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Photoinduced bulk polymerization strategy in melt state for recyclable polydiene derivatives

Nature Chemistry volume 17, pages 1091–1098 (2025) Cite this article

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Abstract

Polydienes, particularly 1,3-butadiene derivatives, are integral to the chemical industry due to their widespread applications. However, current commercial production methods depend largely on gas- or solution-phase processes involving sophisticated initiators, catalysts and additives that require additional purification and cost. Here we introduce an ultraclean photo-melt-bulk polymerization strategy that enables the precise synthesis of high-molecular-weight polydienes without the need for solvents, catalysts or initiators. Using UV irradiation, we can generate long-lived biradicals in muconate derivatives that facilitate controlled chain propagation with minimal termination. This approach also simplifies the synthesis of ABA triblock co-polymers and allows for efficient random co-polymerization, yielding a plastic with excellent mechanical properties and processability. Furthermore, the inherently weaker carbon–carbon bonds in these polymers allow for facile depolymerization into monomers with high yields, providing an efficient pathway for chemical recycling. This work highlights a simple, yet effective polymerization method that aligns with the principles of green chemistry and advances the development of recyclable polymeric materials.

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Fig. 1: Schematic representation of the methods for the preparation of polydienes.
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Fig. 2: Polymerization kinetics and mechanism investigations.
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Fig. 3: Block and random co-polymerization by PMBP.
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Fig. 4: Chemical depolymerization of PME-based polymers.
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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information. Source data are provided with this paper. These data are available via figshare at https://doi.org/10.6084/m9.figshare.27157053 (ref. 49).

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Acknowledgements

P.W. and Q.H. were supported by the Davidson School of Chemical Engineering of Purdue University. The work performed by L.D. was supported by the Charles Davidson Rising Star Professorship research fund. The work performed by A.V.M., L.A.O. and B.M.S. was supported by the Office of Naval Research through the Energetic Materials Program (MURI grant no. N00014-21-1-2476, Program Manager: C. Stoltz). The authors acknowledge J. Sun for help with XRD measurements, X. Zhang and J. He for valuable discussions on polymerization kinetics, A. H. Coffey and C. Zhu for GIWAXS measurements, K. Rodríguez for experimental support and discussion, and G. Beckham for providing bio-derived muconic acid raw materials. This work was supported by the Davidson School of Chemical Engineering of Purdue University and in part by the Research Instrumentation Center in the Department of Chemistry of Purdue University.

Author information

Authors and Affiliations

  1. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Pengfei Wu, Qixuan Hu, Andrew V. Marquardt, Lawal A. Ogunfowora, Jeong Hui Kim, Yuanhao Tang, Chenjian Lin, Brett M. Savoie & Letian Dou

  2. Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Lawal A. Ogunfowora & Letian Dou

  3. Birck Nanotechnology Center, Purdue University, West Lafayette, IN, USA

    Letian Dou

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  1. Pengfei Wu
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Contributions

P.W. and L.D. conceived the idea. P.W. and Q.H. carried out the polymerization studies. Q.H. performed 13C NMR, GC–MS and mechanical tests. A.V.M., L.A.O. and B.M.S. performed the computational studies. J.H.K. performed the AFM measurements. Y.T. performed the GIWAXS analysis. C.L. participated in discussions. P.W. dyed and moulded the ABS-like plastic and performed the stability tests. P.W. wrote the initial draft of the paper. P.W., A.V.M., B.M.S. and L.D. reviewed and revised the paper. L.D. supervised the project.

Corresponding author

Correspondence to Letian Dou.

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Competing interests

L.D., P.W. and Q.H. have filed a patent application regarding the PMBP polymerization process (US patent application no. 63/696,463, 19 September 2024).

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Nature Chemistry thanks Jeremy Demarteau, Hatice Mutlu, Ekaterina Pas and Xinhua Wan for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Polymerization kinetic study triggered by 10 and 20 W lamp.

a, Plot of conversion versus polymerization time for PME-Et homopolymers from different pots using two different UV lamp powers (10 W in black and 20 W in red), as detailed in Supplementary Tables 1–2. The polymer conversions triggered by the 20 W lamp are nearly double those of the 10 W lamp at each polymerization time point. b, Plot of conversion versus molecular weight (Mn) for PME-Et homopolymers from different pots using two different UV lamp powers (10 W in black and 20 W in red), as detailed in Supplementary Tables 1–2. An almost linear increase in polymer Mn throughout the course of polymerization is observed for both lamps. However, the higher y-intercept of the Mn versus conversion plot and the relatively flatter increase in Mn suggest that the concentration of radicals is mainly controlled by the lamp at the initial stage. A stronger lamp can drive faster generation of radicals (biradicals here), offering more chains and leading to a lower Mn increase but higher conversion. SEC profiles of PME-Et homopolymers at different polymerization times using different UV lamp powers: c, 10 W and d, 20 W, as detailed in Supplementary Table 1–2 [HPLC-CHCl3, 35 °C]. Both cases show a shift to higher molecular weight with polymerization time, accompanied by a gradual narrowing of dispersity.

Source data

Extended Data Fig. 2 DOSY spectra of PME-Et prepared via PMBP and FRP.

a, DOSY spectrum of PME-Et from PMBP (Mn ~ 895 kDa, D ~ 1.66); b, DOSY spectrum of PME-Et from FRP (Mn ~ 47 kDa, D ~ 2.75). In both cases, the polymer concentration is 0.5 mg/mL with a volume of 0.55 mL in NMR tube, with the operation temperature set at 25 °C in CDCl3. The consistent center of all dots in the spectra confirms the reliability of these results. From the spectra, it is evident that the diffusion coefficient of PME-Et from PMBP (−10.83) is smaller than that from FRP (-10.18), indicating a higher molecular weight for the polymer prepared via PMBP. Additionally, the dots in Extended Data Fig. 2a are denser and shorter, reflecting a narrower molecular weight dispersity for PMBP-derived polymers, consistent with SEC results. The much lower polymer concentration required for DOSY further confirms the homogeneity of the polymer. Together with the results from 13C NMR and SEC, these findings strongly support the differences in molecular size and structure between the two polymerization strategies.

Extended Data Fig. 3 Mechanism study of self-regulating of radical concentration by EPR.

a, EPR spectra of ME-Et reacted in a sealed EPR tube for several hours using PMBP with a lamp power of 10 W. b, Integrated EPR spectra corresponding to (a), representing the relative number of radicals in the whole system. c, EPR spectra of ME-Et reacted in a sealed EPR tube for several hours using PMBP with a lamp power of 20 W. d, Integrated EPR spectra corresponding to (c), representing the relative number of radicals in the whole system. e, Plot of radical remaining ratio versus polymerization time according to (b) and (d), with the integrated intensity at 1 h set as the reference. f, Mechanism of self-regulating of radical via PMBP, where biradical can generate via UV irradiation and radical counteraction occurs via chain coupling.

Source data

Extended Data Fig. 4 Theoretical polymerization mechanisms deduced equations.

a, Radical coupling pathway (similar to step polymerization) with constant photo-excitation. b, Radical initiation pathway (like conventional chain polymerization) without constant photoexcitation. Where Rp is propagation rate combining both photo irradiation and heating, k, k’, [hv], and [A] represent rate constant driven by photo irradiation, rate constant driven by heating, UV lamp intensity, and monomer concentration, respectively, and subscripts of p, e, and r are propagation, excitation, and relaxation, respectively.

Supplementary information

Supplementary Information (download PDF )

Supplementary Material Synthesis, Discussion, Figs. 1–45 and Tables 1–11.

Source data

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Wu, P., Hu, Q., Marquardt, A.V. et al. Photoinduced bulk polymerization strategy in melt state for recyclable polydiene derivatives. Nat. Chem. 17, 1091–1098 (2025). https://doi.org/10.1038/s41557-025-01821-z

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