Mechanochemical Ring‐Opening Polymerization of Lactide: Liquid‐Assisted Grinding for the Green Synthesis of Poly(lactic acid) with High Molecular Weight

Mechanochemical polymerization of lactide is carried out by using ball milling. Mechanical energy from collisions between the balls and the vessel efficiently promotes an organic‐base‐mediated metal‐ and solvent‐free solid‐state polymerization. Investigation of the parameters of the ball‐milling synthesis revealed that the degree of lactide ring‐opening polymerization could be modulated by the ball‐milling time, vibration frequency, mass of the ball media, and liquid‐assisted grinding. Liquid‐assisted grinding was found to be an especially important factor for achieving a high degree of mechanochemical polymerization. Although polymer‐chain scission from the strong collision energy prevented mechanical‐force‐driven high‐molecular‐weight polymer synthesis, the addition of only a small amount of liquid enabled sufficient energy dissipation and poly(lactic acid) was thereby obtained with a molecular weight of over 1×105 g mol−1. The miller's tale: Mechanochemical polymerization of lactide is carried out by using ball milling. Mechanical energy from the collisions between the balls and the vessel efficiently promoted an organic‐base‐mediated metal‐ and solvent‐free solid‐state polymerization. Addition of a small amount of liquid enabled energy dissipation and poly(lactic acid) was thereby obtained with a molecular weight of over 1×105 g mol−1.