Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers
- Konstantinos Misichronis
- ,
- Jihua Chen
- ,
- Adam Imel
- ,
- Rajeev Kumar
- ,
- James Thostenson
- ,
- Kunlun Hong
- ,
- Mark Dadmun
- ,
- Bobby G. Sumpter
- ,
- Justin G. Kennemur
- ,
- Nikos Hadjichristidis
- ,
- Jimmy W. Mays
- , and
- Apostolos Avgeropoulos
Abstract
A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. 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 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.
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