JP2004528446A - Olefin polymerization catalyst - Google Patents

Abstract

The olefin polymerization catalyst component is prepared by preparing a solution of a transition metal complex of the selected tridentate ligand, adsorbing the complex onto silica or a silica-alumina support, and providing a storage-stable supported transition metal complex component. It is prepared by separating the solution from Olefin polymerization with this component is carried out with high catalyst productivity using a cocatalyst such as a trialkylaluminum compound.

Description

【００３２】
（式中、実線で表される結合は、第二級炭素基が結合している置換アリールの環原子への結合であり、破線で表される両自由結合は水素以外の原子への結合である）を意味する。これらの原子または基は同じであっても異なってもよい。言い換えれば、破線で表される自由原子価はヒドロカルビル、置換ヒドロカルビルまたは不活性官能基への結合であってもよい。第二級炭素基の例には、−ＣＨ（ＣＨ_３）_２、−ＣＨＣｌ_２、−ＣＨ（Ｃ_６Ｈ_５）_２、シクロヘキシル、−ＣＨ（ＣＨ_３）ＯＣＨ_３、および−ＣＨ＝ＣＣＨ_３が挙げられる。
【００３３】
「第三級炭素基」とは、式
【００３４】
【化２】

【００３５】
（式中、実線で表される結合は、第三級炭素基が結合している置換アリールの環原子への結合であり、破線で表される３つの自由結合は水素以外の原子への結合である）の基を意味する。言い換えれば、破線で表される結合は、ヒドロカルビル、置換ヒドロカルビルまたは不活性官能基への結合である。第三級炭素基の例には、−Ｃ（ＣＨ_３）_３、−Ｃ（Ｃ_６Ｈ_５）_３、−ＣＣｌ_３、−ＣＦ_３、−Ｃ（ＣＨ_３）_２ＯＣＨ_３、−Ｃ≡ＣＨ、−Ｃ（ＣＨ_３）_２ＣＨ＝ＣＨ_２、フェニルのようなアリールおよび置換アリールならびに１−アダマンチルが挙げられる。
【００３６】
好ましい２，６−ピリジンカルボキシアルデヒドビスイミンおよび２，６−ジアシルピリジンビスイミンは、式（Ｉ）
【００３７】
【化３】

【００３８】
（式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５はそれぞれ独立して水素、ヒドロカルビル、置換ヒドロカルビルまたは不活性官能基であり（ただし、互いにビシナルであるＲ^１、Ｒ^２およびＲ^３の任意の２つが一緒になって環を形成してもよい）、かつ、
Ｒ^６およびＲ^７はアリール、置換アリールまたは官能基である）
の化合物である。
【００３９】
典型的には（Ｉ）の遷移金属錯体は、式ＬＭＸ_ｍＹ_ｎ（式中、Ｌは２，６−ピリジンジカルボキシアルデヒドビスイミンまたは２，６−ジアシルピリジンビスイミン配位子であり、Ｍは遷移金属であり、Ｘはモノアニオン（１個の負電荷）であり、Ｙは比較的非配位性のモノアニオンであり、ｍ＋ｎはＭの酸化状態に等しい）を有するであろう。典型的には、Ｘのすべてが一座アニオンである場合、その時はｎはゼロであり、ｍはＭの酸化状態に等しい。例えばＸの１つが二座モノアニオンである場合、その時は通常ｎは１であり（ｍ＋ｎが２である場合）。従って、ｍは１以上の整数であってもよいが、ｎは０または１以上の整数であってもよく、好ましくはｎは０または１である。
【００４０】
一座モノアニオンは、ハライドおよびカーボキシレートを含むが、二座モノアニオンはアセチルアセトナート、アリルおよびベンジル型モノアニオンを含む。比較的非配位性のアニオンは上に定義されている。
【００４１】
ＸもＹもヒドロカルビルアニオンまたはハイドライドでない場合、活性な重合（第２方法で）を形成するために典型的に、少なくともＸは、アルキルのようなヒドロカルビルアニオンまたはハイドライドに変換されなければならない（他のアニオンもまた活性であるかもしれない）。これは通常、例えば、金属をアルキル化することができる活性化剤（共触媒）で達成される。「アルキル化する」とは、本明細書では共触媒がＬＭＸ_ｍＹ_ｎと反応して金属をアルキル化する（例えばＬＭ（アルキル）_ｍＹ_ｎを与える）が、任意に同時にアルキル基の１つを引き抜くことによって（特にｎがゼロである場合）比較的非配位性のアニオンを形成することを意味する。「ハイドライド化」は、アルキルアニオンの代わりにハイドライドアニオンを用いることを除いて、アルキル化に類似している。あるいはまた、触媒系の一部として、アルキル基を引き抜いて比較的非配位性のアニオンを形成するために、中性ルイス酸である第２の共触媒が添加されてもよい。これが、使用される特定の金属錯体および使用される共触媒に依存して、使用することができる活性なオレフィン重合触媒を形成するためのただ１つのシナリオであることに注意されたい。
【００４２】
好ましくは、活性化剤（共触媒）は、（１）（ｉ）前記遷移金属錯体の前記遷移金属からアニオンを引き抜いて弱く配位するアニオンを形成することができる、および（ｉｉ）前記遷移金属をアルキル化またはハイドライド化することができるの両方である中性ルイス酸、または（２）（ｉ）前記遷移金属錯体の前記遷移金属からアニオンを引き抜いて弱く配位するアニオンを形成することができる中性ルイス酸と（ｉｉ）前記遷移金属をアルキル化またはハイドライド化することができる別の化合物との組み合わせのいずれかである。より好ましくは、共触媒は、アルキル化化合物および弱く配位するアニオンを形成することができるルイス酸である。
【００４３】
有用なアルキル化化合物は、アルキルアルミニウム化合物（それらがアルミニウムに結合した水素を含有する場合、それらはまたハイドライド化化合物でもあり得る）、アルキル亜鉛化合物、およびグリニャール試薬を含む。アルキル化するおよび比較的非配位性のアニオンを形成するの両方ができる好ましい化合物は、トリメチルアルミニウム、トリエチルアルミニウム、トリ−ｎ−ブチルアルミニウムおよびトリ−ｉ−ブチルアルミニウムをはじめとするトリアルキルアルミニウム化合物、ジエチルアルミニウムクロリド、エチルアルミニウムクロリドおよびエチルアルミニウムセスキクロリドのようなアルキルハロアルミニウム化合物、エトキシジエチルアルミニウムのような（アルコキシ）（アルキル）アルニミウム化合物のようなアルキルアルミニウム化合物である。メチルアルミノキサンのようなアルミノキサンもまた使用されてもよいが、（たとえそれらが他の点では非常に有効であるかもしれないとしても）それらのコストのために、それらは好ましくない。
【００４４】
（Ｉ）において、
Ｒ^１、Ｒ^２およびＲ^３は水素であり、および／または
Ｒ^１およびＲ^３は水素であり、Ｒ^２はトリフルオロメチルであり、および／または
Ｒ^４およびＲ^５はそれぞれ独立してハロゲン、チオアルキル、水素または１〜６個の炭素原子を含むアルキルであり、より好ましくはＲ^４およびＲ^５はそれぞれ独立して水素またはメチルである
ことが一般に好ましい。
【００４５】
（Ｉ）の好ましい一形態において、Ｒ^６およびＲ^７はそれぞれ独立して置換アリール、より好ましくは置換フェニルである。さらにより好ましくは、Ｒ^６は
【００４６】
【化４】

【００４７】
であり、かつ、Ｒ^７は
【００４８】
【化５】

【００４９】
（式中、
Ｒ^８、Ｒ^１２、Ｒ^１３およびＲ^１７はそれぞれ独立してヒドロカルビル、置換ヒドロカルビルまたは不活性官能基であり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６はそれぞれ独立して水素、ヒドロカルビル、置換ヒドロカルビルまたは不活性官能基であり、
ただし、互いにビシナルであるＲ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７の任意の２つが一緒になって環を形成してもよい）。
【００５０】
（ＶＩ）および（ＶＩＩ）において、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６はそれぞれ独立して水素、ハロゲン、または１〜６個の炭素原子を含むアルキルであることが好ましく、これらのそれぞれが水素であることがより好ましく、および／または
Ｒ^１０およびＲ^１５はメチル、フェニルまたは置換フェニル（アルキル置換フェニルのような）であることが好ましく、および／または
Ｒ^８、Ｒ^１２、Ｒ^１３およびＲ^１７はそれぞれ独立してハロゲン、フェニル、置換フェニルまたは１〜６個の炭素原子を含むアルキルであることが好ましく、それぞれが独立してフェニル、置換フェニル（例えば、ｐ−ｔ−ブチルフェニルのようなアルキル置換フェニル）または１〜６個の炭素原子を含むアルキル（ｉ−イソプロピルまたはｔ−ブチルのような）（Ｒ^８およびＲ^１２の両方、またはＲ^１３およびＲ^１７の両方が同一化合物においてｔ−ブチルである場合は好ましくないけれども）であることがより好ましい。
【００５１】
具体的な好ましい化合物は、（上述のＲ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５についての変形の任意のものと組み合わせて）Ｒ^６およびＲ^７がそれぞれ（ＶＩ）および（ＶＩＩ）であるものであり、かつ、
Ｒ^９、Ｒ^１１、Ｒ^１４およびＲ^１６が水素であり、かつ、Ｒ^８、Ｒ^１０、Ｒ^１２、Ｒ^１３、Ｒ^１５およびＲ^１７がメチルであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６が水素であり、Ｒ^８およびＲ^１３がクロロであり、かつ、Ｒ^１２およびＲ^１７がメチルであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７が水素であり、かつ、Ｒ^８およびＲ^１３がフェニルであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７が水素であり、かつ、Ｒ^８およびＲ^１３がｐ−ｔ−ブチルフェニルであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６が水素であり、かつ、Ｒ^８、Ｒ^１２、Ｒ^１３およびＲ^１７がフェニルであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６が水素であり、かつ、Ｒ^８、Ｒ^１２、Ｒ^１３およびＲ^１７がｐ−ｔ−ブチルフェニルであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６が水素であり、かつ、Ｒ^８およびＲ^１３がフェニルであり、かつ、Ｒ^１２およびＲ^１７がハロであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６が水素であり、かつ、Ｒ^８およびＲ^１３がｐ−ｔ−ブチルフェニルであり、かつ、Ｒ^１２およびＲ^１７がハロであり、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５およびＲ^１６が水素であり、かつ、Ｒ^８、Ｒ^１２、Ｒ^１３およびＲ^１７がｉ−プロピルであり、ならびに
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７が水素であり、かつ、Ｒ^８およびＲ^１３がｔ−ブチルである。
【００５２】
（Ｉ）の別の好ましい変形において、Ｒ^６およびＲ^７はそれぞれ独立して置換１−ピロー留である。より好ましくはこの場合Ｒ^６およびＲ^７は、それぞれ、
【００５３】
【化６】

【００５４】
（式中、
Ｒ^１８およびＲ^２１は、（ＶＩ）におけるＲ^８およびＲ^１２の定義、およびそれらの好みに一致し、
Ｒ^２２およびＲ^２５は、（ＶＩＩ）におけるＲ^１３およびＲ^１７の定義、およびそれらの好みに一致し、
Ｒ^１９およびＲ^２０は、（ＶＩ）におけるＲ^９およびＲ^１１の定義、およびそれらの好みに一致し、かつ、
Ｒ^２３およびＲ^２４は、（ＶＩＩ）におけるＲ^１４およびＲ^１６の定義、およびそれらの好みに一致する）
である。
【００５５】
二量体またはオリゴマーが生産される「重合」において、Ｒ^６およびＲ^７は、好ましくはそれぞれ独立して、イミノ窒素に結合した第１環原子を有する置換アリールである、ただし、
Ｒ^６において、前記第１環原子に隣接する第２環原子はハロゲン、第一級炭素基、第二級炭素基または第三級炭素基に結合している、さらにただし、
Ｒ^６において、前記第２環原子がハロゲンまたは第一級炭素基に結合している場合、前記第１環原子に隣接するＲ^６およびＲ^７における他の環原子の０、１または２個はハロゲンもしくは第一級炭素基に結合しており、前記第１環原子に隣接する環原子の残りは水素原子に結合している、または
Ｒ^６において、前記第２環原子が第二級炭素基に結合している場合、前記第１環原子に隣接するＲ^６およびＲ^７における他の環原子の０、１または２個はハロゲン、第一級炭素基または第二級炭素基に結合しており、前記第１環原子に隣接する環原子の残りは水素原子に結合している、または
Ｒ^６において、前記第２環原子が第三級炭素基に結合している場合、前記第１環原子に隣接するＲ^６およびＲ^７における他の環原子の０または１個は第三級炭素基に結合しており、前記第１環原子に隣接する環原子の残りは水素原子に結合している）。
【００５６】
「イミノ窒素原子に結合したＲ^６およびＲ^７における第１環原子」とは、（Ｉ）に示されたイミノ窒素に結合したこれらの基における環原子を意味し、例えば
【００５７】
【化７】

【００５８】
（ＩＩ）または（ＩＩＩ）における環の１−位に示された原子がイミノ窒素原子に結合した第１環原子である（アリール基上に置換されているかもしれない他の基は示されていない）。第１環原子に隣接する環原子は、例えば、これらの隣接原子の自由原子価が破線で示されている（ＩＶ）および（Ｖ）に示されている（（ＩＶ）では２，６−位、（Ｖ）では２，５−位）。
【００５９】
【化８】

【００６０】
好ましい二量化／オリゴマー化実施形態において、Ｒ^６は
【００６１】
【化９】

【００６２】
であり、Ｒ^７は
【００６３】
【化１０】

【００６４】
（式中
Ｒ^８はハロゲン、第一級炭素基、第二級炭素基または第三級炭素基であり、かつ、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７はそれぞれ独立して水素、ヒドロカルビル、置換ヒドロカルビルまたは官能基であり、
ただし、
Ｒ^８がハロゲンまたは第一級炭素基である場合、Ｒ^１２、Ｒ^１３およびＲ^１７の０、１または２個がハロゲンまたは第一級炭素基であり、Ｒ^１２、Ｒ^１３およびＲ^１７の残りは水素であり、または
Ｒ^８が第二級炭素基である場合、Ｒ^１２、Ｒ^１３およびＲ^１７の０または１個がハロゲン、第一級炭素基または第二級炭素基であり、Ｒ^１２、Ｒ^１３およびＲ^１７の残りは水素であり、または
Ｒ^８が第三級炭素基である場合、Ｒ^１２、Ｒ^１３およびＲ^１７の０または１個が第三級炭素基であり、Ｒ^１２、Ｒ^１３およびＲ^１７の残りは水素であり、
かつ、さらにただし、互いにビシナルであるＲ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７の任意の２つが一緒になって環を形成してもよい）。
【００６５】
上の式（ＶＩａ）および（ＶＩＩａ）において、Ｒ^８は、イミノ窒素に結合した第１環原子に隣接する第２環原子に対応し、Ｒ^１２、Ｒ^１３およびＲ^１７は第１環原子に隣接する他の環原子に対応する。
【００６６】
（ＶＩａ）および（ＶＩＩａ）を含有する化合物（Ｉ）において、
Ｒ^８が第一級炭素基である場合、Ｒ^１３は第一級炭素基であり、かつ、Ｒ^１２およびＲ^１７は水素であり、または
Ｒ^８が第二級炭素基である場合、Ｒ^１３は第一級炭素基または第二級炭素基、より好ましくは第二級炭素基であり、かつ、Ｒ^１２およびＲ^１７は水素であり、または
Ｒ^８が第三級炭素基（より好ましくはトリハロメチルのようなトリハロ第三級炭素基）である場合、Ｒ^１３は第三級炭素基（より好ましくはトリハロメチルのようなトリハロ第三級炭素基）であり、かつ、Ｒ^１２およびＲ^１７は水素であり、または
Ｒ^８がハロゲンである場合、Ｒ^１３はハロゲンであり、かつ、Ｒ^１２およびＲ^１７は水素である
ことが特に好ましい。
【００６７】
（ＶＩａ）および（ＶＩＩａ）が現れるすべての具体的な好ましい化合物（Ｉ）において、Ｒ^１、Ｒ^２およびＲ^３は水素であり、および／またはＲ^４およびＲ^５はメチルであることが好ましい。さらに、
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７はすべて水素であり、Ｒ^１３はメチルであり、かつ、Ｒ^８は第一級炭素基、より好ましくはメチルであり、または
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７はすべて水素であり、Ｒ^１３はエチルであり、かつ、Ｒ^８は第一級炭素基、より好ましくはエチルであり、または
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７はすべて水素であり、Ｒ^１３はイソプロピルであり、かつ、Ｒ^８は第一級炭素基、より好ましくはイソプロピルであり、または
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７はすべて水素であり、Ｒ^１３はｎ−プロピルあり、かつ、Ｒ^８は第一級炭素基、より好ましくはｎ−プロピルであり、または
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７はすべて水素であり、Ｒ^１３はクロロであり、かつ、Ｒ^８はハロゲン、より好ましくはクロロであり、または
Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７はすべて水素であり、Ｒ^１３はトリハリメチル、より好ましくはトリフルオロメチルであり、かつ、Ｒ^８はトリハロメチル、より好ましくはトリフルオロメチルである
ことが好ましい。
【００６８】
（Ｉ）の別の好ましい実施形態において、Ｒ^６およびＲ^７はそれぞれ、
【００６９】
【化１１】

【００７０】
（式中、
Ｒ^１８は、Ｒ^８（ＶＩａ）の定義、およびそれらの好みに一致し、
Ｒ^１９、Ｒ^２０およびＲ^２１はそれぞれ、（ＶＩａ）におけるＲ^９、Ｒ^１０およびＲ^１２の定義、およびそれらの好みに一致し、
Ｒ^２２、Ｒ^２３、Ｒ^２４およびＲ^２５はそれぞれ、（ＶＩＩａ）におけるＲ^１３、Ｒ^１４、Ｒ^１６およびＲ^１７の定義、およびそれらの好みに一致する）
である。
【００７１】
上の式（ＶＩＩＩａ）および（ＩＸａ）において、Ｒ^１８は、イミノ窒素に結合した第１環原子に隣接する第２環原子に対応し、Ｒ^２１、Ｒ^２２およびＲ^２５は第１環原子に隣接する他の環原子に対応する。
【００７２】
（Ｉ）と活性な重合触媒を形成する任意の遷移金属が使用されてもよい。好適な遷移金属の例として、周期表（ＩＵＰＡＣ）の３〜１２族に見出されるものが挙げられるかもしれない。８〜１０族遷移金属が好ましく、８および９族遷移金属がより好ましく、ＦｅおよびＣｏが特に好ましく、Ｆｅが特に好ましい。
【００７３】
化合物（Ｉ）およびその遷移金属錯体は、その両方ともまるで完全に記載されているかのようにあらゆる目的のために参照により本明細書に援用される、例えば、ＷＯ ９９／５０２７３およびＷＯ ００／０８０３４に開示されている手順によってだけでなく、先に援用された参考文献に開示されている様々な方法によっても調製されてもよい。
【００７４】
重合（オリゴマー化を含めて）にとって好ましいモノマーは、エチレンおよび式Ｒ^１８ＣＨ＝ＣＨ_２（式中、Ｒ^１８はｎ−アルキル、特に１〜１０個の炭素原子を含むｎ−アルキルである）のアルファ−オレフィンである。エチレンホモポリマー（またはオリゴマー化の場合には、偶数の炭素原子を有する一連のアルファ−オレフィン）を与えるためにはエチレン単独が、またはエチレン共重合体を与えるためにはエチレンと１種以上のアルファ−オレフィン（プロピレン、１−ヘキセン、１−オクテン、１−デセンおよび／または１−ドデセンのような）との組み合わせが好ましい。
【００７５】
本発明（担持触媒構成成分の調製および１種以上のオレフィンの重合の両方）の方法において、遷移金属錯体は好ましくは最初に溶媒に溶解される。溶媒は、金属錯体とさらに錯体を形成してもよいが、実質的に錯体を分解しないことが好ましい。好ましくは、溶媒は非プロトン性溶媒であり、水、アルコールまたはカルボン酸のようなプロトン性溶媒ではない。好ましくは、錯体は１００ｍｌの溶媒当たり少なくとも約０．０００１ｇ、より好ましくは１００ｍｌの溶媒当たり少なくとも約０．０１ｇの溶解度を有するべきである。
【００７６】
好ましくは、次に、錯体が少なくとも部分的に担体上に吸着されるようになるポイントで、好ましくは撹拌下に、溶媒／錯体組み合わせをシリカまたはシリカ−アルミナ（集合的に、担体）と接触させる。錯体が比較的高い溶媒中溶解度を有する場合には特に、吸着は比較的速いかもしれない。この場合、接触は１時間未満行われてもよい。錯体が低い溶媒中溶解度を有する（例えばすべての遷移金属が直ちに溶解しないかもしれない）場合、錯体を溶解してそれを担体上へ吸着させるために、より多くの時間（おそらく約１０時間以上）が必要とされるかもしれない。担体と溶液との混合を確実にするための穏やかな撹拌が好ましい。多くの場合錯体は着色しており、担体上への錯体の吸着の進行を目視により判断することができる。時折、遷移金属錯体のすべては担体上へ吸着されないであろう。存在する錯体の少なくとも約５０％、より好ましくは少なくとも約８０％が吸着されることが好ましい。未吸着の錯体は、さらなる担体上へ吸着されるべくリサイクルされてもよい。
【００７７】
接触段階の後に、溶液および／または溶媒は、例えば溶媒（およびまだその中に溶解している任意の錯体）から担体を濾過する、または混合物を遠心分離して固体から上澄液をデカントする、例えば真空下に蒸発により溶媒を除去する、任意の標準方法によって担体（および吸着された錯体）から分離されてもよい。好ましくは溶液は、上記のように濾過または遠心分離によってのように、担体から液体として分離される。必要ならば、担体および吸着された錯体は、いかなる未吸着の錯体（幾らかの吸着された錯体もまたこのポイントで除去されるかもしれない）も除去するために溶媒で洗浄されてもよい、および／または担体および吸着された錯体は、真空下での蒸発によってのように、乾燥されてもよい。しかしながら、好ましくは溶媒の大部分、好ましくは＞９０％は、溶媒を蒸発させることによって担持錯体から分離されるべきではない（言い換えれば固体担体と液体溶媒（溶液）との物理的分離が実施されるべきである）。担持触媒はまた溶媒／溶液からそれを分離することなく重合プロセスに使用されてもよいが、それは重合での使用の前に溶媒／溶液から分離されることが好ましい。
【００７８】
好ましくは工程（ａ）における遷移金属錯体対担体の比は、担持触媒上の遷移金属の最終量（遷移金属として測定される）が担持触媒構成成分の全重量の約０．０１〜約５．０重量％、より好ましくは約０．０２〜約１．０重量％であるようなものであろう。遷移金属錯体、溶媒および担体の任意の特定セットで、担持触媒構成成分中の遷移金属の特定濃度を得るのに必要な正確な条件を決定するためには少ない量の実験が必要とされるかもしれない。しかしながら、この実験は、十分に、普通の当業者の能力の範囲内にある。一般的に言って、第１方法で存在する担体に対する遷移金属錯体の比が大きければ大きいほど、担持触媒構成成分中の遷移金属の量が大きくなる。
【００７９】
担持触媒ができる限り活性であることを確実にするために、遷移金属錯体が（吸着されずにまたは吸着されて）存在するすべての工程（および貯蔵）が窒素またはアルゴンのような不活性雰囲気下で実施されることが好ましい。
【００８０】
本手順によって製造された担持触媒構成成分は室温で長期間安定であることが分かった。また、この触媒は引火性または自然発火性と考えられる材料を含有する必要がなく、比較的安価な手段によって並外れた用心なしに輸送されるかもしれない。
【００８１】
この担持触媒構成成分は、先に援用された様々な刊行物に開示されているように、オレフィンの重合用の触媒系の一部として使用することができる。
【００８２】
上記の重合法において、アルキル化またはハイドライド化共触媒（好ましくはアルキルアルミニウム化合物またはジアルキル亜鉛化合物）対遷移金属の「モル」の好ましいモル比は、約１〜約２０００、より好ましくは約５〜約１０００、特に好ましくは約３０〜約５００である（これらの最小および最大比のどれも互いにペアにされてもよい）。典型的にはこの共触媒はまた、重合法に有害である重合系中の不純物を除去する化合物である捕捉剤として同時に使用される。従って、この共触媒対遷移金属の比はまた、ある程度、第２方法における有害な不純物のレベルに依存するであろう。
【００８３】
追加のルイス酸が、例えば、アルキルを引き抜いて比較的非配位性のアニオンを形成するために必要とされる場合、一般的に言って、このルイス酸対遷移金属のモル比は典型的には約１〜約５である。
【００８４】
重合法で使用される任意の共触媒がオレフィンモノマーの存在下に、第１方法で製造された担持触媒と接触するか、または共触媒との接触がさらにオレフィンモノマーと接触する直前に（６時間未満、より好ましくは１時間未満、特に好ましくは５分未満）実施されることが好ましい。実際は、共触媒と担持触媒とを重合容器そのものの中で、または重合容器につながるプロセスライン中で一緒に接触させることが特に好ましい。重合法が液相、例えば懸濁重合で行われる場合、担持触媒と任意の共触媒とを懸濁液体媒体に添加することができる。重合が気相重合である場合、微粒の担持触媒は気体によって流動化されてもよく、トリアルキルアルミニウム化合物のような共触媒は気体として添加されてもよい。この目的のために、トリメチルアルミニウムのような比較的揮発性のアルキルアルミニウム化合物が多くの場合好まれる。
【００８５】
２種以上の遷移金属化合物が重合触媒として使用されてもよく、１つまたは両方が同じ担体または異なる担体上に担持されてもよい。かかる混合触媒に関するより多くの情報については、そのすべてがまたまるで完全に記載されているかのようにあらゆる目的のために参照により本明細書に援用されるＷＯ ９８／３８２２８、ＷＯ ９９／５０３１８およびＷＯ ９９／５７１５９だけでなく、先に援用されたＷＯ ９９／４６３０２も参照されたい。典型的な重合条件が用いられてもよく、例えばポリオレフィンの分子量を調節するために水素が使用されてもよい。例えば、それもまたまるで完全に記載されているかのようにあらゆる目的のために参照により本明細書に援用されるＷＯ ９９／６２９６３だけでなく、先に援用されたＷＯ ９９／４６３０２も参照されたい。
【００８６】
重合法の好ましい一形態において、三座配位子の遷移金属錯体は、エチレンを比較的純粋なα−オレフィンへオリゴマー化する。かかるオリゴマー化に関する情報については、例えば、まるで完全に記載されているかのようにあらゆる目的のために参照によりまた援用されるＷＯ ００／７６６５９だけでなく、先に援用された米国特許第６，０６３，８８１号、米国特許第６，１０３，９４６号、ＷＯ ００／５５２１６およびＷＯ ００／７３２４９も参照されたい。エチレンとα−オレフィンとを共重合することができる第２の遷移金属化合物がまたさらに存在する場合、分枝ポリエチレンが得られるであろう。例えば、先に援用されたＷＯ ９９／５０３１８およびＷＯ ００／５５２１６を参照されたい。この場合、第２の遷移金属化合物は第１方法で使用されるものと同じ担体上にあることが好ましく、オリゴマー化触媒と重合触媒とは同時に担体上に置かれてもよい（第１方法におけるように、追加の重合触媒も存在して）。
【００８７】
担体として使用されるシリカ粒子のモルフォロジは、得られたポリマー粒子（シリカを含む）にしばしば複製される。下の実施例の多くの生成物は、かかる複製を示す。シリカ担体モルフォロジの複製は、メチルアルミノキサンのような任意の溶着活性化アルミニウムアルキル化合物の不在下での触媒種の一様な溶着を示していると考えられる。
【実施例】
【００８８】
実施例および実験において、次の省略形を使用する。
ａｃａｃ−アセチルアセトナート
ＩＣＰ−誘導結合高周波プラズマ発光分析法
ｒ．ｂ．−丸底
ＴＨＦ−テトラヒドロフラン
【００８９】
実施例において、すべての圧力はゲージ圧である。実施例において、次の遷移金属錯体を使用する。
【００９０】
【化１２】

【００９１】
１および３は、先に援用した米国特許第５，９５５，５５５号に記載された手順によって製造した。
【００９２】
実施例１
１をＣＨ_２Ｃｌ_２から再結晶した。１（７．０ｍｇ）を無水ＣＨ_２Ｃｌ_２（７ｍｌ）に溶解し、シリカ（０．５ｇ、グレース（Ｇｒａｃｅ）脱水９４８シリカ、グレードＸＰＯ−２４０２、シリカのグラム当たり１ミリモルＯＨ基へ脱水した）を加えた。生じた濃青色混合物を３０分間撹拌した。次に生じた固体を非常に薄い青色の濾液から濾過して乾燥した。収量は０．５ｇ淡青色固体。質量％Ｆｅ（ＩＣＰ）＝０．１４％。
【００９３】
実施例２
１をＣＨ_２Ｃｌ_２から再結晶した。１（７．０ｍｇ）を無水ＣＨ_２Ｃｌ_２（７ｍｌ）に溶解し、シリカアルミナ［０．５ｇ、２００℃で（Ｎ_２を流しながら）脱水したグレース（Ｇｒａｃｅ）Ｍ５１３−１．１０］を加えた。生じた濃青色混合物を６０分間撹拌した。次に生じた固体を無色の濾液から濾過し、ＣＨ_２Ｃｌ_２で洗浄して乾燥した。収量は０．５ｇ淡青色／灰色固体。
【００９４】
実施例３
１をＣＨ_２Ｃｌ_２から再結晶した。１（７．０ｍｇ）を無水ＣＨ_２Ｃｌ_２（７ｍｌ）に溶解し、シリカアルミナ［０．５ｇ、５００℃で（Ｎ_２を流しながら）脱水したグレース（Ｇｒａｃｅ）Ｍ５１３−１．１０］を加えた。生じた濃青色混合物を６０分間撹拌した。次に生じた固体を無色の濾液から濾過し、ＣＨ_２Ｃｌ_２で洗浄して乾燥した。収量は０．５ｇ淡橙色固体。
【００９５】
実施例４
１をＣＨ_２Ｃｌ_２から再結晶した。１（４．０ｍｇ）を無水トルエン（１５ｍｌ）に溶解し、シリカ（０．２５ｇ、グレース（Ｇｒａｃｅ）ＸＰＯ−２４０２脱水９４８シリカ）を加えた。生じた混合物を一晩撹拌した。次に生じた固体をほとんど無色の濾液から濾過し、トルエンおよびペンタンで洗浄して乾燥した。収量は０．５ｇ淡青色固体。
【００９６】
実施例５
再結晶していない１（４．０ｍｇ）を無水トルエン（１５ｍｌ）に溶解し、シリカ（０．２５ｇ、グレース（Ｇｒａｃｅ）ＸＰＯ−２４０２脱水９４８シリカ）を加えた。生じた混合物を一晩撹拌した。次に生じた固体をほとんど無色の濾液から濾過し、トルエンおよびペンタンで洗浄して乾燥した。収量は０．５ｇ淡青色固体。
【００９７】
実験１
Ｃ_２７Ｈ_３１Ｎ_３（１．００ｇ、３９７．５６ｇ／モル、２．５１５ミリモル）とＦｅ（ａｃａｃ）_２（６４４ｍｇ、２５３．１５ｇ／モル、２．５１６ミリモル）と［Ｎａ］［ＢＡＦ］（２．２４ｇ、８９０ｇ／モル、２．５１７ミリモル、ＢＡＦ＝Ｂ［３，５−（ＣＦ_３）_２Ｃ_６Ｈ_３］_４）とをバイアル中へ量り取り、次に撹拌バー付きの５０ｍｌ丸底フラスコ中に入れることによって２を調製した。ＴＨＦ（２５ｍｌ）を加えて暗赤色溶液を与え、それを２４時間撹拌した。ＴＨＦを除去し（生成物はＴＨＦに完全には溶けない）、生成物をトルエンに懸濁させ、セライト（Ｃｅｌｉｔｅ）（登録商標）を通して濾過した。暗赤色溶液から溶媒を除去し、ペンタンを加えて赤色沈殿物を与え、それを濾過し、リンスし、真空下に乾燥して２を与えた。
【００９８】
Ｃ_６４Ｈ_５０ＢＦ_２４ＦｅＮ_３Ｏ_２（１４１５．７２ｇ／モル）に対する元素分析値、理論値：Ｃ，５４．３０；Ｈ，３．５６；Ｎ，２．９７。実験値：Ｃ，５４．３７；Ｈ，３．５８；Ｎ，２．９６。
【００９９】
実施例６
２（１９．６ｍｇ）を無水トルエン（７ｍｌ）に溶解して橙黄色溶液を与え、シリカアルミナ［０．５ｇ、２００℃で（Ｎ_２を流しながら）脱水したグレース（Ｇｒａｃｅ）］を加えた。生じた混合物を６０分間撹拌した。次に固体をほとんど無色の濾液から濾過し、トルエンおよびペンタンで洗浄して乾燥した。収量は０．５ｇ淡橙色／ベージュ色固体。
【０１００】
実施例７
３（７．５ｍｇ）を無水ＣＨ_２Ｃｌ_２（７ｍｌ）に溶解して明黄色溶液を形成し、シリカ（０．５ｇ、グレース（Ｇｒａｃｅ）脱水９４８シリカ）を加えた。生じた混合物を６０分間撹拌した。次に固体を淡黄色濾液から濾過し、トルエンおよびペンタンで洗浄して乾燥した。収量は０．５ｇレモン黄色固体。
【０１０１】
実施例８
ドライボックス中で、ステンレスシリンダー（２５〜４０ｍｌ体積）に実施例１の生成物（７５．８ｍｇ）を、別のシリンダーに１０ｍｌのトリイソブチルアルミニウム溶液（１Ｍヘキサン溶液、アルドリッチ（Ａｌｄｒｉｃｈ））を仕込んだ。連結部の窒素パージ下にシリンダーをオートクレーブ反応器受口に連結した。パージ下にシリンダー加圧ラインもまた連結した。
【０１０２】
イソブタン（１２００ｇ、マテソン（Ｍａｔｈｅｓｏｎ）化学グレード）を、冷却したオートクレーブ（−３０℃）中へ圧力差によって移送した。いったん移送が完了したら、オートクレーブ（オートクレーブ・エンジニアーズ（Ａｕｔｏｃｌａｖｅ Ｅｎｇｉｎｅｅｒｓ）、撹拌付き、１ガロン、３．８Ｌ）を２０℃に加熱し、１０００ｒｐｍで撹拌した。溶媒を０．３６ＭＰａ（水素を含めた全圧）の圧力で水素で飽和した。飽和後に、反応器を８０℃に加熱し、エチレンで１．４ＭＰａに加圧した。トリイソブチルアルミニウム溶液をエチレンで反応器中へ押し入れ、引き続いてエチレンで実施例１からの触媒も押し入れた。最終反応器圧は２．４１ＭＰａであり、エチレンフィードをフィード容器からオートクレーブの側受口に切り換えた。反応を３時間行った。重合の終わりに、反応器をゆっくりとガス抜きし、引き続き反応器を開けるに先立って窒素パージした。ポリマーを一晩乾燥した。ポリマー収量は３５３ｇであり、４．６５ｋｇＰＥ／ｇ触媒（担体を含めて）の触媒効率、または１．５５ｋｇＰＥ／ｇ触媒・時間もしくは１１０９ｋｇＰＥ／ｇＦｅ・時間の重合速度という結果になった。
【０１０３】
実施例９
実施例８と同じ手順に従って、しかし５ｍｌのトリイソブチルアルミニウム溶液と実施例１からの７５．５ｍｇの担持触媒とで、ポリマー収量は３１６ｇであり、４．１８ｋｇＰＥ／ｇ触媒の触媒効率、または１．４０ｋｇＰＥ／ｇ触媒・時間もしくは９９７ｋｇＰＥ／ｇＦｅ・時間の重合速度という結果になった。
【０１０４】
実施例１０
実施例８と同じ手順に従って、しかし１５ｍｌのトリイソブチルアルミニウム溶液と実施例１からの７８．０ｍｇの担持触媒とで、ポリマー収量は２５６ｇであり、３．２８ｋｇＰＥ／ｇ触媒の触媒効率、または１．０９ｋｇＰＥ／ｇ触媒・時間もしくは７８１ｋｇＰＥ／ｇＦｅ・時間の重合速度という結果になった。
【０１０５】
実施例１１
実施例８と同じ手順に従って、しかし１０ｍｌのトリイソブチルアルミニウム溶液と実施例２からの７５．８ｍｇの担持触媒とで、ポリマー収量は１８２ｇであり、２．４ｋｇＰＥ／ｇ触媒の触媒効率、または０．８ｋｇＰＥ／ｇ触媒・時間もしくは５７２ｋｇＰＥ／ｇＦｅ・時間の重合速度という結果になった。
【０１０６】
実施例１２
実施例８と同じ手順に従って、しかし１０ｍｌのトリイソブチルアルミニウム溶液と実施例４からの７４．２ｍｇの担持触媒とで、ポリマー収量は３８０ｇであり、５．１２ｋｇＰＥ／ｇ触媒の触媒効率、または１．７１ｋｇＰＥ／ｇ触媒・時間もしくは１２１９ｋｇＰＥ／ｇＦｅ・時間の重合速度という結果になった。
【０１０７】
実施例１３
実施例８と同じ手順に従って、しかし１０ｍｌのトリイソブチルアルミニウム溶液と実施例４からの７５．４ｍｇの担持触媒とで、ポリマー収量は３７４ｇであり、４．９６ｋｇＰＥ／ｇ触媒の触媒効率、または１．６５ｋｇＰＥ／ｇ触媒・時間もしくは１１８１ｋｇＰＥ／ｇＦｅ・時間の重合速度という結果になった。
【０１０８】
実施例１４
実施例８と同じ手順に従って、しかし５ｍｌのトリイソブチルアルミニウム溶液と実施例３からの７９．８ｍｇの担持触媒とで、ポリマー収量は５１ｇであり、０．６４ｋｇＰＥ／ｇ触媒の触媒効率、または０．２１ｋｇＰＥ／ｇ触媒・時間もしくは１５２ｋｇＰＥ／ｇＦｅ・時間の重合速度という結果になった。
【０１０９】
実施例１５
１（７．０ｍｇ）をシンチレーションバイアル中へ量り取り、約１０ｍｌのトルエンに溶解し、０．７６ミリモルＯＨ／ｇに脱水した０．５ｇのシリカゲル（グレース・ダビッドソン（Ｇｒａｃｅ Ｄａｖｉｄｓｏｎ）９４８）をバイアルに加えた。バイアルを３０分間振盪した。コースガラスフリットを通して混合物を濾過し、固体を室温で真空中一晩乾燥した。
【０１１０】
実施例１６〜２８
実施例８と同じ手順に従って、しかし実施例１５で製造した触媒を異なる水素圧で用いると、下の表に示すポリマー収量という結果になった。
【０１１１】
【表１】

【Technical field】
[0001]
The present invention relates to an olefin polymerization catalyst containing a transition metal complex of a selected tridentate ligand, a method for preparing such a catalyst, and a polymerization method utilizing such a catalyst.
[Background Art]
[0002]
Polyolefins are an important commodity, and many such polymers are made using transition metal complexes as part of a polymerization catalyst system. Recently, there has been much interest in catalysts containing late transition metals such as Fe (iron), Co (cobalt), Ni (nickel) and Pd (palladium). One particular type of olefin polymerization catalyst is 2,6-pyridinedicarboxaldehyde bisimine or 2,6-diacylpyridinebisimine or a minor variation thereof, which is believed to be a tridentate ligand. Typically, it is contained as an iron or cobalt complex. Such complexes, and their use as olefin polymerization bees, especially as ethylene polymerization catalysts, are described in US Pat. These are described in (Patent Document 6), (Patent Document 7), (Patent Document 8), (Patent Document 9), (Patent Document 10), and (Patent Document 11), all of which are completely described. And is incorporated herein by reference for all purposes as if it were done.
[0003]
Variations of these complexes have also found use as "polymerization" catalysts for the dimerization and oligomerization of ethylene and other alpha-olefins to produce alpha-olefins and internal olefins. All of them are incorporated herein by reference for any purpose as if fully described, eg, US Pat. See US Pat.
[0004]
As with all olefin polymerization catalysts, an important consideration is the overall cost of the polymerization catalyst system per unit weight of polyolefin produced. Another important consideration is the form of the resulting polymer product, i.e., if it is to be used, such as relatively non-dusting particles that flow well and preferably have a relatively high bulk density. Whether it is obtained in an easy form and if fouling of the polymerization reactor occurs.
[0005]
Occasionally, the main cost of a polymerization catalyst is not the transition metal complex itself, but the cost of preparing the catalyst and / or the cost of other components needed for the catalyst system. The latter is especially true for many of the so-called single-site catalysts, such as metallocenes and many late transition metal containing catalysts, where aluminoxanes, especially methylaluminoxane, have been found to give excellent results. , Are very expensive compared to other alkylaluminum compounds, thereby increasing the overall catalyst system cost per unit weight of polyolefin produced.
[0006]
This was generally true for transition metal complexes of 2,6-pyridinedicarboxaldehyde bisimine or 2,6-diacylpyridine bisimine, as disclosed in the above incorporated references. For example, some exceptions have been noted by modifying the surface of supports for supported catalysts, and are incorporated herein by reference for all purposes as if fully set forth. See, for example, US Pat. The modified carrier disclosed in this publication allows the use of alkylaluminum compounds in addition to aluminoxane to achieve good polymerization results, but the modification of the carrier itself is based on the units of polyolefin produced. Significantly increases the total polymerization catalyst cost per weight.
[0007]
[Patent Document 1]
U.S. Pat. No. 5,955,555
[Patent Document 2]
WO 99/12981 specification
[Patent Document 3]
WO 99/46302
[Patent Document 4]
WO 99/46303
[Patent Document 5]
WO 99/46304
[Patent Document 6]
WO 00/15646 specification
[Patent Document 7]
WO 00/24788 specification
[Patent Document 8]
WO 00/32641
[Patent Document 9]
WO 00/50470 specification
[Patent Document 10]
WO 00/69869 specification
[Patent Document 11]
WO 00/69923 specification
[Patent Document 12]
U.S. Pat. No. 6,063,881
[Patent Document 13]
U.S. Pat. No. 6,103,946
[Patent Document 14]
WO 00/55216 specification
[Patent Document 15]
WO 00/73249
[Patent Document 16]
WO 00/20467
DISCLOSURE OF THE INVENTION
[Means for Solving the Problems]
[0008]
The present invention is a method for preparing a supported polymerization catalyst component,
(A) dissolving a transition metal complex of 2,6-pyridinedicarboxaldehyde bisimine or 2,6-diacylpyridinebisimine in a solvent to form a solution;
(B) contacting the solution with the support, which is unmodified silica or silica-alumina, for a time sufficient for at least a portion of the metal complex to be adsorbed on the support;
(C) optionally separating the solution and solvent from the carrier;
However, it relates to a method in which substantially no activator is present during steps (a), (b) and (c).
[0009]
The invention also includes a catalyst obtainable or obtainable by the above method.
[0010]
The present invention is a method of polymerizing one or more polymerizable olefins,
(A) dissolving a transition metal complex of 2,6-pyridinedicarboxaldehyde bisimine or 2,6-diacylpyridine bisimine in an organic solvent to form a solution;
(B) contacting the solution with the support, which is silica or silica-alumina, for a time sufficient for at least a portion of the metal complex to be adsorbed on the support, thereby forming a supported catalyst component. When,
(C) optionally separating the solution and solvent from the supported catalyst component;
(D) contacting the supported catalyst component with the one or more polymerizable olefins and one or more activators under polymerization conditions;
However, during the steps (a), (b) and (c), a method substantially free of an activator is further included.
[0011]
These and other features and advantages of the present invention will be more readily understood by those of ordinary skill in the art from reading the following detailed description. It should be appreciated that for clarity, certain features of the invention described below in connection with separate embodiments, may also be provided in combination in a single embodiment. . Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination.
BEST MODE FOR CARRYING OUT THE INVENTION
[0012]
Certain terms are used herein. Some of them are as follows.
[0013]
“Hydrocarbyl groups” are monovalent groups containing only carbon and hydrogen. Examples of hydrocarbyls may include unsubstituted alkyl, cycloalkyl and aryl. Unless otherwise specified, hydrocarbyl groups herein preferably contain 1 to about 30 carbon atoms.
[0014]
By "substituted hydrocarbyl" is meant herein a hydrocarbyl group containing one or more substituents that does not substantially interfere with the operation of the polymerization catalyst system. Suitable substituents for some polymerizations include some or all of halo, esters, keto (oxo), amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether. May be. Preferred substituents when present are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, and amide. Which substituents are useful in which polymerizations may, in some cases, be described in U.S. Pat. It may be determined by reference to 880,241 as well as previously incorporated publications (eg, US Pat. No. 5,955,555). Unless otherwise specified, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. The meaning of "substituted" includes chains or rings containing one or more heteroatoms such as nitrogen, oxygen and / or sulfur, and the free valence of the substituted hydrocarbyl may be at the heteroatom. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl.
[0015]
An “(inert) functional group” as used herein is a group other than a hydrocarbyl or substituted hydrocarbyl, other than participating in “adsorption” (as defined below) of a complex on a carrier. Means a group that is inert under the process conditions to which the compound containing is exposed. The functional groups also do not substantially interfere with any of the processes described herein that may involve the compound in which they are present. Examples of functional groups include halo (fluoro, chloro, bromo and iodo) and -OR³⁰(Where R³⁰Is a hydrocarbyl or substituted hydrocarbyl). Where a functional group may be near a transition metal atom (such as an iron atom), the functional group is more strongly attached to the transition metal atom than the group in those compounds, shown as coordinating to the transition metal atom. They should not be coordinated, ie they should not be replaced by the desired coordinating groups.
[0016]
“Alkyl group” and “substituted alkyl group” have their ordinary meaning (see substituted hydrocarbyl above for substitution). Unless otherwise specified, alkyl and substituted alkyl groups preferably have 1 to about 30 carbon atoms.
[0017]
"Aryl" means a monovalent aromatic group in which the free valence is at a carbon atom of an aromatic ring. Aryl may have one or more aromatic rings, which may be fused, linked by a single bond or other groups.
[0018]
"Substituted aryl" means a monovalent aromatic radical substituted as described in the above definition of "substituted hydrocarbyl". Like aryl, substituted aryl may have one or more aromatic rings, which may be fused or linked by a single bond or other group, but substituted aryl forms a heteroaromatic ring. If so, the free valency of the substituted aryl group can be at a heteroatom (such as nitrogen) of the heteroaromatic ring instead of carbon.
[0019]
By "activator", "cocatalyst" or "catalytic activator" is meant one or more compounds that react with a transition metal compound to form a catalytic species capable of polymerizing a polymerizable olefin. Useful activators include alkylaluminum compounds, certain boron compounds, and other alkylated or hydrided compounds. Typically, the transition metal compounds used in the first method and in steps (a), (b) and (c) of the second method do not themselves initiate polymerization, but provide an active olefin polymerization catalyst. It will require the use of one or more activators to produce.
[0020]
"Substantially no activator" means, for example, that there is no activator other than at very low levels typical of impurities in various components. Means The intent is that the interaction of the transition metal complex with the activator during the loading process does not yield any significant amount of the activating catalyst species. This activation should preferably take place at or near when the catalyst is used in the polymerization process.
[0021]
An "unmodified" support (silica or silica-alumina) is a material (either bound or simply on a surface) that is designed to bind or otherwise attach a transition metal complex to the support. ) Means a carrier that does not contain such a carrier. Such materials include alkylaluminum compounds and other alkylated and hydrided compounds, Lewis acids (bound or not bound to the surface of the support), and other similar compounds. Preferably, the transition metal complex, more preferably the tridentate ligand therein, does not react with the carrier and covalently attaches to the carrier or a group that may be covalently attached thereto. For example, it is preferred that the ligand does not contain hydroxyl (alcohol) groups that react with the silica surface.
[0022]
"Alkylaluminum compound" means a compound having at least one alkyl group directly bonded to aluminum. For example, other groups such as alkoxides, hydrides and halogens may also be attached to the aluminum atom in the compound. Alkyl aluminum compounds are activators.
[0023]
"Silica" or "silica-alumina" means silica or silica-alumina which may or may not be dehydrated, such as by heating. Preferably, the material is partially dehydrated, preferably by heating, before participating in any of the processes described herein. These materials are well known in the art of polymer catalyst supports and often have preferably a high porosity and / or surface area. Often they also have a small and / or controlled particle size.
[0024]
"Polymerization" in its broadest context is meant to include dimerization, oligomerization and polymerization (both homopolymerization and copolymerization).
[0025]
"Polymerization conditions" as used herein means conditions that cause olefin "polymerization" on a catalyst using the same transition metal tridentate complex modified as described herein. In other words, the polymerization catalyst systems described herein may be used under the same conditions as previously reported for the same complex. Such conditions may include temperature, pressure, suspension medium, gas phase, liquid phase, continuous, batch-like polymerization methods, and the like. Supported catalysts are particularly useful in liquid suspension and gas phase polymerizations.
[0026]
“Adsorbed” herein simply means that the first substance adheres to the second substance even if, for example, the adsorbed first substance may be in the presence of a solvent for the first substance. As such (at least partially), it means that the first substance is "attractive" to the second substance. The term "adsorbed" herein has no implicit meaning as to why the first substance sticks to the second substance.
[0027]
By "relatively non-coordinating" (or "weakly coordinating") anion is meant an anion as generally referred to in the art, the coordinating ability of such an anion being known, W. Beck et al., Which have been discussed in the literature, for example, both of which are hereby incorporated by reference for all purposes as if fully described. Chemical Reviews (Chem. Rev.), Vol. 88, pp. 1405-1421 (1988), and S. H. Stares, Chemical Reviews (Chem. Rev.), No. 93, pages 927-942 (1993). Some such anions include R⁹ ₃AlX⁻, R⁹ ₂AlClX⁻, R⁹AlCl₂X⁻And "R⁹AlOX⁻(Wherein, R⁹Is an alkyl) and the aluminum compound of the preceding paragraph and X⁻There are those formed from Another useful non-coordinating anion is BAF⁻{BAF = tetrakis [3,5-bis (trifluoromethyl) -phenyl] borate}, SbF₆ ⁻, PF₆ ⁻, And BF₄ ⁻, Trifluoromethanesulfonate, p-toluenesulfonate, (R_fSO₂)₂N⁻, And (C₆F₅)₄B⁻including.
[0028]
A “tridentate” ligand is a ligand that can be a tridentate ligand, ie, it has three sites, often a heteroatom site, and is immediately coordinated with a transition metal atom. Means a ligand that can be Preferably, all three sites coordinate to the transition metal.
[0029]
"Primary carbon group" refers herein to the formula -CH₂Wherein the free valences are a bond to any other atom and the bond represented by the solid line is a bond to a ring atom of the substituted aryl to which the primary carbon group is attached. Means Accordingly, the free valence may be bonded to a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a sulfur atom, and the like. In other words, the free valence may be hydrogen, hydrocarbyl, substituted hydrocarbyl or a bond to a functional group. Examples of primary carbon groups include -CH₃, -CH₂CH (CH₃)₂, -CH₂Cl, -CH₂C₆H₅, -OCH₃And -CH₂OCH₃Is mentioned.
[0030]
"Secondary carbon group"
[0031]
Embedded image

[0032]
(Wherein the bond represented by the solid line is a bond to the ring atom of the substituted aryl to which the secondary carbon group is attached, and both free bonds represented by the dashed line are bonds to atoms other than hydrogen. Means). These atoms or groups may be the same or different. In other words, the free valence represented by the dashed line may be a bond to a hydrocarbyl, a substituted hydrocarbyl or an inert functional group. Examples of secondary carbon groups include -CH (CH₃)₂, -CHCl₂, -CH (C₆H₅)₂, Cyclohexyl, -CH (CH₃) OCH₃, And -CH = CCH₃Is mentioned.
[0033]
"Tertiary carbon group" is defined by the formula
[0034]
Embedded image

[0035]
(Wherein the bond represented by the solid line is a bond to the ring atom of the substituted aryl to which the tertiary carbon group is bonded, and the three free bonds represented by the broken lines are the bonds to atoms other than hydrogen. ). In other words, the bond represented by the dashed line is a bond to a hydrocarbyl, substituted hydrocarbyl, or inert functional group. Examples of tertiary carbon groups include -C (CH₃)₃, -C (C₆H₅)₃, -CCl₃, -CF₃, -C (CH₃)₂OCH₃, -C≡CH, -C (CH₃)₂CH = CH₂, Aryl and substituted aryl, such as phenyl, and 1-adamantyl.
[0036]
Preferred 2,6-pyridinecarboxaldehyde bisimines and 2,6-diacylpyridine bisimines have the formula (I)
[0037]
Embedded image

[0038]
(Where
R¹, R², R³, R⁴And R⁵Are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group (provided that R is vicinal to each other)¹, R²And R³Any two of may form a ring together), and
R⁶And R⁷Is aryl, substituted aryl or a functional group)
Is a compound of
[0039]
Typically, the transition metal complex of (I) is of the formula LMX_mY_nWherein L is a 2,6-pyridinedicarboxaldehyde bisimine or a 2,6-diacylpyridinebisimine ligand, M is a transition metal, and X is a monoanion (one negative charge). Y is a relatively non-coordinating monoanion and m + n is equal to the oxidation state of M). Typically, when all of X are monodentate anions, then n is zero and m is equal to the oxidation state of M. For example, if one of X is a bidentate monoanion, then n is usually 1 (where m + n is 2). Accordingly, m may be an integer of 1 or more, but n may be 0 or an integer of 1 or more, and preferably n is 0 or 1.
[0040]
Monodentate monoanions include halides and carboxylates, while bidentate monoanions include acetylacetonate, allyl and benzyl type monoanions. Relatively non-coordinating anions are defined above.
[0041]
If neither X nor Y is a hydrocarbyl anion or hydride, typically at least X must be converted to a hydrocarbyl anion or hydride such as an alkyl to form an active polymerization (in the second method) (others). Anions may also be active). This is usually achieved, for example, with an activator (co-catalyst) capable of alkylating the metal. "Alkylating" as used herein means that the cocatalyst is LMX_mY_nTo alkylate the metal (eg, LM (alkyl)_mY_nTo form a relatively non-coordinating anion, optionally at the same time abstracting one of the alkyl groups (especially when n is zero). "Hydration" is similar to alkylation except that a hydride anion is used in place of the alkyl anion. Alternatively, a second cocatalyst, a neutral Lewis acid, may be added as part of the catalyst system to abstract the alkyl group to form a relatively non-coordinating anion. Note that this is only one scenario for forming an active olefin polymerization catalyst that can be used, depending on the particular metal complex used and the cocatalyst used.
[0042]
Preferably, the activator (co-catalyst) is (1) (i) capable of abstracting an anion from the transition metal of the transition metal complex to form a weakly coordinating anion, and (ii) the transition metal A neutral Lewis acid that can both alkylate or hydride, or (2) (i) extract an anion from the transition metal of the transition metal complex to form a weakly coordinating anion Either a combination of a neutral Lewis acid and (ii) another compound capable of alkylating or hydriding the transition metal. More preferably, the cocatalyst is a Lewis acid capable of forming an alkylating compound and a weakly coordinating anion.
[0043]
Useful alkylating compounds include alkylaluminum compounds (if they contain hydrogen bonded to aluminum, they can also be hydrided compounds), alkylzinc compounds, and Grignard reagents. Preferred compounds that can both alkylate and form relatively non-coordinating anions are trialkylaluminum compounds, including trimethylaluminum, triethylaluminum, tri-n-butylaluminum and tri-i-butylaluminum. Alkylhaloaluminum compounds such as diethylaluminum chloride, ethylaluminum chloride and ethylaluminum sesquichloride, and alkylaluminum compounds such as (alkoxy) (alkyl) alminium compounds such as ethoxydiethylaluminum. Aluminoxanes such as methylaluminoxane may also be used, but they are not preferred because of their cost (even though they may be otherwise very effective).
[0044]
In (I),
R¹, R²And R³Is hydrogen, and / or
R¹And R³Is hydrogen and R²Is trifluoromethyl, and / or
R⁴And R⁵Are each independently halogen, thioalkyl, hydrogen or alkyl containing 1 to 6 carbon atoms, more preferably R⁴And R⁵Are each independently hydrogen or methyl
Is generally preferred.
[0045]
In one preferred form of (I), R⁶And R⁷Are each independently a substituted aryl, more preferably a substituted phenyl. Even more preferably, R⁶Is
[0046]
Embedded image

[0047]
And R⁷Is
[0048]
Embedded image

[0049]
(Where
R⁸, R¹², R^ThirteenAnd R¹⁷Are each independently a hydrocarbyl, substituted hydrocarbyl or inert functional group;
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
Where R is vicinal to each other⁸, R⁹, R¹⁰, R¹¹, R¹², R^Thirteen, R¹⁴, R^Fifteen, R¹⁶And R¹⁷Any two of may form a ring together).
[0050]
In (VI) and (VII),
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Are preferably independently hydrogen, halogen, or alkyl containing 1 to 6 carbon atoms, more preferably each of these is hydrogen, and / or
R¹⁰And R^FifteenIs preferably methyl, phenyl or substituted phenyl (such as alkyl-substituted phenyl); and / or
R⁸, R¹², R^ThirteenAnd R¹⁷Is preferably independently halogen, phenyl, substituted phenyl or alkyl containing 1 to 6 carbon atoms, each independently being phenyl, substituted phenyl (e.g. alkyl such as pt-butylphenyl). Substituted phenyl) or alkyl containing 1 to 6 carbon atoms (such as i-isopropyl or t-butyl) (R⁸And R¹²Both, or R^ThirteenAnd R¹⁷Is more preferred, although both are t-butyl in the same compound).
[0051]
Specific preferred compounds are (R¹, R², R³, R⁴And R⁵In combination with any of the variants for⁶And R⁷Are respectively (VI) and (VII), and
R⁹, R¹¹, R¹⁴And R¹⁶Is hydrogen and R⁸, R¹⁰, R¹², R^Thirteen, R^FifteenAnd R¹⁷Is methyl,
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Is hydrogen and R⁸And R^ThirteenIs chloro and R¹²And R¹⁷Is methyl,
R⁹, R¹⁰, R¹¹, R¹⁴, R^Fifteen, R¹⁶And R¹⁷Is hydrogen and R⁸And R^ThirteenIs phenyl,
R⁹, R¹⁰, R¹¹, R¹⁴, R^Fifteen, R¹⁶And R¹⁷Is hydrogen and R⁸And R^ThirteenIs pt-butylphenyl,
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Is hydrogen and R⁸, R¹², R^ThirteenAnd R¹⁷Is phenyl,
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Is hydrogen and R⁸, R¹², R^ThirteenAnd R¹⁷Is pt-butylphenyl,
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Is hydrogen and R⁸And R^ThirteenIs phenyl, and R¹²And R¹⁷Is halo,
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Is hydrogen and R⁸And R^ThirteenIs pt-butylphenyl, and R¹²And R¹⁷Is halo,
R⁹, R¹⁰, R¹¹, R¹⁴, R^FifteenAnd R¹⁶Is hydrogen and R⁸, R¹², R^ThirteenAnd R¹⁷Is i-propyl; and
R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R^Fifteen, R¹⁶And R¹⁷Is hydrogen and R⁸And R^ThirteenIs t-butyl.
[0052]
In another preferred variant of (I), R⁶And R⁷Is each independently a substituted 1-pillow fraction. More preferably in this case R⁶And R⁷Are
[0053]
Embedded image

[0054]
(Where
R¹⁸And R²¹Is the R in (VI)⁸And R¹²According to the definition of, and their preferences,
R²²And R²⁵Is the R in (VII)^ThirteenAnd R¹⁷According to the definition of, and their preferences,
R¹⁹And R²⁰Is the R in (VI)⁹And R¹¹, And their preferences, and
R²³And R²⁴Is the R in (VII)¹⁴And R¹⁶According to their definitions, and their preferences)
It is.
[0055]
In a "polymerization" where dimers or oligomers are produced, R⁶And R⁷Are preferably each independently a substituted aryl having a first ring atom attached to the imino nitrogen, provided that
R⁶Wherein the second ring atom adjacent to the first ring atom is bonded to a halogen, a primary carbon group, a secondary carbon group, or a tertiary carbon group;
R⁶In the above, when the second ring atom is bonded to a halogen or a primary carbon group, R 2 adjacent to the first ring atom⁶And R⁷0, 1 or 2 of the other ring atoms in are attached to a halogen or primary carbon group, and the remainder of the ring atoms adjacent to said first ring atom are attached to hydrogen atoms, or
R⁶In the above, when the second ring atom is bonded to a secondary carbon group, R is adjacent to the first ring atom.⁶And R⁷0, 1 or 2 of the other ring atoms in are bonded to halogen, a primary carbon group or a secondary carbon group, and the rest of the ring atoms adjacent to said first ring atom are bonded to hydrogen atoms. Or
R⁶In the above, when the second ring atom is bound to a tertiary carbon group, R adjacent to the first ring atom⁶And R⁷0 or 1 of the other ring atoms in is bonded to a tertiary carbon group, and the rest of the ring atoms adjacent to the first ring atom are bonded to a hydrogen atom).
[0056]
"R attached to the imino nitrogen atom⁶And R⁷The term "first ring atom" means a ring atom in these groups bonded to the imino nitrogen shown in (I), for example,
[0057]
Embedded image

[0058]
The atom shown at the 1-position of the ring in (II) or (III) is the first ring atom bonded to the imino nitrogen atom (other groups which may be substituted on the aryl group are shown Absent). Ring atoms adjacent to the first ring atom are, for example, the free valences of these adjacent atoms shown in broken lines (IV) and (V) (in (IV) the 2,6-position , (V) in the 2,5-position).
[0059]
Embedded image

[0060]
In a preferred dimerization / oligomerization embodiment, R⁶Is
[0061]
Embedded image

[0062]
And R⁷Is
[0063]
Embedded image

[0064]
(In the formula
R⁸Is a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group, and
R⁹, R¹⁰, R¹¹, R¹⁴, R^Fifteen, R¹⁶And R¹⁷Is each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
However,
R⁸Is halogen or a primary carbon group,¹², R^ThirteenAnd R¹⁷0, 1 or 2 is a halogen or a primary carbon group;¹², R^ThirteenAnd R¹⁷Is hydrogen, or
R⁸Is a secondary carbon group, R¹², R^ThirteenAnd R¹⁷0 or 1 is a halogen, a primary carbon group or a secondary carbon group;¹², R^ThirteenAnd R¹⁷Is hydrogen, or
R⁸Is a tertiary carbon group, R¹², R^ThirteenAnd R¹⁷0 or 1 is a tertiary carbon group, and R¹², R^ThirteenAnd R¹⁷Is hydrogen,
And further provided that R⁸, R⁹, R¹⁰, R¹¹, R¹², R^Thirteen, R¹⁴, R^Fifteen, R¹⁶And R¹⁷Any two of may form a ring together).
[0065]
In the above formulas (VIa) and (VIIa), R⁸Corresponds to a second ring atom adjacent to the first ring atom bonded to the imino nitrogen;¹², R^ThirteenAnd R¹⁷Corresponds to another ring atom adjacent to the first ring atom.
[0066]
In the compound (I) containing (VIa) and (VIIa),
R⁸Is a primary carbon group, R^ThirteenIs a primary carbon group and R¹²And R¹⁷Is hydrogen, or
R⁸Is a secondary carbon group, R^ThirteenIs a primary or secondary carbon group, more preferably a secondary carbon group, and R¹²And R¹⁷Is hydrogen, or
R⁸Is a tertiary carbon group (more preferably, a trihalo tertiary carbon group such as trihalomethyl);^ThirteenIs a tertiary carbon group (more preferably, a trihalo tertiary carbon group such as trihalomethyl);¹²And R¹⁷Is hydrogen, or
R⁸Is a halogen,^ThirteenIs halogen and R¹²And R¹⁷Is hydrogen
Is particularly preferred.
[0067]
In all specific preferred compounds (I) in which (VIa) and (VIIa) appear, R¹, R²And R³Is hydrogen and / or R⁴And R⁵Is preferably methyl. further,
R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R^Fifteen, R¹⁶And R¹⁷Are all hydrogen and R^ThirteenIs methyl and R⁸Is a primary carbon group, more preferably methyl, or
R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R^Fifteen, R¹⁶And R¹⁷Are all hydrogen and R^ThirteenIs ethyl and R⁸Is a primary carbon group, more preferably ethyl, or
R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R^Fifteen, R¹⁶And R¹⁷Are all hydrogen and R^ThirteenIs isopropyl and R⁸Is a primary carbon group, more preferably isopropyl, or
R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R^Fifteen, R¹⁶And R¹⁷Are all hydrogen and R^ThirteenIs n-propyl and R⁸Is a primary carbon group, more preferably n-propyl, or
R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R^Fifteen, R¹⁶And R¹⁷Are all hydrogen and R^ThirteenIs chloro and R⁸Is halogen, more preferably chloro, or
R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R^Fifteen, R¹⁶And R¹⁷Are all hydrogen and R^ThirteenIs trifluoromethyl, more preferably trifluoromethyl, and R⁸Is trihalomethyl, more preferably trifluoromethyl
Is preferred.
[0068]
In another preferred embodiment of (I), R⁶And R⁷Are
[0069]
Embedded image

[0070]
(Where
R¹⁸Is R⁸Consistent with the definition of (VIa), and their preferences,
R¹⁹, R²⁰And R²¹Is the R in (VIa)⁹, R¹⁰And R¹²According to the definition of, and their preferences,
R²², R²³, R²⁴And R²⁵Is the R in (VIIa)^Thirteen, R¹⁴, R¹⁶And R¹⁷According to their definitions, and their preferences)
It is.
[0071]
In the above formulas (VIIIa) and (IXa), R¹⁸Corresponds to a second ring atom adjacent to the first ring atom bonded to the imino nitrogen;²¹, R²²And R²⁵Corresponds to another ring atom adjacent to the first ring atom.
[0072]
Any transition metal that forms an active polymerization catalyst with (I) may be used. Examples of suitable transition metals may include those found in Groups 3-12 of the Periodic Table (IUPAC). Group 8-10 transition metals are preferred, Group 8 and 9 transition metals are more preferred, Fe and Co are particularly preferred, and Fe is particularly preferred.
[0073]
Compound (I) and its transition metal complexes are both incorporated herein by reference for all purposes as if fully described, for example, WO 99/50273 and WO 00/08034. As well as by the various methods disclosed in the previously incorporated references.
[0074]
Preferred monomers for polymerization (including oligomerization) are ethylene and the formula R¹⁸CH = CH₂(Where R¹⁸Is an n-alkyl, especially an n-alkyl containing 1 to 10 carbon atoms). Ethylene alone to provide an ethylene homopolymer (or, in the case of oligomerization, a series of alpha-olefins having an even number of carbon atoms), or ethylene and one or more alphas to provide an ethylene copolymer. Combinations with olefins (such as propylene, 1-hexene, 1-octene, 1-decene and / or 1-dodecene) are preferred.
[0075]
In the process of the present invention (both the preparation of the supported catalyst component and the polymerization of one or more olefins), the transition metal complex is preferably first dissolved in a solvent. The solvent may further form a complex with the metal complex, but preferably does not substantially decompose the complex. Preferably, the solvent is an aprotic solvent, not a protic solvent such as water, alcohol or carboxylic acid. Preferably, the complex should have a solubility of at least about 0.0001 g per 100 ml of solvent, more preferably at least about 0.01 g per 100 ml of solvent.
[0076]
Preferably, the solvent / complex combination is then contacted with silica or silica-alumina (collectively, the support), preferably at a point where the complex becomes at least partially adsorbed on the support. . Adsorption may be relatively fast, especially if the complex has a relatively high solubility in the solvent. In this case, the contact may be made for less than one hour. If the complex has low solubility in solvent (eg, not all transition metals may dissolve immediately), more time (possibly about 10 hours or more) is required to dissolve the complex and adsorb it on the support. May be needed. Gentle agitation to ensure mixing of the carrier and solution is preferred. In many cases, the complex is colored, and the progress of adsorption of the complex on the carrier can be visually judged. Occasionally, not all of the transition metal complex will be adsorbed onto the support. Preferably, at least about 50%, more preferably at least about 80% of the complex present is adsorbed. Unadsorbed complexes may be recycled to be adsorbed on additional carriers.
[0077]
After the contacting step, the solution and / or the solvent may be filtered, for example, by filtering the carrier from the solvent (and any complex still dissolved therein), or by centrifuging the mixture to decant the supernatant from the solids. It may be separated from the carrier (and the adsorbed complex) by any standard method, for example removing the solvent by evaporation under vacuum. Preferably, the solution is separated as a liquid from the carrier, such as by filtration or centrifugation as described above. If necessary, the carrier and the adsorbed complex may be washed with a solvent to remove any unadsorbed complexes (some adsorbed complexes may also be removed at this point). And / or the carrier and the adsorbed complex may be dried, such as by evaporation under vacuum. However, preferably the majority of the solvent, preferably> 90%, should not be separated from the supported complex by evaporating the solvent (in other words a physical separation between the solid support and the liquid solvent (solution) is performed). Should be). Although the supported catalyst may also be used in the polymerization process without separating it from the solvent / solution, it is preferred that it be separated from the solvent / solution before use in the polymerization.
[0078]
Preferably, the ratio of transition metal complex to support in step (a) is such that the final amount of transition metal on the supported catalyst (measured as transition metal) is from about 0.01 to about 5. 0%, more preferably from about 0.02 to about 1.0% by weight. For any particular set of transition metal complex, solvent and support, a small amount of experimentation may be required to determine the exact conditions required to obtain a particular concentration of transition metal in the supported catalyst component. unknown. However, this experiment is well within the capabilities of one of ordinary skill in the art. Generally speaking, the greater the ratio of transition metal complex to support present in the first method, the greater the amount of transition metal in the supported catalyst component.
[0079]
To ensure that the supported catalyst is as active as possible, all steps (and storage) in which the transition metal complex is present (either unadsorbed or adsorbed) are performed under an inert atmosphere such as nitrogen or argon. It is preferred to be implemented in.
[0080]
The supported catalyst components produced by this procedure were found to be stable for long periods at room temperature. Also, the catalyst need not contain materials that are considered flammable or pyrophoric and may be transported by extraordinarily inexpensive means without extraordinary care.
[0081]
This supported catalyst component can be used as part of a catalyst system for the polymerization of olefins, as disclosed in various publications incorporated above.
[0082]
In the above polymerization process, the preferred molar ratio of alkylation or hydride cocatalyst (preferably alkylaluminum compound or dialkylzinc compound) to "mole" of transition metal is from about 1 to about 2000, more preferably from about 5 to about 2000. 1000, particularly preferably about 30 to about 500 (any of these minimum and maximum ratios may be paired with each other). Typically, the cocatalyst is also used simultaneously as a scavenger, a compound that removes impurities in the polymerization system that are detrimental to the polymerization process. Thus, the ratio of cocatalyst to transition metal will also depend to some extent on the level of deleterious impurities in the second method.
[0083]
Generally, the molar ratio of Lewis acid to transition metal is typically where additional Lewis acid is required, for example, to abstract the alkyl to form a relatively non-coordinating anion. Is about 1 to about 5.
[0084]
Any cocatalyst used in the polymerization process is contacted with the supported catalyst prepared in the first process in the presence of the olefin monomer, or the contact with the cocatalyst is immediately prior to further contact with the olefin monomer (6 hours). (Less than 1 hour, particularly preferably less than 5 minutes). In practice, it is particularly preferred to bring the cocatalyst and the supported catalyst together in the polymerization vessel itself or in a process line leading to the polymerization vessel. If the polymerization process is performed in the liquid phase, for example, suspension polymerization, the supported catalyst and optional cocatalyst can be added to the suspension medium. If the polymerization is a gas phase polymerization, the particulate supported catalyst may be fluidized by a gas and a co-catalyst such as a trialkylaluminum compound may be added as a gas. For this purpose, relatively volatile alkylaluminum compounds such as trimethylaluminum are often preferred.
[0085]
More than one transition metal compound may be used as a polymerization catalyst, and one or both may be supported on the same or different supports. For more information on such mixed catalysts, see WO 98/38228, WO 99/50318 and WO 98/38228, which are hereby incorporated by reference for all purposes as if fully set forth. See not only 99/57159, but also WO 99/46302, previously incorporated. Typical polymerization conditions may be used, for example, hydrogen may be used to adjust the molecular weight of the polyolefin. See, for example, WO 99/62963, which is hereby incorporated by reference for all purposes as if fully described, as well as WO 99/46302, which was previously incorporated. .
[0086]
In one preferred form of the polymerization process, the transition metal complex of the tridentate ligand oligomerizes ethylene to a relatively pure α-olefin. For information on such oligomerization, see, for example, WO 00/76659, which is also incorporated by reference for all purposes as if fully described, as well as previously incorporated US Pat. No. 6,063. See also, U.S. Patent No. 6,103,946; WO 00/55216 and WO 00/73249. If there is also a second transition metal compound capable of copolymerizing ethylene and an α-olefin, a branched polyethylene will be obtained. See, for example, WO 99/50318 and WO 00/55216, previously incorporated. In this case, the second transition metal compound is preferably on the same support as that used in the first method, and the oligomerization catalyst and the polymerization catalyst may be simultaneously placed on the support (in the first method). As such, additional polymerization catalysts are also present).
[0087]
The morphology of the silica particles used as carriers is often replicated in the resulting polymer particles (including silica). Many products of the examples below show such replications. It is believed that replication of the silica support morphology is indicative of uniform deposition of the catalytic species in the absence of any weld-activated aluminum alkyl compound such as methylaluminoxane.
【Example】
[0088]
The following abbreviations are used in the examples and experiments.
acac-acetylacetonate
ICP-inductively coupled high frequency plasma emission spectrometry
r. b. -Round bottom
THF-tetrahydrofuran
[0089]
In an embodiment, all pressures are gauge pressures. In the examples, the following transition metal complexes are used.
[0090]
Embedded image

[0091]
1 and 3 were made by the procedure described in previously incorporated U.S. Patent No. 5,955,555.
[0092]
Example 1
1 for CH₂Cl₂Recrystallized from 1 (7.0 mg) in anhydrous CH₂Cl₂(7 ml) and silica (0.5 g, Grace dehydrated 948 silica, grade XPO-2402, dehydrated to 1 mmol OH groups per gram of silica) was added. The resulting dark blue mixture was stirred for 30 minutes. The resulting solid was then filtered from the very light blue filtrate and dried. Yield 0.5 g pale blue solid. % By mass Fe (ICP) = 0.14%.
[0093]
Example 2
1 for CH₂Cl₂Recrystallized from 1 (7.0 mg) in anhydrous CH₂Cl₂(7 ml), and silica alumina [0.5 g, (N₂Dehydrated Grace M513-1.10] was added. The resulting dark blue mixture was stirred for 60 minutes. The resulting solid was then filtered from the colorless filtrate, CH₂Cl₂And dried. Yield 0.5 g pale blue / grey solid.
[0094]
Example 3
1 for CH₂Cl₂Recrystallized from 1 (7.0 mg) in anhydrous CH₂Cl₂(7 ml) and silica alumina [0.5 g, (N₂Dehydrated Grace M513-1.10] was added. The resulting dark blue mixture was stirred for 60 minutes. The resulting solid was then filtered from the colorless filtrate, CH₂Cl₂And dried. Yield 0.5 g pale orange solid.
[0095]
Example 4
1 for CH₂Cl₂Recrystallized from 1 (4.0 mg) was dissolved in anhydrous toluene (15 ml) and silica (0.25 g, Grace XPO-2402 dehydrated 948 silica) was added. The resulting mixture was stirred overnight. The resulting solid was then filtered from the almost colorless filtrate, washed with toluene and pentane and dried. Yield 0.5 g pale blue solid.
[0096]
Example 5
The unrecrystallized 1 (4.0 mg) was dissolved in anhydrous toluene (15 ml) and silica (0.25 g, Grace XPO-2402 dehydrated 948 silica) was added. The resulting mixture was stirred overnight. The resulting solid was then filtered from the almost colorless filtrate, washed with toluene and pentane and dried. Yield 0.5 g pale blue solid.
[0097]
Experiment 1
C₂₇H₃₁N₃(1.00 g, 397.56 g / mol, 2.515 mmol) and Fe (acac)₂(644 mg, 253.15 g / mol, 2.516 mmol) and [Na] [BAF] (2.24 g, 890 g / mol, 2.517 mmol, BAF = B [3,5- (CF₃)₂C₆H₃]₄Was weighed into a vial and then placed in a 50 ml round bottom flask with a stir bar to prepare 2. THF (25 ml) was added to give a dark red solution, which was stirred for 24 hours. The THF was removed (the product was not completely soluble in THF) and the product was suspended in toluene and filtered through Celite®. The solvent was removed from the dark red solution and pentane was added to give a red precipitate, which was filtered, rinsed and dried under vacuum to give 2.
[0098]
C₆₄H₅₀BF₂₄FeN₃O₂(1415.72 g / mol) Elemental analysis, theoretical: C, 54.30; H, 3.56; N, 2.97. Found: C, 54.37; H, 3.58; N, 2.96.
[0099]
Example 6
2 (19.6 mg) was dissolved in anhydrous toluene (7 ml) to give an orange-yellow solution. Silica alumina [0.5 g, (N₂Dehydrated Grace] was added. The resulting mixture was stirred for 60 minutes. The solid was then filtered from the almost colorless filtrate, washed with toluene and pentane and dried. Yield 0.5 g pale orange / beige solid.
[0100]
Example 7
3 (7.5 mg) in anhydrous CH₂Cl₂(7 ml) to form a light yellow solution, and silica (0.5 g, Grace dehydrated 948 silica) was added. The resulting mixture was stirred for 60 minutes. The solid was then filtered from the pale yellow filtrate, washed with toluene and pentane and dried. Yield 0.5 g lemon yellow solid.
[0101]
Example 8
In a dry box, a stainless steel cylinder (25-40 ml volume) was charged with the product of Example 1 (75.8 mg) and another cylinder was charged with 10 ml of a triisobutylaluminum solution (1 M hexane solution, Aldrich). . The cylinder was connected to the autoclave reactor port under a nitrogen purge of the connection. A cylinder pressure line was also connected under the purge.
[0102]
Isobutane (1200 g, Matheson chemical grade) was transferred by differential pressure into a chilled autoclave (−30 ° C.). Once the transfer was complete, the autoclave (Autoclave Engineers, 1 gallon, 3.8 L with stirring) was heated to 20 ° C. and stirred at 1000 rpm. The solvent was saturated with hydrogen at a pressure of 0.36 MPa (total pressure including hydrogen). After saturation, the reactor was heated to 80 ° C. and pressurized to 1.4 MPa with ethylene. The triisobutylaluminum solution was pushed into the reactor with ethylene, followed by the catalyst from Example 1 with ethylene. The final reactor pressure was 2.41 MPa and the ethylene feed was switched from the feed vessel to the side port of the autoclave. The reaction was performed for 3 hours. At the end of the polymerization, the reactor was gently vented and subsequently purged with nitrogen prior to opening the reactor. The polymer was dried overnight. The polymer yield was 353 g, resulting in a catalyst efficiency of 4.65 kg PE / g catalyst (including the support) or a polymerization rate of 1.55 kg PE / g catalyst-hour or 1109 kg PE / g Fe-hour.
[0103]
Example 9
Following the same procedure as in Example 8, but with 5 ml of the triisobutylaluminum solution and 75.5 mg of the supported catalyst from Example 1, the polymer yield is 316 g, the catalytic efficiency of 4.18 kg PE / g catalyst, or 1. The result was a polymerization rate of 40 kg PE / g catalyst · hr or 997 kg PE / g Fe · hr.
[0104]
Example 10
Following the same procedure as in Example 8, but with 15 ml of the triisobutylaluminum solution and 78.0 mg of the supported catalyst from Example 1, the polymer yield is 256 g, catalytic efficiency of 3.28 kg PE / g catalyst, or 1. The result was a polymerization rate of 09 kg PE / g catalyst · hr or 781 kg PE / g Fe · hr.
[0105]
Example 11
Following the same procedure as in Example 8, but with 10 ml of the triisobutylaluminum solution and 75.8 mg of the supported catalyst from Example 2, the polymer yield is 182 g, with a catalytic efficiency of 2.4 kg PE / g catalyst, or a catalytic efficiency of 0.4 kg. A polymerization rate of 8 kg PE / g catalyst · hr or 572 kg PE / g Fe · hr resulted.
[0106]
Example 12
Following the same procedure as in Example 8, but with 10 ml of the triisobutylaluminum solution and 74.2 mg of the supported catalyst from Example 4, the polymer yield is 380 g, the catalytic efficiency of 5.12 kg PE / g catalyst, or 1. This resulted in a polymerization rate of 71 kg PE / g catalyst · h or 1219 kg PE / g Fe · h.
[0107]
Example 13
Following the same procedure as in example 8, but with 10 ml of the triisobutylaluminum solution and 75.4 mg of the supported catalyst from example 4, the polymer yield is 374 g, the catalytic efficiency of 4.96 kg PE / g catalyst, or 1. The result was a polymerization rate of 65 kg PE / g catalyst · hr or 1181 kg PE / g Fe · hr.
[0108]
Example 14
Following the same procedure as in Example 8, but with 5 ml of the triisobutylaluminum solution and 79.8 mg of the supported catalyst from Example 3, the polymer yield is 51 g, with a catalytic efficiency of 0.64 kg PE / g catalyst, or 0.1 g. A polymerization rate of 21 kg PE / g catalyst · hr or 152 kg PE / g Fe · hr resulted.
[0109]
Example 15
1 (7.0 mg) was weighed into a scintillation vial, dissolved in about 10 ml of toluene and dehydrated to 0.76 mmol OH / g, 0.5 g of silica gel (Grace Davidson 948) was placed in the vial. added. The vial was shaken for 30 minutes. The mixture was filtered through a course glass frit and the solid was dried in vacuo at room temperature overnight.
[0110]
Examples 16 to 28
Following the same procedure as in Example 8, but using the catalyst prepared in Example 15 at different hydrogen pressures resulted in the polymer yields shown in the table below.
[0111]
[Table 1]

Claims (17)

A method for preparing a supported polymerization catalyst component,
(A) dissolving a transition metal complex of 2,6-pyridinedicarboxaldehyde bisimine or 2,6-diacylpyridinebisimine in a solvent to form a solution;
(B) contacting the solution with the support, which is unmodified silica or silica-alumina, for a time sufficient for at least a portion of the metal complex to be adsorbed on the support;
(C) optionally separating the solution and solvent from the carrier;
However, a method wherein substantially no activator is present during steps (a), (b) and (c). The method according to claim 1, wherein step (b) is performed with stirring. Transition metal complex wherein _LMX m _{Y n} (wherein, L is 2,6-pyridinedicarboxylic carboxaldehyde bisimine or 2,6 acylpyridines - a bisimine ligand, M is a transition metal, X is a mono 2. The method of claim 1, wherein the anion is Y, is a relatively non-coordinating monoanion, and m + n is equal to the oxidation state of M. The ligand is of the formula (I)

(Where
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group (provided that any of R ¹ , R ² and R ³ which are vicinal to each other) And the two may form a ring together), and
R ⁶ and R ⁷ are aryl, substituted aryl or a functional group)
4. The method of claim 3, comprising: R ¹ , R ² and R ³ are hydrogen, or R ¹ and R ³ are hydrogen and R ² is trifluoromethyl;
R ⁴ and R ⁵ are each independently hydrogen or methyl;
R ⁶

And R ⁷ is

(Where
R ⁸ , R ¹² , R ¹³ and R ¹⁷ are each independently a hydrocarbyl, a substituted hydrocarbyl or an inert functional group;
R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
And any two of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^16, and R ¹⁷ , which are vicinal to each other, form a ring together. 5. The method of claim 4, wherein R ¹ , R ² and R ³ are hydrogen;
R ⁴ and R ⁵ are hydrogen or methyl;
R ⁹ , R ¹¹ , R ¹⁴ and R ¹⁶ are hydrogen and R ⁸ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and R ¹⁷ are methyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, R ⁸ and R ¹³ are chloro, and R ¹² and R ¹⁷ are methyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are hydrogen, and R ⁸ and R ¹³ are phenyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are hydrogen, and , R ⁸ and R ¹³ are pt-butylphenyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, and R ⁸ , R ¹² , R ¹³ and R ¹⁷ is phenylene , And the or ^{R 9, R 10, R 11} , R 14, R 15 and ^{R 16} are hydrogen ^{and, R 8, R 12, R} 13 and ^{R 17} are p-t-butylphenyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, and R ⁸ and R ¹³ are phenyl, and R ¹² and R ¹⁷ are halo, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, and R ⁸ and R ¹³ are pt-butylphenyl, and R ¹² and R ¹⁷ are halo, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen and R ⁸ , R ¹² , R ¹³ and R ¹⁷ are i-propyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ^{1 4.} The method according to claim 5, wherein R <^15> , R <^16> and R <^17> are hydrogen and R < ⁸ > and R < ¹³ > are t-butyl. R ¹ , R ² and R ³ are hydrogen, or R ¹ and R ³ are hydrogen, and R ² is trifluoromethyl;
R ⁴ and R ⁵ are each independently hydrogen or methyl;
R ⁶

And R ⁷ is

(Where
R ⁸ is halogen, a primary carbon group, a secondary carbon group, or a tertiary carbon group, and
R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
However,
When R ⁸ is a halogen or a primary carbon group, zero, one or two of R ¹² , R ¹³ and R ¹⁷ are a halogen or a primary carbon group, and the remainder of R ¹² , R ¹³ and R ¹⁷ Is hydrogen, or when R ⁸ is a secondary carbon group, zero or one of R ¹² , R ¹³ and R ¹⁷ is halogen, a primary or secondary carbon group, and R ¹² , the remainder of ^{R 13} and ^{R 17} are hydrogen, or if ^{R 8} is a tertiary carbon ^group, zero or one of R ^{12, R 13} and ^{R 17} is a tertiary carbon ^{group, R 12} , R ¹³ and the remainder of R ¹⁷ are hydrogen;
And further provided that any two of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹³ , R ¹⁴ , R ¹⁵ , R ^16, and R ¹⁷ , which are vicinal to each other, form a ring together 5. The method of claim 4, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen and R ¹³ and R ⁸ are methyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen and R ⁸ and R ¹³ are ethyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen and R ⁸ and R ¹³ are isopropyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are All are hydrogen and R ⁸ and R ¹³ are n-propyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen; and , ⁸ and ^{R 13} is chloro, or ^{R 9, R 10, R 11} , R 12, R 14, R 15, R 16 and ^{R 17} are all hydrogen, and, ^{R 8} and ^{R 13} are trifluoromethyl The method of claim 7, wherein A polymerization catalyst component obtained by the method according to claim 1. A method of polymerizing one or more polymerizable olefins,
(A) dissolving a transition metal complex of 2,6-pyridinedicarboxaldehyde bisimine or 2,6-diacylpyridine bisimine in an organic solvent to form a solution;
(B) contacting the solution with the support, which is silica or silica-alumina, for a time sufficient for at least a portion of the metal complex to be adsorbed on the support, thereby forming a supported catalyst component. ,
(C) optionally separating the solution and solvent from the supported catalyst component;
(D) contacting the supported catalyst component with the one or more polymerizable olefins and one or more activators under polymerization conditions;
However, a method wherein substantially no activator is present during steps (a), (b) and (c). 7. The method according to claim 6, wherein step (b) is performed with stirring. Transition metal complex wherein _LMX m _{Y n} (wherein, L is 2,6-pyridinedicarboxylic carboxaldehyde bisimine or 2,6 acylpyridines - a bisimine ligand, M is a transition metal, X is a mono 7. The method of claim 6, wherein the anion is Y, is a relatively non-coordinating monoanion, and m + n is equal to the oxidation state of M. The ligand is of the formula (I)

(Where
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group (provided that any of R ¹ , R ² and R ³ which are vicinal to each other) And the two may form a ring together), and
R ⁶ and R ⁷ are aryl, substituted aryl or a functional group)
The method of claim 7, comprising: R ¹ , R ² and R ³ are hydrogen, or R ¹ and R ³ are hydrogen, and R ² is trifluoromethyl;
R ⁴ and R ⁵ are each independently hydrogen or methyl;
R ⁶

And R ⁷ is

(Where
R ⁸ is R ¹² , R ¹³ and R ¹⁷ are each independently a hydrocarbyl, a substituted hydrocarbyl or an inert functional group;
R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
And any two of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^16, and R ¹⁷ , which are vicinal to each other, form a ring together. 13. The method of claim 12, wherein R ¹ , R ² and R ³ are hydrogen;
R ⁴ and R ⁵ are hydrogen or methyl;
R ⁹ , R ¹¹ , R ¹⁴ and R ¹⁶ are hydrogen and R ⁸ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ and R ¹⁷ are methyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, R ⁸ and R ¹³ are chloro, and R ¹² and R ¹⁷ are methyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are hydrogen, and R ⁸ and R ¹³ are phenyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are hydrogen, and , R ⁸ and R ¹³ are pt-butylphenyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, and R ⁸ , R ¹² , R ¹³ and R ¹⁷ is phenylene , And the or ^{R 9, R 10, R 11} , R 14, R 15 and ^{R 16} are hydrogen ^{and, R 8, R 12, R} 13 and ^{R 17} are p-t-butylphenyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, and R ⁸ and R ¹³ are phenyl, and R ¹² and R ¹⁷ are halo, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, and R ⁸ and R ¹³ are pt-butylphenyl, and R ¹² and R ¹⁷ are halo, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen and R ⁸ , R ¹² , R ¹³ and R ¹⁷ are i-propyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ^{1 4, R 15, R 16} and ^{R 17} are hydrogen, and, ^{R 8} and ^{R 13} are t- butyl The method of claim 13. R ¹ , R ² and R ³ are hydrogen, or R ¹ and R ³ are hydrogen, and R ² is trifluoromethyl;
R ⁴ and R ⁵ are each independently hydrogen or methyl;
R ⁶

And R ⁷ is

(Where
R ⁸ is halogen, a primary carbon group, a secondary carbon group, or a tertiary carbon group, and
R ⁹ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
However,
When R ⁸ is a halogen or a primary carbon group, zero, one or two of R ¹² , R ¹³ and R ¹⁷ are a halogen or a primary carbon group, and the remainder of R ¹² , R ¹³ and R ¹⁷ Is hydrogen, or when R ⁸ is a secondary carbon group, zero or one of R ¹² , R ¹³ and R ¹⁷ is halogen, a primary or secondary carbon group, and R ¹² , the remainder of ^{R 13} and ^{R 17} are hydrogen, or if ^{R 8} is a tertiary carbon ^group, zero or one of R ^{12, R 13} and ^{R 17} is a tertiary carbon ^{group, R 12} , R ¹³ and the remainder of R ¹⁷ are hydrogen;
And further provided that any two of R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ which are vicinal to each other, form a ring together 13. The method of claim 12, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen and R ¹³ and R ⁸ are methyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen and R ⁸ and R ¹³ are ethyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen and R ⁸ and R ¹³ are isopropyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are All are hydrogen and R ⁸ and R ¹³ are n-propyl, or R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are all hydrogen; and , ⁸ and ^{R 13} is chloro, or ^{R 9, R 10, R 11} , R 12, R 14, R 15, R 16 and ^{R 17} are all hydrogen, and, ^{R 8} and ^{R 13} are trifluoromethyl The method of claim 15, wherein