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, Apostolos Avgeropoulos

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

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 Xeff = 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.

Original languageEnglish
Pages (from-to)2354-2363
Number of pages10
JournalMacromolecules
Volume50
Issue number6
DOIs
StatePublished - Mar 28 2017

Funding

This work was supported by the Materials Science and Engineering Division, U.S. Department of Energy (DoE), Office of Basic Energy Sciences (BES), LLC, at Oak Ridge National Laboratory (ORNL). Part of the research was done at the Center for Nanophase Materials Sciences which is a DOE Office of Science User Facility. A.A. also thanks the Nuclear Magnetic Resonance Spectroscopy Facility and the Electron Microscopy Unit of the University of Ioannina. J.G.K. thanks the FSU Materials and Energy Hiring Initiative and the Donors of the American Chemical Society Petroleum Research Fund (55378-DNI7) for partial support during the preparation of this manuscript. N.H. acknowledges the support of King Abdullah University of Science and Technology (KAUST).

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