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| - Polyphosphazenes with Novel Architectures: Influence on PhysicalProperties and Behavior as Solid Polymer Electrolytes
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| - Three types of polyphosphazenes with different architectures have been synthesized andcharacterized. The influence of the polymer architecture on solid ionic conductivity was of particularinterest. The first type includes linear oligo- and polyphosphazenes with the general formula [NP(OCH2CH2OCH2CH2OCH3)2]n (MEEP) with different chain lengths. The second type consists of a series oftriarmed star-branched polyphosphazenes with the general formula N{CH2CH2NH(CF3CH2O)2P[NP(OCH2CH2OCH2CH2OCH3)2]n}3 with different arm lengths. These were synthesized via the reaction of the tridentate initiator [N{CH2CH2NH(CF3CH2O)2PN−PCl3+}3][PCl6-]3 with the phosphoranimine Cl3PNSiMe3in CH2Cl2 followed by halogen replacement with sodium (methoxyethoxy)ethoxide. The molecular weightsin this system were carefully controlled by variation of the monomer-to-initiator ratios, and the effect ofpolymer molecular weight on solid ionic conductivity was examined. The third polymer system wasdesigned to examine the effect of complex branching on ionic conductivity. Thus, a highly branchedpolymer containing five branches from a cyclotriphosphazene pendent side group (with 26 ethyleneoxyunits per repeat unit) was synthesized. The conductivity of this polymer in the presence of three differentsalts has been measured and compared to the behavior of MEEP with a corresponding molecular weight.The mechanism of ion transport in these systems is discussed.
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