Tuning a robust system: N,O zinc guanidine catalysts for the ROP of lactide

Abstract

Non-toxic, highly active and robust complexes are the holy grail as ideal green catalysts for the polymerisation of biorenewable and biodegradable polylactide. Four new zinc guanidine complexes [ZnCl₂(TMG4NMe₂asme)], [ZnCl₂(TMG5Clasme)], [ZnCl₂(TMG5Measme)] and [ZnCl₂(TMG5NMe₂asme)] with different electron-donating and electron-withdrawing groups on the ligand's aromatic backbone have been synthesised. Ligands are derived from low-cost commercially available compounds and have been converted by a three- or four-step synthesis process into the desired ligand in good yields. The compounds have been fully characterised and tested in the ROP of rac-LA under industrially relevant conditions. The complexes are based on the recently published structure [ZnCl₂(TMGasme)] which has shown high activity in the polymerisation of lactide at 150 °C. Different substituents in the para-position of the guanidine moiety significantly increase the polymerisation rate whereas positioning substituents in the meta-position causes no change in the reaction rate. With molecular weights over 71 000 g mol⁻¹ being achievable, the best system produces polymers for multiple industrial applications and its polymerisation rate approaches that of Sn(Oct)₂. The robust systems are able to polymerise non-purified lactide. The initiation of the polymerisation is suggested to occur due to impurities in the monomer.