Preparation of α-Carbalkoxyalkyl Methacrylates by Pyrolysis of the Corresponding α-Acetoxyisobutyrates

Filachione, E. M.; Fein, M. L.; Lengel, J. H.; Fisher, C. H.

doi:10.1021/ja01182a028

Cited by 7 publications

(3 citation statements)

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“…The reaction was quenched by addition of acid resin, decanted, and removal excess alcohol by distillation provides the desired glycolate ester typically in >95% yield. Both 2‐hydroxyethyl glycolate62 and allyl glycolate63 are known molecules.…”

Section: Methodsmentioning

confidence: 99%

Transforming polylactide into value‐added materials

Leibfarth

Moreno

Hawker³

et al. 2012

J. Polym. Sci. A Polym. Chem.

101

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The production of chemical building blocks and polymer precursors from biorenewable and sustainable resources is an attractive method to bypass traditional fossil fuel derived materials. Accordingly, we report the organocatalytic recycling of postconsumer polylactide (PLA) into value-added small molecules. This strategy, using the highly active transesterification catalyst triazabicyclodecene, is shown to completely depolymerize PLA in the presence of various alcohols into valuable lactate esters. Using previously used PLA packaging material, the depolymerization is complete in minutes at room temperature and fully retains the stereochemistry of the lactate species. Further, the modularity and utility of this methodology with respect to polyester substrate is detailed by using a variety of functional alcohols to depolymerize both PLA and polyglycolide, with the corresponding ester smallmolecules being used to make new polymeric materials. The opportunities to transform waste streams into value-added chemicals and new materials through simple and versatile chemistry hold significant potential to extend the lifecycle of renewable chemical feedstocks. KEYWORDS: biodegradable; depolymerization; glycolate ester; lactate ester; organic catalysis; polyesters; polyglycolide; polylactide; recycling; transesterification INTRODUCTION As society increasingly deals with inherently limited natural resources, the utilization of 7% of fossil fuels for the production of plastics is a significant drain on petrochemical feedstocks.1 With the demand for polymeric materials increasing, it is imperative to develop building blocks based on renewable and sustainable resources.2 The conversion of biomass to value-added small molecules and polymer precursors is an attractive method to bypass traditional fossil fuel-based chemical production.3-5 For example, polylactide (PLA) has emerged as one of the most promising biorenewable and biodegradable polymers due to its utility in packaging, textile, and biomedical applications. [6][7][8][9] The recent addition of Natureworks TM LLC facility in the US has put annual production capacity of PLA at over 150,000 tons, making it a high-volume commodity material. [10][11][12] This largescale production and the predicted annual growth rate of 19% for bioplastics 13 assures that many new PLA derived products will enter the marketplace in the coming decades.

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Section: Methodsmentioning

confidence: 99%

Transforming polylactide into value‐added materials

Leibfarth

Moreno

Hawker³

et al. 2012

J. Polym. Sci. A Polym. Chem.

101

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“…A large number of patents describe the preparation of aliphatic polyesters from hydroxycarboxylic acids. [20][21][22][23][24] Braud et al 25 synthesised PCL oligomers by polycondensation of 6-hydroxyhexanoic acid under vacuum-thereby removing the water produced during the reaction and displacing the equilibrium towards the formation of the polymer. The reaction was performed without the addition of catalyst and was complete in 6 h at a temperature that was gradually increased from 80 to 150 1C.…”

Section: Polycondensationmentioning

confidence: 99%

Synthesis of polycaprolactone: a review

2009

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Polycaprolactone (PCL) is an important polymer due to its mechanical properties, miscibility with a large range of other polymers and biodegradability. Two main pathways to produce polycaprolactone have been described in the literature: the polycondensation of a hydroxycarboxylic acid: 6-hydroxyhexanoic acid, and the ring-opening polymerisation (ROP) of a lactone: epsilon-caprolactone (epsilon-CL). This critical review summarises the different conditions which have been described to synthesise PCL, and gives a broad overview of the different catalytic systems that were used (enzymatic, organic and metal catalyst systems). A surprising variety of catalytic systems have been studied, touching on virtually every section of the periodic table. A detailed list of reaction conditions and catalysts/initiators is given and reaction mechanisms are presented where known. Emphasis is put on the ROP pathway due to its prevalence in the literature and the superior polymer that is obtained. In addition, ineffective systems that have been tried to catalyse the production of PCL are included in the electronic supplementary information for completeness (141 references).

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“….3 mm. (7). sec-Butyl lactate, 2-ethylhexyl lactate, and methyl isobutyl carbinyl lactate were prepared by alcoholysis of methyl lactate.…”

Section: Acknowledgmentmentioning

confidence: 99%