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

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.

Data availability

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.

Author information

Authors and Affiliations

Authors

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.

Corresponding author

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. (2022). https://doi.org/10.1038/s41557-022-01097-7

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