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Ketene-Based Route to rigid Cyclobutanediol Monomers for the Replacement of BPA in High Performance Polyesters

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journal contribution
posted on 2012-11-20, 00:00 authored by Daniel J. Burke, Takehiro Kawauchi, Matthew J. Kade, Frank A. Leibfarth, Brenden McDearmon, Martin Wolffs, Paul H. Kierstead, Bongjin Moon, Craig J. Hawker
Recently, polyesters based on the diol monomer 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCBDO) have been shown to exhibit excellent thermal stability, mechanical properties, and optical clarity. In particular, the ability of TMCBDO to replace bisphenol A as a diol monomer in polycarbonates and polyesters has resulted in significant commercial and academic interest in these types of monomers. Herein, we report a versatile synthetic strategy based on the dimerization of ketenes derived from the thermal treatment of Meldrum’s acid for the synthesis of structurally diverse cyclobutanediol (CBDO) monomers. This strategy allows a library of CBDO monomers amenable to standard polyester polymerization procedures to be prepared and the structural diversity of these CBDO monomers provides polymers with tunable physical properties, such as glass transition temperature ranging from 120 to 230 °C. The versatility and modularity of this Meldrum’s acid-based approach to substituted cyclobutanediols, combined with the ease of synthesis, will be important for the further development of high-performance polyester materials that are not based on bisphenol A.