Microphase separation in block-random copolymers of styrene, 4-acetoxystyrene, and 4-hydroxystyrene

Jeffrey D. Quinn, Richard A. Register

Research output: Contribution to journalArticlepeer-review

24 Scopus citations


"Block-random" copolymers-where one or more blocks are themselves random copolymers-offer a flexible modification to the usual block copolymer architecture. For example, in a poly(A)-poly(A-ran-B) diblock consisting of monomer units A and B, the interblock segregation strength can be continuously tuned through the B content of the random block, allowing the design of block copolymers with accessible order-disorder transitions at arbitrarily high molecular weights. Moreover, the development of controlled radical polymerizations has greatly expanded the palette of accessible monomer units A and B, including units with strongly interacting functional groups. We synthesize a range of copolymers consisting of styrene (S) and ace- toxystyrene (AS) units, including copolymers where one block is P(S-ran-AS), through nitroxide-mediated radical polymerization. At sufficiently high molecular weights, near-symmetric PS-PAS diblocks show well-ordered lamellar morphologies, while dilution of the repulsive S-AS interactions in PS-P(S-ran-AS) diblocks yields a phase-mixed morphology. Cleavage of a sufficient fraction of the AS units in a phasemixed PS-P(S-ran-AS) diblock to hydrogen-bonding hydroxystyrene (HS) units yields, in turn, a microphase-separated melt.

Original languageEnglish (US)
Pages (from-to)2106-2113
Number of pages8
JournalJournal of Polymer Science, Part B: Polymer Physics
Issue number21
StatePublished - Nov 1 2009

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Materials Chemistry


  • Block copolymers
  • Copolymerization
  • Functionalization of polymers
  • Radical polymerization
  • SAXS


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