Scalable production of mechanically tunable block polymers from sugar

Proc Natl Acad Sci U S A. 2014 Jun 10;111(23):8357-62. doi: 10.1073/pnas.1404596111. Epub 2014 May 27.

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.

Keywords: biobased production; block copolymer; mevalonate pathway; rubbery polyester.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Biosynthetic Pathways
  • Carbohydrates / chemistry
  • Chromatography, Gel
  • Elastic Modulus
  • Elastomers / chemistry*
  • Elastomers / metabolism
  • Escherichia coli / genetics
  • Escherichia coli / metabolism
  • Genetic Engineering
  • Magnetic Resonance Spectroscopy
  • Mevalonic Acid / chemistry
  • Mevalonic Acid / metabolism
  • Models, Chemical
  • Molecular Structure
  • Polyesters / chemistry*
  • Polyesters / metabolism
  • Polymerization
  • Polymers / chemistry*
  • Polymers / metabolism
  • Pyrones / chemistry*
  • Pyrones / metabolism
  • Scattering, Small Angle
  • Stress, Mechanical
  • Temperature
  • X-Ray Diffraction

Substances

  • Carbohydrates
  • Elastomers
  • Polyesters
  • Polymers
  • Pyrones
  • delta-valerolactone
  • poly(lactide)
  • Mevalonic Acid