Random Copolymer Effect in Self-Assembled Hydrogen-Bonded P(S-co-4VP)(PDP) Side-Chain Polymers

Joost de Wit, Gert Alberda van Ekenstein, Evgeny Polushkin, Juuso Korhonen, Janne Ruokolainen, Gerrit ten Brinke*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

14 Citations (Scopus)
230 Downloads (Pure)

Abstract

Random copolymers of styrene and 4-vinylpyridine P(S(1-x)-co-4VP(x)) were synthesized to study the effect of the random copolymer "repulsion" on the self-assembly in hydrogen-bonded complexes with pentadecylphenol (one PDP molecule per 4VP group). The major trends observed as a function of the fraction of styrene monomers 1 - x in the random copolymer are a decrease in order-disorder transition temperature, T(ODT), and a decrease in the periodic length scale of the ordered lamellar state. The lower T(ODT) results from a partial shielding in the disordered state of the highly unfavorable styrene/4-vinylpyridine interactions by the PDP alkyl tails. The reduced layer thickness in the ordered state is due to the relaxation into a more coil-like conformation of the alkyl tails of the PDP amphiphiles, made possible by the presence of styrene units. The self-assembly properties of P(S(1-x)-co-4VP(x))(PDP)(1.0) are compared with those of the lamellar self-assembled homopolymer-based P4VP(PDP)(x) system, where x denotes the number of PDP molecules per 4VP repeat unit. As in P(S(1-x)-co-4VP(x))(PDP)(1.0), in P4VP(PDP)(x) also only a fraction x of the total number of monomers of the macromolecule may potentially hydrogen bond with PDP molecules at any given instant. In contrast to P(S(1-x)-co-4VP(x))(PDP)(1.0), for P4VP(PDP),, however, the long period is found to increase for decreasing values of x.

Original languageEnglish
Pages (from-to)2009-2014
Number of pages6
JournalMacromolecules
Volume42
Issue number6
DOIs
Publication statusPublished - 24-Mar-2009

Keywords

  • HUGGINS INTERACTION PARAMETER
  • SURFACTANT SYSTEMS
  • DIBLOCK COPOLYMERS
  • LENGTH SCALES
  • BLENDS
  • POLY(4-VINYLPYRIDINE)
  • PENTADECYLPHENOL
  • POLYSTYRENE
  • TEMPERATURE
  • MISCIBILITY

Cite this