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Transfer and propagation reactions in free‐radical copolymerization
Author(s) -
Davis Thomas P.,
Heuts Johan P.A.,
BarnerKowollik Christopher,
Harrisson Simon,
Morrison David A.,
Yee Lachlan H.,
KapfensteinDoak Heidi M.,
Coote Michelle L.
Publication year - 2002
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/1521-3900(200206)182:1<131::aid-masy131>3.0.co;2-c
Subject(s) - copolymer , polar , chemistry , selectivity , solvent , solvent effects , polymer chemistry , ring (chemistry) , materials science , polymer , organic chemistry , catalysis , physics , astronomy
The contribution of entropic factors to the penultimate unit effect in free‐radical copolymerizations is discussed and exemplified. In addition, significant penultimate unit effects on radical selectivity in transfer reactions are demonstrated and are shown to have a significant polar component. Further, ring‐opening copolymerization studies are presented and describe surprising results that seem to originate from strong solvent effects in copolymerization. These results could not have been predicted with current knowledge, prior to the experiment. The present contribution demonstrates in detail that radical reactions are highly complex and there are significant dangers and drawbacks in employing simplified kinetic models when in search of fundamental understanding.