https://pubs.rsc.org/en/Content/ArticlePDF/2016/GC/C6GC00605A

Itaconic acid – a versatile building block for renewable polyesters with enhanced functionality

The field of biorenewable polymers is ever-expanding, aided by the interest of the general public to adopt more sustainable practices for natural resource utilization as well as waste generation. This review summarizes recent efforts to synthesize biobased thermoplastics with glass transition temperature (Tg) values exceeding that of polylactic acid (PLA), near 55 °C. A high Tg is essential for materials that aspire to replace any incumbent commodity plastics employed in the amorphous state. The first section focuses on commercial bioplastics and describes: approaches toward biorenewable polyethylene terephthalate (PET); efforts to improve the Tg of PLA; and advances toward polyethylene furanoate (PEF). The remaining sections catalogue a wide variety of novel, high Tg bioplastics categorized as: aromatic biopolymers, carbocyclic and heterocyclic biopolymers, and vinyl-type biopolymers synthesized via radical polymerization.

The quest for high glass transition temperature bioplastics

Push–pull alkenes, which bear electron-donating and -accepting group(s) at both termini of a C═C double bond, respectively, are of interest not only for their unique electronic properties but also for their importance as versatile building blocks in organic synthesis. In the world of ketene acetals having the push–pull alkene skeleton, ketene N,S-acetal is most likely the biggest family according to the number and types of these compounds. The first ketene N,S-acetal compound was reported in 1956. As a cyclic ketene N,S-acetal compound, nithiazine, the first lead structure of neonicotinoid insecticides, was reported in 1978. The characteristics of ketene N,S-acetals, which have the structural feature of ketene S,S-acetals and enaminones, make them versatile and easy to use, especially in cyclization and multicomponent reactions for the synthesis of various heterocyclic systems and related natural products. There has been an increasing wealth of information about the synthesis and synthetic applications of...

Chemistry of Ketene N,S-Acetals: An Overview.

Biorefinery aims at the conversion of biomass and renewable feedstocks into fuels and platform chemicals, in analogy to conventional oil refinery. In the past years, the scientific community has defined a number of primary building blocks that can be obtained by direct biomass decomposition. However, the large potential of this “renewable chemical space” to contribute to the generation of value added bio-active compounds and materials still remains unexplored. In general, biomass derived building blocks feature a diverse range of chemical functionalities. In order to be integrated into value-added compounds, they require additional functionalization and/or covalent modification thereby generating secondary building blocks. The latter can be thus regarded as functional components of bio-active molecules or materials and represent an expansion of the renewable chemical space. This perspective highlights the most recent developments and opportunities for the synthesis of secondary biomass derived building blocks and their application to the preparation of value added products.

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Alexandra M. Medway

Papers

Heterocycle construction using the biomass-derived building block itaconic acid