All-Polyhydroxyalkanoate Triblock Copolymers via a Stereoselective-Chemocatalytic Route

Westlie, Andrea H.; Hesse, Sarah A.; Tang, Xiaoyan; Quinn, Ethan C.; Parker, Celine R.; Takacs, Christopher J.; Tassone, Christopher J.; Chen, Eugene Y.-X.

doi:10.1021/acsmacrolett.3c00162

Title: All-Polyhydroxyalkanoate Triblock Copolymers via a Stereoselective-Chemocatalytic Route

Journal Article · 24 April 2023 · ACS Macro Letters

DOI: https://doi.org/10.1021/acsmacrolett.3c00162 · OSTI ID:1992924

^[1];

^[2];

^[1];

^[1]; Parker, Celine R. ^[1]; Takacs, Christopher J. ^[2]; Tassone, Christopher J. ^[2];

^[1]

Colorado State University, Fort Collins, CO (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Biodegradable polyhydroxyalkanoate (PHA) homopolymers and statistical copolymers are ubiquitous in microbially produced PHAs, but the step-growth polycondensation mechanism the biosynthesis operates on presents a challenge to access well-defined block copolymers (BCPs), especially higher-order tri-BCP PHAs. We report a stereoselective-chemocatalytic route to produce discrete hard–soft–hard ABA all-PHA tri-BCPs based on the living chain-growth ring-opening polymerization of racemic (rac) 8-membered diolides (rac-8DL^R; R denotes the two substituents on the ring). Depending on the composition of the soft B block, originated from rac-8DL^R (R = Et, ⁿBu), and its ratio to the semicrystalline, high-melting hard A block, derived from rac-8DL^Me, the resulting all-PHA tri-BCPs with high molar mass (M_n up to 238 kg mol^–1) and low dispersity (Ð: = 1.07) exhibit tunable mechanical properties characteristic of a strong and tough thermoplastic, elastomer, or a semicrystalline thermoplastic elastomer.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515; AC36-08GO28308; NSF-1955482

OSTI ID:: 1992924

Journal Information:: ACS Macro Letters, Vol. 12, Issue 5; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (36)

The chemomechanical properties of microbial polyhydroxyalkanoates Laycock, Bronwyn; Halley, Peter; Pratt, Steven Progress in Polymer Science, Vol. 38, Issue 3-4 https://doi.org/10.1016/j.progpolymsci.2012.06.003	journal	March 2013
Recent Advances in Metal‐Mediated Stereoselective Ring‐Opening Polymerization of Functional Cyclic Esters towards Well‐Defined Poly(hydroxy acid)s: From Stereoselectivity to Sequence‐Control Li, Hui; Shakaroun, Rama M.; Guillaume, Sophie M. Chemistry – A European Journal, Vol. 26, Issue 1 https://doi.org/10.1002/chem.201904108	journal	December 2019
Carbonylative Polymerization of Epoxides Mediated by Tri‐metallic Complexes: A Dual Catalysis Strategy for Synthesis of Biodegradable Polyhydroxyalkanoates Yang, Jin‐Chuang; Yang, Jun; Li, Wen‐Bing Angewandte Chemie International Edition, Vol. 61, Issue 9 https://doi.org/10.1002/anie.202116208	journal	January 2022
Consequences of Polylactide Stereochemistry on the Properties of Polylactide-Polymenthide-Polylactide Thermoplastic Elastomers Wanamaker, Carolyn L.; Bluemle, Michael J.; Pitet, Louis M. Biomacromolecules, Vol. 10, Issue 10 https://doi.org/10.1021/bm900721p	journal	October 2009
Poly(hydroxyalkanoate) Block or Random Copolymers of β-Butyrolactone and Benzyl β-Malolactone: A Matter of Catalytic Tuning Jaffredo, Cédric G.; Carpentier, Jean-François; Guillaume, Sophie M. Macromolecules, Vol. 46, Issue 17 https://doi.org/10.1021/ma401332k	journal	August 2013
Strong, Resilient, and Sustainable Aliphatic Polyester Thermoplastic Elastomers Watts, Annabelle; Kurokawa, Naruki; Hillmyer, Marc A. Biomacromolecules, Vol. 18, Issue 6 https://doi.org/10.1021/acs.biomac.7b00283	journal	May 2017
Discrete Metal Catalysts for Stereoselective Ring-Opening Polymerization of Chiral Racemic β-Lactones Carpentier, Jean-François Macromolecular Rapid Communications, Vol. 31, Issue 19 https://doi.org/10.1002/marc.201000114	journal	June 2010
Catalyzed Chemical Synthesis of Unnatural Aromatic Polyhydroxyalkanoate and Aromatic–Aliphatic PHAs with Record-High Glass-Transition and Decomposition Temperatures Westlie, Andrea H.; Chen, Eugene Y. -X. Macromolecules, Vol. 53, Issue 22 https://doi.org/10.1021/acs.macromol.0c02110	journal	November 2020
Chemical synthesis of perfectly isotactic and high melting bacterial poly(3-hydroxybutyrate) from bio-sourced racemic cyclic diolide Tang, Xiaoyan; Chen, Eugene Y. -X. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04734-3	journal	June 2018
Investigating the structure–property relationship of bacterial PHA block copolymers Mcchalicher, C.; Srienc, F. Journal of Biotechnology, Vol. 132, Issue 3 https://doi.org/10.1016/j.jbiotec.2007.04.014	journal	November 2007
Synthesis of novel biodegradable elastomers based on poly[3-hydroxy butyrate] and poly[3-hydroxy octanoate] via transamidation reaction Hazer, Baki; Akyol, Elvan; Şanal, Timur Polymer Bulletin, Vol. 76, Issue 2 https://doi.org/10.1007/s00289-018-2410-2	journal	June 2018
Biodegradable Polyhydroxyalkanoates by Stereoselective Copolymerization of Racemic Diolides: Stereocontrol and Polyolefin‐Like Properties Tang, Xiaoyan; Westlie, Andrea H.; Caporaso, Lucia Angewandte Chemie International Edition, Vol. 59, Issue 20 https://doi.org/10.1002/anie.201916415	journal	March 2020
Microbial production of polyhydroxyalkanoates (PHAs) and its copolymers: A review of recent advancements Anjum, Anbreen; Zuber, Mohammad; Zia, Khalid Mahmood International Journal of Biological Macromolecules, Vol. 89 https://doi.org/10.1016/j.ijbiomac.2016.04.069	journal	August 2016
Synthetic biodegradable polyhydroxyalkanoates (PHAs): Recent advances and future challenges Westlie, Andrea H.; Quinn, Ethan C.; Parker, Celine R. Progress in Polymer Science, Vol. 134 https://doi.org/10.1016/j.progpolymsci.2022.101608	journal	November 2022
Metal-Free Catalyzed Ring-Opening Polymerization of β-Lactones: Synthesis of Amphiphilic Triblock Copolymers Based on Poly(dimethylmalic acid) Coulembier, Olivier; Mespouille, Laetitia; Hedrick, James L. Macromolecules, Vol. 39, Issue 12 https://doi.org/10.1021/ma060552n	journal	May 2006
From Anionic Ring-Opening Polymerization of β-Butyrolactone to Biodegradable Poly(hydroxyalkanoate)s: Our Contributions in This Field Adamus, Grażyna; Domiński, Adrian; Kowalczuk, Marek Polymers, Vol. 13, Issue 24 https://doi.org/10.3390/polym13244365	journal	December 2021
Polylactide–Poly(6-methyl-ε-caprolactone)–Polylactide Thermoplastic Elastomers Martello, Mark T.; Hillmyer, Marc A. Macromolecules, Vol. 44, Issue 21 https://doi.org/10.1021/ma201063t	journal	November 2011
CO ₂ -Controlled One-Pot Synthesis of AB, ABA Block, and Statistical Terpolymers from β-Butyrolactone, Epoxides, and CO ₂ Kernbichl, Sebastian; Reiter, Marina; Adams, Friederike Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b01295	journal	May 2017
Poly(hydroxyalkanoates): A Fifth Class of Physiologically Important Organic Biopolymers? Müller, Hans-Martin; Seebach, Dieter Angewandte Chemie International Edition in English, Vol. 32, Issue 4 https://doi.org/10.1002/anie.199304771	journal	April 1993
(Co)polymerization of (−)-menthide and β-butyrolactone with yttrium-bis(phenolates): tuning material properties of sustainable polyesters Adams, Friederike; Pehl, Thomas M.; Kränzlein, Moritz Polymer Chemistry, Vol. 11, Issue 27 https://doi.org/10.1039/D0PY00379D	journal	January 2020
Bacterial Synthesis of PHA Block Copolymers Pederson, Erik N.; McChalicher, Christopher W. J.; Srienc, Friedrich Biomacromolecules, Vol. 7, Issue 6 https://doi.org/10.1021/bm0510101	journal	May 2006
Installing Controlled Stereo-Defects Yields Semicrystalline and Biodegradable Poly(3-Hydroxybutyrate) with High Toughness and Optical Clarity Quinn, Ethan C.; Westlie, Andrea H.; Sangroniz, Ainara Journal of the American Chemical Society, Vol. 145, Issue 10 https://doi.org/10.1021/jacs.2c12897	journal	March 2023
Microbial Synthesis of Functional Homo-, Random, and Block Polyhydroxyalkanoates by β-Oxidation Deleted Pseudomonas entomophila Li, Shijun; Cai, Longwei; Wu, Linping Biomacromolecules, Vol. 15, Issue 6 https://doi.org/10.1021/bm500669s	journal	May 2014
Stereocontrolled ring-opening polymerization of cyclic esters: synthesis of new polyester microstructures Thomas, Christophe M. Chem. Soc. Rev., Vol. 39, Issue 1 https://doi.org/10.1039/B810065A	journal	January 2010
Alternating Isotactic Polyhydroxyalkanoates via Site- and Stereoselective Polymerization of Unsymmetrical Diolides Zhang, Zhen; Shi, Changxia; Scoti, Miriam Journal of the American Chemical Society, Vol. 144, Issue 43 https://doi.org/10.1021/jacs.2c08791	journal	October 2022
Toughening Poly(3-hydroxybutyrate) by Using Catalytic Carbonylative Terpolymerization of Epoxides Yang, Jin-Chuang; Yang, Jun; Zhang, Tie-Ying Macromolecules, Vol. 56, Issue 2 https://doi.org/10.1021/acs.macromol.2c02438	journal	January 2023
Toward Infinitely Recyclable Plastics Derived from Renewable Cyclic Esters Tang, Xiaoyan; Chen, Eugene Y. -X. Chem, Vol. 5, Issue 2 https://doi.org/10.1016/j.chempr.2018.10.011	journal	February 2019
Toughening Biodegradable Isotactic Poly(3-hydroxybutyrate) via Stereoselective Copolymerization of a Diolide and Lactones Tang, Xiaoyan; Shi, Changxia; Zhang, Zhen Macromolecules, Vol. 54, Issue 20 https://doi.org/10.1021/acs.macromol.1c01199	journal	October 2021
Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) copolymer elastomers Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T. Polymer Chemistry, Vol. 6, Issue 19 https://doi.org/10.1039/C5PY00202H	journal	January 2015
Simple and Rapid Access toward AB, BAB and ABAB Block Copolyesters from One-Pot Monomer Mixtures Using an Indium Catalyst Bruckmoser, Jonas; Rieger, Bernhard ACS Macro Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acsmacrolett.2c00468	journal	August 2022
Chemical syntheses of biodegradable polymers Okada, Masahiko Progress in Polymer Science, Vol. 27, Issue 1 https://doi.org/10.1016/S0079-6700(01)00039-9	journal	February 2002
Polyhydroxyalkanoates, challenges and opportunities Wang, Ying; Yin, Jin; Chen, Guo-Qiang Current Opinion in Biotechnology, Vol. 30 https://doi.org/10.1016/j.copbio.2014.06.001	journal	December 2014
Enhanced Mechanical Properties of Aliphatic Polyester Thermoplastic Elastomers through Star Block Architectures Liffland, Stephanie; Hillmyer, Marc A. Macromolecules, Vol. 54, Issue 20 https://doi.org/10.1021/acs.macromol.1c01357	journal	October 2021
A microbial polyhydroxyalkanoates (PHA) based bio- and materials industry Chen, Guo-Qiang Chemical Society Reviews, Vol. 38, Issue 8 https://doi.org/10.1039/b812677c	journal	January 2009
Stereosequenced crystalline polyhydroxyalkanoates from diastereomeric monomer mixtures Tang, Xiaoyan; Westlie, Andrea H.; Watson, Eli M. Science, Vol. 366, Issue 6466 https://doi.org/10.1126/science.aax8466	journal	November 2019
Renewable-Resource Thermoplastic Elastomers Based on Polylactide and Polymenthide Wanamaker, Carolyn L.; O'Leary, Leslie E.; Lynd, Nathaniel A. Biomacromolecules, Vol. 8, Issue 11 https://doi.org/10.1021/bm700699g	journal	November 2007