Polymer-supported metal catalysts for the heterogeneous polymerisation of lactones

A series of metal complexes were immobilised onto an inert poly(styrene) (PS) support and utilised in the solvent free ring-opening polymerisation (ROP) of various lactones. PS-L^HZnOAc, PS-L^HSnOct and PS-L^ClSnOct were identified as the most successful heterogeneous catalysts for the ROP of l-lactide. Investigations by in situ ATR-FT-IR revealed conversions reaching ca. 90% in 6, 2.3 hours and 55 minutes, respectively, with excellent molecular weight control and dispersities (_M 1.15-1.17). Catalyst loadings as low as 15 ppm metal and TOF values of up to 810 h^-1 could also be achieved. Higher molecular weights could be targeted (ca. 35 kDa) whilst maintaining low dispersities in comparison to the industrial standard. Catalyst reuse was also possible, with up to 7 reuse cycles, albeit accompanied by a progressive reduction in conversion. Energy-Dispersive X-ray (EDX) spectroscopy and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) showed low metal content in the unpurified polymer (as low as 335 ppm, similar to what is found in polymer purified by classical methods), suggesting these systems as promising reusable catalysts for the industrial production of metal-free renewable polymers.