Synthesis and Characterization of Triphenylphosphine Oxide-Containing Poly(Aryl Imide)-Poly(Dimethyl Siloxane) Randomly Segmented Copolymers

Abstract

Poly(aryl imide)-poly(dimethyl siloxane) randomly segmented copolymers were synthesized by essentially a one-step solution imidization process in a solvent system consisting of predominately o-dichlorobenzene with a small amount of n-methylpyrolidone. This solvent combination was selected because of its ability to afford homogeneous solutions throughout the polymerization process. This enabled copolymers of any desired poly(dimethyl siloxane) composition to be prepared. A hydrolytically stable triphenylphosphine oxide containing diamine, bis(3-amino-phenoxy-4′-phenyl)phenylphosphine oxide, was utilized as a chain extender and together with oxydiphthalic anhydride formed the hard segment in these copolymers. The soft segment was formed from α,ω-aminopropyl poly(dimethyl siloxane) oligomers of controlled molecular weight. The presence of phosphorus and silicon contributes several unique properties to the system, including enhanced solubility, thermal stability, and flame resistance. High molecular weight copolymers containing up to 60% (w/w) of the poly(dimethyl siloxane) segments were successfully prepared using this method. Gel permeation chromatography analysis, based on a universal calibration curve in CHCl₃, was performed to determine the molecular weights and distribution. These copolymers with 40-60% (w/w) poly(dimethyl siloxane) exhibited upper T_g values ranging from 130 to 180°C and showed substantial char yields at 750°C in air, which increased with siloxane content. Dynamic mechanical analysis confirmed the anticipated microphase behavior by the presence of two separate glass-transition regions. Both small angle x-ray scattering and transmission electron microscopy measurements determined on well-characterized transparent cast films were used to better demonstrate the multiphase nature of these copolymers.     

High-order numerical simulation and modelling of the interaction of energetic and inert materials

We present an integrated algorithm on a Eulerian grid, for multimaterial simulations of energetic and inert materials modelled by non-ideal equations of state. We employ high-resolution shock capturing numerical algorithms for each material inside its domain and use an overlap domain method across the interface, maintained by a recently developed, hybrid, level-set algorithm. For applications to condensed explosives we implement a non-ideal, wide-ranging equation of state and reaction rate law. For inert materials, like plastic, metal, water, etc., we implement a (linear in the pressure) Mie–Grüneisen, (U _p ?U _s ), equation of state. We present a series of verifications of the integrated multimaterial code and show validations against experiment. We show examples of simulations of various experiments associated with real or planned experiments, some of which contain energetic materials (specifically the condensed explosives PBX-9502 and PBX-9501).     

Multiple periodic solutions for a nonlinear suspension bridge equation

We investigate nonlinear oscillations in a fourth-order partialdifferential equation which models a suspension bridge. Previouswork establishes multiple periodic solutions when a parameterexceeds a certain eigenvalue. In this paper, we use Leray-Schauderdegree theory to prove that if the parameter is increased further,beyond a second eigenvalue, then additional solutions are created.     

Experiments with longitudinally polarized electrons in a storage ring using a siberian snake

We report on first measurements with polarized electrons stored in a medium-energy ring and with a polarized internal target. Polarized electrons were injected at 442 MeV (653 MeV), and a partial (full) Siberian snake was employed to preserve the polarization. Longitudinal polarization at the interaction point and polarization lifetime of the stored electrons were determined with laser backscattering. Spin observables were measured for electrodisintegration of polarized 3He, with simultaneous detection of scattered electrons, protons, neutrons, deuterons, and 3He nuclei, over a large phase space.     

DNA vaccine containing the mycobacterial hsp65 gene prevented insulitis in MLD-STZ diabetes

Background  

Our group previously demonstrated that a DNA plasmid encoding the mycobacterial 65-kDa heat shock protein (DNA-HSP65) displayed prophylactic and therapeutic effect in a mice model for tuberculosis. This protection was attributed to induction of a strong cellular immunity against HSP65. As specific immunity to HSP60 family has been detected in arthritis, multiple sclerosis and diabetes, the vaccination procedure with DNA-HSP65 could induce a cross-reactive immune response that could trigger or worsen these autoimmune diseases.     

Mesoscale simulation of morphology in hydrated perfluorosulfonic acid membranes

Current fuel cell proton exchange membranes rely on a random network of conducting hydrophilic domains to transport protons across the membrane. Despite extensive investigation, details of the structure of the hydrophilic domains in these membranes remain unresolved. In this study a dynamic self-consistent mean field theory has been applied to obtain the morphologies of hydrated perfluorosulfonic acid membranes (equivalent weight of 1100) as a model system for Nafion at several water contents. A coarse-grained mesoscale model was developed by dividing the system into three components: backbone, side chain, and water. The interaction parameters for this model were generated using classical molecular dynamics. The simulated morphology shows phase separated micelles filled with water, surrounded by side chains containing sulfonic groups, and embedded in the fluorocarbon matrix. The size distribution and connectivity of the hydrophilic domains were analyzed and the small angle neutron scattering (SANS) pattern was calculated. At low water content (lambda<6, where lambda is the number of water molecules per sulfonic group) the isolated domains obtained from simulation are nearly spherical with a domain size smaller than that fitted to experimental SANS data. At higher water content (lambda>8), the domains deform into elliptical and barbell shapes as they merge. The simulated morphology, hydrophilic domain size and shape are generally consistent with some experimental observations.     

Donor-sigma-acceptor molecules incorporating a nonadecyl-swallowtailed perylenediimide acceptor

Donor-sigma-acceptor-lipid molecules were prepared by using perylenetetracarboxylic diimide as the acceptor, starting from perylenetetracarboxylic dianhydride. One imide nitrogen was attached to a "swallowtail" lipid (a long alkyl tail connected at midchain), which imparts enough solubility to make the system tractable and provides a lipophilic region suitable for promoting Langmuir-Blodgett monolayer formation. The other imide link was to a donor group (pyrene, ferrocene, tetramethylphenylenediamine, phenyl) through a short alkyl sigma bridge. Features of the 1H and 13C NMR spectra of swallowtailed perylenediimides are interpreted as resulting from restricted rotation about the imide C-N bond; the 13C NMR spectra and stereochemistry of these molecules are contrasted with the case of the related bis-(2,5-di-tert-butylphenyl)perylenetetracarboxylic diimide.