Free-Radical Polymerization: Kinetics and Mechanism

doi:10.1515/ci.2002.24.5.27

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Free-Radical Polymerization: Kinetics and Mechanism

Published/Copyright: September 1, 2009

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From the journal Chemistry International -- Newsmagazine for IUPAC Volume 24 Issue 5

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Free-Radical Polymerization: Kinetics and Mechanism

M. Buback and A. L. German, editors

Macromolecular Symposium, Vol. 182, pp. 1-303, 2002. Wiley-VCH, 2002, ISBN 3-527-30472-x

Nowadays, many polymerization processes of commercial interest are based on the free-radical principle. The free-radical process is often preferred over other methods of preparation as it is rather robust and less sensitive to trace amounts of impurities. However, until the late 1980s the prevailing opinion was that free-radical polymerization was a mature technique, unable to afford polymers with well-defined structures, and lacking the ability to yield narrow molecular weight distributions and block copolymers.

In 1985, a small group of chemists discussed the possibility of holding a meeting devoted to radical polymerization. Chemists Ken O’Driscoll and Saverio Russo organized such a conference (SML-87) in Santa Margherita Ligure, Italy, in May 1987. It was a great success, demonstrating that there was indeed a renaissance in the radical polymerization field, and it catalyzed an even stronger resurgence immediately afterwards.

In May 1996 the second conference (SML-96) of the same title was held, again in Santa Margherita Ligure, and again arranged by O’Driscoll and Russo. The IUPAC-Sponsored "International Symposium on Free- Radical Polymerization: Kinetics and Mechanism" (SML’01), held in June 2001 in Ciocco, Tuscany, was the third conference in the series, and continued the tradition of holding these meetings in Italy.

SML’01 was attended by 235 scientists from 25 countries, with a good balance between attendees from industry and academia. It is also noteworthy that quite a large number of Ph.D. students, mostly from European countries, attended and actively participated in the scientific program.

During the five-day program, 23 invited main lectures, 11 contributed papers, and 135 posters were presented. Most of the main lectures and some of the short lectures are in this issue of Macromolecular Symposia.

The symposium comprised six major themes:

Fundamentals of Free-Radical Polymerization
Free-Radical Polymerization in Supercritical Fluids
Polymer Characterization
Polymer Reaction Engineering
Controlled Radical Polymerization
Polymerization in Heterogeneous Systems

In looking back, it is striking that not a single paper at SML-87 dealt with "living radicals" (in the current sense of the term), Atom Transfer Radical Polymerization or Reversible Addition Fragmentation Chain. At the second meeting, SML-96, these topics were addressed in only a small number of papers. But at SML’0l, they dominated large sections of the program.

Through this series of three conferences, important lines of development become clearly visible:

Our knowledge of the basic kinetics and mechanisms of free-radical polymerization has increased tremendously over the past years, due to the advent of new powerful experimental techniques like pulsed laser polymerization and advanced mass spectrometry.
The explanations of anomalies in traditional radical polymerization kinetics have been couched in terms that have tended partially to shift from termination towards propagation.
The overwhelming progress in the area of "Controlled (or Living) Radical Polymerization" (CRP), has created a more definable link between polymerization conditions and polymer (micro) structure.
Hand in hand with the rapid developments in the chemistry of CRP and in the understanding of its kinetics and mechanisms, increasing attention is being given to emulsion systems, which will facilitate the commercialization of CRP.

The above advances now offer the opportunity to introduce high degrees of control over physical and chemical properties through the manipulation of molecular weight, polydispersity, intramolecular chemical composition distribution, glass transition temperature, branching and branching distribution, particle morphology in heterogeneous systems, and the incorporation of functional groups. Improved control over the resultant properties will lead to more efficient polymer production and new polymer products.

www.iupac.org/publications/macro/2002/182_preface.html

Published Online: 2009-09-01

Published in Print: 2002-09

Articles in the same Issue

https://doi.org/10.1515/ci.2002.24.5.27