Chemical modification of lignins: Towards biobased polymers
Introduction
The petrochemical boom of the second half of the last century has marked the strong development of the production of synthetic polymers. The availability of a growing number of monomers from fossil resources has supplanted during a period of time the use of biobased chemicals and their corresponding polymers. For different reasons, mainly economic, modest investments were devoted for a long time to the development of renewable resources in chemistry. Nevertheless, the increasing use of fossil fuels associated with the lack of availability of some petrol fractions and an increasing awareness concerning the human impacts on the environment have led to a renewed strong interest in the use of sustainable resources for energy and material [1]. This growing interest about a green and sustainable chemistry has also contributed to call attention to biomass and specifically on lignocellulosic feedstock as a promising, renewable and vast resource for chemicals, mainly without competition with food applications compared to, e.g., starch or vegetable oils. Lignocellulosic biomass is mainly composed of carbohydrate polymers (cellulose and hemicellulose), and aromatic polymers (lignin and tannin). After cellulose, lignin is the second most abundant polymer from biomass and the main one based on aromatic units. It can be isolated from wood, annual plants such as wheat straw or agricultural residues (sugar cane bagasse) by different extraction processes. Research on lignin chemistry is not recent. Progress concerning lignin characterization in the mid-nineteenth century contributed to the development of new materials based on renewable resources. Improved technologies associated with papermaking, wood processing and textile also contributed to the development of these polymers from biomass [2] that could be integrated in biorefineries [3], [4] to produce a large range of outputs such as materials, power, chemicals and fuel. The following reviews the major breakthrough in lignin by mainly development of biorefinery industries and new processes to convert this biomacromolecule into value-added products.
One objective of this review is to provide overview and background information on economic aspects concerning the use of lignin from its extraction by several processes to its thermal conversion or chemical modification. Beyond the presentation of the different chemical investigations performed on lignin, special stress will be laid on potential applications for production of chemicals and polymers.
Section snippets
Historical outline
A period of about 170 years has passed since the French chemist, Anselme Payen (1795–1871) treated wood with nitric acid and caustic soda, recovering two different products [5]. He called the first one “cellulose” and the other material with higher carbon content was considered as an incrusting material, in which the fiber-forming cellulose was imbedded. The Payen's “incrustation theory” [6] marks the beginning of the history of what latter was named “lignin”, a word derived from the Latin
Concept of biorefinery
The objective of chemical pulping processes is to remove enough lignin to separate cellulosic fibers one from another to produce a suitable pulp for the manufacture of paper and other related products [15]. Until recently, lignin has been considered for a long time as a waste from pulp and paper industry that serves only as fuel to power paper mills. During kraft pulping process, the resulting black liquor (containing between 35 and 45% of lignin) [50] is concentrated with an evaporator train
General background
The huge potential of lignin gives several opportunities to take advantage of its versatility for multiple applications. The main uses of lignin have been classified into two different groups, (i) without chemical modification, lignin is directly incorporated into matrix to give new or improved properties, and (ii) with chemical modification to prepare a large range of chemicals, building blocks and polymers.
Lignin has been subjected to a vast array of reactions for both fundamental and applied
Conclusion
Over 70 million tons of lignin are produced annually in the world and around 95% of that production are burned. The remaining 5% is used for commercial applications including additives, dispersants, binders or surfactants. Observing the number of studies performed on lignin, new technologies for extracting and processing it, lignin is receiving greater attention as the aromatic compounds (C6, etc.) from oil exploitation become more rare, and more costly. In this way, the concept of a
Acknowledgments
We are grateful for Alsace Region, Oséo and ANRT for their financial support.
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