Anionic polymerization of methyl methacrylate initiated with late transition‐metal halides/organolithium/triisobutylaluminum systems

Anionic polymerization of methyl methacrylate (MMA) initiated with late transition‐metal halides [manganese chloride (MnCl₂), iron dichloride (FeCl₂), iron trichloride (FeCl₃), cobalt chloride (CoCl₂), or nickel bromide (NiBr₂)]/organolithium [nButyllithium (nBuLi) or phenyllithium (PhLi)]/triisobutylaluminum (iBu₃Al) systems is described. Except for the system with NiBr₂, the polymerizations of MMA afforded narrow molecular weight distribution poly(methyl methacrylate)s (PMMAs) with high molecular weights in quantitative yields at 0 °C in toluene. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) analyses of the PMMAs obtained by the systems with FeCl₂, FeCl₃, and CoCl₂ revealed that the polymers had hydrogen (H) at both chain ends. Accordingly, the reaction of the transition‐metal halides with the organolithium in the presence of iBu₃Al should result in the formation of transition‐metal hydride [M‐H]^? species, which was nucleophilic enough to initiate the MMA polymerization. Because the presence of a six‐membered cyclic structure resulting from backbiting was confirmed from the MALDI‐TOF MS analyses of the PMMA obtained with the metal halide (FeCl₂, FeCl₃, or CoCl₂)/organolithium systems in the absence of iBu₃Al, the introduction of H at the ω‐chain end indicated that iBu₃Al should prevent the backbiting. However, the MnCl₂/nBuLi/iBu₃Al initiating system gave PMMAs bearing H at the α chain end and six‐membered cyclic structure at the ω chain end. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1962–1977, 2003     

Palladium‐mediated copolymerization of diazocarbonyl compounds with phenyldiazomethane

Phenyldiazomethane was found to be polymerized by the reaction with palladium‐based initiating systems. Homopolymerization of phenyldiazomethane afforded a polymer, whose main chain consists of phenylmethylene framework (–CHPh–) and azo groups (–N?N–). The incorporation of the azo group was suggested from the results of elemental analyses, and confirmed by Raman spectroscopy. Palladium‐mediated copolymerization of phenyldiazomethane with (E)‐1‐diazo‐3‐nonen‐2‐one or ethyl diazoacetate proceeded to give copolymers having phenylmethylene framework, azo group, and acylmethylene or ethoxycarbonylmethylene framework in the main chain, with a variety of their compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1536–1545, 2007     

Visualization of unsteady shock oscillations in the High-enthalpy flow field around double cones

The presence of an adverse pressure gradient, shock/shock interaction and shock wave/boundary layer interaction often induces flow separation around bodies. However, the effect of dissociated flow on separated flow characteristics, especially at hypersonic speeds, is still not clear, and considerable differences are observed between experiments and numerical simulations. In this investigation, the unsteady separated flow features around double cones are visualized in the Shock Wave Research Center (SWRC) free-piston driven shock tunnel at a nominal Mach Number of 6.99 using multiple optical techniques. The time resolved shock structure oscillations in the flow field around double cones (first cone, semi-apex angle = 25°; second cone, semi-apex angles=50°, 65°, 68° and 70°) have been visualized using a high-speed image converter camera (IMACON) at a nominal stagnation enthalpy of 4.8 MJ/kg. In addition, flow visualization studies around the double cone is also carried out using Schlieren and double exposure holographic interferometry in order to precisely locate the separation point and measure the separation length. The presence of a triple shock structure in front of the second cone and a non-linear unsteady shock structure oscillation in the flow field are the significant results from visualization studies on the 25° /65°, 25° /68° and 25°/70° double cones. On the other hand, the flow field around 25° /50° is relatively steady and Type V shock/shock interaction is observed. Illustrative numerical simulation studies are carried out by solving N-S equations to complement the experiments. The simulated flow features around a double cone agree well qualitatively with experiments.     

A study of the interaction between two triple points

In the Mach reflection of plane shock on a concave double wedge, after two triple points collide with each other, the wave pattern is usually complicated. In this paper, firstly, a shock dynamic approach is used for studying this problem. In this approach, the method of shock-shock polar is used for better understanding the pattern of disturbance propagation. A downward-traveling shock-shock disturbance on the Mach stem is predicted theoretically. Secondly, based on the idea of shock dynamic approach, a gas dynamic model is built for studying the same problem. A similar result is obtained and the formation of the downward-traveling triple point is analyzed. This downward-traveling disturbance propagates and reflects between the upward-traveling shock-shock locus and the wall surface, causing the Mach number of Mach stem to increase and making the wave configuration approach to the one in the Mach reflection on a single wedge.Received: 19 April 2004, Accepted: 2 December 2004, Published online: 16 March 2005[/PUBLISHED]Correspondence to: P. Xie, Z.Y. Han     

Ultraviolet laser photo-modulation voltammetry of tetraphenylborate at a liquid/liquid interface.

Photo-modulation voltammetry was applied to detecting the photolysis of tetraphenylborate (TPhB) at a water/1,2-dichloroethane (DCE) interface by using a He-Cd laser emitting a beam with a major 325-nm line and minor lines of shorter wavelengths. When the interface was irradiated from the water-phase side, a new wave appeared in the photomodulation voltammogram, suggesting that TPhB was photolyzed and the anionic product was transferred across the interface. The concentration dependence of the photocurrents was successfully explained by a theory based on the photolytic process at the interface.     

Side‐chain crystallization behavior of graft copolymers consisting of amorphous main chain and crystalline side chains: Poly(methyl methacrylate)‐graft‐poly(ethylene glycol) and poly(methyl acrylate)‐graft‐poly(ethylene glycol)

Graft copolymers consisting of amorphous main chain, poly(methyl methacrylate) (PMMA), or poly(methyl acrylate) (PMAc), and crystalline side chains, poly(ethylene glycol) (PEG), have been prepared by copolymerization of PEG macromonomers with methyl methacrylate or methyl acrylate (MMAx or MACx, respectively). Because of the compatibility of PMMA/PEG and PMAc/PEG, from small‐angle X‐ray scattering results, the main and side chains in graft copolymers were suggested to be homogeneous in the molten state. Differential scanning calorimetry (DSC) cooling scans revealed that PEG side chains for graft copolymers with large PEG fractions were crystallized when the sample was cooled, with a cooling rate of 10 °C/min. The spherulite pattern observed by a polarized optical microscope suggested the growth of PEG crystalline lamellae. Crystallization of PEG in MMAx was more restrained than in MACx. From these results, we have concluded that the crystallization behavior of the grafted side chains is strongly influenced by the glass transition of a homogeneously molten sample as well as dilution of the crystallizable chains. Domain spacings for isothermally crystallized graft copolymers were described by interdigitating chain packing in crystalline–amorphous lamellar structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 79–86, 2005     

Multielement determination of trace metals in river water (certified reference material, JSAC 0301-1) by high efficiency nebulization ICP-MS after 100-fold preconcentration with a chelating resin-packed minicolumn.

The determination of 34 trace metals in a river water certified reference material (CRM), i.e. JSAC 0301-1, which was issued by the Japan Society for Analytical Chemistry in January 2004, was performed by ICP-MS with a high efficiency nebulizer after preconcentration with a laboratory-made chelating resin-packed minicolumn, with which trace metals were concentrated 100-fold from 50 mL of a river water sample to 0.5 mL of the final analysis solution. Trace metals in JSAC 0301-1 were observed in the concentration range from 19 microg L(-1) of Al to 0.000053 microg L(-1) of Bi. It was found that most of the concentrations of trace metals, including rare earth elements (REEs), in JSAC 0301-1 were lower than those in JAC 0031, which was also a previously issued CRM prepared with water from the same river as that of JSAC 0301-1. The low concentrations of trace metals in JSAC 0301-1 might be attributed to the fact that there was a heavy rain before collecting the original water sample to prepare the present CRM. Furthermore, the REE distribution patterns of JSAC 0301-1, JAC 0031 and the average values of river water samples in Japan were parallel to each other. These results indicate that the distributions of REEs in JSAC 0301-1 and JAC 0031 were the typical ones of river water samples in Japan.     

Study on Optimum Incident Angles of Cross Polarized Four-Wave Mixing with a Photorefractive Crystal

We consider the optimum incident angles of cross polarized four-wave mixing with a photorefractive crystal. First, the phase matching angles are obtained for two operation modes: one in which the writing beams are ordinary rays and the reading beam is an extraordinary ray, we call this Mode 1. The other in which the writing beams are extraordinary rays and the reading beam is an ordinary ray, Mode 2. Next, practicable ranges of the incident angles are calculated considering of the total internal reflection of the phase conjugate beam in cases where the two writing beams illuminate the same surface of the BaTiO₃ crystal and where they illuminate the neighboring right-angled surfaces, respectively. Then, the coupling coefficient is determined as a function of the incident angle, and the optimum incident angles for effective beam interaction in Mode 1 and Mode 2 are estimated.