Adv Polym Sci (2013) 259: 1–50
DOI: 10.1007/12_2012_179
# Springer-Verlag Berlin Heidelberg 2012
Published online: 22 August 2012
Controlled Polymerization in Flow Microreactor
Systems
Aiichiro Nagaki and Jun-ichi Yoshida
Abstract Flow microreactors are expected to make a revolutionary change in
chemical synthesis in various fields of polymer synthesis. In fact, extensive studies
on cationic polymerization, anionic polymerization, radical polymerization, coordination polymerization, polycondensation, and ring-opening polymerization using
flow microreactor systems have opened new possibilities in polymer chemistry and
the polymer industry. This article provides, in a concise form, a current overall
picture of polymerization using flow microreactors.
Keywords Controlled polymerization Á Fast mixing Á Flow Á Microreactor Á
Molecular weight control Á Molecular weight distribution control Á
Residence time control Á Temperature control
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1
Characteristic Features of Flow Microreactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2
Cationic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3
Anionic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4
Radical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.5
Ring-Opening Polymerization Using Flow Microreactor Systems . . . . . . . . . . . . . . . .. . 29
1.6
Polycondensation Using Flow Microreactor Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.7
Ziegler–Natta Polymerization Using Flow Microreactor Systems . . . . . . . . . . . . . . . . . . 33
1.8
Fabrication of Polymeric Structures Inside Microchannels Using Fluid Flow . . . . . 34
1.9
Industrial Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
1.10 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
A. Nagaki and J.-i. Yoshida (*)
Department of Synthetic and Biological Chemistry, Graduate School of Engineering,
Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
e-mail: yoshida@sbchem.kyoto-u.ac.jp
DOI: 10.1007/12_2012_179
# Springer-Verlag Berlin Heidelberg 2012
Published online: 22 August 2012
Controlled Polymerization in Flow Microreactor
Systems
Aiichiro Nagaki and Jun-ichi Yoshida
Abstract Flow microreactors are expected to make a revolutionary change in
chemical synthesis in various fields of polymer synthesis. In fact, extensive studies
on cationic polymerization, anionic polymerization, radical polymerization, coordination polymerization, polycondensation, and ring-opening polymerization using
flow microreactor systems have opened new possibilities in polymer chemistry and
the polymer industry. This article provides, in a concise form, a current overall
picture of polymerization using flow microreactors.
Keywords Controlled polymerization Á Fast mixing Á Flow Á Microreactor Á
Molecular weight control Á Molecular weight distribution control Á
Residence time control Á Temperature control
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1
Characteristic Features of Flow Microreactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2
Cationic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3
Anionic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4
Radical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.5
Ring-Opening Polymerization Using Flow Microreactor Systems . . . . . . . . . . . . . . . .. . 29
1.6
Polycondensation Using Flow Microreactor Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.7
Ziegler–Natta Polymerization Using Flow Microreactor Systems . . . . . . . . . . . . . . . . . . 33
1.8
Fabrication of Polymeric Structures Inside Microchannels Using Fluid Flow . . . . . 34
1.9
Industrial Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
1.10 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
A. Nagaki and J.-i. Yoshida (*)
Department of Synthetic and Biological Chemistry, Graduate School of Engineering,
Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan
e-mail: yoshida@sbchem.kyoto-u.ac.jp