Dispersion Polymerization
Seigou Kawaguchi ( ) 1 · Koichi Ito2
1 Department of Polymer Science and Engineering, Faculty of Engineering,
Yamagata University, 4–3–16 Jonan, 992–8510 Yonezawa, Japan
skawagu@yz.yamagata-u.ac.jp
2 Department of Materials Science, Toyohashi University of Technology,
1–1 Tempaku-cho, 441–8580 Toyohashi, Japan
itoh@tutms.tut.ac.jp
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2 Microsphere Syntheses by Linear and Block Polymer Dispersants . . . . . . . 303
2.1 Functional Microspheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
2.2 Living Dispersion Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . 306
2.3 Microspheres from Non-Vinyl Monomers . . . . . . . . . . . . . . . . . . . . 307
3 Microsphere Syntheses by Reactive Dispersants, Macromonomers, Inimers,
and Transurfs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
4 Particle Size Control in Dispersion (Co-)Polymerization . . . . . . . . . . . . 315
4.1 Theoretical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
4.2 Comparison of Experiment with Theory . . . . . . . . . . . . . . . . . . . . . 319
5 Chain Conformation of Grafted Polymer Chains at the Particle Surface . . . . 321
6 Conclusions and Future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Abstract Dispersion polymerization is an attractive method for producing micron-size
monodisperse polymer particles in a single batch process. Great progress in this field has
been achieved over the past two decades. This article presents an overview of the recent
progress in the preparation of polymeric microspheres via dispersion polymerization in
organic media, focusing on the preparation of novel functional particles, the design of
microspheres using macromonomers, and on understanding mechanisms for the control of
particle size. Examples of functional microspheres obtained by dispersion polymerization
in the presence of linear polymers, block polymers, and macromonomers are tabulated, and
new developments are highlighted. Particle size control in dispersion polymerization in
the presence of macromonomers is discussed, and experimental results for poly(ethylene
oxide)-grafted particles are compared with theoretical expectations for ideal core-shell
particles.
Keywords Functional microsphere · Macromonomer · Block copolymer · Graft copolymer ·
Particle size control
Adv Polym Sci (2005) 175: 299–328
DOI 10.1007/b100118
© Springer-Verlag Berlin Heidelberg 2005

Symbols and Abbreviations
AIBN 2,2¢-azobisisobutyronitrile
AAm acrylamide
ATR attenuated total reflection
BMA n-butyl methacrylate
Boc-AMST boc-p-aminostyrene
CMS chloromethylstyrene
Cs chain transfer constant
D mean separation between PEO anchor points
DSM dynamic swelling method
DVB divinylbenzene
EDMA ethylene dimethacrylate
EG ethylene glycol
ESCA electron spectroscopy
f initiator efficiency
FTIR Fourier transform infrared spectroscopy
GMA glycidyl methacrylate
GTP group transfer polymerization
HEMA 2-hydroxyethyl methacrylate
HLB hydrophobic-lipophilic-balance
HPC hydroxypropylcellulose
HPMA 2-hydroxypropyl methacrylate
[I]o initiator concentration
kd decomposition rate constant
kp propagation rate constant
kt termination rate constant
k2 diffusion-controlled rate constant for coalescence between similar-sized
particles
MD molecular weight of macromonomer
MMA methyl methacrylate
MW molecular weight
Mw weight average molecular weight
N number of particles per liter
n number of chains grafted onto surface
NA Avogadro’s number
NAD nonaqueous dispersion
NIPAM N-isopropyl methacrylate
NMR nuclear magnetic resonance
NVC N-vinyl carbazole
PAA poly(acrylic acid)
PANI polyaniline
PB poly(1,3-butadiene)
PBMA poly(n-butyl methacrylate)
PCL poly(e-caprolactone)
PDMAEMA poly(2-(dimethylamino)ethyl methacrylate
PDMS poly(dimethylsiloxane)
PDVB polydivinylbenezene
PE polyethylene
PEG poly(ethylene glycol)
PEO poly(ethylene oxide)
300 S. Kawaguchi · K. Ito