Determination of Rate Constants of Free-Ion and Paired-Ion Propagations in the Cationic Polymerization of Styrene by Trifluoromethanesulfonic Acid

Toyoki Kunitake, Kunihide Takarabe

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The propagation step of the cationic polymerization of styrene was studied in detail with the CF3SO3H initiator in dichloroethane at -1 to 30 °C. The apparent rate constant of propagation Kp, app was estimated from the time course of the carbocation (P+) formation and monomer consumption by the combination of stopped-flow spectroscopy and the rapid quenching technique. Then kp, app was separated into the rate constants of the free-ion and paired-ion propagations (kp+ and kp±) on the basis of the dependence of kpfipp on [P+] and of the effect of a common ion salt. The values of kp+ and kp± were (2-30) × 105 M-1 s-1 and (0.4-1.2) X 105 M-1 s-1, respectively, in the temperature range studied. The ratio kp+ / kpα was 6-24, which is much smaller than those observed for the anionic polymerization.

Original languageEnglish
Pages (from-to)1067-1071
Number of pages5
JournalMacromolecules
Volume12
Issue number6
DOIs
Publication statusPublished - Jan 1 1979

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Cationic polymerization
Styrene
Rate constants
Ions
Application programs
Acids
Ethylene Dichlorides
Rapid quenching
Anionic polymerization
Salts
Monomers
Spectroscopy
trifluoromethanesulfonic acid
Temperature

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Determination of Rate Constants of Free-Ion and Paired-Ion Propagations in the Cationic Polymerization of Styrene by Trifluoromethanesulfonic Acid. / Kunitake, Toyoki; Takarabe, Kunihide.

In: Macromolecules, Vol. 12, No. 6, 01.01.1979, p. 1067-1071.

Research output: Contribution to journalArticle

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AB - The propagation step of the cationic polymerization of styrene was studied in detail with the CF3SO3H initiator in dichloroethane at -1 to 30 °C. The apparent rate constant of propagation Kp, app was estimated from the time course of the carbocation (P+) formation and monomer consumption by the combination of stopped-flow spectroscopy and the rapid quenching technique. Then kp, app was separated into the rate constants of the free-ion and paired-ion propagations (kp+ and kp±) on the basis of the dependence of kpfipp on [P+] and of the effect of a common ion salt. The values of kp+ and kp± were (2-30) × 105 M-1 s-1 and (0.4-1.2) X 105 M-1 s-1, respectively, in the temperature range studied. The ratio kp+ / kpα was 6-24, which is much smaller than those observed for the anionic polymerization.

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