By Krzysztof Matyjaszewski, Axel H. E. Müller
Written by way of a hugely prestigious and an expert crew of most sensible scientists within the box, this ebook offers an summary of the present prestige of controlled/living polymerization, combining the bogus, mechanistic and application-oriented facets. From the contents: * Anionic Vinyl Polymerization * Carbocationic Polymerization * Radical Polymerization * Coordinative Polymerization of Olefins * Ring-Opening Polymerization of Heterocycles * Ring-Opening Metathesis Polymerization * Macromolecular Architectures * complicated sensible Macromolecules * Synthesis of Block and Graft Copolymers * Bulk and resolution constructions of Block Copolymers * business functions whereas a few of the fabric is predicated on chapters taken from the four-volume paintings "Macromolecular Engineering", it truly is thoroughly up to date and rewritten to mirror the focal point of this monograph. Must-have wisdom for polymer and natural chemists, plastics technologists, fabrics scientists and chemical engineers.
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Additional resources for Controlled and Living Polymerizations: From Mechanisms to Applications
The mole fractions of free ions and ion pairs participating in the propagation are α and 1 − α, respectively [75, 83–86]. 3 Dependence of the experimental rate constant of the anionic polymerization of styrene, kp,exp , in THF with sodium counterion on the concentration of active chain ends, [P∗ ]. Circles denote experiments in the presence of sodium tetraphenylborate . 4 Participation of free ions in the anionic polymerization of styrene in THF. 8) √ Thus, the slope of a plot of kp,exp vs.
The polarity of the solvent in which anion is prepared and used, the intermolecular ionic interactions, and the size of metallic counterion all dictate the characteristics of a particular carbanion. The stabilization of anions through intermolecular interaction leads to the formation of different associated states called aggregates. The nature of anion aggregation is governed by various factors such as the charge density of anion, interionic distances, the dielectric constant, and the donating properties of the solvent .
Glusker et al. and Schulz et al. suggested that the polymerization is controlled due to the absence of intramolecular solvation of the counterion. In highly solvating media such as DME, the counterion is externally solvated with solvent coordination, thereby suppressing intramolecular termination via backbiting reaction at low temperature [155, 156, 189, 193]. Their results suggested that only one kind of active species is involved in the MMA polymerization, which they assigned as a peripherally solvated contact ion pair.