Epichlorohydrin (ECH) was polymerized through a cationic ring-opening polymerization reaction using hydroxyl-terminated polybutadiene as an initiator. ECH was very slowly added to the reactant mixture containing a Lewis acid catalyst to promote an activated monomer mechanism (AMM) rather than an active chain-end mechanism (ACM). The triblock copolymer PECH-PB-PECH was separated from the resulting polymers using a fractional precipitation method; however, unlike previous reports of the preparation of a fully azidated PECH-PB-PECH, the substitution of the chlorine moiety in PECH with an azide moiety at high temperatures was not completely accomplished due to the entanglement of the partly azidated PECH-PB-PECH and unreacted PECH-PB-PECH.
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