By Krzysztof Matyjaszewski, Axel H. E. Müller
Written by way of a hugely prestigious and an expert group of best scientists within the box, this e-book presents 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 buildings of Block Copolymers * commercial purposes whereas many of the fabric is predicated on chapters taken from the four-volume paintings "Macromolecular Engineering", it's thoroughly up to date and rewritten to mirror the point of interest of this monograph. Must-have wisdom for polymer and natural chemists, plastics technologists, fabrics scientists and chemical engineers.
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Extra 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.
Nonpolar ligands with high electron density, such as durene (tetramethylstyrene) or tetraphenylethylene, also affect the aggregation equilibrium and lead to an increase in the rate of polymerization followed by a decrease at higher concentrations. This is explained in terms of the formation of 1 : 1 and 2 : 1 π-complexes with the living chain ends . Lewis Acids (µ-Ligands): Retarded Anionic Polymerization Lewis acids such as alkyl aluminum, alkyl zinc, alkyl magnesium, and lithium alkoxides form mixed aggregates with living chain ends of carbanions and signiﬁcantly stabilize the ion pairs.
In general, the coordination of ligands with enolate ion pairs enhances the rate of interconversion between aggregated and nonaggregated chain ends, thereby altering the kinetics of propagation and to some extent suppressing the side reactions [174, 190, 210–226]. Wang et al.  have classiﬁed the coordination of ligands with enolate ion pairs into the following types: 1. σ -type coordination with Lewis bases such as crown ethers [212, 213], cryptands , or tertiary amines [216–219]; 2. µ-type coordination with Lewis acids such as alkali alkoxides [228–231], lithium halides [197, 211, 232], lithium perchlorate [215, 233], aluminum alkyls [221–224], boron alkyls  and zinc alkyls ; 3.