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. 2022 Sep 7;13(39):11496-11505.
doi: 10.1039/d2sc02536a. eCollection 2022 Oct 12.

Mechanochemical ring-opening metathesis polymerization: development, scope, and mechano-exclusive polymer synthesis

Gue Seon Lee  1 , Hyo Won Lee  1 , Hyun Sub Lee  1 , Taeyang Do  1 , Jean-Louis Do  2 , Jeewoo Lim  3 , Gregory I Peterson  4 , Tomislav Friščić  2 , Jeung Gon Kim  1   5
Affiliations

Mechanochemical ring-opening metathesis polymerization: development, scope, and mechano-exclusive polymer synthesis

Gue Seon Lee et al. Chem Sci. .

Abstract

Ruthenium-alkylidene initiated ring-opening metathesis polymerization has been realized under solid-state conditions by employing a mechanochemical ball milling method. This method promotes greenness and broadens the scope to include mechano-exclusive products. The carbene- and pyridine-based Grubbs 3rd-generation complex outperformed other catalysts and maintained similar mechanistic features of solution-phase reactions. High-speed ball milling provides sufficient mixing and energy to the solid reaction mixture, which is composed of an initiator and monomers, to minimize or eliminate the use of solvents. Therefore, the solubility and miscibility of monomers and Ru-initiators are not limiting factors in solid-state ball milling. A wide variety of solid monomers, including ionomers, fluorous monomers, and macromonomers, were successfully polymerized under ball milling conditions. Importantly, direct copolymerization of immiscible (ionic/hydrophobic) monomers exemplifies the synthesis of mechano-exclusive polymers that are difficult to make using traditional solution procedures. Finally, the addition of a small amount of a liquid additive (i.e., liquid-assisted grinding) minimized chain-degradation, enabling high-molecular-weight polymer synthesis.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Fig. 1
Fig. 1. Mech-ROMP using ball mill grinding.
Scheme 1
Scheme 1. Structures of Ru-initiators used in this study.
Fig. 2
Fig. 2. Conversion and Mnvs. ball milling time of neat 1a and G3.
Fig. 3
Fig. 3. SEC traces obtained for selected polymers from Table 5.
Fig. 4
Fig. 4. SEC traces of [1a]/[G3] = 100, 200, and 300. [1a (50 mg), G3, and DCE (20 μL) in a 10 mL zirconia jar, three 8 mm zirconia balls, and 30 Hz vibration for 30 min].
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