Abstract
Sustainable chemistry requires application of green processes and often starting materials originate from renewable resources. Biomass-derived monomers based on five-membered γ-butyrolactone ring represent suitable candidates to replace sources of fossil origin. α-Methylene-γ-butyrolactone, β-hydroxy-α-methylene-γ-butyrolactone, and β- and γ-methyl-α-methylene-γ-butyrolactones bearing exocyclic double bond are available directly by isolation from plants or derived from itaconic or levulinic acids available from biomass feedstock. Exocyclic double bond with structural similarity with methacrylates is highly reactive in chain-growth polymerization. Reaction involves the linking of monomer molecules through vinyl double bonds in the presence of initiators typical for radical, anionic, zwitterionic, group-transfer, organocatalytic, and coordination polymerizations. The formed polymers containing pendant ring are characterized by high glass transition temperature (Tg > 195°C) and render decent heat, weathering, scratch, and solvent resistance. The monomers can also be hydrolyzed to open the lactone ring and form water-soluble monomers. Subsequent radical copolymerization in the presence of cross-linker can yield to hydrogels with superior degree of swelling and highly tunable characteristics, depending on the external stimuli. The five-membered lactone ring allows copolymerization of these compounds by ring opening polymerization to provide polyesters with preserved methylene functionality. In addition, both the lactone ring and the methylene double bond can be attacked by amines. Polyaddition with di- or multi-amines leads to functional poly(amidoamines) with properties tunable by structure of the amines. In this mini-review, we summarize the synthetic procedures for preparation of polymeric materials with interesting properties, including thermoplastic elastomers, acrylic latexes, stimuli-sensitive superabsorbent hydrogels, functional biocompatible polyesters, and poly(amidoamines).
Highlights
The research in the field of renewable or sustainable materials gained increased attention mainly due to the examining the possibility to replace petroleum-based raw materials as polymer materials for large commodity and specialty chemical markets (Vikas, 2012)
Functional Renewable Polymers acid or from bacterial biosynthesis as degradable polyesters have been studied for a longer time
The group of unsaturated lactones were significantly less extensively studied so far. Their advantage, is that they carry two different functional moieties, namely, vinyl and lactone, in one molecule, while both of them are polymerizable. These monomers can be taken as replacement ofacrylates in vinyl-addition polymerization or asmonomers for preparation of degradable polyesters employing lactone ringopening polymerization (ROP) (Figure 1)
Summary
The research in the field of renewable or sustainable materials gained increased attention mainly due to the examining the possibility to replace petroleum-based raw materials as polymer materials for large commodity and specialty chemical markets (Vikas, 2012). The main advantage of these monomers is in enhanced functionality of the final polymers bearing either pendant double bond, pendant lactone ring, or other pendant substituents allowing for various post-functionalizations or employing combination with other polymerization technique for production of desired materials. The most studies of MBL derivatives describe their polymerization exclusively via vinyl addition of exo-methylene double bond without ring opening of lactone ring using various polymerization techniques, including free radical (Akkapeddi, 1979a), reversible deactivation (Mosnácek and Matyjaszewski, 2008), coordination (Miyake et al, 2010a), group transfer (Miyake et al, 2010b), or anionic polymerization (Hu et al, 2011; Figure 1).
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