TERMINATION OF LIVING ANIONIC POLYMERIZATIONS USING CHLOROSILANE DERIVATIVES - A GENERAL SYNTHETIC METHODOLOGY FOR THE SYNTHESIS OF END-FUNCTIONALIZED POLYMERS

The transformation of living polymer chain ends is the most widely used technique to synthesize end-functionalized polymeric materials. Herein we report the development of a new synthetic methodology which is able to give very high degrees of functionalization to living anionic polymer chains. This methodology is based on termination reactions with chlorosilane derivatives containing protected functional groups and is described with particular emphasis on the introduction of primary aliphatic amines and primary aliphatic alcohols. The extent of functionalization was verified by using conventional techniques such as gel permeation chromatography (GPC), end group titration, multinuclear magnetic resonance spectroscopy, and TLC, but was also examined by using time-off-flight secondary ion mass spectrometry (TOF-SIMS). The usefulness of these materials for construction of supramolecular assemblies is illustrated by the coupling of the polymeric amine to [Ru(bpy)(2)(4-CH3-4'-CO(2)Hbpy)]-(PF6)(2) (bpy = 2,2'-bipyridine).