Polymerisation im festen Zustand

5. Internationales Makromolekulares Symposium

Abstract

By careful investigation of the principles of organic solid-state chemistry some new preparative methods have been developed which allow the synthesis of quite regular and unusual polymers. These methods are based on the proper understanding and use of the packing properties of organic molecules within their crystals. Typical examples are the synthesis of sterically uniform polymers of extremely high molecular weight with cyclobutane rings in the base unit starting from diolefins as reported by Hasegawa and coworkers and the synthesis of macroscopic single-crystals of high-polymers which exhibit a backbone of conjugated triple- and doublebonds starting from di- or triacetylenes as reported by Wegner and his coworkers. The synthetic aspects and the scope of these reactions will be discussed. As it turns out, some new routes to direct synthesis of chiral polymers from achiral monomers lie within the scope of these reactions. Considering general packing properties, the failure of vinyl monomers to polymerize into ordered polymers by solid-state polymerization becomes well understood. Some of these monomers are, however, well suited to show polymerizability inside monolayers or inclusion compounds. Examples for such reactions are discussed in relation to the forementioned topochemical polymerizations.