Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2023 May 9;14(21):5689-5698.
doi: 10.1039/d2sc06040j. eCollection 2023 May 31.

Radical ring-opening polymerization of sustainably-derived thionoisochromanone

Emily A Prebihalo  1 , Anna M Luke  1 , Yernaidu Reddi  1 , Christopher J LaSalle  1 , Vijay M Shah  1 , Christopher J Cramer  2 , Theresa M Reineke  1
Affiliations

Radical ring-opening polymerization of sustainably-derived thionoisochromanone

Emily A Prebihalo et al. Chem Sci. .

Erratum in

Abstract

We present the synthesis, characterization and radical ring-opening polymerization (rROP) capabilities of thionoisochromanone (TIC), a fungi-derivable thionolactone. TIC is the first reported six-membered thionolactone to readily homopolymerize under free radical conditions without the presence of a dormant comonomer or repeated initiation. Even more, the resulting polymer is fully degradable under mild, basic conditions. Computations providing molecular-level insights into the mechanistic and energetic details of polymerization identified a unique S,S,O-orthoester intermediate that leads to a sustained chain-end. This sustained chain-end allowed for the synthesis of a block copolymer of TIC and styrene under entirely free radical conditions without explicit radical control methods such as reversible addition-fragmentation chain transfer polymerization (RAFT). We also report the statistical copolymerization of ring-retained TIC and styrene, confirmed by elemental analysis and energy-dispersive X-ray spectroscopy (EDX). Computations into the energetic details of copolymerization indicate kinetic drivers for ring-retaining behavior. This work provides the first example of a sustainable feedstock for rROP and provides the field with the first six-membered monomer susceptible to rROP, expanding the monomer scope to aid our fundamental understanding of thionolactone rROP behavior.

PubMed Disclaimer

Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. (A) General rROP mechanism via a generic thionolactone, (B) structures of DOT, thCL (R1 = H, C4H9) and DBT, and (C) TIC synthesis.
Fig. 2
Fig. 2. (A) SEC-MALS trace of p(TIC) using AIBN at 70 °C in DMF, (B) monomer conversion vs. time of TIC polymerization (green) and a styrene polymerization control (black), via free-radical conditions under N2 at 70 °C, (C) DSC thermogram of p(TIC) (green) and polystyrene of the same molar mass (black), and (D) SEC-MALS trace of p(TIC) before (green) and after degradation (blue) via sodium thiomethoxide-mediated thiolysis.
Fig. 3
Fig. 3. (A) Key mechanistic steps for the homopolymerization of TIC and (B) Gibbs free energy (kcal mol−1; 343.15 K; SMD(DMF)/PBE0-D3/6-311++G(d,p)//M06-2X/6-31+G(d,p) level of theory) profile on the potential energy surface for homopolymerization of TIC.
Fig. 4
Fig. 4. (A) Synthesis of p(TIC-b-styrene), (B) SEC-MALS traces of p(TIC) and the block copolymer resulting from chain-extension, and (C) DSC thermograms of p(TIC-b-styrene) (purple trace) and polystyrene of similar molar mass (black trace).
Fig. 5
Fig. 5. (A) Synthesis of p(TIC-co-styrene), (B) key mechanistic steps for the copolymerization of TIC and styrene, and (C) Gibbs free energy (kcal mol−1; 343.15 K; SMD(DMF)/PBE0-D3/6-311++G(d,p)//M06-2X/6-31+G(d,p) level of theory) profile on the potential energy surface for copolymerization of TIC and styrene.
See this image and copyright information in PMC

References

    1. Geyer R. Jambeck J. R. Law K. L. Production, Use, and Fate of All Plastics Ever Made. Sci. Adv. 2017;3:25–29. doi: 10.1126/sciadv.1700782. doi: 10.1126/sciadv.1700782. - DOI - DOI - PMC - PubMed
    1. Schneiderman D. K. Hillmyer M. A. 50th Anniversary Perspective: There Is a Great Future in Sustainable Polymers. Macromolecules. 2017;50(10):3733–3749. doi: 10.1021/acs.macromol.7b00293. doi: 10.1021/acs.macromol.7b00293. - DOI - DOI
    1. Wan D. Satoh K. Kamigaito M. Okamoto Y. Xanthate-Mediated Radical Polymerization of N-Vinylpyrrolidone in Fluoroalcohols for Simultaneous Control of Molecular Weight and Tacticity. Macromolecules. 2005;38:10397–10405. doi: 10.1021/ma0515230. doi: 10.1021/ma0515230. - DOI - DOI
    1. Öztürk T. Savaş B. Meyvacı E. Kılıçlıoğlu A. Hazer B. Synthesis and Characterization of the Block Copolymers Using the Novel Bifunctional Initiator by RAFT and FRP Technics: Evaluation of the Primary Polymerization Parameters. J. Polym. Res. 2020;27(3):1–7. doi: 10.1007/s10965-020-2043-7. - DOI
    1. Barner-kowollik C. Buback M. Charleux B. Coote M. L. Drache M. Fukuda T. Goto A. Klumperman B. Lowe A. B. Mcleary J. B. Moad G. Monteiro M. J. Sanderson R. D. Tonge M. P. Vana P. Mechanism and Kinetics of Dithiobenzoate-Mediated RAFT Polymerization. I. The Current Situation. J. Polym. Sci., Part A: Polym. Chem. 2006;44:5809–5831. doi: 10.1002/pola. doi: 10.1002/pola.21589. - DOI - DOI