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 language | English |
|---|---|
| Pages (from-to) | 1067-1071 |
| Number of pages | 5 |
| Journal | Macromolecules |
| Volume | 12 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Jan 1 1979 |
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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 journal › Article
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TY - JOUR
T1 - Determination of Rate Constants of Free-Ion and Paired-Ion Propagations in the Cationic Polymerization of Styrene by Trifluoromethanesulfonic Acid
AU - Kunitake, Toyoki
AU - Takarabe, Kunihide
PY - 1979/1/1
Y1 - 1979/1/1
N2 - 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.
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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U2 - 10.1021/ma60072a011
DO - 10.1021/ma60072a011
M3 - Article
AN - SCOPUS:0042034968
VL - 12
SP - 1067
EP - 1071
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 6
ER -