Phase Diagram of Tapered Copolymers Based on Isoprene and Styrene

Although several phase diagrams of block copolymers prepared by sequential monomer addition are known today, the phase diagrams of the corresponding tapered copolymers have not been reported in detail and this despite the industrial importance of the latter. A phase diagram based on a series of tapered diblock copolymers is reported, generated by the sec-butyllithium initiated statistical anionic copolymerization of styrene and isoprene in cyclohexane. This affords copolymers with polyisoprene volume fractions, f, in the range of 0.43 f < 0.82 and total molar mass in the range of 46-160 kg mol(-1). The phase diagram consists of lamellae, hexagonally packed cylinders, weakly ordered hexagonally packed cylinders (CYL), and perforated (PL) as well as irregular bicontinuous morphologies. The phase state in the tapered copolymers bears some similarities and several distinct differences in comparison to the respective copolymers prepared by conventional sequential monomer addition. It is shown that the weakly ordered CYL/PL morphologies comprise a large part of the phase diagram that is significantly extended in comparison to diblock copolymers prepared sequentially. On the other hand, the composition range for the bicontinuous morphologies is similar in the two systems (0.64 f(PI) < 0.68).