Radio-frequency plasma polymers containing ionic phosphonate groups. 1. Copolymerization of perfluoroallylphosphonic acid and chlorotrifluoroethylene

Michael J. Danilich, Dominic F Gervasio, Donald J. Burton, Roger E. Marchant

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Radio-frequency plasma polymer and copolymer films, ranging in thickness from 9 to 660 nm, were prepared from perfluoroallylphosphonic acid (PAPA) and chlorotrifluoroethylene (CTFE). ac conductance measurements showed that the apparent conductivity of the films increased from 1.7 to 4.2 mS/cm as the PAPA content of the comonomer feed was increased from 0 to 100%. Cyclic voltammetry in the presence of chloride indicated that the films were anionic and showed that they were strongly adherent to gold electrodes in aqueous media. As the PAPA content of the comonomer feed was increased, the advancing water contact angle of the films decreased from 98.4° to 8.3° and the solid surface tension (γs) of the films increased from 25.4 to 72.5 dyn/cm. High-resolution ESCA and FTIR spectroscopies indicated that increasing the PAPA content of the comonomer feed caused a change in the polymer structure from a highly fluorinated, lightly cross-linked Teflon-like structure to a lightly fluorinated, highly cross-linked structure containing phosphonic acid groups. A mechanism for the formation of the ionic polymer films is proposed in which retention of the phosphonic acid moiety occurs via cleavage of PAPA into fluorocarbon and phosphonate fragments followed by reincorporation of the phosphonic acid into the growing plasma polymer film.

Original languageEnglish (US)
Pages (from-to)5567-5574
Number of pages8
JournalMacromolecules
Volume28
Issue number16
StatePublished - Jan 1 1995
Externally publishedYes

Fingerprint

Organophosphonates
Copolymerization
Polymers
Plasmas
Acids
Polymer films
Fluorocarbons
Polytetrafluoroethylene
Gold
Cyclic voltammetry
Contact angle
Surface tension
Chlorides
Copolymers
chlorotrifluoroethylene
Spectroscopy
Polytetrafluoroethylenes
Electrodes
Water
phosphonic acid

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Radio-frequency plasma polymers containing ionic phosphonate groups. 1. Copolymerization of perfluoroallylphosphonic acid and chlorotrifluoroethylene. / Danilich, Michael J.; Gervasio, Dominic F; Burton, Donald J.; Marchant, Roger E.

In: Macromolecules, Vol. 28, No. 16, 01.01.1995, p. 5567-5574.

Research output: Contribution to journalArticle

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AB - Radio-frequency plasma polymer and copolymer films, ranging in thickness from 9 to 660 nm, were prepared from perfluoroallylphosphonic acid (PAPA) and chlorotrifluoroethylene (CTFE). ac conductance measurements showed that the apparent conductivity of the films increased from 1.7 to 4.2 mS/cm as the PAPA content of the comonomer feed was increased from 0 to 100%. Cyclic voltammetry in the presence of chloride indicated that the films were anionic and showed that they were strongly adherent to gold electrodes in aqueous media. As the PAPA content of the comonomer feed was increased, the advancing water contact angle of the films decreased from 98.4° to 8.3° and the solid surface tension (γs) of the films increased from 25.4 to 72.5 dyn/cm. High-resolution ESCA and FTIR spectroscopies indicated that increasing the PAPA content of the comonomer feed caused a change in the polymer structure from a highly fluorinated, lightly cross-linked Teflon-like structure to a lightly fluorinated, highly cross-linked structure containing phosphonic acid groups. A mechanism for the formation of the ionic polymer films is proposed in which retention of the phosphonic acid moiety occurs via cleavage of PAPA into fluorocarbon and phosphonate fragments followed by reincorporation of the phosphonic acid into the growing plasma polymer film.

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