A new series of solid polymer electrolyte materials based on the poly(organophosphazene) system has been designed and synthesized. The new polymers contain linear or branched oligoethyleneoxy side chains. The polymers were characterized by 31 P, 13 C, and 1 H-NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and elemental analysis. The ambient temperature (25°C) ionic conductivities of the polymers complexed with lithium triflate were measured by complex impedance analysis. The polymers that bear linear oligoethyleneoxy side chains [NP{O(CH2CH2O)n-CH3}2], have low glass transition temperatures that range from -84 to -75°C. These polymers have properties that are similar to those of the classical counterpart poly[bis(2-(2-methoxyethoxy)ethoxy)-phosphazene. They have low dimensional stabilities and undergo viscous flow even at room temperature. The polymers with branched oligoethyleneoxy side chains (podands) have similar glass transition temperatures, in the range of -82 to -79°C. However, the bulk dimensional stabilities of the branched polymers are significantly higher than those of the corresponding linear side chain series. The branched side chain polymers resist viscous flow and readily form thin, free-standing films. The podand polymers also dissolve lithium triflate to form ionically conducting materials with conductivity levels similar to those of the polymers bearing linear side chains.

A series of mixed-substituent poly(organophosphazenes) with the general structure {NP[OCH2CH2OCH2CH2OCH3] x [O(CH2) y CH3]2-x } n , where x = 1 and y = 2−9 was synthesized. These polymers are candidates for use as solid polymeric, ionic conduction media. The polymers were characterized by 1H, 13C, and 31P nuclear magnetic resonance spectroscopy, gel permeation chromatography, elemental microanalysis, infrared spectroscopy, and differential scanning calorimetry. The polymers were complexed with LiSO3CF3 and ambient temperature (25 °C) ionic conductivity studies were performed with the use of complex impedance analysis. The effect of changes in the length of the alkyl component of the alkoxy groups on conductivity was examined. A maximum conductivity as a function of the concentration of lithium triflate was found for each system. The conductivity decreased with an increase in the alkyl group side-chain length. These polymers were compared to the polyphosphazene single-substituent polymer [NP(OCH2CH2OCH2CH2OCH3)2] n , as well as to the n-alkyloxy single-substituent polymers {NP[O(CH2) x CH3]2} n , where x = 2−9.

Form Approvea TION PAGEoM6 No 0704ý0788 7 AD-A264 915 tef,j I u t epre ntcn m ~efrfve" M~10%Wf-I%.qJ( Reproduction in whole, or in part, is permitted for any purpose of the United States government. This document has been approved for public release and sale; its distribution is unlimited. AbstractCyclic and high polymeric phosphazenes that bear 3-(4-oxyphenyl)-1-phenyl-2-propen-1-one (4-oxychalcone) side groups have been prepared in order to study their photochemical behavior. Small molecule cyclic trimers of the general formula N 3 P 3 R 5 R' where R= phenoxy, 2,2,2-trifluoroethoxy, chloro and 4-oxychalcone and R'= 4-oxychalcone were synthesized in order to model the crosslinking reactions at the high polymer level. Single-substituent and cosubstituent polymeric phosphazenes [NPRR' 2 ]n, where R= phenoxy, 2,2,2-trifluoroethoxy or 4-oxychalcone, and R'= 4-oxychalcone were also prepared. Their photolytic crosslinking was followed by ultraviolet spectroscopy.

No abstract

The behavior of nonlinear optical (NLO) groups linked to a polyphosphazene chain was studied by solid-state NMR spectroscopy. A series of poly(organophosphazenes) was prepared with the general structure [NP(RN(CH3)C6H4NO2)x{O(CH2CH2O)2CH3}2-x]n, where x < 0.5 and the spacer group R ) O(CH2)2, O(CH2)6, or OCH2(2-pyrrolidino), in addition to the stilbene-containing polyphosphazene [NP{O(CH2)2N(CH3)C6H4CHdCHC6H4NO2}0.4{O(CH2CH2O)2CH3}1.6]n. Structural characterization for the above polymers was achieved by 31 P NMR spectroscopy, differential scanning calorimetry, and elemental microanalysis. (Methoxyethoxy)ethoxy (MEE) cosubstituent poly(organophosphazenes) bearing O(CH2)2N(CH3)C6H4NO2 and O(CH2)6N(CH3)C6H4NO2 side groups were selected for study by roomtemperature and variable-temperature solid-state 31 P and 13 C NMR spectroscopy. The variabletemperature solid-state 13 C NMR spectra indicated that the use of a longer spacer group between the polymer backbone and the aromatic portion of the NLO side group lowers the temperature at which chromophore motion is quenched. This implied that the use of such structures may accelerate the randomization of NLO side group orientation at ambient temperatures following poling. This behavior was mirrored in the solid-state variable-temperature 31 P NMR spectra, which suggested that side chain and polymer backbone motion may be coupled.