Chen Ling, Ryan W. Clarke, Gloria Rosetto, Shu Xu, Robin M. Cywar, Dong Hyun Kim, Levi J. Hamernik, Stefan J. Haugen, William E. Michener, Sean P. Woodworth, Torrey M. Lind, Kelsey J. Ramirez, Meltem Urgun-Demirtas, Davinia Salvachúa, Christopher W. Johnson, Nicholas A. Rorrer* and Gregg T. Beckham*,
{"title":"Tunable and Degradable Dynamic Thermosets from Compatibilized Polyhydroxyalkanoate Blends","authors":"Chen Ling, Ryan W. Clarke, Gloria Rosetto, Shu Xu, Robin M. Cywar, Dong Hyun Kim, Levi J. Hamernik, Stefan J. Haugen, William E. Michener, Sean P. Woodworth, Torrey M. Lind, Kelsey J. Ramirez, Meltem Urgun-Demirtas, Davinia Salvachúa, Christopher W. Johnson, Nicholas A. Rorrer* and Gregg T. Beckham*, ","doi":"10.1021/acssuschemeng.5c0094310.1021/acssuschemeng.5c00943","DOIUrl":null,"url":null,"abstract":"<p >Polyhydroxyalkanoates (PHAs) are versatile, biobased polyesters that are often targeted for use as degradable thermoplastic replacements for polyolefins. Given the substantial chemical diversity of PHA, their potential as cross-linked polymers could also enable similar platforms for reversible, degradable thermosets. In this work, we genetically engineered <i>Pseudomonas putida</i> KT2440 to synthesize poly(3-hydroxybutyrate-<i>co</i>-3-hydroxyundecenoate) (PHBU), which contains both 3-hydroxybutyrate and unsaturated 3-hydroxyundecenoate components. To reduce the brittleness of this polymer, we physically blended PHBU with the soft copolymer poly(3-hydroxydecanonate-<i>co</i>-3-hydroxyundecenoate) in mass ratios of 1:3, 1:1, and 3:1. Upon observing varying degrees of immiscibility by scanning electron microscopy, we installed dynamic boronic ester cross-links via thiol–ene click chemistry, which resulted in compatibilized dynamic thermoset blends ranging in hard, medium, and soft rubber or elastomer thermomechanical profiles. These dynamic thermoset blends were subjected to controlled biological degradation experiments in freshwater conditions, achieving timely mass loss despite the cross-linked architectures. Overall, this work highlights a two-component platform for the production of degradable and reprocessable dynamic thermoset blends suitable for several classes of cross-linked polymer technologies from tailored, biological PHA copolymers.</p><p >Microbially produced polymers are cross-linked to form rubber-like materials. These biobased materials can be reprocessed and are biodegradable.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 9","pages":"3817–3829 3817–3829"},"PeriodicalIF":7.1000,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acssuschemeng.5c00943","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Sustainable Chemistry & Engineering","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acssuschemeng.5c00943","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Polyhydroxyalkanoates (PHAs) are versatile, biobased polyesters that are often targeted for use as degradable thermoplastic replacements for polyolefins. Given the substantial chemical diversity of PHA, their potential as cross-linked polymers could also enable similar platforms for reversible, degradable thermosets. In this work, we genetically engineered Pseudomonas putida KT2440 to synthesize poly(3-hydroxybutyrate-co-3-hydroxyundecenoate) (PHBU), which contains both 3-hydroxybutyrate and unsaturated 3-hydroxyundecenoate components. To reduce the brittleness of this polymer, we physically blended PHBU with the soft copolymer poly(3-hydroxydecanonate-co-3-hydroxyundecenoate) in mass ratios of 1:3, 1:1, and 3:1. Upon observing varying degrees of immiscibility by scanning electron microscopy, we installed dynamic boronic ester cross-links via thiol–ene click chemistry, which resulted in compatibilized dynamic thermoset blends ranging in hard, medium, and soft rubber or elastomer thermomechanical profiles. These dynamic thermoset blends were subjected to controlled biological degradation experiments in freshwater conditions, achieving timely mass loss despite the cross-linked architectures. Overall, this work highlights a two-component platform for the production of degradable and reprocessable dynamic thermoset blends suitable for several classes of cross-linked polymer technologies from tailored, biological PHA copolymers.
Microbially produced polymers are cross-linked to form rubber-like materials. These biobased materials can be reprocessed and are biodegradable.
期刊介绍:
ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment.
The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.