Morphologies of poly(cyclohexadiene) diblock copolymers: Effect of conformational asymmetry

Concerted experimental and theoretical investigations have been carried out to understand the microphase separation in diblock copolymer melts containing poly (1,3-cyclohexadiene), PCHD, as one of the constituents. In particular, we have studied diblock copolymer melts containing polystyrene (PS), polybutadiene (PB), and polyisoprene (PI) as the second block. We have systematically varied the ratio of 1,2-/1,4-microstructures of poly (1,3-cyclohexadiene) to tune the conformational asymmetry between the two blocks and characterized the effects of these changes on the morphologies using transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). Our experimental investigations reveal that the melts of PCHD-b-PB, PCHD-b-PS and PCHD-b-PI containing nearly equal fractions of each component and high percentage of 1,4-microstructures in the PCHD block form cylindrical rather than lamellar morphologies as expected in symmetric diblock copolymers. In contrast, the morphologies of PCHD-b-PB, PCHD-b-PS and PCHD-b-PI containing PCHD block with higher 1,2-microstructure are found to be disordered at 110 °C. The change in the morphological behavior is in good agreement with our numerical calculations using the random phase approximation and self-consistent field theory for conformationally asymmetric diblock copolymer melts. Also, the effects of composition fluctuations are studied by extending the Brazovskii–Leibler–Fredrickson–Helfand (J. Chem. Phys. 87, 697 (1987)) theory to conformationally asymmetric diblock copolymer melts. These results allow the understanding of the underlying self-assembly process that highlights the importance of the conformational asymmetry in tuning the morphologies in block copolymers.