Synthesis and solution properties of amphiphilic cyclopolymers and terpolymers of 4‐methoxycarbonyl‐1,1‐diallylpiperidinium chloride, diallyloctadecylammonium chloride, and sulfur dioxide

Abstract

AbstractThe cycloterpolymerization of a hydrophilic monomer, 4‐methoxycarbonyl‐1,1‐diallylpiperidinium chloride, with a hydrophobic monomer, diallyloctadecylammonium chloride (3–7 mol %), and sulfur dioxide in dimethyl sulfoxide with azobisisobutyronitrile as the initiator afforded a series of water‐soluble cationic polyelectrolytes (CPEs) at well over 90% yields. Acidic (HCl) hydrolysis of the ester groups in CPEs to CO2H groups gave the cationic acid salts (CASs), which on treatment with 1 equiv of NaOH, furnished polyzwitterions (PZs). Contrary to the well‐known behavior that the normal PZs are only soluble in brine, PZ in the absence of the hydrophobe was found to be soluble in salt‐free water. The solution properties of the resulting series of interconvertible polymers (CPE → CAS ⇋ PZ) were investigated by viscometric techniques. At a shear rate of 0.36 s−1, 2 g/dL solutions of CPE having 0, 3, 5, and 7 mol % hydrophobe in salt‐free water at 30°C were found to have apparent viscosity values of 4000, 164,000, 670,000, and 1,430,000 cps, respectively. Polymer–surfactant interactions were investigated with the cationic surfactant cetyltrimethylammonium bromide (CTAB). Tremendous increases in the viscosity values of the CPE having 7 mol % of the hydrophobe were observed in the presence of the surfactant at a shear rate of 0.36 s−1; a 0.75 g/dL solution of the polymer in salt‐free water was found to have apparent viscosity values of 18,000 and 235,000 cps in the absence and presence, respectively, of 3 mM CTAB. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010