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Poly(lactic acid) (PLA) was degraded to methyl lactate (Me-La) by an imino monophenolate Zn(1) 2 catalyst in the presence of tetrahydrofuran, as the solvent, and methanol, as the protic source. As well as solution-based polymerization and degradation, catalyst stability was assessed and discussed. The chemical degradation of four different commercial samples of PLA, varying in molecular weight, was studied. The effect of PLA concentration (0.05−0.2 g mL −1 ), reaction temperature (40−130 °C), and catalyst concentration (4−16 wt %) on conversion, yield, and selectivity were studied and results statistically analyzed. Mass-transfer limitations were assessed by utilizing two different PLA particle sizes and altering the stirring speed. Results revealed that the main variables affecting PLA degradation are temperature and catalyst concentration. It was possible to observe Me-La formation even at 40 °C, although the reaction times were significantly longer when compared to the highest temperatures. Conversions of 100%, as determined by 1H NMR spectroscopy and gel permeation chromatography, were possible in short times (<15 min) depending on temperature and catalyst concentration. A reaction mechanism for the production of Me-La from PLA, which considers the formation of chain-end groups as intermediates is presented and values for the kinetic constants are determined from the model. The activation energy for the initial degradation step was in the range 39−65 kJ mol −1 , decreasing with increasing catalyst loading.

Plastics are an indispensable material with numerous benefits and advantages compared to traditional materials, such as glass and paper. However, their widespread use has caused significant environmental pollution and most plastics are currently nonrenewable. Biobased polymers represent an important step for tackling these issues, however, the end-of-life disposal of such materials needs to be critically considered to allow for a transition to a circular economy for plastics. Poly(lactic acid) (PLA) is an important example of a biobased polymer, which is also biodegradable. However, industrial composting of PLA affords water and carbon dioxide only and in the natural environment, PLA has a slow biodegradation rate. Therefore, recycling processes are important for PLA, particularly chemical recycling, which affords monomers and useful platform chemicals, maintaining the usefulness and value of the material. This review covers the different methods of PLA chemical recycling, highlighting recent trends and advances in the area.

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 ...

A range of simple ethylenediamine based Zn(II) and Mg(II) complexes have been prepared and their structures determined via NMR spectroscopy and X-ray crystallography. Preparation of these complexes was also demonstrated to be scalable, with 25 g of Zn(1) 2 being readily produced. These complexes were trialed for the ring opening polymerisation (ROP) of lactide under industrially relevant conditions. Their reactivity has been related to their structure in solution. Incredibly high activity is achieved in the majority of cases including low catalytic loading and high temperatures, under industrially relevant conditions (180°C 10 000 : 1 : 100 [LA] : [Zn] : [BnOH]), with high conversion achieved within 10 minutes and TOFs in excess of 100 000 h −1 achieved. The performance of these initiators for polymer production is supported by GPC, DSC and IR spectroscopy which all highlight the excellent control achieved. † Electronic supplementary information (ESI) available: Full experimental data, including ligand, complex, and polymer characterisation data. CCDC 1844404-1844413. For ESI and crystallographic data in CIF or other electronic format see