Influence of block sequence and molecular weight on morphological, rheological and dielectric properties of weakly and strongly segregated styrene-isoprene triblock copolymers

In this work, morphological, thermal, viscoelastic and dielectric properties of triblock copolymers consisting of styrene (S) and isoprene (I) blocks are discussed. SIS and ISI triblock copolymers were synthesized by sequential anionic polymerization, three of them exhibiting molecular weights below the entanglement molecular weight M$_e$, three of them exhibiting molecular weights in the order of M$_e$ and two of them exhibiting molecular weights above M$_e$. The objective of this work is the investigation of the influence of molecular weight and block sequence on relaxation of the block copolymer chains. Morphological investigations using small angle X-ray scattering and transmission electron microscopy studies reveal that a larger molecular weight is associated with a more pronounced microphase separation. The presence of two glass transition temperatures reveals microphase separation of the PI and PS blocks. The Fox-Flory equation was applied in order to describe the molecular weight dependence of the glass transition temperature of the polyisoprene and the polystyrene blocks. The analysis of rheological data reveals a Maxwell fluid behavior for the weakly segregated block copolymers, whereas for the strongly segregated block copolymers a pronounced elastic behavior at low frequencies of small amplitude shear oscillations was observed. In the intermediate regime of molecular weight, a complex viscoelastic behavior appears. The plateau modulus $G_{N}^o$ is influenced by the sequence of the PS and the PI blocks (SIS or ISI). Our analysis of segmental and normal mode relaxation in dielectric spectroscopy experiments show that the relaxation processes are strongly influenced by the block sequence (PI blocks tethered at one or both ends) and the molecular weight. As a result, the block sequence in triblock copolymers influences dynamical properties in the glassy state and in the melt