Synthesis, Characterization and Solution Properties of Hydrophobically Modified Polyelectrolyte Poly(AA-co-TMSPMA)

The hydrophobically modified polyelectrolyte was synthesized using precipitation polymerization of acrylic acid and 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate (TMSPMA) in various molar ratios in supercritical carbon dioxide. FT-IR, 1H NMR, capillary viscometry, rotational viscometer, transmission electron microscopy and fluorescence spectroscopy were used to characterize this copolymer. The viscosity of the copolymers showed a strong dependence on pH with a maximum at pH=5.5. Associating morphologies of the copolymer were observed by TEM. Associating morphologies of poly(AA-co-TMSPMA) solution changed from a global structure to a shell-core structure with increasing hydrophobic levels. A solution of sample PAT4 with a shell-core structure had the largest viscosity value. In addition, the critical micelle concentration of copolymer solution, cmc, was determined from the relative viscosity. The critical micelle concentration was further confirmed by fluorescence spectroscopy using 1-pyrenemethylamine hydrochloride, PyMeA⋅HCl, as a cationic fluorescent probe. The cmc was determined from the intensity ratios, the first to the third emission peaks I1/I3, and the excimer to monomer IE/IM ratio of the pyrene probe as a function of concentration.