The emerging utility of ketenes in polymer chemistry

Abstract

The continued evolution of functional materials that contribute to pressing societal challenges requires the development of powerful synthetic methodologies in polymer systems. Since their discovery by Staudinger in the early 20th century, the unique chemistry of ketenes have fascinated synthetic chemists and been the driver of revolutionary applications in photolithography, medicinal chemistry, and commodity materials. The versatile chemistry of ketenes, specifically their ability to act as an electrophile and/or undergo cycloaddition reactions, has recently been shown to provide a powerful platform for the design of next-generation materials. This Highlight focuses on the history of ketenes in materials science and their recent renaissance in polymer chemistry, with specific focus being given to methodologies that provide reliable access to this important functional group in polymer systems.

Preparation of Meldrum's acid‐functionalized polyimides exhibiting organo‐soluble, reactive, self‐crosslinkable, and colorless features

“…31 Ketene has been widely utilized in polymer chemistry for polymer synthesis and functionalization. 32 The self-addition dimerization reaction of ketene groups also contributes to crosslinking polymer chains. [33][34][35][36] The synthesis route of MA-functionalized PIs needs a MA-containing diamine compound, MADA in this work, as a monomer.…”

Revisiting thiol‐yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation

“…This polymer was successfully functionalized with both 1‐octanethiol 20 and the more complex catechol derivative CatSH 19 (Fig. ) that has been shown to provide polymers with strong adhesion under a variety of environments …”

High Molecular Weight Polyester Obtained by Polymerization of Dimethylketene Using Metallocene Initiators: A Step toward Ziegler–Natta Supporting Application in Non‐Olefin Systems

“…Ketenes are highly reactive molecules derivated from carboxylic acids, which contain two consecutive double bonds (CCO) . The existence of ketenes has been established more than 100 years ago, since the first diphenylketene (Ph 2 CCO) was synthesized and isolated by Staudinger in 1905 .…”