Abstract
A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-
cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) were synthesized. Microphase
separation in the bulk was examined with transmission electron microscopy (TEM) and smallangle
x-ray scattering (SAXS) and compared to computational analysis of the predicted
morphological phase diagram for this system. Due to the high conformational asymmetry
between PS and PCHD, these materials self-assemble into typical and atypical morphologies
expected for linear diblock copolymer systems. Rheological measurements were conducted and
revealed order-disorder transition temperatures (TODT) for the first time for PS-b-PCHD
copolymers resulting in a working expression for the effective interaction parameter χeff = 32/T –
0.016. Furthermore, we performed computational studies that coincide with the experimental
results. These copolymers exhibit well-ordered structures even at high temperatures (~260 0C)
providing therefore a better insight concerning their microphase separation in the nanoscale and
leading to their potential use as materials in nanotechnology and/or nanolithography applications.
