For many years, olefin metathesis has been a central topic of industrial and academic research because of its great synthetic utility. The employed initiators cover a wide range of compounds, from simple transition-metal salts to highly sophisticated and well-defined alkylidene complexes. Currently, ruthenium-based catalysts are at the center of attention because of their remarkable tolerance toward oxygen, moisture, and numerous functionalities. This article focuses on recent developments in the field of ring-opening metathesis polymerization using ruthenium-based catalysts. ruthenium-based initiators and their applications to the preparation of advanced polymeric materials are briefly reviewed.
Especially since the turn of the century, metathesis has become one of the most attractive developments in organic synthesis, particularly for the synthesis of polymers. A major reason for this has been the discovery of a wide range of new catalysts. The development of Ru‐based catalysts has opened up new avenues of synthesis due to their functional group tolerance. It this review, homogeneous, heterogeneous, and immobilized catalysts are described. It is shown that
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C NMR spectroscopy is a valuable tool for the evaluation of the microstructure of polymers synthesized from bicyclic monomers, such as norbornene and its derivatives. Acyclic diene metathesis polymerization (ADMET) is also addressed. Indeed, the intermolecular reaction of α,ω‐dienes yielding ethene has become increasingly important over the past 10 years. Degradation of polymers via cross‐metathesis of unsaturated polymers with olefins can be used for analytical purposes and for the design of tailor‐made polymers. This article also discuses about the growing interest in terminally functionalized polymers and oligomers. Synthetic strategies based on metathesis reactions are discussed in some detail. The section titled Macromolecular Engineering summarizes trends in polymer chemistry involving metathesis polymerization combined with other chain growth mechanisms to synthesize block and graft copolymers with novel molecular structures. In addition, this article details synthetic routes to advanced materials based on ring‐opening metathesis polymerization (ROMP). Furthermore, some of the industrial polymers synthesized via ROMP are introduced and discussed in some detail. This review concludes with a discussion on mono‐, bi‐, and tri‐cyclic monomers and their ring‐opening polymerizations.
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