Intramolecular energy transferable (2,2‐diphenylvinyl)phenyl substituted poly(p‐phenylenevinylene) derivative with efficient photoluminescence and electroluminescence

A poly(p‐phenylenevinylene) (PPV) derivative containing a bulky (2,2‐diphenylvinyl)phenyl group in the side chain, EHDVP‐PPV, was synthesized by Gilch route. The reduced tolane‐bisbenzyl (TBB) defects, as well as the structure of the polymer, was confirmed by various spectroscopic methods. The intramolecular energy transfer from the (2,2‐diphenylvinyl)phenyl side group to the PPV backbone was studied by UV‐vis and photoluminescence (PL) of the obtained polymer and model compound. The polymer film showed maximum absorption and emission peaks at 454 and 546 nm, respectively, and high PL efficiency of 57%. A yellow electroluminescence (λ_max = 548 nm) was obtained with intensities of 6479 cd/m² when the light‐emitting diodes of ITO/PEDOT/EHDVP‐PPV/LiF/Al were fabricated. The maximum power efficiency of the devices was 0.729 lm/W with a turn‐on voltage of 3.6 V. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5636–5646, 2004     

Radiolytic unsaturation decay in polyethylene. Part III—the effect of certain chain transfer agents

Small amounts of certain halogenated compounds are found to have, at most, only a slight enhancing effect on the radiolytic decay rates of added poly-unsaturated compounds in polyethylene, but significantly increase the elastic modulus at 433 K (melt modulus) obtained thereby. Experiments with model chlorine-containing additives suggest that this increase is due to a more random distribution of polymer and monomer mediated crosslinks in the polymer, that it does not result from a significant increase in crosslinking and that it is mediated by chlorine atoms, in a similar manner to radiolytic hydrogen atoms, through facilitation of long range free radical migration. Although low molecular weight chloro-paraffins inhibit radiolytically induced growth of melt modulus in monomer containing polyethylenes, even very small additions of chlorinated polyethylenes, which form a separate phase, increase the melt modulus. This again indicates that the active species is the chlorine radical.     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

Addition–fragmentation chain transfer: Molecular weight distributions and retardation in the system methyl methacrylate/methyl α‐(bromomethyl)acrylate

A detailed investigation of addition–fragmentation chain transfer (AFCT) in the free‐radical polymerization of methyl methacrylate (MMA) in the presence of methyl α‐(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (k_add) over 60–120 °C resulted in E_add = 21.7 kJ mol^?1 and A_add = 2.18 × 10⁶ M^?1 s^?1 and a very weak temperature dependence of the chain‐transfer constant (E_add ≈ E_p). The rate coefficient for fragmentation of adduct radicals at 60 °C was estimated as k_f ≈ 39 s^?1 on the basis of experimental data of the MMA conversion and the concentration of 2‐carbomethoxy‐2‐propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2640–2650, 2004     

CATALYSIS OF POLYSTYRENE N-HYDROXYL SULFONAMIDE FOR ESTERIFICATION OF BUTANOL WITH ACETIC ANHYDRIDE

1. INTRODUCTION The development of efficient polymer-supported catalysts has attracted much attention [1]. For obtaining polymeric catalysts, catalytically active groups were introduced onto polymers mostly by copolymerization of the appropriate monomers bearing the desired catalyticfunctionalities (e.g. imidazole, OH, and COOH) or by modification of preformed polymers.Another possibility involves the attachment of side chains, containing the desired arrangement of functional groups, o…     

Optimization of Mass Transfer Processes in the Zone of the Air Electrode of a Fuel Cell with a Solid Polymer Electrolyte

A two-dimensional mathematical model for the transport of reactants in a fuel cell with a solid polymer electrolyte is developed. The model is used for analyzing spatial distributions of the concentration of reactants and current density over the cell. The effect of the catalytic-layer activity, reactant speed, bipolar-plate geometry, thickness and porosity of current collector and/or gas-diffusion sublayer, and the reaction mixture composition on the fuel cell efficiency is estimated theoretically and experimentally.     

Conjugacy relationship between M-convex and L-convex functions in continuous variables

By extracting combinatorial structures in well-solved nonlinear combinatorial optimization problems, Murota (1996,1998) introduced the concepts of M-convexity and L-convexity to functions defined over the integer lattice. Recently, Murota–Shioura (2000, 2001) extended these concepts to polyhedral convex functions and quadratic functions in continuous variables. In this paper, we consider a further extension to more general convex functions defined over the real space, and provide a proof for the conjugacy relationship between general M-convex and L-convex functions.Mathematics Subject Classification (1991): 90C10, 90C25, 90C27, 90C35This work is supported by Grant-in-Aid of the Ministry of Education, Culture, Sports, Science and Technology of Japan     

Some heteroclinic solutions of a model of skin pattern formation

In this paper we study travelling wave solutions to a system of four non‐linear partial differential equations, which arise in a tissue interaction model for skin morphogenesis. Under the ‘small‐stress’ assumption we prove the existence and uniqueness (up to a translation) of solutions with the dermis and epidermis cell densities being positive, which are a perturbation of a uniform epidermal cell density. We discuss the problem of the minimal wave‐speed. Copyright © 2004 John Wiley & Sons, Ltd.     

TTF-porphyrin dyads as novel photoinduced electron transfer systems

A TTF-linked porphyrin dyad and its zinc complex have been synthesized as novel photosystems with a redox-active pendant. The two chromophores of these dyads are not interactive in the absorption spectra, but the fluorescence of the porphyrin chromophore is dramatically quenched by intramolecular electron transfer from the TTF pendant.