Quantitative comparison of theory and experiment on living radical polymerization kinetics. 1. Nitroxide-mediated polymerization

Chiaki Yoshikawa; Atsushi Goto; Takeshi Fukuda

doi:10.1021/ma012203t

Quantitative comparison of theory and experiment on living radical polymerization kinetics. 1. Nitroxide-mediated polymerization

Chiaki Yoshikawa, Atsushi Goto, Takeshi Fukuda^*

^*Corresponding author for this work

Kyoto University

Research output: Contribution to journal › Article › peer-review

35 Citations (Scopus)

Abstract

The kinetic theories on the polymerization rate and polydispersity for the persistent radical-mediated living radical polymerization were quantitatively tested by experiments for the bulk polymerization of styrene with PS-DEPN with or without BPO at 80°C, where PS is polystyrene, DEPN is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, and BPO is benzoyl peroxide. For the BPO-free system, experiments agreed with the theories on an absolute scale, showing a 2/3-order time dependence of conversion index and a 3/8k_d-dependent time evolution of polydispersity index, where k_d is the dissociation rate constant. It was also experimentally demonstrated for the first time that the conventional initiation can not only increase the conversion but also lower the polydispersity at a given polymerization time t (at least when t is small), as was predicted by the theories.

Original language	English
Pages (from-to)	5801-5807
Number of pages	7
Journal	Macromolecules
Volume	35
Issue number	15
DOIs	https://doi.org/10.1021/ma012203t
Publication status	Published - Jul 16 2002
Externally published	Yes

ASJC Scopus Subject Areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Quantitative comparison of theory and experiment on living radical polymerization kinetics. 1. Nitroxide-mediated polymerization",

abstract = "The kinetic theories on the polymerization rate and polydispersity for the persistent radical-mediated living radical polymerization were quantitatively tested by experiments for the bulk polymerization of styrene with PS-DEPN with or without BPO at 80°C, where PS is polystyrene, DEPN is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, and BPO is benzoyl peroxide. For the BPO-free system, experiments agreed with the theories on an absolute scale, showing a 2/3-order time dependence of conversion index and a 3/8kd-dependent time evolution of polydispersity index, where kd is the dissociation rate constant. It was also experimentally demonstrated for the first time that the conventional initiation can not only increase the conversion but also lower the polydispersity at a given polymerization time t (at least when t is small), as was predicted by the theories.",

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T1 - Quantitative comparison of theory and experiment on living radical polymerization kinetics. 1. Nitroxide-mediated polymerization

AU - Yoshikawa, Chiaki

AU - Goto, Atsushi

AU - Fukuda, Takeshi

PY - 2002/7/16

Y1 - 2002/7/16

N2 - The kinetic theories on the polymerization rate and polydispersity for the persistent radical-mediated living radical polymerization were quantitatively tested by experiments for the bulk polymerization of styrene with PS-DEPN with or without BPO at 80°C, where PS is polystyrene, DEPN is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, and BPO is benzoyl peroxide. For the BPO-free system, experiments agreed with the theories on an absolute scale, showing a 2/3-order time dependence of conversion index and a 3/8kd-dependent time evolution of polydispersity index, where kd is the dissociation rate constant. It was also experimentally demonstrated for the first time that the conventional initiation can not only increase the conversion but also lower the polydispersity at a given polymerization time t (at least when t is small), as was predicted by the theories.

AB - The kinetic theories on the polymerization rate and polydispersity for the persistent radical-mediated living radical polymerization were quantitatively tested by experiments for the bulk polymerization of styrene with PS-DEPN with or without BPO at 80°C, where PS is polystyrene, DEPN is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, and BPO is benzoyl peroxide. For the BPO-free system, experiments agreed with the theories on an absolute scale, showing a 2/3-order time dependence of conversion index and a 3/8kd-dependent time evolution of polydispersity index, where kd is the dissociation rate constant. It was also experimentally demonstrated for the first time that the conventional initiation can not only increase the conversion but also lower the polydispersity at a given polymerization time t (at least when t is small), as was predicted by the theories.

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Quantitative comparison of theory and experiment on living radical polymerization kinetics. 1. Nitroxide-mediated polymerization

Abstract

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