No abstract

Highly active and exclusive transesterifications of methyl 10-undecenoate with alcohols (cyclohexanemethanol, 1,4-cyclohexanedimethanol, 10-undecen-1-ol, 3-hexanol) have been demonstrated by Cp′TiCl3 (Cp′ = Cp, C5Me5) at 100–120 °C. The CpTiCl3 enabled depolymerization of poly­(ethylene adipate) by the transesterification (>99% conv., 0.25–0.5 mol % Ti) at 120 °C; the depolymerization completed after 6 h at 150 °C (0.5 mol % Ti).

Exclusive chemical conversions of polyesters [poly(ethylene adipate) (PEA), poly(butylene adipate) (PBA), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT)] to the corresponding monomers (diethyl adipate, diethyl terephthalate, ethylene glycol, 1,4-butane diol) by transesterification with ethanol using Cp’TiCl3 (Cp’ = Cp, Cp*) catalyst have been demonstrated. The present acid-base-free depolymerizations by Cp’TiCl3 exhibited completed conversions (>99%) of PET, PBT to afford diethyl terephthalate and ethylene glycol or 1,4-butane diol exclusively (selectivity >99%) without formation of any other by-products in the NMR spectra (150–170 °C, Ti 1.0, or 2.0 mol%). The resultant reaction mixture after the depolymerization of PBA with ethanol via the CpTiCl3 catalyst (1.0 mol%, 150 °C, 3 h), consisting of diethyl adipate and 1,4-butane diol, was heated at 150 °C in vacuo for 24 h to afford high molecular weight recycled PBA with unimodal molecular weight distribution (Mn = 11,800, Mw/Mn = 1.6), strongly demonstrating a possibility of one-pot (acid-base-free) closed-loop chemical recycling.