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: 41 Session 3: Chemical modification processes for the biomass

Abstract for a poster

New challenges for lignin: towards the synthesis of polymeric materials.

Stphanie Laurichesse1*, Luc Avrous1
1

LIPHT- Laboratoire dIngnierie des Polymres pour les Hautes Technologies, UdS-CNRS, Strasbourg, France * E-mail : stephanie.laurichesse@etu.unistra.fr

In recent years, a significant attention has been paid on bio-based polymer, among which are polymers synthesized from wood raw material. Lignin, an amorphous and phenolic polymer is, after cellulose, the most abundant biopolymer corresponding to 15-30% of the wood composition. Nowadays, several technical lignins are commercially available and are produced at large scale (Kraft, Lignosulfonate and soda lignin). While currently often used as a filler or additive, lignin is rarely exploited as a raw material for chemical products. It may however be an excellent alternative to chemical feedstock due to its numerous chemical active sites. In this work, we have investigated the use of lignin to initiate polymerization reactions. Aliphatic and phenolic hydroxyls are the most important functional groups affecting the reactivity of lignin. This high number of hydroxyl groups has thus been considered for chemical modification or polymer synthesis. However, depending on the origin and the separation process, lignin materials differ considerably one from another, with variations in molecular weight, in solubility capacity and in the amount of functional groups. In the present study, we choose to work with sulfur-free lignin to avoid side reactions. Therefore, a lignin provided from a soda extraction process was used to carry out polymerization reactions. The aim of this study is to enhance the reactivity of lignin by modifying the lignins structure. In that frame, different ways of chemical modification have been considered. The first one is the enhancement of the availability of hydroxyl groups by grafting long polymer chains on lignin. -Caprolactone has been used as a monomer for Ring-Opening Polymerization, lignin being the macroinitiator. By this way, a star structure macromolecule has been synthesized: lignin is the core of the architecture and grafted polymer chains with various molecular weights constitute the arms. The effect of the reaction temperature, the chemical nature and the amount of catalyst have been studied in order to determine the optimal reaction parameters in order to graft long polycaprolactone (PCL) chains onto lignin molecule. NMR analyses were used to monitor the formation of lignin-based PCL and GPC measurements have confirmed the grafting. By adding low Tg polymers grafts, the chain flexibility and mobility of the lignin could increase and this product get thermoplastic properties. The high number of hydroxyl functions on lignin may limit the thermoplastic properties that can be brought by chain grafting. A partial acetylation has been achieved to reduce the number of active sites. The modified lignin is expected to provide a better control of the functionality with 45, 60 or 80% less hydroxyl functions. After this reaction step, the grafting of long polymer chains can be considered using the remaining hydroxyl functions The complexity and the unresolved structure of lignin is still a challenge and the final objective of this work is to broaden this study to more common lignin such as Kraft lignin.