Reactions of Living Polytetrahydrofuran with Amines V ‐ Tertiary Amine Terminated Polybutadienes; The Synthesis of Novel Ionically Linked Block Copolymers

The reactions of mono- and difunctional tertiary amine ended polybutadienes with mono- and difunctional living cationic poly THF have been studied. It is shown that the reaction to form quaternary ammonium linking groups takes place rapidly in all cases, and AB. ABA, BAB and (AB) block copolymers have been prepared. The efficiency of the process is extremely high and the degree of conversion is essentially controlled by the efficiency with which the terminal tertiary amine groups can be introduced on to the polybutadiene. The block copolymers show anomalous behaviour on gel permeation chromatography columns and this has been related to a specific interaction of the created ionic groups with polar species on the column packing. This effect is greatest with (AB) block copolymers where substantial proportions are retained indefinitely on the columns.