Chemical analysis and aqueous solution properties of charged amphiphilic block copolymers PBA-b-PAA synthesized by MADIX

J Colloid Interface Sci. 2007 Dec 15;316(2):897-911. doi: 10.1016/j.jcis.2007.08.025. Epub 2007 Aug 19.

Abstract

We have linked the structural and dynamic properties in aqueous solution of amphiphilic charged diblock copolymers poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA, synthesized by controlled radical polymerization, with the physico-chemical characteristics of the samples. Despite product imperfections, the samples self-assemble in melt and aqueous solutions as predicted by monodisperse microphase separation theory. However, the PBA core are abnormally large; the swelling of PBA cores is not due to AA (the Flory parameter chi(PBA/PAA), determined at 0.25, means strong segregation), but to h-PBA homopolymers (content determined by liquid chromatography at the point of exclusion and adsorption transition, LC-PEAT). Beside the dominant population of micelles detected by scattering experiments, capillary electrophoresis CE analysis permitted detection of two other populations, one of h-PAA, and the other of free PBA-b-PAA chains, that have very short PBA blocks and never self-assemble. Despite the presence of these free unimers, the self-assembly in solution was found out of equilibrium: the aggregation state is history dependant and no unimer exchange between micelles occurs over months (time-evolution SANS). The high PBA/water interfacial tension, measured at 20 mN/m, prohibits unimer exchange between micelles. PBA-b-PAA solution systems are neither at thermal equilibrium nor completely frozen systems: internal fractionation of individual aggregates can occur.

MeSH terms

  • Acrylates / chemical synthesis*
  • Acrylates / chemistry*
  • Chemical Phenomena
  • Chemistry, Physical
  • Micelles
  • Particle Size
  • Polymers / chemical synthesis*
  • Polymers / chemistry
  • Solutions / chemistry
  • Water / chemistry

Substances

  • Acrylates
  • Micelles
  • Polymers
  • Solutions
  • poly(butyl acrylate)-b-poly(acrylic acid)
  • Water
  • n-butyl acrylate
  • acrylic acid