For more than 40 years, the synthesis of C2‐symmetric indenyl‐based racemic metallocenes for the isoselective polymerization of propylene relied on a tedious separation of the produced rac and meso isomers. Status quo, latter are considered wasteful as they produce atactic polypropylene (aPP) rather than isotactic polypropylene (iPP) if activated with methylaluminoxane (MAO). Unexpectedly, the in situ activation of meso hafnocene I yielded perfectly isotactic polypropylene. We verified an isomerization of the meso compound to the corresponding racemic one upon triisobutylaluminum (TIBA) addition via nuclear magnetic resonance (NMR) spectroscopy and established an easy and convenient polymerization protocol, enabling productivities comparable to pure rac‐I if applied to pure meso‐I or a mixture of both isomers. With this established isomerization protocol, the potential yield of iPP was enhanced by more than 400 %. This protocol was also shown to be applicable to other meso hafnocenes and some initial mechanistic insights were received.
Für über 40 Jahre basierte die Synthese von racemischen C 2 -symmetrischen indenyl-Metallocenen für die isospezifische Polymerisation von Propylen auf einer sehr aufwändigen Trennung der beiden hergestellten rac und meso Isomere. Bis heute gelten letztere als unerwünscht, da sie ataktisches Polypropylen (aPP) anstatt isotaktischem Polypropylen (iPP) produzieren, wenn sie mit Methylaluminoxan (MAO) aktiviert werden. Überraschenderweise lieferte die in situ Aktivierung des meso Hafnocens I perfekt isotaktisches Polypropylen. Über Kernspinresonanzspektroskopie (NMR) konnten wir eine Isomerisierung der meso Verbindung zur entsprechenden rac Verbindung nach Zugabe von Triisobutylaluminum (TIBA) nachweisen und ein praktisches Polymerisationsprotokoll etablieren, welches vergleichbare Produktivitäten für reines meso-I und Isomerengemische verglichen mit reinem rac-I lieferte. Durch dieses Isomerisierungsprotokoll wurde die potentielle Ausbeute an iPP um mehr als 400 % gesteigert. Es wurde gezeigt, dass dieses Protokoll auf weitere meso Verbindungen anwendbar ist und erste mechanistische Einblicke wurden erhalten.
This paper presents the "CL/TB" programming interface for Allegro CL (an implementation of Common Lisp.) and the relational database management system TransBase. The interface and its components are presently running on SUN UNIX workstations but can easily be installed on all major UNIX workstations. CL/TB supports data manipulation, data definition, and data control. The database system is called by sending SQL-statements as strings from Allegro CL. Basically, CL/TB offers the prominent services of the underlying TransBase programming interface (TBX). The services are successfully integrated into the functional environment of Lisp and enhanced by many additional features to improve ease of use, programming security, and error support. Thus operating on a database system via CL/TB is easy even for unexperienced users. Furthermore CL/TB is compatible with the relational algebra R-Lisp.Structure, design, implementation, and performance data axe presented and its application is illustrated by examples.
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