As eries of Zn II complexes, based on propylenediamineS chiff bases, have been prepared and fully characterized. X-ray crystallography and NMR spectroscopy identified significant differences in the solid and solution state for the Zn II species. All complexes have been applied to the ring-opening polymerization of l-lactidew ith emphasis on industrial conditions. High conversion and good molecularw eight control were generally achievablef or Zn(A-D) 2 ,a nd high-molecular-weight poly(lactic acid) (PLA) was prepared in 1min at a1 0000:1:33 [lactide]/ [Zn]/[BnOH] loading. The more active Zn II catalysts were also appliedt oP LA degradation to alkyl lactateu nder mild conditions. Zn(A-B) 2 demonstrated high activity and selectivity in this process with PLA being consumed within 1h at 50 8C. Zn(C-D) 2 were shown to be less active, and these observations can be relatedt ot he catalysts' structure and the degradation mechanism. Initialr esultsf or the degradation of poly(ethylene terephthalate) and mixed feeds are also presented, highlighting the broader applicability of the systems presented.Owing to the inevitable depletion of fossil fuel resources, and inherentc arbon emissions, alternatives to petrochemical plastics are desperately needed. [1] Poly(lactic acid) (PLA) is apotential replacement for fossil-fuel-derived plastics used for packaging applications. [2,3] PLA has the added advantageo f being biocompatible and therefore suitable for biomedical applications. [4,5] Because it is derived from annually harvested crops, PLA is biorenewable and has promising green credentials in terms of CO 2 emissions and life-cycle assessment. [6,7] High-molecular-weight PLA is preferentially prepared from the cyclic dimer of lactic acid, lactide (LA), through ring-opening polymerization (ROP). [8] CurrentP LA research seeks to reduce energy/material input of LA monomer synthesis, [9][10][11][12] demonstrate ande lucidate stereoselective initiation [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] and prepare robust initiators to compete with Sn(Oct) 2 under industrial conditions. [30][31][32][33][34] Plastic waste andp ollution are af urther 21 st century challenge forboth academia and industry.Although PLA is biodegradable under high-temperature industrial conditions, it will not readily degrade in the natural environmenta nd therefore will contribute to the millions of tonnes of waste in landfill and in oceans. [35][36][37] End-of-life plastic waste managementi s key to tackling this issue, andi ti si mperative this is addressed for all aspiring materials such as PLA. For PLA, chemical recycling is ap articularly attractive route because it can produce value-added products such as alkyl lactates, lactic acid and acrylic acid. [38,39] These can be usefuli nt heir own right or used to reform LA, and therefore PLA, to facilitate ac ircular-economy approach. Lactic acid, for example, is regarded as ap latform chemical, and alkyl lactates are considered green solvents. [40][41][42][43][44] The conversion of PLA ...
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