Determination of the Rate Constants of the Elementary Steps in the Cationic Polymerization of Styrene by Trifluoromethanesulfonic Acid

Toyoki Kunitake, Kunihide Takarabe

研究成果: ジャーナルへの寄稿記事

34 引用 (Scopus)

抄録

The cationic polymerization of styrene initiated by CF3S03H was investigated in 1, 2-dichloroethane at -1 to 30 0C by the stopped flow/rapid scan spectroscopy which was combined with the rapid quenching technique. The rate constants of the elementary steps, initiation (fe), propagation (kp), spontaneous transfer and termination (kt), and transfer to monomer (ktm), were determined at four temperatures on the basis of the time courses of the cation formation, monomer consumption, and molecular weight of the quenched polymer. The kp value varied from 5 × 104 to 2 × 105 M-1 s'1 in the temperature range studied, and kv was 100-300 s'1. The lifetime of the propagating species ranged from 5 to 100 ms. (n-Bu)4N+CF3SO3 was added as a common ion salt, but its influence on the rate constants was small. The activation energy as determined from the Arrhenius plots was 7 and 15 kcal/mol for the kp and km processes, respectively. The transfer constants ktm/kp and kt/kp were close to 0.01 at the 0-30 °C range, in agreement with those reported for the H2SO4.

元の言語英語
ページ(範囲)1061-1067
ページ数7
ジャーナルMacromolecules
12
発行部数6
DOI
出版物ステータス出版済み - 1 1 1979

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Cationic polymerization
Styrene
Rate constants
Monomers
Acids
Rapid quenching
Arrhenius plots
Cations
Polymers
Activation energy
Salts
Positive ions
Molecular weight
Spectroscopy
Ions
Temperature
trifluoromethanesulfonic acid

All Science Journal Classification (ASJC) codes

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

これを引用

Determination of the Rate Constants of the Elementary Steps in the Cationic Polymerization of Styrene by Trifluoromethanesulfonic Acid. / Kunitake, Toyoki; Takarabe, Kunihide.

:: Macromolecules, 巻 12, 番号 6, 01.01.1979, p. 1061-1067.

研究成果: ジャーナルへの寄稿記事

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abstract = "The cationic polymerization of styrene initiated by CF3S03H was investigated in 1, 2-dichloroethane at -1 to 30 0C by the stopped flow/rapid scan spectroscopy which was combined with the rapid quenching technique. The rate constants of the elementary steps, initiation (fe), propagation (kp), spontaneous transfer and termination (kt), and transfer to monomer (ktm), were determined at four temperatures on the basis of the time courses of the cation formation, monomer consumption, and molecular weight of the quenched polymer. The kp value varied from 5 × 104 to 2 × 105 M-1 s'1 in the temperature range studied, and kv was 100-300 s'1. The lifetime of the propagating species ranged from 5 to 100 ms. (n-Bu)4N+CF3SO3 was added as a common ion salt, but its influence on the rate constants was small. The activation energy as determined from the Arrhenius plots was 7 and 15 kcal/mol for the kp and km processes, respectively. The transfer constants ktm/kp and kt/kp were close to 0.01 at the 0-30 °C range, in agreement with those reported for the H2SO4.",
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N2 - The cationic polymerization of styrene initiated by CF3S03H was investigated in 1, 2-dichloroethane at -1 to 30 0C by the stopped flow/rapid scan spectroscopy which was combined with the rapid quenching technique. The rate constants of the elementary steps, initiation (fe), propagation (kp), spontaneous transfer and termination (kt), and transfer to monomer (ktm), were determined at four temperatures on the basis of the time courses of the cation formation, monomer consumption, and molecular weight of the quenched polymer. The kp value varied from 5 × 104 to 2 × 105 M-1 s'1 in the temperature range studied, and kv was 100-300 s'1. The lifetime of the propagating species ranged from 5 to 100 ms. (n-Bu)4N+CF3SO3 was added as a common ion salt, but its influence on the rate constants was small. The activation energy as determined from the Arrhenius plots was 7 and 15 kcal/mol for the kp and km processes, respectively. The transfer constants ktm/kp and kt/kp were close to 0.01 at the 0-30 °C range, in agreement with those reported for the H2SO4.

AB - The cationic polymerization of styrene initiated by CF3S03H was investigated in 1, 2-dichloroethane at -1 to 30 0C by the stopped flow/rapid scan spectroscopy which was combined with the rapid quenching technique. The rate constants of the elementary steps, initiation (fe), propagation (kp), spontaneous transfer and termination (kt), and transfer to monomer (ktm), were determined at four temperatures on the basis of the time courses of the cation formation, monomer consumption, and molecular weight of the quenched polymer. The kp value varied from 5 × 104 to 2 × 105 M-1 s'1 in the temperature range studied, and kv was 100-300 s'1. The lifetime of the propagating species ranged from 5 to 100 ms. (n-Bu)4N+CF3SO3 was added as a common ion salt, but its influence on the rate constants was small. The activation energy as determined from the Arrhenius plots was 7 and 15 kcal/mol for the kp and km processes, respectively. The transfer constants ktm/kp and kt/kp were close to 0.01 at the 0-30 °C range, in agreement with those reported for the H2SO4.

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