Kinetic Study of the Polymerization of Alkyl Vinyl Ethers by HI/12 Catalyst

The polymerization of alkyl vinyl ethers initiated by hydrogen iodide and iodine catalyst has been studied in detail. The polymerization showed living behavior in nonpolar solvents at low (-15°) temperatures as reported earlier by others. The observed rate of polymerization under the reaction conditions was linearly dependent on the initial concentration of hydrogen iodide and iodine, respectively. However, the monomer concentration did not influence the rate of polymerization (apparent zero order). From the observed rate equation, two possible reaction schemes were proposed and attempts were made to distinguish them by using UV/visible spectroscopy and ¹³ C-NMR spectroscopy. In both schemes a reversible interaction between monomer and an iodine molecule was postulated as a necessary elemental reaction to fit the observed expression for rate of polymerization. From the spectroscopic analysis results, the interaction between the iodide compound (chain end) and the iodine molecule seems to be very weak compared to the interaction between monomer and the iodine molecule.     

Naphthodithiophene‐Diketopyrrolopyrrole‐Based donor–Acceptor alternating π‐Conjugated polymers for Organic thin‐Film transistors

Novel naphtho[1,2‐b:5,6‐b′]dithiophene (NDT) and diketopyrrolopyrrole (DPP)‐containing donor‐acceptor conjugated polymers (PNDTDPPs) with different branched side chains were synthesized via Pd(0)‐catalyzed Stille coupling reaction. Octyldodecyl (OD) and dodecylhexadecyl (DH) groups were tethered to the DPP units as the side chains. The soluble fraction of PNDTDPP‐OD polymer in chloroform has much lower molecular weight than that of PNDTDPP‐DH polymer. PNDTDPP‐DH polymer bearing relatively longer DH side chains exhibited much better charge‐transport behavior than PNDTDPP‐OD polymer with shorter OD side chains. The thermally annealed PNDTDPP‐DH polymer thin films exhibited an outstanding charge carrier mobility of ～1.32 cm² V^?1 s^?1 (I_on/I_off ～ 10⁸) measured under ambient conditions, which is almost six times higher than that of thermally annealed PNDTDPP‐OD polymer thin films. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5280–5290     

Catalytic Enantioselective Reactions Part 7. Synthesis of New β-Aminoalcohols Derived from α-D-Glucose as Chiral Catalysts for the Catalytic Enantioselective Addition of Diethylzinc to Aldehydes

A series of new 1, 2-O-isopropylidene-3-O-methyl-6-deoxy-6-N, N-dialkylamino-α-D-glucofuranoses 1 and 1, 2-O-isopropylidene-3, 6-dideoxy-6-N, N-dialkylamino-α-D-glucofuranoses 1′ were prepared from α-D-glucose and their enantiose-lectivities compared as chiral catalysts for the ethylation of benzaldehyde and heptanal with diethylzinc.     

Synthesis of a Tricyclic Bisguanidine Compound Structurally Related to Saxitoxin and its Identification in Paralytic Shellfish Toxin‐Producing Microorganisms

We recently reported the chemical synthesis and identification of the genetically predicted biosynthetic intermediates of saxitoxin (STX), including a 2‐aminoimidazole‐bearing monoguanidine compound (Int‐C′2) in two paralytic shellfish toxin (PST)‐producing microorganisms. In this study, we achieved the direct conversion of Int‐C′2 into a tricyclic bisguanidine compound (called Cyclic‐C′), which is structurally related to STX, through oxidative intramolecular guanidine transfer to 2‐aminoimidazole catalyzed by Pd/C under basic conditions in air. By using HPLC‐MS analysis, Cyclic‐C′ was also identified in the PST‐producing microorganisms, suggesting that Cyclic‐C′ is either another biosynthetic intermediate or a shunt product of PSTs. In addition, a weak inhibitory activity of Cyclic‐C′ to the voltage‐gated sodium channels was detected by using a cell‐based assay.     

Cesium release during high-temperature pre-treatment of fuel fragments with a burn-up of 61 GWd/tU

The electrolytic reduction process in pyroprocessing of used fuel requires that fuel fragments be pre-treated to remove cesium and iodine. The effect of high temperatures and fuel fragment size on release of cesium was investigated over 10 h at a temperature of 1300–1400 °C for fuel fragments with an O/U ratio of 2.2. Re-fragmentation of the original fragments was observed as changes in cesium release count rates as fuel was heated from 484 to 1329 °C. The release of cesium is highly dependent on the size of fuel fragments and most of the cesium is released as the temperature is held at the maximum target value.     

Synthesis of 7-Hydroxyspiropyran

The 7-acetoxyspiropyrans (4a and 4b) have been prepared by the reaction of Fischer's bases (3) with 2,4-diacetoxybenzaldehyde in refluxing ethanol in moderate yields. The acetyl group of 7-acetoxy-spiropyran 4a was easily removed to give a 7-hydroxyspiropyran 6 in high yield under the basic condition.     

Synthesis and Characterization of Acrylonitrile-EPDM-1-Vinylnaphthalene Graft Terpolymer

Abstract

The graft copolymerizations of acrylonitrile (AN) and 1-vinyl-naphthalene (1-VN) onto ethylene-propylene-diene terpolymer (EPDM) were carried out with benzoyl peroxide (BPO) as an initiator in toluene. The effects of the mole ratio of 1-VN to AN, initiator concentration, reaction time, reaction temperature, and EPDM concentration on the graft copolymerizations were examined. The synthesized graft terpolymers, acrylonitrile-EPDM-1-vinylnaphthalene (AEV₁), were identified by IR spectra. The thermal stability and tensile strength of AEV₁ were greatly improved compared with those of ABS. The light resistance and weatherability of AEV₁ were better than those of ABS when subjected to UV light for longer than 96 hours.     

A direct reinitialization approach of level‐set/splitting finite element method for simulating incompressible two‐phase flows

Computation of a moving interface by the level‐set (LS) method typically requires reinitialization of LS function. An inaccurate execution of reinitialization results in incorrect free surface capturing and thus errors such as mass gain/loss so that an accurate and robust reinitialization process in the LS method is essential for the simulation of free surface flows. In the present study, we pursue further development of the reinitialization process, which directly corrects the LS function after advection is carried out by using the normal vector to the interface instead of solving the reinitialization equation of hyperbolic type. The Taylor–Galerkin method is adopted to discretize the advection equation of the LS function and the P1P1 splitting finite element method is applied to solve the Navier–Stokes equation. The proposed algorithm is validated with the well‐known benchmark problems, i.e. stretching of a circular fluid element, time‐reversed single‐vortex, solitary wave propagation, broken dam flow and filling of a container. The simulation results of these flows are in good agreement with previously existing experimental and numerical results. Copyright © 2010 John Wiley & Sons, Ltd.