1. Patrice Dole, INRA UMR FARE, patrice.dole@reims.inra.fr …what about lignins?

2. Lignins / material physicochemistry Overview of green materials Use of Lignin properties for green materials

3. O O O O O O

4. Intrinsic mobility Rigid aromatic tridimensionnal structure High Tg : In situ lignin : 200°C Extracted lignin : 120 to 180°C depending on Mw GeometryLow molecular weight and Non linear structure No entanglements Bad cohesion InteractionsSemi polar aromatic structure Solubility parameter around 11/12 (cal/cm 3 ) 1/2 Association properties  Lignin is plasticized by water Tg = 80°C in water saturation conditions FunctionnalityPhenolsRadical reactivity AlcoolsCondensation reactions Depolymerization Two families of bondsEasy partial hydrolysis, very difficult total depolymerization Extracted lignin is a polymer ?

5. Lignins / material physicochemistry Overview of green materials Use of Lignin properties for green materials

6. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Lignocellulosic materials Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks

7. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks Packaging Little markets Construction products Automotive market

8. Lignins / material physicochemistry Overview of green materials Use of Lignin properties for green materials

9. Rigid aromatic structure High Tg Aromatic Semi polar structure Solubility parameter around 11/12 (cal/cm 3 ) 1/2 Association properties Hydrated lignin Tg = 80°C Non linear structure and Low molecular weight No entanglements Bad cohesion PhenolsRadical reactivity AlcoolsCondensation reactions Two families of bonds Easy partial hydrolysis Thermoplastic behaviour Cohesion is only due to strong interactions Bad cohesion

10. 101001000 Strain(%) PS PET PP PBAT PLA MB PHB PLA PHB Pro PCL barquette film H H H PLA Pro Starch Hemi 0.1 1 10 100 Stress (MPa) Increasing Matrix Molecular weight and/or increasing its linearity lignin increasing low Mw plasticizer content

11. 101001000 Strain(%) 0.1 1 10 100 Stress (MPa) High interactions between macromolecules Low interactions between macromolecules use the possibility to play with polymer interactions  formulation with interacting species the only way is to modify the polymer network geometry The best general strategy to improve the mechanical properties of natural polymers depends on the initial level of interactions between macromolecules

12. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks

13. Rigid aromatic structureHigh Tg Semi polar structureSolubility parameter around 11/12 (cal/cm 3 ) 1/2 Hydrated lignin Tg = 80°C Non linear structure and Low molecular weight No entanglements Bad cohesion PhenolsRadical reactivity AlcoolsCondensation reactions Two families of bondsEasy partial hydrolysis Heterogeneous blends: lignin can be used as substituent of gelatinized starch in « starch based plastics » (use as amorphous organic filler) Homogeneous blends: Use as active molecule  the activity is a function of the solubility in continuous phase OR materials constituted by a lignin continuous phase

14. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks lignocellulosic materials

15. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics lignocellulosic materials Natural polymers monomers macromonomers Blends Composites Thermoplastics 3 D networks Rigid aromatic structure High Tg Semi polar structure Solubility parameter around 11/12 Hydrated lignin Tg = 80°C Non linear structure and Low molecular weight No entanglements Bad cohesion PhenolsRadical reactivity AlcoolsCondensation reactions Two families of bonds Easy partial hydrolysis Autoadhesion of fibers in binderless fiberboards T<Tg=80°C T<Tg=200°C lignin and hemicelluloses considered as an in situ 3D matrix irreversible strain Possibility to apply an irreversible strain: creep properties at T>Tg + crosslinking T>Tg Possibility to crosslink the network ability of phenolic compounds to combine with degradation products wet dry

16. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks

17. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers Blends Composites Thermoplastics 3 D networks Rigid aromatic structure High Tg Semi polar structure Solubility parameter around 11/12 Hydrated lignin Tg = 80°C Non linear structure and Low molecular weight No entanglements Bad cohesion PhenolsRadical reactivity AlcoolsCondensation reactions Two families of bonds Easy partial hydrolysis The nature of the main component at fiber surface depends on various factors, Variability of compatibility  variability of mechanical properties Apolar polymers Lignin Semi polar polymers Hemicelluloses Cellulose Solubility parameter Thermoplastic lignocellulosic composites, result from the association of fibers and thermoplastic apolar or semi polar polymers

18. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks

19. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks Rigid aromatic structureHigh Tg Semi polar structureSolubility parameter around 11/12 (cal/cm 3 ) 1/2 Hydrated lignin Tg = 80°C Non linear structure and Low molecular weight No entanglements Bad cohesion PhenolsRadical reactivity AlcoolsCondensation reactions Two families of bondsEasy partial hydrolysis Adapted MW to be used as reactive oligomer lignin is not a perfect polyol molecule for a well defined network: - too high functionnality - repartition of functionnality - non linear geometry

20. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks

21. PE Tg = -120°C Tf = 120°C PCLTg = -60°C Tf = 60°C PBSA Tg = -45°C Tf = 114°C PEA Tg = -30°C Tf = 112°C PPTg = -15°C Tf = 165°C PHBV 15 Tg = +5°C Tf = 145°C PHB Tg = +10°C Tf = 175°C PLA Tg = +58°C Tf = 152°C EVOHTg = 60°CTf = 190°C PETTg = 90°CTf = 270°C PSTg = 95 Starch Hemicelluloses Cellulose Tg > 200°C 0% HRT degradation < Tf The first criteria for the substitution of a polymer is the mechanical behaviour which is closely linked to Tg

22. PE Tg = -120°C Tf = 120°C PCLTg = -60°C Tf = 60°C PBSA Tg = -45°C Tf = 114°C PEA Tg = -30°C Tf = 112°C PPTg = -15°C Tf = 165°C PHBV 15 Tg = +5°C Tf = 145°C PHB Tg = +10°C Tf = 175°C PLA Tg = +58°C Tf = 152°C EVOHTg = 60°CTf = 190°C PETTg = 90°CTf = 270°C PSTg = 95 Starch Hemicelluloses Cellulose Tg > 200°C 0% HRT degradation < Tf

23. PE Tg = -120°C Tf = 120°C PCLTg = -60°C Tf = 60°C PBSA Tg = -45°C Tf = 114°C PEA Tg = -30°C Tf = 112°C PPTg = -15°C Tf = 165°C PHBV 15 Tg = +5°C Tf = 145°C PHB Tg = +10°C Tf = 175°C PLA Tg = +58°C Tf = 152°C EVOHTg = 60°CTf = 190°C PETTg = 90°CTf = 270°C PSTg = 95 Starch Hemicelluloses Cellulose Tg > 200°C 0% HRT degradation < Tf Natural polymers like starch or proteins are bad substitutes (low mechanical properties, hydrophily)  interesting rigid green monomers ?

24. Bio rafinery Renewable ressources Fibers Natural polymers BlendsComposites 3 D networks Rigid aromatic structure High Tg Semi polar structure Solubility parameter around 11/12 Hydrated lignin Tg = 80°C Non linear structure and Low molecular weight No entanglements Bad cohesion PhenolsRadical reactivity AlcoolsCondensation reactions Two families of bonds Easy partial hydrolysis Direct cracking leads to a wide variety of products Lignin is a potential abundant ressource of aromatic rigid monomers..for radical polymerization or polycondensation ?? Lignin is more available than orange juice ! Find a strategy to obtain pure low molecular weight compounds from lignin?

25. ? ? One step classical cracking the high variety of scission reactions implies a high variety of secondary reactions

26. ? ? One step classical cracking

27. Bio rafinery Fossil ressources Renewable ressources Biodegradable plastics Fibers Natural polymers monomers macromonomers BlendsComposites Thermoplastics 3 D networks