Adv Polym Sci (2013) 262: 191–238
DOI: 10.1007/12_2013_248
© Springer-Verlag Berlin Heidelberg 2013
Published online: 6 November 2013
Chain-Growth Condensation Polymerization
for Controlled Synthesis of Polymers
Yoshihiro Ohta and Tsutomu Yokozawa
Abstract Typical condensation polymerization is classified as a step-growth
polymerization, in which the molecular weight of polymer obtained is difficult to
control and the molecular weight distribution theoretically approaches 2 at high
conversion. However, the mechanism of condensation polymerization of some
monomers has been converted from step-growth to chain-growth by means of
activation of the polymer end group by changing substituent effects between the
monomer and the polymer, and activation of the polymer end group by intramolecular transfer to it of the catalyst. In this review, we describe the development of
chain-growth condensation polymerization (CGCP) through the substituent
effect and by catalyst transfer. Furthermore, construction of well-defined polymer
architectures, such as block copolymers, star polymers, and graft copolymers by
utilizing CGCP is also presented.
Keywords Catalyst-transfer Á Chain-growth condensation polymerization Á Living
polymerization Á Polycondensation Á π-Conjugated polymers
Contents
1 Introduction . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . 193
2 Early Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
3 CGCP Through the Substituent Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.1 CGCP Through the Resonance Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.2 CGCP Through the Inductive Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Y. Ohta and T. Yokozawa (*)
Department of Material and Life Chemistry, Kanagawa University, Rokkakubashi,
Kanagawa-ku, Yokohama 221-8686, Japan
e-mail: yokozt01@kanagawa-u.ac.jp
DOI: 10.1007/12_2013_248
© Springer-Verlag Berlin Heidelberg 2013
Published online: 6 November 2013
Chain-Growth Condensation Polymerization
for Controlled Synthesis of Polymers
Yoshihiro Ohta and Tsutomu Yokozawa
Abstract Typical condensation polymerization is classified as a step-growth
polymerization, in which the molecular weight of polymer obtained is difficult to
control and the molecular weight distribution theoretically approaches 2 at high
conversion. However, the mechanism of condensation polymerization of some
monomers has been converted from step-growth to chain-growth by means of
activation of the polymer end group by changing substituent effects between the
monomer and the polymer, and activation of the polymer end group by intramolecular transfer to it of the catalyst. In this review, we describe the development of
chain-growth condensation polymerization (CGCP) through the substituent
effect and by catalyst transfer. Furthermore, construction of well-defined polymer
architectures, such as block copolymers, star polymers, and graft copolymers by
utilizing CGCP is also presented.
Keywords Catalyst-transfer Á Chain-growth condensation polymerization Á Living
polymerization Á Polycondensation Á π-Conjugated polymers
Contents
1 Introduction . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . 193
2 Early Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
3 CGCP Through the Substituent Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.1 CGCP Through the Resonance Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.2 CGCP Through the Inductive Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Y. Ohta and T. Yokozawa (*)
Department of Material and Life Chemistry, Kanagawa University, Rokkakubashi,
Kanagawa-ku, Yokohama 221-8686, Japan
e-mail: yokozt01@kanagawa-u.ac.jp