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Recyclable cyclic bio-based acrylic polymer via pairwise monomer enchainment by a trifunctional Lewis pair

Nature Chemistry volume 15, pages 366–376 (2023)Cite this article

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Abstract

The existing catalyst/initiator systems and methodologies used for the synthesis of polymers can access only a few cyclic polymers composed entirely of a single monomer type, and the synthesis of such authentic cyclic polar vinyl polymers (acrylics) devoid of any foreign motifs remains a challenge. Here we report that a tethered B-P-B trifunctional, intramolecular frustrated Lewis pair catalyst enables the synthesis of an authentic cyclic acrylic polymer, cyclic poly(γ-methyl-α-methylene-γ-butyrolactone) (c-PMMBL), from the bio-based monomer MMBL. Detailed studies have revealed an initiation and propagation mechanism through pairwise monomer enchainment enabled by the cooperative and synergistic initiator/catalyst sites of the trifunctional catalyst. We propose that macrocyclic intermediates and transition states comprising two catalyst molecules are involved in the catalyst-regulated ring expansion and eventual cyclization, forming authentic c-PMMBL rings and concurrently regenerating the catalyst. The cyclic topology of the c-PMMBL polymers imparts an ~50 °C higher onset decomposition temperature and a much narrower degradation window compared with their linear counterparts of similar molecular weight and dispersity, while maintaining high chemical recyclability.

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Fig. 1: Hypothesized REP pathway leading to c-PMMBL.
Fig. 2: Characterization of polymer topology.
Fig. 3: Isolation and structural characterization of reactive intermediates.
Fig. 4: Polymerization kinetics and possible kinetic scenarios for MMBL polymerization.
Fig. 5: Proposed REP mechanism for creating c-PMMBL.
Fig. 6: Comparison of the properties of PMMBL with different topologies.

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Full experimental details and the data supporting the findings of this study are available within the article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos. 22071077 and 21871107) to Y.Z. and the US National Science Foundation (NSF-1904962) to E.Y.-X.C. The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript.

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Authors and Affiliations

  1. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, Jilin, China

    Yanjiao Song, Jianghua He & Yuetao Zhang

  2. Department of Chemistry, Colorado State University, Fort Collins, CO, USA

    Reid A. Gilsdorf & Eugene Y.-X. Chen

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  1. Yanjiao Song
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Contributions

Y.Z. and Y.S. conceived the idea and designed the experiments. Y.S. and R.A.G performed the experiments and characterizations. Y.S., J.H., Y.Z. and E.Y.-X.C. analysed the data, wrote parts of the manuscript and provided input. Y.Z. directed the project.

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Correspondence to Yuetao Zhang.

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Competing interests

Y.Z., Y.S. and J.H. are named inventors on a Chinese patent application (number 202111184369.9) submitted by Jilin University that covers the preparation and characterization of cyclic PMMBL. The other authors (R.A.G. and E. Y.-X.C.) declare no competing interests.

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Nature Chemistry thanks Kai Guo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods 1–5, Figs. 1–46 and Tables 1 and 2.

Supplementary Video 1

Mass spectra collected from the degradation of l-PMMBL scanned from 30 to 623 °C at 10 °C min−1, m/z from 1 to 130 amu, showing evolution of ion reflux. Source data for Supplementary Fig. 37.

Supplementary Video 2

Mass spectra collected from the degradation of c-PMMBL scanned from 30 °C to 623 °C at 10 °C min−1, m/z from 1 to 130 amu, showing evolution of ion reflux. Source data for Supplementary Fig. 40.

Supplementary Video 3

Mass spectra collected from the degradation of l-PMMBL scanned during isothermal treatment at 300 °C for 60 min, m/z from 1 to 130 amu, showing evolution of ion reflux. Snapshot shown in Supplementary Fig. 42.

Supplementary Video 4

Mass spectra collected from the degradation of c-PMMBL scanned during isothermal treatment at 300 °C for 60 min, m/z from 1 to 130 amu, showing evolution of ion reflux. Snapshot shown in Supplementary Fig. 44.

Supplementary Data 1

Crystal data and structure refinement, and bond lengths and angles for compound 1A; CCDC reference 2111456.

Supplementary Data 2

Crystallographic data for compound 1A; CCDC reference 2111456.

Supplementary Data 3

Structure factor file for compound 1A; CCDC reference 2111456.

Supplementary Data 4

Crystal data and structure refinement, and bond lengths and angles for compound 2; CCDC reference 2111528.

Supplementary Data 5

Crystallographic data for compound 2; CCDC reference 2111528.

Supplementary Data 6

Structure factor file for compound 2; CCDC reference 2111528.

Supplementary Data 7

Supplementary statistical source data for the polymerization kinetics of Supplementary Fig. 24.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Fig. 4

Statistical source data.

Source Data Fig. 6

Statistical source data.

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Song, Y., He, J., Zhang, Y. et al. Recyclable cyclic bio-based acrylic polymer via pairwise monomer enchainment by a trifunctional Lewis pair. Nat. Chem. 15, 366–376 (2023). https://doi.org/10.1038/s41557-022-01097-7

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