1 School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070; 2 State Key Laboratory of Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070
Abstract: Ring-opening metathesis polymerization (ROMP) of cyclic olefins, a well-established reaction, is one of the most effective means to transform carbon-carbon double bonds and has been widely used in polymer science and organic chemistry. ROMP of cyclic olefins occurs in the presence of a metal carbene catalyst which breaks the carbon-carbon double bonds of the cyclic olefins and connects them into new unsaturated polymers. The research over the cyclic olefins metathesis polymerization was initiated in the 1950s, focusing originally on the catalytic polymerization of cyclic olefins using Ziegler-Natta catalytic systems consisting of transition metal complexes mainly based on Ti, Re, W, Mo, etc. Since the middle of the 1980s, the investigations were concentrated on the polymerization mechanism and alkylidene or carbene catalysts. With the establishment of well-defined, stable and efficient catalysts, the researchers’ concern has been turned to new applications of cycloolefin polymers, and also to developing new cycloolefin ROMP monomers. For the ROMP reaction, norbornene and its derivatives have been studied extensively since they are highly reactive, easily accessible and relatively low-cost. Besides the expansion of the monomer species available for ROMP, continuous research endeavors have been made to enhance the ROMP resultant polymers’ performance and application potential, mainly from the aspects of the steric hindrance, chemical configuration, pendant polarities of norbornene-based monomers, and the copolymerization of other cyclic olefins or norbornene-based monomers, as well as conjunction with other polymerization methods. The ROMP of norbornene and its derivatives also made certain advances in the fields of flame retardancy, ion exchange or proton exchange membranes, nanomaterials, biomedical materials and so on, in which flame retardant materials made from norbornene or norbornene derivatives have long been researched and broadly achieved industrialization. In the field of exchange membranes, researchers concentrate on applying norbornene-based polymer membranes to fuel cell due to their thermal stability, acid and alkali resistance, and electrical conductivity. Nanomaterials is one of the most popular research fields in recent years, and nano-metal/polymer composites and magnetic polymer nanocomposites have realized tentative application. The biomedical materials especially drug delivery systems which involve norbornene derivatives have displayed impressive potential, though the industrialization and commercialization still deserve further exploration. Additionally, the norbornene-derivative-based graft polymers, block polymers, liquid crystal polymers, and conductive polymers have also drawn researchers’ attention. We herein briefly describe the reaction mechanism of ROMP with norbornene and its derivatives as monomer, as well as the ROMP catalysts’ multistage development, i.e. multi-component catalytic systems, molybdenum- or tungsten-based catalytic systems, and ruthenium-based catalytic systems. Moreover, the paper mainly focuses on the recent research progress of ROMP process and products with respect to the norbornene species in the above mentioned fields, and ends with a prospective discussion over the expected new directions of this emerging research topic.
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2018, Vol. 32 
