Upper Critical Solution Temperature Behavior of pH-Responsive Amphoteric Statistical Copolymers in Aqueous Solutions.

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.

Micellar formation of cationic surfactants.

The micellar structure of six alkyl trimethylammonium halides was studied via conductivity. It was found that the aggregation number increased with the decreasing carbon chain length. Furthermore, Br- significantly enhanced the micellar formation over Cl-. However, the aggregation number and ionization degree remain similar for both anions. The modelling results validate that the counter-anions affect micellar formation via equilibrium constants, instead of their hydration size. In particular, the association constants between surfactant (both monomer and micelle) and Br- are significantly higher than Cl-. This is consistent with the qualitative description of hydrated Br- in the literature. The experimental and modelling results confirm that micelles are formed via "ion-paring/hydration" structure, instead of the conventional "packing" concept.

Ultrasound- and Thermo-Responsive Ionic Liquid Polymers.

Poly(sodium 2-acrylamido-2-methylpropanesulfonate) (PAMPSNa) was prepared via reversible addition-fragmentation chain transfer (RAFT) radical polymerization. An ionic liquid polymer (PAMPSP4448) was then prepared by exchanging the pendant counter cation from sodium (Na⁺) to tributyl-n-octylphosphonium (P4448⁺). We studied the ultrasound- and thermo-responsive behaviors of PAMPSP4448 in water. When the aqueous PAMPSP4448 solution was heated from 5 to 50 °C, the solution was always transparent with 100% transmittance. Unimers and interpolymer aggregates coexisted in water in the temperature range 5⁻50 °C. Generally, hydrogen bonding interactions are broken as the temperature increases due to increased molecular motion. Above 25 °C, the size of the interpolymer aggregates decreased, because hydrophobic interactions inside them were strengthened by dehydration accompanying cleavage of hydrogen bonds between water molecules and the pendant amide or sulfonate groups in PAMPSP4448. Above 25 °C, sonication of the aqueous solution induced an increase in the collision frequency of the aggregates. This promoted hydrophobic interactions between the aggregates to form larger aggregates, and the aqueous solution became turbid. When the temperature was decreased below 8 °C, hydrogen bonds reformed between water molecules and the pendant amide or sulfonate groups, allowing PAMPSP4448 to redissolve in water to form a transparent solution. The solution could be repeatedly controlled between turbidity and transparency by sonication and cooling, respectively.

Micelle and Surface Tension of Double-Chain Cationic Surfactants.

Since the early 20th century, the slightly disparate measurements of a surfactant's critical micelle concentration, via either surface tension or electrical conductivity, have been assumed one and the same. As a consequence, the possibility that micelles can adsorb at the air/water surface has been disregarded and has led to some abnormalities in the literature that remain as yet unresolved. In this paper, we closely examined the two critical concentrations for a double-chain cationic surfactant. We confirmed that the two concentrations represent two different physical phenomena. Furthermore, the results verified the existence of surface micelles, which are different from the bulk micelles. The formation of the surface micelles can be explained by the structural changes of the adsorption layer, which was also corroborated by molecular simulations. The findings open new challenges to examine the surface adsorption, which  offers new insights into the molecular levels.