Regioselective synthesis of renewable bisphenols from 2,3-pentanedione and their application as plasticizers
Literature Information
Wouter Schutyser, Steven-Friso Koelewijn, Michiel Dusselier, Joice Thomas, Feng Yu, Maria Josefina Carbone, Mario Smet, Peter Van Puyvelde, Wim Dehaen, Bert F. Sels
2,3-Pentanedione (2,3-PD), a bio-based chemical derived from lactic acid, has the potential to serve as a precursor for the synthesis of novel bisphenols. We developed a solvent-free catalytic strategy for the condensation of phenol with 2,3-PD by using acid catalysts at temperatures ranging from 323 to 373 K. Various soluble and solid acids exhibit high activity, while a high chemoselectivity to bisphenol requires a high phenol to 2,3-PD molar ratio. Bisphenol yields as high as 84% are for instance reported in an excess of phenol in the presence of Nafion NR50. Recycling of the Nafion catalyst after washing with ethanol at room temperature is demonstrated. The regioselectivity in the bisphenol fraction is influenced by the acid strength. A clear trend is presented in which the regioselectivity towards the desired p,p′-isomers increases with increasing acid strength, showing p,p′/o,p′-isomer ratios as high as 100. A tentative mechanism is discussed based on the ionic versus non-ionic pathway. The purified 2,3-PD-derived p,p′-bisphenols are assessed as plasticizers for polyethylene terephthalate (PET), showing promising properties similar to that of the reference bisphenol A, but with a broader processing window due to the lower melting point and higher thermal stability under an inert atmosphere.
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Green Chemistry provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on, but not limited to, the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998). Green chemistry is the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry is at the frontiers of this continuously-evolving interdisciplinary science and publishes research that attempts to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. Submissions on all aspects of research relating to the endeavour are welcome. The journal publishes original and significant cutting-edge research that is likely to be of wide general appeal. To be published, work must present a significant advance in green chemistry. Papers must contain a comparison with existing methods and demonstrate advantages over those methods before publication can be considered. For more information please see this Editorial. Coverage includes the following, but is not limited to: Design (e.g. biomimicry, design for degradation/recycling/reduced toxicity…) Reagents & Feedstocks (e.g. renewables, CO2, solvents, auxiliary agents, waste utilization…) Synthesis (e.g. organic, inorganic, synthetic biology…) Catalysis (e.g. homogeneous, heterogeneous, enzyme, whole cell…) Process (e.g. process design, intensification, separations, recycling, efficiency…) Energy (e.g. renewable energy, fuels, photovoltaics, fuel cells, energy storage, energy carriers…) Applications (e.g. electronics, dyes, consumer products, coatings, pharmaceuticals, preservatives, building materials, chemicals for industry/agriculture/mining…) Impact (e.g. safety, metrics, LCA, sustainability, (eco)toxicology…) Green chemistry is, by definition, a continuously-evolving frontier. Therefore, the inclusion of a particular material or technology does not, of itself, guarantee that a paper is suitable for the journal. To be suitable, the novel advance should have the potential for reduced environmental impact relative to the state of the art. Green Chemistry does not normally deal with research associated with 'end-of-pipe' or remediation issues.










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