ABSTRACT
Amphoteric statistical equivalent copolymers (P(2VP/NaSS) n ) composed of 2-vinylpyridine (2VP) and anionic sodium p-styrenesulfonate (NaSS) were prepared via reversible addition-fragmentation chain transfer polymerization. The degrees of polymerization (n) were 19 and 95. The monomer reactivity ratio, time conversion profile, and 1H nuclear magnetic resonance diffusion-ordered spectra suggested that the copolymerization of 2VP and NaSS provided statistical or near to random copolymers. P(2VP/NaSS) n exhibited an upper critical solution temperature (UCST) in acidic aqueous solutions on the basis of the charge interactions between the protonated cationic 2VP and anionic NaSS units. With an increase in pH value, the interaction was weakened because of the deprotonation of the 2VP units, thus reducing the UCST. At high [NaCl], the electrostatic interactions among the polymers were weakened because of the screening effect, and again, the UCST was reduced. With an increase in polymer concentration, the intra- and interpolymer interactions increased because of some entanglement, and the UCST consequently increased. Electrostatic interactions among the polymer chains with high molecular weight occurred easier than those among the low-molecular-weight polymer chains, which increased the UCST. The UCST also increased when deuterium oxide was used instead of hydrogen oxide, which was due to the isotopic effect. Hence, the UCST of P(2VP/NaSS) n can be adjusted according to the desired application.
ABSTRACT
Strong polyampholytes comprising cationic vinylbenzyl trimethylammonium chloride (VBTAC) bearing a pendant quaternary ammonium group and anionic sodium p-styrenesulfonate (NaSS) bearing a pendant sulfonate group were prepared via reversible addition-fragmentation chain-transfer polymerization. The resultant polymers are labelled P(VBTAC/NaSS)n, where n indicates the degree of polymerization (n = 20 or 97). The percentage VBTAC content in P(VBTAC/NaSS)n is always about 50 mol%, as revealed by ¹H NMR measurements, meaning that P(VBTAC/NaSS)n is a close to stoichiometrically charge-neutralized polymer. Although P(VBTAC/NaSS)n cannot dissolve in pure water at room temperature, the addition of NaCl or heating solubilizes the polymers. Furthermore, P(VBTAC/NaSS)n exhibits upper critical solution temperature (UCST) behavior in aqueous NaCl solutions. The UCST is shifted to higher temperatures by increasing the polymer concentration and molecular weight, and by decreasing the NaCl concentration. The UCST behavior was measured ranging the polymer concentrations from 0.5 to 5.0 g/L.
