Polyphosphazenes with novel architectures: Influence on physical properties and behavior as solid polymer electrolytes

Harry R. Allcock; Nicolas J. Sunderland; Ramakrishna Ravikiran; James M. Nelson

doi:10.1021/ma9804491

Polyphosphazenes with novel architectures: Influence on physical properties and behavior as solid polymer electrolytes

Harry R. Allcock, Nicolas J. Sunderland, Ramakrishna Ravikiran, James M. Nelson

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53 Scopus citations

Abstract

Three types of polyphosphazenes with different architectures have been synthesized and characterized. The influence of the polymer architecture on solid ionic conductivity was of particular interest. The first type includes linear oligo- and polyphosphazenes with the general formula [N=P(OCH₂-CH₂OCH₂CH₂OCH ₃)₂]_n (MEEP) with different chain lengths. The second type consists of a series of triarmed star-branched polyphosphazenes with the general formula N{CH₂CH₂NH(CF₃CH₂O) ₂P[N=P(OCH₂-CH₂OCH₂CH ₂OCH₃)₂]_n}₃ with different arm lengths. These were synthesized via the reaction of the tridentate initiator [N{CH₂CH₂NH(CF₃CH₂O) ₂P=N-PCl₃ ⁺}₃][PCl₆ ^-]₃ with the phosphoranimine Cl₃P=NSiMe₃ in CH₂Cl₂ followed by halogen replacement with sodium (methoxyethoxy)ethoxide. The molecular weights in this system were carefully controlled by variation of the monomer-to-initiator ratios, and the effect of polymer molecular weight on solid ionic conductivity was examined. The third polymer system was designed to examine the effect of complex branching on ionic conductivity. Thus, a highly branched polymer containing five branches from a cyclotriphosphazene pendent side group (with 26 ethyleneoxy units per repeat unit) was synthesized. The conductivity of this polymer in the presence of three different salts 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.

Original language	English (US)
Pages (from-to)	8026-8035
Number of pages	10
Journal	Macromolecules
Volume	31
Issue number	23
DOIs	https://doi.org/10.1021/ma9804491
State	Published - Nov 17 1998

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Polyphosphazenes with novel architectures: Influence on physical properties and behavior as solid polymer electrolytes",

abstract = "Three types of polyphosphazenes with different architectures have been synthesized and characterized. The influence of the polymer architecture on solid ionic conductivity was of particular interest. The first type includes linear oligo- and polyphosphazenes with the general formula [N=P(OCH2-CH2OCH2CH2OCH 3)2]n (MEEP) with different chain lengths. The second type consists of a series of triarmed star-branched polyphosphazenes with the general formula N{CH2CH2NH(CF3CH2O) 2P[N=P(OCH2-CH2OCH2CH 2OCH3)2]n}3 with different arm lengths. These were synthesized via the reaction of the tridentate initiator [N{CH2CH2NH(CF3CH2O) 2P=N-PCl3 +}3][PCl6 -]3 with the phosphoranimine Cl3P=NSiMe3 in CH2Cl2 followed by halogen replacement with sodium (methoxyethoxy)ethoxide. The molecular weights in this system were carefully controlled by variation of the monomer-to-initiator ratios, and the effect of polymer molecular weight on solid ionic conductivity was examined. The third polymer system was designed to examine the effect of complex branching on ionic conductivity. Thus, a highly branched polymer containing five branches from a cyclotriphosphazene pendent side group (with 26 ethyleneoxy units per repeat unit) was synthesized. The conductivity of this polymer in the presence of three different salts 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.",

author = "Allcock, {Harry R.} and Sunderland, {Nicolas J.} and Ramakrishna Ravikiran and Nelson, {James M.}",

year = "1998",

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doi = "10.1021/ma9804491",

language = "English (US)",

volume = "31",

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T1 - Polyphosphazenes with novel architectures

T2 - Influence on physical properties and behavior as solid polymer electrolytes

AU - Allcock, Harry R.

AU - Sunderland, Nicolas J.

AU - Ravikiran, Ramakrishna

AU - Nelson, James M.

PY - 1998/11/17

Y1 - 1998/11/17

N2 - Three types of polyphosphazenes with different architectures have been synthesized and characterized. The influence of the polymer architecture on solid ionic conductivity was of particular interest. The first type includes linear oligo- and polyphosphazenes with the general formula [N=P(OCH2-CH2OCH2CH2OCH 3)2]n (MEEP) with different chain lengths. The second type consists of a series of triarmed star-branched polyphosphazenes with the general formula N{CH2CH2NH(CF3CH2O) 2P[N=P(OCH2-CH2OCH2CH 2OCH3)2]n}3 with different arm lengths. These were synthesized via the reaction of the tridentate initiator [N{CH2CH2NH(CF3CH2O) 2P=N-PCl3 +}3][PCl6 -]3 with the phosphoranimine Cl3P=NSiMe3 in CH2Cl2 followed by halogen replacement with sodium (methoxyethoxy)ethoxide. The molecular weights in this system were carefully controlled by variation of the monomer-to-initiator ratios, and the effect of polymer molecular weight on solid ionic conductivity was examined. The third polymer system was designed to examine the effect of complex branching on ionic conductivity. Thus, a highly branched polymer containing five branches from a cyclotriphosphazene pendent side group (with 26 ethyleneoxy units per repeat unit) was synthesized. The conductivity of this polymer in the presence of three different salts 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.

AB - Three types of polyphosphazenes with different architectures have been synthesized and characterized. The influence of the polymer architecture on solid ionic conductivity was of particular interest. The first type includes linear oligo- and polyphosphazenes with the general formula [N=P(OCH2-CH2OCH2CH2OCH 3)2]n (MEEP) with different chain lengths. The second type consists of a series of triarmed star-branched polyphosphazenes with the general formula N{CH2CH2NH(CF3CH2O) 2P[N=P(OCH2-CH2OCH2CH 2OCH3)2]n}3 with different arm lengths. These were synthesized via the reaction of the tridentate initiator [N{CH2CH2NH(CF3CH2O) 2P=N-PCl3 +}3][PCl6 -]3 with the phosphoranimine Cl3P=NSiMe3 in CH2Cl2 followed by halogen replacement with sodium (methoxyethoxy)ethoxide. The molecular weights in this system were carefully controlled by variation of the monomer-to-initiator ratios, and the effect of polymer molecular weight on solid ionic conductivity was examined. The third polymer system was designed to examine the effect of complex branching on ionic conductivity. Thus, a highly branched polymer containing five branches from a cyclotriphosphazene pendent side group (with 26 ethyleneoxy units per repeat unit) was synthesized. The conductivity of this polymer in the presence of three different salts 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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Polyphosphazenes with novel architectures: Influence on physical properties and behavior as solid polymer electrolytes

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