Anionic Polymerization. Kinetics, Mechanisms and Synthesis

Publication Date (Print): November 30, 1981 ... DOI: 10.1021/bk-1981-0166 ... A grand jury in Houston indicted Arkema and two of its executives on cri...
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1106 Organometallics, Vol. 1, No. 8, 1982 rhodium catalyst conthing a tris(tertiary phosphine) is described by Meek et al. Other articles involving mainly catalysis studies are on the palladium phosphine catalyzed addition of vinylic groups from vinylic halides to olefins (Heck), hydroformylation using rhodium catalysts (Kastrup, Merola, and Oswald), decarbonylation reactions with rhodium catalysts (Pignolet et al.), and oxidation of tertiary phosphines, ketones, and cyclic alcohols using R&(C0),8 and Re2(CO)locatalyst systems (Roundhill et al.). Perhaps the newest area which sparks an interest is the oxidative addition of water to platinum (Yoshida and Otsuka; Bennett et al.), rhodium, and iridium (James et al.). In addition there were some good review articles on phosphine coordination chemistry not directly involving catalyais such as 31PNMR of solids (Maciel), structural details of p-phosphido compounds (Carty), and some good old favorites such as poly(tertiary phosphines) (King), 31P NMR of platinum coordination compounds (Pidcock), and dinuclear complexes of palladium (Balch) and platinum (Puddephatt et al.) with bis(dipheny1phosphino)methane as a bridging ligand. Overall, the book serves its purpose of providing some excellent reviews of rather timely subject material for researchers interested in phosphine coordination complexes. I thought the ‘catalytic aspects” implied in the title suffers a bit from overstatement, however, since many of the articles were not concerned with catalysis or only remotely so. Only two of the articles originated from industrid laboratories. An appendix gives authors and titles for papers presented at the poster session of the conference. The book contains an index and over IO0 references. Samuel 0. Grim, University of Maryland

Anionic Polymerization. Kinetics, Mechanisms and Synthesis. Edited by J. E. McGrath. ACS Symposium Series No. 166. American Chemical Society, Washington, D.C. 1981. xiii + 592 pages. $45.95. This useful volume contains the papers presented at a symposium held at the March 1980 American Chemical Society meeting. The text documents the state of the art of this important area of polymer technology. Of the 35 papers about a third present new experimental results while the others are critical reviews. Many of the papers contain extensive references, and there is a 12-page index. Readers active in the field will find the book a useful summary of the myriad of syntheses which have been carried out and the current views of the mechanisms postulated for these systems. The reader new to the area will be led to the salient references and learn the investigators active in research. In anionic polymerization the carbanions where monomer enchainment occurs are long-lived, free from termination and

Book Reviews transfer. “Living”systems can thus be prepared under suitable experimental conditions and manipulated further. The macromolecular carbanion can be used to initiate the polymerization of another monomer to form a block copolymer, and the process can be repeated, if desired. Alternately, the unterminated block copolymer can be coupled by a suitable reagent to form a multiblock copolymer. Linear and “star”-shaped block copolymers can be synthesized. Several chapters describe these transformations. These block copolymers have particularly attractive properties as thermoplastic elastomers. The items of commerce are derived from polystyrene endblocks and polydiene center blocks, which are hydrogenated in some of the grades. Anionic polymerizations are of particular utility in the synthesis of special macromolecular structures. Chapters discuss the preparation of mono- and difuntional chain end polymers and macromolecules containing ammonium groups along the chain. The technique yields polymers with narrow molecular weight distributions and offers a route to model networks for physical characterization. Reports of the historical development of the field give a useful perspective. There is much interest in the detailed nature of the polymeric carbanion-counterion species. Various techniques have been used to study the state of aggregation and the stereochemistry of the chain end of the living polystyrene and diene polymers. The presence of ligands such as ethers, crown ethers, and polyamines, for example, N,N,N’N’-tetramethylethylenediamine,can have effects on polydiene structure, the degree of living polymer association, and polymerization kinetics. These aspects are the subject of several papers. While the studies of the polymerization of dienes in hydrocarbon solvents and styrene in aromatic diluents by organolithium reagents receive much attention, other anionic systems are discussed. The anionic polymerization of methacrylates with cesium, sodium,lithium, and magnesium counterions in THF and toluene is the subject of several reports. The anionic polymerization of vinyl pyridine, 1acrylates, lactones, and acrolein with several initiators is discussed. Polystyrylcesium, lithium amides, and cyclic sulfonium zwitterions as initiators are described. The reaction of polymeric carbanions with oxygen and sulfur has been studied, and their use to prepare polymeric azo initiators has also been studied. The book is printed by photo-offset from camera ready typescripts. There is some variation of the type size and quality of the f i i e s from chapter to chapter. In a few of the papers tables and figures while still legible are reproduced faintly. Professor J. E. McGrath is to be commended for organizing the symposium and shepherding this volume to publication. Irving Kuntz, Exxon Chemical Company