Phase behavior of polystyrene and poly(styrene-ran-styrenesulfonate) blends

Nancy C. Zhou, Chen Xu, Wesley R. Burghardt, Russell J. Composto, Karen I. Winey*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Scopus citations


The blend miscibilities of deuterated polystyrene (dPS) and sulfonated poly(styrene-ran-styrenesulfonate) (P(S - SS)) are examined by using forward recoil spectrometry (FRES) to probe the intermixing of bilayer films. This method directly determined the equilibrium coexistence compositions for dPS:P(S - SS x) blends where the degree of sulfonation (x) ranged from 0.2 to 2.6 mol %. In the temperature range 150-190°C, FRES profiles reveal full miscibility for x ≤ 0.2 mol % and complete immiscibility for x ≥ 2.6 mol %. Partial miscibility exists in dPS:P(S - SS x) blends with x = 0.7, 1.0, and 1.2 mol %, where between 150 and 190°C the coexisting compositions show upper critical solution temperature (UCST) phase behavior. Blend interaction parameters, Χ blend, are calculated using the Flory - Huggins theory and the coexisting compositions of the partially miscible bilayers. The copolymer blend theory estimates the styrene - styrenesulfonate segmental interaction parameter to be extraordinarily large, Χ s/ss ≥ 25. While the applicability of mean-field approaches is limited in this profoundly incompatible system, recent theories about random copolymers have established criteria for "self-demixing" due to their inherent compositional variations. Our estimate of the monomer - monomer interaction parameter suggests the potential for demixing in P(S - SS x) random copolymers that possess even a narrow distribution of compositions.

Original languageEnglish (US)
Pages (from-to)2373-2379
Number of pages7
Issue number6
StatePublished - Mar 21 2006

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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