Synthesis and solution properties of comblike polymers from octadecyl methacrylate and acrylic acid

Abstract.

Amphiphilic polymers consisting of a statistical distribution of octadecyl methacrylate (ODMA) and acrylic acid in respective molar ratios of 83–22 and 17–78 mol% and in a molecular-weight range of 2.35–4.70×10⁴ gmol^–1 have been synthesized. The series of polymers consisting of various mole fractions of ODMA and acrylic acid are expected to exhibit unique characteristics resembling ionomer to hydrophobically modified polyelectrolytes. The changes in the I ₃/I ₁ emission intensity ratios of pyrene, occurring in the presence of tetrahydrofuran (THF) solutions of the polymers have been taken as the main basis for inferring solution structures. The polymers are found to form random-coil to collapsed-coil/aggregated structures in THF solvent depending on the copolymer compositions. The polymer consisting of 83 mol% ODMA and 17 mol% acrylic acid behaves as an ionomer, capable of forming collapsed-coil structures at concentrations of 0.02 gml^–1 and above as shown by a very high I ₃/I ₁ of 1.20 (I ₃/I ₁ of pyrene in THF is 0.85). In contrast, the poly(octadecyl methacrylate) homopolymer and the sets of copolymers consisting of a very high proportion of acrylic acid to an extent of 73 mol% and above contribute to almost negligible or very small changes in I ₃/I₁ similar to the homopolymer, poly(octadecyl methacrylate), suggesting the formation of random-coil structures.