフィン／エチレンのモル比を０．４２にし、反応温度を１８０℃にした以外は実施例１と同様に行った。得られた共重合体の生産速度は４６ｋｇ／ｈであった。
【００５７】
比較例１
低密度飽和炭化水素を注入しない以外は実施例１と同様に行った。
【００５８】
比較例２
低密度飽和炭化水素を注入せず、反応圧力を９００ｋｇｆ／ｃｍ²にした以外は実施例３と同様に行った。
【００５９】
比較例３
低密度飽和炭化水素を注入しない以外は実施例５と同様に行った。
【００６０】
比較例４
低密度飽和炭化水素を注入せず、反応圧力を９００ｋｇｆ／ｃｍ²にした以外は実施例８と同様に行った。
【００６１】
各例の結果を表１に示す。
【００６２】
【表１】

【００６３】
【発明の効果】
以上の結果のように、高温高圧法エチレン／α−オレフィン共重合体の製造方法において、本発明を用いると高圧分離器の分離能力の向上や高圧分離器で分離された未反応単量体混合物中に同伴された高分子量の共重合体の析出・分離の向上が図られ、高圧循環工程の分離器の内壁や熱交換器の配管に該共重合体が付着・堆積して分離器の分離能力を低下させたり、熱交換器の配管を閉塞させることなく、所望の密度の共重合体を長期にわたり得ることができるようになる。
【図面の簡単な説明】
【図１】本発明のエチレン／α−オレフィン共重合体の製造方法の工程の１例を示す工程図である。
【符号の説明】
１：エチレンの供給ライン
２：α−オレフィンの供給ライン
５：触媒の供給ライン
７：圧力調整弁
８：高圧分離器
９，１１，１４：熱交換器
１０，１２，１５，１７：分離器
１３：低圧分離器
１９：反応器
Ａ，Ｂ，Ｃ，Ｄ，Ｅ：低密度飽和炭化水素の注入ライン
２２：高圧循環工程[0001]
BACKGROUND OF THE INVENTION
300 to 4000 kgf / cm in the presence of an olefin polymerization catalyst²At a reaction temperature of from 1 to 300 ° C., ethylene and an α-olefin having 3 or more carbon atoms were copolymerized in a reactor, and the resulting reaction mixture was 40 to 300 kgf / cm.²The unreacted monomer mixture is separated from the copolymer by the density difference by a separator (this separator is referred to as a “high pressure separator” in this specification), and the unreacted monomer mixture is separated from the copolymer. By cooling, the copolymer entrained therein is precipitated, and the unreacted monomer is recovered by separating the copolymer deposited in the separator (in this specification, the unreacted monomer separated in the high-pressure separator is recovered). The process of separating the copolymer entrained in the reaction monomer mixture and recovering the unreacted monomer is called the “high pressure circulation process.” The separator used for this separation is also referred to as the “high pressure circulation process. On the other hand, the process of recovering the unreacted monomer remaining in the copolymer by further reducing the pressure of the copolymer separated by the high-pressure separator is hereinafter referred to as “low-pressure circulation process”. ), And the unreacted monomer obtained was made from raw ethylene and α-olefin having 3 or more carbon atoms. Method for producing the ethylene / alpha-olefin copolymer which comprises supplying to the reactor with the emission (hereinafter, referred to as "method for producing a high temperature high pressure ethylene / alpha-olefin copolymer.") Is known.
[0002]
(In this specification, “melting point” means that a sample is melted at 200 ° C. for 5 minutes in a differential scanning calorimeter and then solidified by lowering the temperature to 30 ° C. at a rate of 10 ° C./min. (The maximum peak temperature of the endothermic curve obtained by raising the temperature at a rate of minutes, and “the density of the copolymer” is measured according to JIS K6760.)
[0003]
[Prior art]
By the way, in a method for producing a high-temperature / high-pressure ethylene / α-olefin copolymer using a metallocene catalyst as a catalyst, a high molecular weight copolymer adheres to and accumulates on the inner wall of a separator in a high-pressure circulation process or on a pipe of a heat exchanger. As a result, the separation capacity of the separator is lowered, or the pipes of the heat exchanger are blocked, resulting in an inoperable state in a short time.
[0004]
On the other hand, when a Ziegler type catalyst is used, such a problem hardly occurs. When Ziegler type catalysts are used, the copolymer obtained has a wide molecular weight distribution as is well known, and the copolymer entrained by the unreacted monomer mixture in the high-pressure circulation process is mainly a low molecular weight with a low melting point. (Weight average molecular weight is several thousand or less). In this system, it is presumed that this is a liquid and a high molecular weight that would be entrained in a small amount is washed away. On the other hand, in the case of using a metallocene catalyst, the molecular weight distribution of the copolymer obtained is narrow as is well known, and a low molecular weight (which should push away the attached high molecular weight) is not generated, so it adheres and accumulates. The unreacted monomer is accompanied by the same molecular weight as the product (weight average molecular weight tens of thousands or more).
[0005]
The above problem is what the present inventors have found for the first time.
[0006]
[Problems to be solved by the invention]
In the solution of the above-mentioned problem, that is, the method for producing a high-temperature high-pressure ethylene / α-olefin copolymer, the present invention improves the separation performance of the high-pressure separator and in the unreacted monomer mixture separated by the high-pressure separator. In order to improve the precipitation and separation of the high molecular weight copolymer entrained in the high-pressure circulation process, the high molecular weight copolymer adheres to and accumulates on the inner wall of the separator and the heat exchanger pipe, and the separator is separated. An object is to provide a method capable of obtaining a copolymer having a desired density (particularly, a relatively low density) over a long period of time without causing a decrease in capacity or blocking the piping of a heat exchanger. Is.
[0007]
[Means for Solving the Problems]
The present inventors coexisted a saturated hydrocarbon having a density lower than that of the unreacted monomer mixture with the reaction mixture to increase the density difference between the unreacted monomer, the saturated hydrocarbon mixture and the copolymer. As a result, the separability between the mixture and the copolymer in the high-pressure separator is improved, the amount of the copolymer entrained in the unreacted monomer mixture is reduced, and the copolymer in the low density region is further reduced. The inventors have found that they can be obtained and have completed the present invention.
[0008]
  That is, the present inventionMetallocene catalystIn the presence of 300-4000 kgf / cm²The reaction mixture obtained was copolymerized with ethylene and an α-olefin having 3 or more carbon atoms at a reaction temperature of from the melting point of the copolymer to a reaction temperature of 300 ° C., and the resulting reaction mixture was 40 to 300 kgf / cm²And the unreacted monomer mixture and the copolymer are separated by a high pressure separator, and the copolymer entrained in the unreacted monomer mixture is separated by a separator in a high pressure circulation process. In the method for producing an ethylene / α-olefin copolymer, the reaction monomer is recovered, and the obtained unreacted monomer is supplied to a reactor together with raw material ethylene and an α-olefin having 3 or more carbon atoms. A saturated hydrocarbon having a carbon number of 4 or less but lower than the density of the unreacted monomer mixture in the high pressure separator (hereinafter referred to as “low density saturated hydrocarbon”) is reacted in the high pressure separator. It is related with the manufacturing method of the ethylene / alpha-olefin copolymer characterized by making it coexist.
[0009]
Hereinafter, the present invention will be described in detail.
[0010]
The reactor used in the present invention may be either an autoclave type or a tube type. An example of a process in the case of using an autoclave type for the reactor will be described with reference to FIG. The raw ethylene and α-olefin are supplied from the respective supply lines (1) and (2), and are pressurized to a predetermined reaction pressure by the compressors (3) and (4), while the catalyst is a catalyst injection pump ( 5) to the reactor (19). Then, in the reactor, polymerization is carried out while stirring with a stirrer, and a reaction terminator is injected from (6) in order to prevent reaction after the reactor. The reaction pressure in the reactor is controlled by a pressure regulating valve (7), and the reaction temperature is controlled by the amount of catalyst injected. The ethylene / α-olefin copolymer and unreacted monomer mixture polymerized in the reactor are separated by a high-pressure separator (8), and the unreacted monomer mixture is separated from the heat exchanger (22) in the high-pressure circulation step (22). 9), returned to the compressor (4) via the separator (10), the heat exchanger (11) and the separator (12). On the other hand, the ethylene / α-olefin copolymer separated from the high pressure separator is depressurized by a pressure regulating valve and then sent to the low pressure separator (13), where it further remains in the ethylene / α-olefin copolymer. The unreacted monomer mixture and the ethylene / α-olefin copolymer were separated into the heat exchanger (14) and the separator (15) of the low-pressure circulation step (23). After that, it is recompressed by the low-pressure compressor (16), passed through the separator (17), and then returned to the compressor (3). Further, the separated ethylene / α-olefin copolymer is extracted by an extruder (18) below the low pressure separator (13).
[0011]
As described above, the reaction conditions may be those usually employed. That is, the reaction temperature is the melting point of the copolymer to 300 ° C, preferably the melting point to 270 ° C, and the reaction pressure is 300 to 4000 kgf / cm.²However, considering production costs, 500 to 2000 kgf / cm²Is preferred. The operating pressure in the low pressure circulation process is 0.1 to 35 kgf / cm², Preferably 0.5-20 kgf / cm²And the operating pressure of the high-pressure circulation process is 40 to 300 kgf / cm², Preferably 80-250 kgf / cm²It is. The operating temperatures of the low-pressure circulation process and the high-pressure circulation process are both 50 to 250 ° C., preferably 70 to 230 ° C.
[0012]
The low density saturated hydrocarbon for injection used in the present invention is methane, ethane, propane, n-butane, isobutane, and the saturated hydrocarbon having a density lower than that of the unreacted monomer mixture in the high pressure separator. 1 type may be used, or 2 or more types may be mixed and used for it. Here, when a substance other than the low density saturated hydrocarbon, for example, nitrogen is used, the compatibility of the nitrogen with the unreacted monomer mixture is worse than that of the saturated hydrocarbon. The critical point on the vapor-liquid equilibrium of the monomer mixture increases, the α-olefin in the unreacted monomer mixture condenses and dissolves in the copolymer in a large amount, and the quality of the copolymer decreases. Since the calorific value of nitrogen during compression is much greater than that of the saturated hydrocarbon, there is a risk of damage to the compressor due to an increase in the nitrogen concentration, and the concentration cannot be as high as that of the saturated hydrocarbon. is there.
[0013]
The injection location of the low density saturated hydrocarbon may be any location where the injected saturated hydrocarbon will flow into the high-pressure separator (8), and a plurality of locations may be selected. For example, the suction side (A) of the compressor (4) for supplying the mixture of the raw material and the recovered monomer shown in FIG. 1 to the reactor (19), (B) of the ethylene supply line (1), α -(C) in the olefin feed line (2), (D) in the inflow line of the reaction mixture to the high pressure separator (8), and inflow of the unreacted monomer mixture into the separator (10) in the high pressure circulation process. (E) of a line etc. can be mentioned.
[0014]
When the low-density saturated hydrocarbon is injected from the inlet of the high-pressure separator, the saturated hydrocarbon is preferably injected while being heated to a reaction temperature of +10 to 60 ° C., particularly a reaction temperature of +10 to 40 ° C. When the temperature of the saturated hydrocarbon becomes lower than the reaction temperature + 10 ° C., the temperature of the unreacted monomer mixture and the copolymer is lowered by the injection of the saturated hydrocarbon, so that the unreacted monomer mixture and the copolymer This is because the difference in density of the high pressure separator may be reduced and the separation performance of the high pressure separator may be reduced. On the other hand, when the reaction temperature is higher than + 60 ° C., the heat load on the heat exchanger in the high pressure circulation process increases.
[0015]
Separation of the unreacted monomer mixture and the copolymer in the high-pressure separator is possible due to the density difference between them, but in order to obtain a low-density copolymer, α in the unreacted monomer mixture -When the olefin concentration is increased, the density of the unreacted monomer mixture approaches the density of the copolymer and the density difference decreases. In such a situation, a large amount of copolymer is entrained in the unreacted monomer mixture, and the copolymer adheres and accumulates on the inner wall of the separator in the high-pressure circulation process or on the pipe of the heat exchanger, thereby separating the copolymer. Reduce the separation capacity of the heat exchanger or block the heat exchanger piping. Therefore, in the present invention, as shown by the following formula (a), saturation is achieved by injecting saturated hydrocarbons having a density lower than that of the unreacted monomer mixture under the condition of a constant temperature and pressure. Compared to the case where no hydrocarbon is present, the density of the unreacted monomer mixture is reduced, the density difference is widened to improve the separation ability, and it is difficult for the copolymer to adhere to and deposit on the inner wall of the equipment. is doing. The density difference at this time varies depending on the type of α-olefin and the average residence time of the unreacted monomer mixture and copolymer in the separator, but when the α-olefin is 1-butene, 0.40, In the case of 1-hexene, it is preferably larger than 0.315.
[0016]
Copolymer density-density of unreacted monomer mixture
= (D0 + dI0) × (P₁/ 120) x (T₁/ 433) (a)
d0: Pressure 120 kgf / cm², Difference in density between unreacted monomer mixture and copolymer without injection of low density saturated hydrocarbon under temperature of 160 ° C (depending on the type of α-olefin)
dI0: Pressure 120 kgf / cm², Expansion of density difference due to low density saturated hydrocarbon injection under temperature of 160 ° C (depending on the type of low density saturated hydrocarbon and α-olefin)
P₁: Total pressure of high-pressure separator [kgf / cm²]
T₁: High-pressure separator temperature [K]
(This equation has been found by experiments by the present inventors.)
The amount of low density saturated hydrocarbon to be injected is equal to the amount dissolved and entrained in the copolymer and discharged out of the system, that is, the amount of low density saturated hydrocarbon withdrawn from the extruder (18), The amount varies depending on the type of low-density saturated hydrocarbon, the type of α-olefin and the amount ratio of α-olefin / ethylene in the copolymer and monomer mixture, the temperature and pressure of the system, etc. The amount of the low-density saturated hydrocarbon concentration with respect to the total with the unreacted monomer mixture is preferably 4 to 48 mol%, more preferably 5 to 40 mol%. When the concentration of the low density saturated hydrocarbon is less than 4 mol%, the effect of increasing the density difference between the unreacted monomer mixture and the copolymer, that is, the value of dI0 in the above formula (a) is small, and the high pressure separation The effect of improving the separation capacity in the vessel and the effect of suppressing the adhesion and deposition of the copolymer to the piping in the high-pressure circulation process are small. Further, when the concentration of the low density saturated hydrocarbon is larger than 48 mol%, an increase in load in the process of degassing the unreacted monomer from the copolymer after the extruder (18) and saturated hydrocarbons that do not undergo a copolymerization reaction are caused. Destabilization of the reaction caused by a decrease in the copolymerization reaction rate in the reactor, and further, the difference in the ethylene / α-olefin amount ratio at the reactor inlet and outlet (the difference is due to the copolymerization reaction in the reactor). It is caused by the consumption of ethylene and α-olefin being different from each other. This may cause deterioration in quality such as expansion of the composition distribution of the copolymer due to increase.
[0017]
The presence of low-density saturated hydrocarbons in the high-pressure separator improves the separability between the unreacted monomer mixture and the copolymer in the high-pressure separator, particularly with respect to the total of the unreacted monomer mixture. If the concentration of the low-density saturated hydrocarbon is adjusted to 4 to 48 mol%, obstacles due to the adhesion and deposition of the copolymer in the high-pressure circulation process can be greatly reduced, but the unreacted monomer mixture and the copolymer Are not completely separated. The copolymer entrained in a small amount in the unreacted monomer mixture is cooled and precipitated in the high-pressure circulation step, and adheres to the piping or the like. When it is desired to reduce the amount of such a small amount of copolymer adhering to the piping and to lengthen the period until the piping is closed, the low-density saturated hydrocarbon is separated from the high-pressure circulation process separator (10). Inject at the entrance. As explained below, when the low-density saturated hydrocarbon comes into contact with the unreacted monomer mixture, the solubility of the copolymer in the unreacted monomer mixture decreases, and most of it is precipitated and separated. This is because the precipitation of the copolymer in the heat exchanger and piping, which are removed by the vessel and have many troubles due to subsequent adhesion and deposition, is suppressed.
[0018]
Even when low density saturated hydrocarbons are injected at this position, if the injected amount of the saturated hydrocarbons is too small, the effect is poor. On the other hand, if the injected amount is too large, unreacted monomer from the copolymer after the extruder (18). Destabilization of the reaction caused by increased load in the process of degassing the body, and the non-copolymerized saturated hydrocarbon causing a decrease in the copolymerization reaction rate in the reactor, and ethylene / α at the reactor inlet and outlet -There is also a possibility that the quality may be lowered such as expansion of the composition distribution of the copolymer due to an increase in the difference in the olefin content ratio.
[0019]
The injection amount of the low density saturated hydrocarbon is preferably adjusted so that the concentration of the saturated hydrocarbon is 5 to 50 mol% with respect to the total of the saturated hydrocarbon injected unreacted monomer mixture, 5-40 mol% is desirable. Thus, when injecting low density saturated hydrocarbons in the high pressure circulation process, the concentration of the saturated hydrocarbons is lower in the high pressure separator than the injection location, for example, the concentration in the high pressure circulation process is 5 to 50 mol. %, The concentration in the high-pressure separator is 4 to 48 mol%.
[0020]
When the low-density saturated hydrocarbon is injected from the inlet of the separator (10) in the high-pressure circulation process, heat exchange is performed between the high-pressure separator (8) and the separator (10) as shown in FIG. If there is a vessel (9), the injection point at the inlet of the heat exchanger causes the copolymer deposited from the unreacted monomer mixture to block the pipe of the heat exchanger. It must be provided between the heat exchanger and the separator, for example in FIG. Thus, conventionally, a heat exchanger for cooling and precipitating the copolymer is provided between the high-pressure separator and the separator in the high-pressure circulation process, but in applying the present invention, Installation of this heat exchanger is not necessarily required. When used together with the heat exchanger (9), the operating temperature of this heat exchanger is the melting point of the copolymer + 10-60 ° C., preferably the melting point of the copolymer + 10-40 ° C. When the operating temperature is higher than the melting point of the copolymer + 60 ° C., the cooling effect of the unreacted monomer mixture is small. On the other hand, when the operating temperature is lower than the melting point of the copolymer + 10 ° C., adhesion and solidification occur on the inner wall of the heat exchanger. Because there is a risk of it happening.
[0021]
In addition, by injecting saturated hydrocarbons having 4 or less carbon atoms into the unreacted monomer mixture supplied to the separator (10) in the high-pressure circulation step, the copolymer is less likely to adhere to and deposit on the piping or the like. As is apparent from the following equation, the solubility of the high molecular weight ethylene / α-olefin copolymer in the monomer mixture is determined under the condition that the temperature and pressure are constant, and the α in the unreacted monomer mixture is -Decreasing with decreasing olefin concentration, and the copolymer is precipitated in the fluid at once.
[0022]
    w = 0.3 × exp (a × T₂× P₂× (100-Yn) / 100)
  w: Relative solubility of high molecular weight copolymer in unreacted monomer mixture (pressure 200 kgf / cm², Solubility at a temperature of 200 ° C. [based on g-copolymer / g-unreacted monomer mixture]
  a: Solubility coefficient (varies depending on the type of α-olefin)
    1-hexene a = 1.190 × 10^-6× YM + 1.374 × 10^-5
    1-butene a = 6.216 × 10^-7× YM + 1.374 × 10^-5
  P₂: Total pressure [kgf / cm²]
  T₂: Temperature of unreacted monomer mixture [K]
  YM: α-olefin concentration [mol%] in the unreacted monomer
  Yn: saturated hydrocarbon concentration of 4 or less carbon atoms in the unreacted monomer [mol%]
(This equation has been found by experiments by the present inventors.)
  The olefin polymerization catalyst used in the present invention isMetallocene catalystFor example, as a metallocene catalyst, a) a transition metal compound containing a transition metal of Group 4 of the periodic table, b) a protonic acid, a Lewis acid, an ionized ionic compound or a Lewis acidic compound, and c) a group of Periodic Table 1, Group 2, Although the catalyst which consists of an organometallic compound containing any one of 13 group, Sn, or Zn is mentioned, it is not limited to this.
[0023]
The transition metal compound containing a transition metal of Group 4 of the periodic table used in the present invention has the following general formulas (1) and (2).
[0024]
[Chemical 1]

[0025]
[Chemical 2]

[0026]
[Wherein, M1 is a titanium atom, a zirconium atom or a hafnium atom, and each Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or arylalkyl. R1 and R2 are each independently the following general formula (3), (4), (5) or (6)
[0027]
[Chemical 3]

[0028]
(In the formula, each R 6 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, arylalkyl group or alkylaryl group having 6 to 20 carbon atoms.)
The ligand forms a sandwich structure together with M1, and R4 and R5 are each independently represented by the following general formula (7), (8), (9) or (10 )
[0029]
[Formula 4]

[0030]
(In the formula, each R7 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, arylalkyl group or alkylaryl group having 6 to 20 carbon atoms.)
Wherein the ligand forms a sandwich structure with M1, and R3 is represented by the following general formula (11):
[0031]
[Chemical formula 5]

[0032]
(In the formula, each R8 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, arylalkyl group or alkylaryl group having 6 to 20 carbon atoms, and M2 is a carbon atom, a silicon atom, Germanium atom or tin atom.)
And R 4 and R 5 are cross-linked and p is an integer of 1 to 5. ]
It is represented by
[0033]
Examples of the compound represented by the general formula (1) or (2) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, Bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (butylcyclopentadi) Enyl) zirconium dichloride, bis (butylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopenta Enyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) hafnium dichloride, methylenebis (cyclopentadienyl) titanium dichloride, methylenebis ( Cyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) hafnium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, methylenebis (methylcyclopentadienyl) hafnium dichloride , Methylenebis (butylcyclopentadienyl) titanium dic , Methylene bis (butylcyclopentadienyl) zirconium dichloride, methylene bis (butyl cyclopentadienyl) hafnium dichloride, methylene bis (tetramethylcyclopentadienyl) titanium dichloride, methylene bis (tetramethylcyclopentadienyl) zirconium dichloride, methylene bis ( Tetramethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, ethylenebis (tetrahydroindenyl) ) Zirconium dichloride, ethylenebis (tetrahydroi) Ndenyl) hafnium dichloride, ethylenebis (2-methyl-1-indenyl) titanium dichloride, ethylenebis (2-methyl-1-indenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) hafnium dichloride, isopropylidene ( Cyclopentadienyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-) 2,7-dimethyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconi Mudichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, isopropyl Riden (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenyl Methylene (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) Hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopenta Dienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-2) , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, dimethyl Silanediylbis (cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, Dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (butylcyclopenta) Dienyl) zirconium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) hafniu Dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (3-methylcyclopenta) Dienyl) titanium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (indenyl) Titanium dichloride, dimethylsilanediylbis (2-methyl-indenyl) titanium dichloride, dimethylsilanediylbis (tetrahydroindenyl) titanium dichlora Dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-2) , 7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) ) Zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride Dimethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) Zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl- 2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylsilane) Lopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (4-t-butyl- 2-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-indenyl) hafnium dichloride, Dimethylsilanediylbis (tetrahydroindenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) Hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride , Diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (3-methylcyclopentadiene) Enyl) titanium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium Um dichloride, diethylsilanediylbis (indenyl) titanium dichloride, diethylsilanediylbis (2-methyl-indenyl) titanium dichloride, diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9- Fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) Titanium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethyl) Clopentadienyl) zirconium dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (Tetramethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, diethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, diethylsilanediyl (Cyclopentadienyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl- 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diethylsilanediylbis (2,4,5- Trimethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, diethylsilanediyl Bis (tetramethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (indenyl) hafnium dichloride, diethylsilanediylbis (2-methyl-indenyl) hafnium dichloride Diethylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, Diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) titanium dichloride, diphenylsilanedii Bis (4-t-butyl-2-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (indenyl) titanium dichloride, diphenylsilanediylbis (2 -Methyl-indenyl) titanium dichloride, diphenylsilanediylbis (tetrahydroindenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl) -9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) tita Nium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (3-methylcyclo) Pentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) ) Zirconium dichloride, diphenylsilanediylbis (2-methyl-indenyl) zirconium dichloride, diphenylsilanediylbis (tetrahydro) Loindenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadiyl) Enyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (3-methylcyclopentadi) Enyl) hafnium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (teto) Methylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (indenyl) hafnium dichloride, diphenylsilanediylbis (2-methyl-indenyl) hafnium dichloride, diphenylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diphenylsilanediyl (cyclo Pentadienyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-) Butyl-9-fluorenyl) hafnium dichloride and the like, and dimethyl, diethyl, dihydro, and diphenyl isomers of the group 4 transition metal compounds, A dibenzyl body etc. can be illustrated.
[0034]
The protonic acid used in the present invention has the following general formula (12)
[HL1_l] [M2R5_Four] (12)
(Wherein H is a proton, L 1 is independently a Lewis base, 1 is 0 <l ≦ 2, M 2 is a boron atom, an aluminum atom or a gallium atom, and R 5 is each independently (This is a halogen-substituted aryl group having 6 to 20 carbon atoms.)
It is a compound represented by these.
[0035]
The Lewis acid has the following general formula (13)
[C] [M2R5_Four] (13)
(In the formula, C is a carbonium cation or a tropylium cation, M2 is a boron atom, an aluminum atom, or a gallium atom, and R5 is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
It is a compound represented by these.
[0036]
The ionized ionic compound has the following general formula (14):
[M3L2_m] [M2R5_Four] (14)
(Wherein M3 is a metal cation selected from Groups 2, 8, 9, 10, 11, or 12 of the periodic table, L2 is a Lewis base or a cyclopentadienyl group, m Is 0 ≦ m ≦ 2, M2 is a boron atom, an aluminum atom or a gallium atom, and R5 is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
It is a compound represented by these.
[0037]
The Lewis acidic compound has the following general formula (15)
[M2R5_Three] (15)
(In the formula, M2 represents a boron atom, an aluminum atom or a gallium atom, and R5 each independently represents a halogen-substituted aryl group having 6 to 20 carbon atoms.)
It is a compound represented by these.
[0038]
The protonic acid represented by the general formula (12), the Lewis acid represented by the general formula (13), the ionized ionic compound represented by the general formula (14) or the general formula used as a constituent of the catalyst of the present invention The Lewis acidic compound represented by (15) is a compound that can convert the above transition metal compound into a cationic compound, and is weakly coordinated and / or interacts with the generated cationic compound, but does not react. Is a compound that provides
[0039]
Specific examples of the protonic acid represented by the general formula (12) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) borate, Hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, Dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) al Nate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, tri-n-butylammonium tetrakis (pentafluorophenyl) aluminate, and the like. However, it is not limited to these.
[0040]
Specific examples of the Lewis acid represented by the general formula (13) include trityltetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) aluminate, tropyliumtetrakis (pentafluorophenyl) borate, and tropyliumtetrakis. (Pentafluorophenyl) aluminate and the like can be mentioned, but are not limited thereto.
[0041]
As the ionized ionic compound represented by the general formula (14), specifically, lithium salts such as lithium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) aluminate, or ether complexes thereof, Ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) aluminate, silver salts such as silver tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) aluminate, etc. However, it is not limited to these.
[0042]
Specific examples of the Lewis acidic compound represented by the general formula (15) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4). , 5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum and the like. However, it is not limited to these.
[0043]
The organometallic compound containing Group 1, Group 2, Group 13, Sn or Zn used in the present invention is represented by the following general formula (16).
M5R16_n                                (16)
[Wherein, M5 is an element of Group 1, Group 2, Group 13, Sn or Zn of the periodic table. R16 each independently represents a hydrogen atom, an alkyl group or alkoxy group having 1 to 20 carbon atoms, or an aryl group, aryloxy group, arylalkyl group, arylalkoxy group, alkylaryl group or alkylaryloxy group having 6 to 20 carbon atoms. And at least one R 16 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, arylalkyl group or alkylaryl group having 6 to 20 carbon atoms. n is equal to the oxidation number of M5. ]
It is a compound represented by these.
[0044]
Examples of the compound represented by the general formula (16) include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triamylaluminum, dimethylaluminum. Ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide, di-n-butyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, di- n-propylaluminum hydride, diisobutylaluminum hydride, di-n It can be exemplified butyl aluminum hydride or the like.
[0045]
A) a transition metal compound containing a transition metal of Group 4 of the periodic table, b) a protonic acid, a Lewis acid, an ionized ionic compound or a Lewis acidic compound, and c) a Group 1, Group 2, Group 13, Sn or Examples of a method for preparing a catalyst from an organometallic compound containing any one of Zn include, but are not limited to, a method in which these compounds are mixed in an inert solvent. Further, the amount of the protonic acid, Lewis acid, ionized ionic compound or Lewis acidic compound in the catalyst is preferably 0.1 to 100 times mol, particularly 0.5 to 30 times mol for the transition metal compound. It is preferable to do. Furthermore, the amount of the organometallic compound is not particularly limited, but is preferably 1 to 10,000 times mol of the transition metal compound.
[0046]
Examples of the α-olefin having 3 or more carbon atoms to be copolymerized in the present invention include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene. Or two or more of them may be mixed. The α-olefin is not limited to the above.
[0047]
【Example】
The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
[0048]
Example 1
In a process for producing a high-temperature high-pressure ethylene / α-olefin copolymer having a 10-liter stirred reactor, ethane was used as a low-density saturated hydrocarbon, and ethylene and α were obtained from (A) immediately before the compressor (4). -Ethane was injected at an injection rate of 1.4 kg / h for a total circulating amount of olefin of 360 kg / h. The monomer supply temperature to the reactor is 40 ° C., and the reaction pressure is 900 kgf / cm.²The reaction temperature was 160 ° C., and continuous operation for 170 hours was performed with stirring at 1500 rpm. The production rate of the obtained copolymer was 32 kg / h. The metallocene catalyst includes diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triisobutylaluminum with a boron / zirconium molar ratio of 1.2, aluminum A toluene solution prepared at a molar ratio of / zirconium of 250 and a zirconium concentration of 650 μmol / l was used.
[0049]
Example 2
Propane is used for low-density saturated hydrocarbons, and propane is injected at an injection rate of 10.7 kg / h from ethylene supply line (1) (B) for a total circulation rate of 350 kg / h of ethylene and α-olefin. The reaction temperature was 200 ° C., and diphenylmethylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride was used instead of the metallocene-catalyzed diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, The same operation as in Example 1 was performed except that the zirconium concentration was changed to 300 μmol / l. The production rate of the obtained copolymer was 41 kg / h.
[0050]
Example 3
From the inlet (D) of the high-pressure separator (8), ethane is injected at an injection rate of 5.7 kg / h with a total circulation rate of 300 kg / h of ethylene and α-olefin, and heated to 180 ° C. for reaction. The α-olefin / ethylene molar ratio at the reactor inlet was 2.33, and the reaction pressure was 1500 kgf / cm.²The procedure was the same as in Example 1 except that. The production rate of the obtained copolymer was 32 kg / h.
[0051]
Example 4
1-Butene was used as the α-olefin, and ethane was injected at an injection rate of 6.0 kg / h from the ethylene supply line (1) (B) for a total circulation rate of 300 kg / h of ethylene and α-olefin. The same procedure as in Example 1 was conducted except that the molar ratio of α-olefin / ethylene at the reactor inlet was 1.30 and the reaction temperature was 180 ° C. The production rate of the obtained copolymer was 35 kg / h.
[0052]
Example 5
1-Butene is used as the α-olefin, and ethane is injected at a flow rate of 2.8 kg / h from (C) of the α-olefin supply line (2) with respect to a total circulation rate of 310 kg / h of ethylene and α-olefin. This was carried out in the same manner as in Example 1 except that the molar ratio of α-olefin / ethylene at the reactor inlet was 2.33 and the reaction temperature was 140 ° C. The production rate of the obtained copolymer was 26 kg / h.
[0053]
Example 6
From the inlet (E) of the separator (10), ethane was injected at an injection rate of 0.6 kg / h with respect to the unreacted monomer mixture amount of 360 kg / h, and the molar ratio of α-olefin / ethylene at the reactor inlet Was carried out in the same manner as in Example 1 except that the ratio was changed to 0.43. The production rate of the obtained copolymer was 39 kg / h.
[0054]
Example 7
Propane is used as the low density saturated hydrocarbon, and from the inlet (E) of the separator (10), propane is injected at an injection amount of 2.6 kg / h with respect to the unreacted monomer mixture amount of 360 kg / h. The inlet α-olefin / ethylene molar ratio was 0.44, and instead of the metallocene catalyst diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethylfluorine) was used. This was carried out in the same manner as in Example 1 except that the concentration of zirconium was changed to 300 μmol / l using (olenyl) zirconium dichloride. The production rate of the obtained copolymer was 39 kg / h.
[0055]
Example 8
From the inlet (E) of the separator (10), ethane was injected at an injection rate of 1.6 kg / h with respect to the unreacted monomer mixture amount of 360 kg / h, and the molar ratio of α-olefin / ethylene at the reactor inlet 1.00, reaction pressure 1500 kgf / cm²The procedure was the same as in Example 1 except that. The production rate of the obtained copolymer was 39 kg / h.
[0056]
Example 9
No heat exchanger (9) was provided, and ethane was injected at an injection rate of 0.6 kg / h from the inlet (E) of the separator (10) with an unreacted monomer mixture amount of 360 kg / h. The same procedure as in Example 1 was conducted except that the α-olefin / ethylene molar ratio at the reactor inlet was 0.42, and the reaction temperature was 180 ° C. The production rate of the obtained copolymer was 46 kg / h.
[0057]
Comparative Example 1
It carried out like Example 1 except not injecting low density saturated hydrocarbon.
[0058]
Comparative Example 2
Without injecting low-density saturated hydrocarbons, the reaction pressure is 900 kgf / cm²The procedure was the same as in Example 3 except that.
[0059]
Comparative Example 3
It carried out like Example 5 except not inject | pouring a low density saturated hydrocarbon.
[0060]
Comparative Example 4
Without injecting low-density saturated hydrocarbons, the reaction pressure is 900 kgf / cm²The procedure was the same as in Example 8 except that the above was changed.
[0061]
The results of each example are shown in Table 1.
[0062]
[Table 1]

[0063]
【The invention's effect】
As described above, in the method for producing a high-temperature high-pressure ethylene / α-olefin copolymer, when the present invention is used, the separation performance of the high-pressure separator is improved and the unreacted monomer mixture separated by the high-pressure separator. The separation and separation of the high-molecular-weight copolymer entrained in the separator is improved, and the copolymer adheres to and accumulates on the inner wall of the separator and the heat exchanger pipe in the high-pressure circulation process. A copolymer having a desired density can be obtained over a long period of time without reducing the capacity or blocking the piping of the heat exchanger.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a process diagram showing one example of a process of a method for producing an ethylene / α-olefin copolymer of the present invention.
[Explanation of symbols]
1: Ethylene supply line
2: α-olefin supply line
5: Catalyst supply line
7: Pressure regulating valve
8: High pressure separator
9, 11, 14: heat exchanger
10, 12, 15, 17: Separator
13: Low pressure separator
19: Reactor
A, B, C, D, E: Low density saturated hydrocarbon injection line
22: High-pressure circulation process

Claims (3)

In the presence of a metallocene catalyst, a reaction mixture obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms at a reaction pressure of 300 to 4000 kgf / cm ² and a reaction temperature of the melting point of the copolymer to 300 ° C. Is reduced to 40 to 300 kgf / cm ² , the unreacted monomer mixture and the copolymer are separated by a high-pressure separator, and the copolymer entrained in the unreacted monomer mixture is separated in the high-pressure circulation step. The unreacted monomer is recovered by separation with a separator, and the obtained unreacted monomer is supplied to the reactor together with raw material ethylene and an α-olefin having 3 or more carbon atoms. In the method for producing a polymer, a saturated hydrocarbon having 4 or less carbon atoms, but having a density lower than that of the unreacted monomer mixture in the high-pressure separator (hereinafter referred to as “low-density saturated hydrocarbon”). Reaction mixing in high pressure separator A method for producing an ethylene / α-olefin copolymer characterized by coexisting with a product. 2. The ethylene / α-olefin copolymer according to claim 1, wherein the concentration of the low density saturated hydrocarbon in the high pressure separator is adjusted to 4 to 48 mol% with respect to the total of the unreacted monomer mixture. A method for producing a polymer. Unreacted monomer mixture separated from the high pressure separator at the inlet of the separator of the initially reaching high circulating step, injecting a low-density saturated hydrocarbon unreacted monomer mixture, the low-density saturated hydrocarbon The ethylene / α- of claim 2, wherein the saturated hydrocarbon injection amount is adjusted so that the concentration of the saturated hydrocarbon in the injected unreacted monomer mixture is 5 to 50 mol%. A method for producing an olefin copolymer.

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