3 years ago

Cross-metathesis functionalized exo-olefin derivatives of lactide

Cross-metathesis functionalized exo-olefin derivatives of lactide
Michael P. Shaver, Fern Sinclair
Poly(lactic acid) is at the forefront of research into alternative replacements to fossil fuel derived polymers, yet preparation of derivatives of this key biodegradable polymer remain challenging. This article explores the use of two derivatives of lactide, each of which features an exocyclic olefin, and their pre-polymerization modification by olefin cross-metathesis. Methylenation of lactide with Tebbe's reagent generates a novel 5-methylenated lactide monomer, (3S,6S)-3,6-dimethyl-5-methylene-1,4-dioxan-2-one, complementing the previously reported 3-methylenated (6S)-3-methylene-6-methyl-1,4-dioxan-2,5-dione. While ring-opening of each monomer is not productive, olefin cross-metathesis can be used to functionalize each of the exocyclic olefins to produce a family of monomers. The ring-opening polymerization of these new monomers, and their hydrogenated congeners, is facilitated by organo- and Lewis-acid catalysts. Together, they offer a new strategy for derivatizing and altering the properties of poly(lactic acid). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018. Poly(lactic acid) is a sustainable alternative to many petroleum derived polymers, but chemical modification of its parent monomer lactide is challenging. This article details the synthesis and reactivity of two exocyclic olefin derivatives of the lactide monomer, detailing its sensitivity to various non-productive ring-opening reactions. The article also showcases the use of olefin cross-metathesis as a tool to functionalize these lactide derivatives, including preparation of asymmetric diesters that can be polymerized to prepare aliphatic polyesters with modified thermal properties.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/pola.28947

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