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Cited by 203biodegradable polymer synthesis and propertiesAdvanced Polymer Synthesis and CharacterizationBlock Copolymer Self-Assembly

Scalable production of mechanically tunable block polymers from sugar

Open access
Xiong, Mingyong, Schneiderman, Deborah K., Bates, Frank S., Hillmyer, Marc A., Zhang, Kechun·2014·Proceedings of the National Academy of Sciences
DOI 10.1073/pnas.1404596111PMC PMC4060720
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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.

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  • Comparing methyl-substituted δ-valerolactones, the bulk polymerization of δ1 is both most exothermic and most entropically unfavored.

    “Comparing the methyl-substituted δ -valerolactones, the bulk polymerization of δ 1 is both most exothermic and most entropically unfavored.”

    From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [14]

    The “Polymerization of βMδVL” section (page unavailable) reports bulk polymerization of one methyl-substituted δ-valerolactone with negative polymerization enthalpy and entropy. It does not identify that monomer as δ1 or compare methyl-substituted δ-valerolactones, so it cannot establish that δ1 is the most exothermic and most entropically unfavored. (LLM, conf=0.78)

    Experimental — accuracy not yet measured

  • Recent advances in synthetic biology have enabled the microbial production of monomers, including lactones, from inexpensive renewable starting materials.

    “Recent advances in synthetic biology have enabled the microbial production of monomers, including lactones, from inexpensive renewable starting materials.”

    From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [14]

  • The effect of alkyl substituent size and location on the standard state enthalpy and entropy of polymerization has not been experimentally studied in a systematic manner.

    “Although thermodynamic parameters have been reported for the polymerization of several substituted δ -valerolactone monomers, the e ff ect of alkyl substituent size and location on the standard state enthalpy ( Δ H p ° ) and entropy ( Δ S p ° ) of polymerization has not been experimentally studied in a systematic manner.”

    From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [14]

    The “Polymerization of βMδVL” section reports enthalpy and entropy values for one alkyl-substituted δ-valerolactone and refers to previous work on related monomers. It does not address whether substituent size and location had been studied systematically; searches for those terms found no such statement in our copy. No page number is available for this passage. (LLM, conf=0.72)

    Experimental — accuracy not yet measured

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Cites

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Cited by

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Authors
Xiong, M., Schneiderman, D. K., Bates, F. S., Hillmyer, M. A., & Zhang, K.
Affiliations
  • Departments of aChemical Engineering and Materials Science and
  • University of Minnesota (US)
ORCID
Venue
Proceedings of the National Academy of Sciences
Publisher
National Academy of Sciences
Published
2014-05-27
Volume
111
Issue
23
Pages
8357-8362
ISSN
  • 0027-8424 (ISSN-L)
  • 1091-6490
DOI
10.1073/pnas.1404596111
PMC
PMC4060720
OpenAlex
W2116140115
Cited by
203
References
3
Citations by year
2026: 11 · 2025: 16 · 2024: 21 · 2023: 21 · 2022: 13 · 2021: 17 · 2020: 11 · 2019: 12 · 2018: 20 · 2017: 26 · 2016: 22 · 2015: 10 · 2014: 3
FWCI
7.71
Type
journal article
Language
en
Open access
Locations
  • Proceedings of the National Academy of Sciences (publishedVersion)
  • PubMed Central (publishedVersion)
  • PubMed (publishedVersion)
Funders
  • National Science Foundation (DE-AC02–06CH11357, 1136607)
  • U.S. Department of Energy (DE‐ AC02‐06CH11357, AC02‐06CH11357, 06CH11357, DE-AC02-)
  • University of Minnesota
  • Office of Science (AC02‐06CH11357, DE-AC02, 06CH11357, DE-AC02-06CH11357)
  • College of Science and Engineering, University of Minnesota
  • Division of Chemistry (CHE-1136607)
  • Argonne National Laboratory (DE- AC02-06-CH11357, DE-AC02, AC02–06CH11357, Contract DE-AC02-06CH11357, 06CH11357)
Topics
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
Keywords
bio-based polymers, block copolymerization, polylactic acid, triblock copolymers, mevalonate, biodegradable plastics, elastomers, controlled polymerization
MeSH terms
Carbohydrates, Chromatography, Gel, Escherichia coli, Genetic Engineering, Mevalonic Acid, Models, Chemical, Magnetic Resonance Spectroscopy, Polyesters, Polymers, Pyrones, Stress, Mechanical, Temperature, X-Ray Diffraction, Molecular Structure, Elastomers, Scattering, Small Angle, Biosynthetic Pathways, Elastic Modulus, Polymerization

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