Rate coef®cients of free-radical polymerization deduced from
pulsed laser experiments
Sabine Beuermann, Michael Buback
*
Institute of Physical Chemistry, Georg-August-University Go
È
ttingen, Tammannstrasse 6, D-37077 Go
È
ttingen, Germany
Received 25March 2001; revised 30 June 2001; accepted 9 July 2001
Abstract
Pulsed laser techniques have enormously improved the quality by which rate coef®cients of individual steps in
free-radical polymerization may be measured. Pulsed laser initiated polymerization (PLP) in conjunction with
size-exclusion chromatography (SEC) yields the propagation rate coef®cient, k
p
. The PLP-SEC-technique has been
applied to a wide variety of homopolymerizations and copolymerizations, either in bulk or in solution. In addition
to reporting kinetic data, experimental details of PLP, of SEC, and of the limitations associated with the accurate
determination of the MWD are discussed. The single pulse (SP)-PLP method, which combines PLP with time-
resolved NIR spectroscopy, allows for a very detailed insight into the termination rate coef®cient, k
t
, for homo- and
copolymerizations. k
t
data are reported as a function of temperature, pressure, monomer conversion, solvent
concentration, and partly also of chain length. This review considers literature up to December 2000. q 2002
Elsevier Science Ltd. All rights reserved.
Keywords: Pulsed laser induced polymerization; Homopolymerization; Copolymerization; Propagation rate coef®cients;
Termination rate coef®cients
Contents
1. Introduction .................................................................. 192
2. PLP±SEC experiments directed toward the determination of propagation rate coef®cients ......... 195
2.1. Experimental considerations .................................................. 195
2.1.1. Pulsed-laser initiated polymerizations ...................................... 195
2.1.2. Size-exclusion chromatographic analysis of polymer from PLP ................... 198
2.2. Propagation rate coef®cients in homopolymerizations ................................ 201
2.2.1. Styrene and substituted styrenes .......................................... 201
2.2.2. Methacrylic acid esters ................................................ 203
2.2.3. Acrylic acid esters .................................................... 204
Prog. Polym. Sci. 27 (2002) 191±254
0079-6700/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0079-6700(01)00049-1
www.elsevier.com/locate/ppolysci
* Corresponding author.
E-mail addresses: mbuback@gwdg.de (M. Buback), sbeuerm@gwdg.de (S. Beuermann).