title: Scalable production of mechanically tunable block polymers from sugar.
abstract: Development of sustainable and biodegradable materials is essential for future growth of the chemical industry. For a renewable product to be commercially competitive, it must be economically viable on an industrial scale and possess properties akin or superior to existing petroleum-derived analogs. Few biobased polymers have met this formidable challenge. To address this challenge, we describe an efficient biobased route to the branched lactone, β-methyl-δ-valerolactone (βMδVL), which can be transformed into a rubbery (i.e., low glass transition temperature) polymer. We further demonstrate that block copolymerization of βMδVL and lactide leads to a new class of high-performance polyesters with tunable mechanical properties. Key features of this work include the creation of a total biosynthetic route to produce βMδVL, an efficient semisynthetic approach that employs high-yielding chemical reactions to transform mevalonate to βMδVL, and the use of controlled polymerization techniques to produce well-defined PLA-PβMδVL-PLA triblock polymers, where PLA stands for poly(lactide). This comprehensive strategy offers an economically viable approach to sustainable plastics and elastomers for a broad range of applications.
authors.affiliation: Departments of Chemical Engineering and Materials Science and.
authors.forename: Mingyong
authors.initials: M
authors.lastname: Xiong
authors.affiliation: Chemistry, University of Minnesota, Minneapolis, MN 55455-0431.
authors.forename: Deborah K
authors.initials: DK
authors.lastname: Schneiderman
authors.affiliation: Departments of Chemical Engineering and Materials Science and.
authors.forename: Frank S
authors.initials: FS
authors.lastname: Bates
authors.affiliation: Chemistry, University of Minnesota, Minneapolis, MN 55455-0431 kzhang@umn.edu hillmyer@umn.edu.
authors.forename: Marc A
authors.initials: MA
authors.lastname: Hillmyer
authors.affiliation: Departments of Chemical Engineering and Materials Science and kzhang@umn.edu hillmyer@umn.edu.
authors.forename: Kechun
authors.initials: K
authors.lastname: Zhang
mesh_terms: D053898:Biosynthetic Pathways; D002241:Carbohydrates / Q000737:chemistry; D002850:Chromatography, Gel; D055119:Elastic Modulus; D020724:Elastomers / Q000737:chemistry* / Q000378:metabolism; D004926:Escherichia coli / Q000235:genetics / Q000378:metabolism; D005818:Genetic Engineering; D009682:Magnetic Resonance Spectroscopy; D008798:Mevalonic Acid / Q000737:chemistry / Q000378:metabolism; D008956:Models, Chemical; D015394:Molecular Structure; D011091:Polyesters / Q000737:chemistry* / Q000378:metabolism; D058105:Polymerization; D011108:Polymers / Q000737:chemistry* / Q000378:metabolism; D011753:Pyrones / Q000737:chemistry* / Q000378:metabolism; D053838:Scattering, Small Angle; D013314:Stress, Mechanical; D013696:Temperature; D014961:X-Ray Diffraction
chemical_list: D002241:Carbohydrates; D020724:Elastomers; D011091:Polyesters; D011108:Polymers; D011753:Pyrones; C052207:delta-valerolactone; C033616:poly(lactide); D008798:Mevalonic Acid
keywords: biobased production; block copolymer; mevalonate pathway; rubbery polyester