Polystyrene-poly(2-ethylhexylmethacrylate) block copolymers: Synthesis, bulk phase behavior, and thin film structure

Ha Kyung Kwon, Vanessa E. Lopez, Raleigh L. Davis, So Youn Kim, Adam B. Burns, Richard A. Register

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Anionic polymerization was employed to synthesize well-defined diblock copolymers of polystyrene and poly(2-ethylhexylmethacrylate), PS-PEHMA. Diblock morphologies in bulk and in substrate-supported thin films were characterized by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM), respectively. PS-PEHMA diblocks exhibited thermotropic order-disorder transitions; one diblock showed a thermoreversible transition between lamellae and a higher-temperature morphology assigned as perforated lamellae. Unlike PS-poly(alkylmethacrylate) diblocks where the alkyl group is n-butyl or n-pentyl, PS-PEHMA diblocks showed a typical decreasing Flory interaction parameter with increasing temperature. Thin films of PS-cylinder-forming PS-PEHMA diblocks showed a strong preference for the cylinders to lie in the plane of the film; films of incommensurate thickness readily formed terraces. Films of commensurate thickness were easily aligned over macroscopic areas through the application of mechanical shear.

Original languageEnglish (US)
Pages (from-to)2059-2067
Number of pages9
Issue number8
StatePublished - Apr 10 2014

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry


  • Block copolymer
  • Phase behavior
  • Thin film


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