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Photoinduced inverse vulcanization

Nature Chemistry volume 14, pages 1249–1257 (2022)Cite this article

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Abstract

The inverse vulcanization (IV) of elemental sulfur to generate sulfur-rich functional polymers has attracted much recent attention. However, the harsh reaction conditions required, even with metal catalysts, constrains the range of feasible crosslinkers. We report here a photoinduced IV that enables reaction at ambient temperatures, greatly broadening the scope for both substrates and products. These conditions enable volatile and gaseous alkenes and alkynes to be used in IV, leading to sustainable alternatives for environmentally harmful plastics that were hitherto inaccessible. Density functional theory calculations reveal different energy barriers for thermal, catalytic and photoinduced IV processes. This protocol circumvents the long curing times that are common in IV, generates no H2S by-products, and produces high-molecular-weight polymers (up to 460,000 g mol−1) with almost 100% atom economy. This photoinduced IV strategy advances both the fundamental chemistry of IV and its potential industrial application to generate materials from waste feedstocks.

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Fig. 1: IV of elemental sulfur with alkenes and alkynes.
Fig. 2: Photocatalytic IV.
Fig. 3: Representative crosslinkers/co-monomers and characterization for one of the obtained polymers.
Fig. 4: Calculated energy profiles for the formation of poly(S-DIB) by S8 with DIB under various conditions.

Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files. Should any raw data files be needed in another format they are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

The authors acknowledge funding from the National Nature Science Foundation of China (numbers 22061038, 21825301), the Key Talent Projects of Gansu Province [2019]39, the Nature Science Foundation of Gansu Province (number 20YF3GA032), the National Key R&D Program of China (number 2018YFA0208602), the Shanghai Municipal Science and Technology Major Project (number 2018SHZDX03), the Programme of Introducing Talents of Discipline to Universities (number B16017), the Shanghai Science and Technology Committee (number 175207750100) and the China Postdoctoral Science Foundation (number 2020M673640XB, 2020M671020), the Natural Science Foundation of Gansu Province (20YF3GA023) and Engineering and Physical Sciences Research Council (EPSRC) (EP/v026887/1). P.Y., C.Z. and S.C. thank the China Scholarship Council (CSC) for awarding their PhD scholarships. T.H. was supported by a Royal Society University Research Fellowship. L.C., W.Z., A.I.C. and X.W. acknowledge the Leverhulme Trust via the Leverhulme Research Centre for Functional Materials Design for funding. We thank the Materials Innovation Factory (MIF) team members for their support in operating instruments. We also thank X. Zhu for his contribution to discussion and design of the figures, and D. Lester for GPC measurement.

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  1. These authors contributed equally: Jinhong Jia, Jingjiang Liu.

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Northwest Normal University, Lanzhou, P. R. China

    Jinhong Jia, Jingjiang Liu, Congcong Miao, Xi-Cun Wang, Xiaofeng Wu, Tom Hasell & Zheng-Jun Quan

  2. Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Research Centre, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, P. R. China

    Zhi-Qiang Wang, Xue-Qing Gong, Chengxi Zhao, Linjiang Chen, Andrew I. Cooper & Xiaofeng Wu

  3. Leverhulme Research Centre for Functional Materials Design, Materials Innovation Factory, and Department of Chemistry, University of Liverpool, Liverpool, UK

    Tao Liu, Chengxi Zhao, Linjiang Chen, Wei Zhao, Andrew I. Cooper & Xiaofeng Wu

  4. Department of Chemistry, University of Liverpool, Liverpool, UK

    Peiyao Yan, Shanshan (Diana) Cai & Tom Hasell

  5. School of Chemistry, University of Birmingham, Edgbaston, Birmingham, UK

    Linjiang Chen

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Contributions

Z.-J.Q., X.W. and T.H. conceived the project. J.J. carried out the experimental works. J.J. and J.L. performed the characterizations. X.G., L.C., X.W. and T.H. conceived the computational simulations strategy. Z.-Q.W., T.L. and C.Z. performed the calculations. P.Y., W.Z., C.M. and S.C. carried out the control reactions, parallel experiments, in situ coating experiments, mercury adsorption, and performed the characterizations. X.-C.W. accessed FTIR, GPC spectra and confirmed the data. A.I.C. discussed the results and thoroughly revised the manuscript. All authors interpreted the data and contributed to the preparation of the manuscript.

Corresponding authors

Correspondence to Xue-Qing Gong, Andrew I. Cooper, Xiaofeng Wu, Tom Hasell or Zheng-Jun Quan.

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Extended data

Extended Data Fig. 1 The chemical structures of all the crosslinkers/comonomers used in this research and proposed mechanism for photoinduced IV reaction.

a, Previous reported crosslinkers with high boiling points. b, Low-boiling points alkenes and alkynes. c, Gaseous comonomers. d, Proposed mechanism for photoinduced IV reaction.

Extended Data Fig. 2 Solubility of the resultant sulfur-rich polymers.

a, Comparison of solubility of the poly(S-DIB) produced under thermal, thermal + Zn(DTC)2, light of 435 nm and 380 nm. The picture taken within a few minutes after solvents (1 mL) were added into the vial contained polymers (5 mg). b, Representatives of solubility in DMF for sulfur-rich polymers presented in this study. c, Comparison of the solubility in DMF for selected samples without (top, A) and with (bottom, B) grinding + sonication at 60 °C for 40 min.

Extended Data Fig. 3 Comparison of characterization for soluble, insoluble fractions and the mixture of poly(S-DIB) generated by photoinduced IV.

a, 13C solid NMR of insoluble fraction and the mixture. b, FTIR spectra. c, PXRD spectra. d, TGA spectra. e, DSC spectra. f, Elemental analysis. g-m, XPS spectra.

Source data

Extended Data Fig. 4 Comparison of characterizations of different batches (three repeats) of soluble and insoluble fraction of the S-DIB polymers generated by photoinduced IV.

a,1H NMR spectra of dissolved matter. b, FTIR spectra of dissolved matter. c, PXRD of dissolved matter. d, TGA of dissolved matter. e, DSC spectra of dissolved matter. f, elemental analysis of dissolved matter. g, FTIR spectra of insoluble fractions. h, PXRD of insoluble fractions. i, TGA of insoluble fractions. j, DSC spectra of insoluble fractions. k, elemental analysis of insoluble fractions.

Source data

Extended Data Fig. 5 Detection of H2S production.

a, Pb(OAc)2 test paper results for the detection of H2S production of IV under different reaction conditions (From left to right: Thermal 160 °C, thermal 135 °C + Cat, photo 435 nm @ r.t.). b, Pb(OAc)2 solution (2 mmol%) results for the detection of H2S production of IV under different reaction conditions (Top: Thermal 140 °C, 5 h; Bottom: photo 435 nm @ r.t. for 48 h). For reaction conditions please see Supplementary Information.

Extended Data Fig. 6 Examination of the homogeneity of the resultant sulfur-rich polymers by photoinduced IV.

a, samples from different parts of the resultant polymers in flask. b, FTIR spectra. c, PXRD spectra. d, TGA spectra. e, DSC spectra. f, samples from different parts of the resultant polymers on glass slide. g, TGA spectra. h, DSC spectra. i, elemental analysis of all those different parts of resultant polymers. For reaction conditions please see the Supplementary Information.

Source data

Extended Data Fig. 7 TGA spectra of representative sulfur-rich polymers generated by photoinduced IV.

All the results show good thermal stabilities of the obtained polymers by photoinduced IV reaction.

Source data

Extended Data Fig. 8 PXRD spectra of representative sulfur-rich polymers generated by photoinduced IV.

All results show amorphas materials obtained without any residual of crystalline S8.

Source data

Extended Data Fig. 9 In-situ coating of sulfur-rich polymers on the filter paper by photoinduced IV.

a, d, photographs of bottom and top view of filter paper. b, e, filter paper adsorbed with sulfur. c, f, in situ coated poly(S-DIB) on the filter paper. g, h, SEM images of filter paper. (i, j), SEM images of filter paper adsorbed with sulfur. (k, l), SEM images of in situ coated poly(S-DIB) on the filter paper. a1, SEM image polymer-coated filter paper. b1, EDS map of polymer-coated filter paper. c1, colour-element relationship of red for sulfur, d1, colour-element relationship of green for carbon. e1, Colour-element relationship of blue for oxygen. f1. colour-element relationship of purple for chromium.

Extended Data Fig. 10 Calculation results and key intermediates of IV reaction.

a, calculation conditions. b, thermal activities. c, thermal with catalysts. d, photoinduced conditions. The results indicated that the activity of S8 can be significantly improved through the altered catalytic route and that the calculations suggest that the S8 ring-opening can occur by light irradiation only under its excited state at room temperature.

Supplementary information

Supplementary Information

Supplementary Figs. 1–115, Tables 1–8 and Discussion.

Source data

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Jia, J., Liu, J., Wang, ZQ. et al. Photoinduced inverse vulcanization. Nat. Chem. 14, 1249–1257 (2022). https://doi.org/10.1038/s41557-022-01049-1

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