Boosting Effect of Amphiphilic Random Copolymers for Bicontinuous Phases.

Amphiphilic random copolymers, poly(oxyethylene)/poly(oxypropylene) butyl ethers (C4EmPn), have been used as raw materials for cosmetics. This paper reports on the influence of amphiphilic random copolymers on mixtures of n-decane, water, and a nonionic surfactant, hexa(oxyethylene) dodecyl ether (C12E6). Bicontinuous phases are formed from decane/water/C12E6 mixtures at high C12E6 weight fractions (> 70 wt%). Adding C4EmPn to decane/water/C12E6 mixtures brings about the formation of bicontinuous phases and a decrease in the amount of the surfactant required for their formation, indicating efficiency boosting. The bicontinuous phase formation region in the phase diagram of the decane/water/C12E6+C4E5P5 system is largest at a specific C4E5P5 weight fraction in the C12E6/C4E5P5 mixture. When a hydrophobic polymer, in which the poly(ethylene oxide) group in C4EmPn is absent, is added to decane/water/C12E6 mixtures, no efficiency boosting is observed. These results suggest that the adjustment of the hydrophilicity-hydrophobicity balance of C12E6/C4EmPn mixture causes the efficiency boosting.

The deformation of hydrogel microspheres at the air/water interface.

The deformation of soft hydrogel microspheres (microgels) adsorbed at the air/water interface was investigated for the first time using large poly(N-isopropyl acrylamide)-based microgels synthesized by a modified aqueous precipitation polymerization method. The deformation of the micron-sized soft microspheres could be visualized clearly and analyzed quantitatively at the air/water interface.

A simple feature of yielding behavior of highly dense suspensions of soft micro-hydrogel particles.

The highly dense suspensions of soft micro-hydrogels with a narrow size distribution (typically ϕeff > 0.9 where ϕeff is the apparent volume fraction of the particle), which form a regular lattice structure, exhibit a simple feature in the yielding behavior: the yield strain γc [ca. 2.5% and ca. 4.8% for poly(N-isopropylmethacrylamide) (PNIPMA) and poly(N-isopropylacrylamide) (PNIPA) hydrogel particles, respectively] is nearly insensitive to the cross-link concentration (cx), particle diameter (Dh), and particle concentration (c) in the limited c range examined here, and γc is almost constant in a wide range of equilibrium shear moduli over two orders of magnitude. In addition, no appreciable difference in γc is observed in the dense pastes with crystalline and glassy structures which are formed by mono- and bidisperse microgels, respectively. This is in contrast to a finite difference in γc for the crystal and glass formed by the hard sphere reported by Koumakis et al. [Soft Matter, 4, 2008 (2008)]. Furthermore, the highly dense suspensions of NIPA core-NIPMA shell microgels are similar in γc to those of NIPMA microgels. These results indicate that γc for the highly dense suspensions of soft micro-hydrogels depends primarily on the kind of constituent polymer near the particle surface. The yield strain γc is expected to be governed by short-range interactions such as adhesion and friction.

Multilayered composite microgels synthesized by surfactant-free seeded polymerization.

We report on a simple and rapid method to produce multilayered composite microgels. Thermosensitive microgels were synthesized by aqueous free radical precipitation polymerization using N-isopropylacrylamide (NIPAm) as a monomer. Using the microgels as cores, surfactant-free seeded polymerization of an oil-soluble monomer, glycidyl methacrylate (GMA), was carried out at 70 °C, where the microgels were highly deswollen in water. All of the oil-soluble monomers were polymerized, and the resultant polymers were attached on the pre-existing microgel cores, resulting in hard shell formation. It is worth mentioning that secondary particles of oil-soluble monomers have never been formed during the polymerization. The composite microgels were characterized by electron microscopy and dynamic light scattering. In particular, X-ray photoelectron spectroscopy (XPS) measurements revealed that the surface of the composite microgels was composed of a hydrogel layer, although microgel cores were covered by polyGMA shell. The mechanism of the trilayered composite microgel formation will be discussed.