Redox-active polymers by group-transfer polymerization: physical, electrochemical and electronic properties

André Laschewsky, Michael Ward

Research output: Contribution to journalArticle

Abstract

A variety of redox-active polymers and copolymers containing N,N,N′,N′-tetraalkyl-1,4-phenylenediamine were synthesized, preferentially based on methacrylates and sorbates. Group-transfer polymerization proved to be the polymerization method of choice, in order to protect the rather sensitive functional groups. Electrochemical studies indicated that oxidation of the redox-active group generally occurred at low oxidation potentials (∼0.25 V vs. SCE), generating stable poly(radical ions). Structural variation of the polymers did not alter the redox behaviour significantly. Owing to their low oxidation potential, the polymers are easily oxidized, or form charge-transfer complexes with many electron acceptors. Whereas the native polymers are insulators, exhibiting electrical conductivities smaller than 10-12Ω-1cm-1, exposure to iodine yielded materials that absorbed up to 85% iodine (w/w) with conductivities in the range 10-2 to 10-4Ω-1cm-1. The conductivities measured are virtually equal for all polymers studied, being rather insensitive to the detailed polymer structure.

Original languageEnglish (US)
Pages (from-to)146-159
Number of pages14
JournalPolymer
Volume32
Issue number1
DOIs
StatePublished - 1991

Fingerprint

Electrochemical properties
Electronic properties
Polymers
Physical properties
Polymerization
Iodine
Oxidation
Methacrylates
Functional groups
Oxidation-Reduction
Charge transfer
Copolymers
Ions
Electrons

Keywords

  • conductivity
  • cyclic voltammetry
  • group transfer polymerization
  • redox polymers
  • TMPD
  • Wurster's blue

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics

Cite this

Redox-active polymers by group-transfer polymerization : physical, electrochemical and electronic properties. / Laschewsky, André; Ward, Michael.

In: Polymer, Vol. 32, No. 1, 1991, p. 146-159.

Research output: Contribution to journalArticle

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AB - A variety of redox-active polymers and copolymers containing N,N,N′,N′-tetraalkyl-1,4-phenylenediamine were synthesized, preferentially based on methacrylates and sorbates. Group-transfer polymerization proved to be the polymerization method of choice, in order to protect the rather sensitive functional groups. Electrochemical studies indicated that oxidation of the redox-active group generally occurred at low oxidation potentials (∼0.25 V vs. SCE), generating stable poly(radical ions). Structural variation of the polymers did not alter the redox behaviour significantly. Owing to their low oxidation potential, the polymers are easily oxidized, or form charge-transfer complexes with many electron acceptors. Whereas the native polymers are insulators, exhibiting electrical conductivities smaller than 10-12Ω-1cm-1, exposure to iodine yielded materials that absorbed up to 85% iodine (w/w) with conductivities in the range 10-2 to 10-4Ω-1cm-1. The conductivities measured are virtually equal for all polymers studied, being rather insensitive to the detailed polymer structure.

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