Sustainable Polymeric Materials from Renewable Resources

Dear Colleagues,

Naturally occurring polymers were among the first materials used by men. The modification of polymers from renewable resources, such as casein, natural rubber, and cellulose, was applied in the 19th century to obtain useful polymeric materials. Synthetic polymers dominated over the past few decades. Today, there appears to be a continuously growing interest in the development of sustainable, safe, and environmentally friendly plastics from renewable resources as a result of increasing concerns regarding the depletion of fossil resources, disposal, and related issues.

Although there are several options to produce energy from renewable resources, the only alternative to fossil-based materials is biomass. The application of the biorefinery concept and the green chemistry principles in ecologically benign materials production opens a new era. Generally, three different routes can be followed in order to arrive to bio-based polymers. The first pathway involves the chemical modification of natural polymers, such as starch, cellulose, or chitin. The second route is associated with the isolation or synthesis of bioplastics from biomass (lignin, cellulose, starch, plant oils) through a two-step process, involving firstly the preparation of drop-in (traditional) monomers, e.g., ethylene, 1,2-ethanediol, or terephthalic acid, or of novel monomers, such as lactide or 2,5-furandicarboxylic acid, and then the polymerization of these monomers to produce bio-based plastics. Amongst bioplastics, bio-polyethylene (bio-PE) or bio-poly(ethylene terephthalate) (bio-PET) are currently available. On the other hand, highly promising new polymers, such as poly(lactic acid) and poly(ethylene 2,5-furandicarboxylate) (PEF), or even thermosetting polymers can be synthesized using renewable sources.

Finally, a third route involves the use of carbon dioxide in polymer synthesis. The first example is the production of polymer through photosynthesis or in microorganisms, e.g., biosynthesis of poly(hydroxy-alkanoate)s. Furthermore, CO₂ can also be used in the preparation of non-isocyanate polyurethanes.

Apart from the use of proper monomers and the subsequent homopolymer production, copolymerization, blending, and the use of bio-based additives, like lignocellulose fibers for biocomposites, are considered the four main strategies for obtaining bio-based sustainable polymeric materials with tailored properties. Among polymers from renewable resources, there are many recyclable, yet nondegradable homopolymers synthesized from biomass derived monomers (PEF, bio-PE, bio-PET), but there are also biodegradable polyesters, including poly(lactic acid) (PLA), poly(β-hydroxybutyrate) (PHB), poly(butylene adipate) (PBA), poly(butylene succinate) (PBS), and others.

In this collection, an attempt is made to follow the current progress in the production of sustainable polymeric materials from renewable resources, starting from biomass-derived monomers and then extending in the synthesis, properties, uses, and applications of homopolymers and copolymers, but also blends and composites from renewable resources.

Prof. Dr. George Z. Papageorgiou
Guest Editor

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