A Novel Estimation Method of the Distribution of Carboxyl Groups Within Copolymer Particles Using Isothermal Titration Calorimeter

Summary: A novel quantitative method using isothermal titration calorimeter (ITC) for the estimation of the distribution of carboxyl groups within polymer particles has been proposed. The method has been employed to clarify the difference in the distribution between the particles prepared by batch emulsion copolymerization of styrene and methacrylic acid under inefficient and efficient stirring conditions. At inefficient stirring, monomer was floating as a layer on the aqueous medium, whereas at efficient stirring, the monomer phase was dispersed as droplets. Under inefficient stirring, methacrylic acid (MAA) polymerized faster than styrene (S) due to a slower diffusion rate of S than MAA into the aqueous medium, while under efficient stirring, S and MAA copolymerized at similar rates. ITC measurement showed that under inefficient stirring, the carboxyl groups were distributed mainly in the center of the particles, and their number decreased toward the surface. On the other hand, under efficient stirring, carboxyl groups were distributed homogeneously inside the particle.     

Effect of Ampoule Rotation on Growth of InGaAs Ternary Bulk Crystals from Solution

In_xGa_1-xAs (x = 0.045) ternary bulk crystals were grown on GaAs seeds from an In–Ga–As solution by the temperature-difference method modified to rotate a growth ampoule. The effect of ampoule rotation on the profiles of the composition and the growth rate were investigated. The In compositional profiles were uniform irrespective of the ampoule rotation. On the other hand, the growth rate at the center of the crystal increased from 40 μm/h at 0 rpm to 55 μm/h at 100 rpm. The profile of growth rate changed from concave to convex toward the seed due to the ampoule rotation. Flow patterns and compositional profiles in the solution were simulated by solving four equations: Navier-Stokes, continuity, energy, and solute diffusion. The ampoule rotation enhanced the transportation of As component from the GaAs feed toward the seed at the central region in the solution. This led to the increase of the growth rate.     

Preparation of Polymer-Supported Chiral 1,2-Diamine as an Efficient Ligand for Asymmetric Hydrogenation Catalyst

An enantiopure 1,2-diamine having two phenolic hydroxy groups was synthesized, and attached to chloromethylated poly(styrene) through a benzyl ether linkage. The polymer-supported Ru precatalysts were prepared from the polymeric chiral 1,2-diamine and RuCl₂/BINAP complex. In the presence of t-BuOK the polymeric catalyst system worked well in asymmetric hydrogenation of aromatic ketones in a mixed solvent of 2-propanol and DMF. The insoluble polymeric catalyst was readily separated from the reaction mixture and reused at least several times without loss of the catalytic activity.