Effect of molecular architecture on microstructural characteristics in some polysiloxaneimide multiblock copolymers

Efforts to correlate molecular characteristics with microstructural dimensions in microphase-separated diblock and triblock copolymers have been very successful, resulting in relationships that can be utilized to design materials with a specific microstructure and, consequently, with particular thermomechanical properties. However, similar efforts in the arena of multiblock copolymers have not been nearly as extensive, despite the increasing interest and diversity of this class of materials. In the present work, energy-filtered electron microscopy (EFEM) and small-angle neutron scattering (SANS) are used in a complementary fashion to probe the phase behavior of a series of three polysiloxaneimide (PSI) multiblock copolymers with different molecular architectures. Despite their relatively short segment lengths, all three materials exhibit signs of microphase separation at ambient temperature. SANS data are obtained from chemically unaltered materials and are subsequently interpreted with the Teubner-Strey model for microemulsions. Resultant microstructural dimensions are in good agreement with those measured from EFEM micrographs. Additional insight into the intramolecular sequencing of each copolymer is obtained from scaling relationships.