Nano-segregated morphologies and the resulting thermoplastic
elastomer
(TPE) properties, e.g., in multiblock copolymers based on isoprene
(I) and styrene (S), depend on chain architecture (overall molar mass,
block number, composition profile). In this work nonconventional (IS)
n
I type multiblock copolymers possessing two
flexible polyisoprene end blocks are introduced. Molar masses between
120 and 400 kg·mol–1 and block numbers ranging
from 3 to 13 with either precisely defined blocks or tapered segment
structures were obtained by (i) sequential monomer addition or (ii)
statistical S/I copolymerization steps, respectively. All polymers
are based on a 30/70 molar ratio styrene/isoprene (36 vol % PS). The
materials were investigated with respect to their self-assembly and
mechanical response, respectively, by small-angle X-ray scattering
(SAXS) and tensile tests. While the sequential multiblock copolymers
generally exhibited strong segregation into well-ordered lamellar
morphologies and more extended chain conformations, their tapered
counterparts showed only weak order and a smaller scaling exponent
δ with d ∼ N
δ. In addition, a higher bridge-to-loop ratio was found for the sequential
multiblock copolymers. On the other hand, the tapered structures exhibited
accessible order–disorder transition temperatures for low molar
masses and high block numbers, which is relevant for processing. Generally,
tensile tests revealed high toughness (20–70 MJ·m–3) for the multiblock copolymers bearing at least two
polystyrene blocks, with the tapered structures being softer and more
flexible. The stiffness also increased with increasing block number,
reflecting shrinking of the domain sizes. Moreover, the maximum deformation
was found to increase with the overall molar mass. With their soft,
albeit resilient properties, these materials with low T
g polyisoprene end blocks are promising as a substitute
for plasticized polymers, e.g., poly(vinyl chloride), avoiding migration
and release of a plasticizer.