Microphase-separated poly(styrene-b-isoprene)n multiblock copolymers with constant block lengths

Linear multiblock copolymers, like their diblock analogues, are capable of ordering into periodic microstructures when the blocks are sufficiently incompatible. In this work, a series of four linear poly(styrene-b-isoprene)n (SI)n (1 ≤ n ≤ 4) multiblock copolymers with nearly equal block lengths has been synthesized via living sequential anionic polymerization. All of the copolymers are microphase-separated, as discerned by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS), and exhibit lamellar morphologies in which the microdomain periodicity decreases with n. This behaviour suggests that the middle blocks contract the microdomains along the lamellar normal. Microstructural characteristics are compared with predictions from formalisms proposed for linear multiblock copolymers and, along with conformational considerations, are used to interpret the thermal and tensile properties of the copolymers.