Poly(phosphazene-ethylene oxide) di- and triblock copolymers as solid polymer electrolytes

Harry R. Allcock; Robbyn Prange; Thomas J. Hartle

doi:10.1021/ma001851u

Poly(phosphazene-ethylene oxide) di- and triblock copolymers as solid polymer electrolytes

Harry R. Allcock, Robbyn Prange, Thomas J. Hartle

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67 Scopus citations

Abstract

The synthesis of polyphosphazene-co-poly(ethylene oxide) block copolymers with well-defined molecular weights has been accomplished via end-functionalized polymer intermediates. Mono-and diamine-terminated poly(ethylene oxides) (PEO = (CH₂CH₂O)_n-CH₂CH₂-) were used to produce polymer-based phosphoranimines, CH₃O-(CH₂CH₂O)_n-CH₂ CH₂-NH(CF₃CH₂O)₂ P=NSiMe₃ and Me₃SiN=P(OCH₂-CF₃) NH-(CH₂CH₂O)_n-CH₂CH₂ -NH(CF₃CH₂O) ₂P=NSiMe₃. These were then converted to macroinitiators via reaction with PCl₅ to produce CH₃O-PEO-NH[(CF₃CH₂O)₂ P=NPCl₃]⁺[PCl₆]^- and [Cl₃PN=P(OCH₂-CF₃) NH-PEO-NH[(CF₃CH₂O)₂ P=NPCl₃]²⁺[PCl₆]₂^-, respectively. These macroinitiators were used to polymerize Cl₃P=NSiMe₃ in a living manner to produce diblock copolymers of polyphosphazenes with poly(ethylene oxide) or triblock copolymers with poly(ethylene oxide) blocks flanked by polyphosphazene Components. In addition, the monophosphoranimine-terminated PEO was employed as a terminator in the living, cationic polymerization of Cl₃P=NSiMe₃ to produce triblock copolymers with a polyphosphazene block flanked by two poly(ethylene oxide) blocks. Polymers for use as solid-ionic conduction media or hydrogels were produced by nucleophilic replacement of the chlorine atoms along the polyphosphazene segments by methoxyethoxyethoxy units. The ionic conductivities of these materials, after complexation with varying ratios of lithium triflate, ranged from 7.6 × 10^-6 to 1.0 × 10^-4 S cm^-1 for a temperature range of 20-80 °C.

Original language	English (US)
Pages (from-to)	5463-5470
Number of pages	8
Journal	Macromolecules
Volume	34
Issue number	16
DOIs	https://doi.org/10.1021/ma001851u
State	Published - Jul 31 2001

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/ma001851u

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@article{f152b5c78cf240f9b1264737cad8dbd0,

title = "Poly(phosphazene-ethylene oxide) di- and triblock copolymers as solid polymer electrolytes",

abstract = "The synthesis of polyphosphazene-co-poly(ethylene oxide) block copolymers with well-defined molecular weights has been accomplished via end-functionalized polymer intermediates. Mono-and diamine-terminated poly(ethylene oxides) (PEO = (CH2CH2O)n-CH2CH2-) were used to produce polymer-based phosphoranimines, CH3O-(CH2CH2O)n-CH2 CH2-NH(CF3CH2O)2 P=NSiMe3 and Me3SiN=P(OCH2-CF3) NH-(CH2CH2O)n-CH2CH2 -NH(CF3CH2O) 2P=NSiMe3. These were then converted to macroinitiators via reaction with PCl5 to produce CH3O-PEO-NH[(CF3CH2O)2 P=NPCl3]+[PCl6]- and [Cl3PN=P(OCH2-CF3) NH-PEO-NH[(CF3CH2O)2 P=NPCl3]2+[PCl6]2-, respectively. These macroinitiators were used to polymerize Cl3P=NSiMe3 in a living manner to produce diblock copolymers of polyphosphazenes with poly(ethylene oxide) or triblock copolymers with poly(ethylene oxide) blocks flanked by polyphosphazene Components. In addition, the monophosphoranimine-terminated PEO was employed as a terminator in the living, cationic polymerization of Cl3P=NSiMe3 to produce triblock copolymers with a polyphosphazene block flanked by two poly(ethylene oxide) blocks. Polymers for use as solid-ionic conduction media or hydrogels were produced by nucleophilic replacement of the chlorine atoms along the polyphosphazene segments by methoxyethoxyethoxy units. The ionic conductivities of these materials, after complexation with varying ratios of lithium triflate, ranged from 7.6 × 10-6 to 1.0 × 10-4 S cm-1 for a temperature range of 20-80 °C.",

author = "Allcock, {Harry R.} and Robbyn Prange and Hartle, {Thomas J.}",

year = "2001",

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doi = "10.1021/ma001851u",

language = "English (US)",

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TY - JOUR

T1 - Poly(phosphazene-ethylene oxide) di- and triblock copolymers as solid polymer electrolytes

AU - Allcock, Harry R.

AU - Prange, Robbyn

AU - Hartle, Thomas J.

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Y1 - 2001/7/31

N2 - The synthesis of polyphosphazene-co-poly(ethylene oxide) block copolymers with well-defined molecular weights has been accomplished via end-functionalized polymer intermediates. Mono-and diamine-terminated poly(ethylene oxides) (PEO = (CH2CH2O)n-CH2CH2-) were used to produce polymer-based phosphoranimines, CH3O-(CH2CH2O)n-CH2 CH2-NH(CF3CH2O)2 P=NSiMe3 and Me3SiN=P(OCH2-CF3) NH-(CH2CH2O)n-CH2CH2 -NH(CF3CH2O) 2P=NSiMe3. These were then converted to macroinitiators via reaction with PCl5 to produce CH3O-PEO-NH[(CF3CH2O)2 P=NPCl3]+[PCl6]- and [Cl3PN=P(OCH2-CF3) NH-PEO-NH[(CF3CH2O)2 P=NPCl3]2+[PCl6]2-, respectively. These macroinitiators were used to polymerize Cl3P=NSiMe3 in a living manner to produce diblock copolymers of polyphosphazenes with poly(ethylene oxide) or triblock copolymers with poly(ethylene oxide) blocks flanked by polyphosphazene Components. In addition, the monophosphoranimine-terminated PEO was employed as a terminator in the living, cationic polymerization of Cl3P=NSiMe3 to produce triblock copolymers with a polyphosphazene block flanked by two poly(ethylene oxide) blocks. Polymers for use as solid-ionic conduction media or hydrogels were produced by nucleophilic replacement of the chlorine atoms along the polyphosphazene segments by methoxyethoxyethoxy units. The ionic conductivities of these materials, after complexation with varying ratios of lithium triflate, ranged from 7.6 × 10-6 to 1.0 × 10-4 S cm-1 for a temperature range of 20-80 °C.

AB - The synthesis of polyphosphazene-co-poly(ethylene oxide) block copolymers with well-defined molecular weights has been accomplished via end-functionalized polymer intermediates. Mono-and diamine-terminated poly(ethylene oxides) (PEO = (CH2CH2O)n-CH2CH2-) were used to produce polymer-based phosphoranimines, CH3O-(CH2CH2O)n-CH2 CH2-NH(CF3CH2O)2 P=NSiMe3 and Me3SiN=P(OCH2-CF3) NH-(CH2CH2O)n-CH2CH2 -NH(CF3CH2O) 2P=NSiMe3. These were then converted to macroinitiators via reaction with PCl5 to produce CH3O-PEO-NH[(CF3CH2O)2 P=NPCl3]+[PCl6]- and [Cl3PN=P(OCH2-CF3) NH-PEO-NH[(CF3CH2O)2 P=NPCl3]2+[PCl6]2-, respectively. These macroinitiators were used to polymerize Cl3P=NSiMe3 in a living manner to produce diblock copolymers of polyphosphazenes with poly(ethylene oxide) or triblock copolymers with poly(ethylene oxide) blocks flanked by polyphosphazene Components. In addition, the monophosphoranimine-terminated PEO was employed as a terminator in the living, cationic polymerization of Cl3P=NSiMe3 to produce triblock copolymers with a polyphosphazene block flanked by two poly(ethylene oxide) blocks. Polymers for use as solid-ionic conduction media or hydrogels were produced by nucleophilic replacement of the chlorine atoms along the polyphosphazene segments by methoxyethoxyethoxy units. The ionic conductivities of these materials, after complexation with varying ratios of lithium triflate, ranged from 7.6 × 10-6 to 1.0 × 10-4 S cm-1 for a temperature range of 20-80 °C.

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JO - Macromolecules

JF - Macromolecules

IS - 16

ER -

Poly(phosphazene-ethylene oxide) di- and triblock copolymers as solid polymer electrolytes

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