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LignoStarch Tailored modification of starch by radiation-grafting of lignin
Dhriti Khandal, Christophe Bliard, X. Coqueret, Pierre-Yves Mikus, Patrice Dole, Stephanie Baumberger, Jeremie Soulestin, Marie France Lacrampe
To cite this version:
Dhriti Khandal, Christophe Bliard, X. Coqueret, Pierre-Yves Mikus, Patrice Dole, et al.. LignoStarch Tailored modification of starch by radiation-grafting of lignin. ANR SUSTAINABLE CHEMISTRY CONFERENCE, Oct 2012, Lyon, France. 2012. �hal-02279995�
LignoStarch
Tailored modification of starch by radiation-grafting of lignin
CP2D 2007
D. Khandal,
1)
C. Bliard,
1)
X. Coqueret,
1)
P. Y. Mikus,
2)
P. Dole,
2)
S. Baumberger,
3)
J. Soulestin,
4)
and M.F. Lacrampe
4)
1) ICMR, UMR CNRS 7312, 2)FARE, UMR INRA, Université de Reims Champagne Ardenne,
3) INRA UMR 1318 Institut JPB - AgroParisTech Versailles, 4) DTPCIM - Ecole des Mines de Douai
Thermoplastic Starch (TPS) represents ca 80% of the biopolymer market, however, unlike petroleum based polymers, TPS is still manufactured by traditional methods of extrusion and injection molding.
Starch is a semi-crystalline renewable biopolymer made of glucose units existing as a mixture of linear polymer chains (amylose) and branched polymer chains (amylopectin). Due to its hydrophyllic nature, starch products show retrogradation and varying mechanical properties with time.
Lignin, another renewable biopolymer and a by-product of the paper industry is hydrophobic and limits water sensitivity of TPS blends. Electron Beam radiation-induced grafting of lignin models onto starch/maltodextrin is shown to result in physical stability of the blends with limited loss of mechanical properties, improved surface hydrophobicity, and to impede long-term retrogradation.
Introduction
The research was carried out in 4 domains: Method development, Mechanical Properties, Surface Properties, and Radiation-induced
modifications.
Concept
Surface hydrophilicity decreases of the starch lignin blends after irradiation.
Mechanical Properties can be modified in presence of Lignin-like additives. Radiation-induced grafting of aromatic additives competes chain scission. Final blend properties depend on blend composition and radiation parameters.
- Hydrophobic surfaces can be obtained with qwater >110°
- Mechanical properties can be modified in presence of lignin-like monomers despite the ever existing chain scission
- Deformation breaking mechanisms monitored by videotraction
- Composition (plasticizer, aromatic additive) and radiation parameters determine final properties
- Aromatic additives exert strong protective effect against scission
- Starch molecular architecture can be tailored as desired
Salient Results
xxx@xxx.fr
CONTACT :
Prof. Xavier Coqueret, Institut Chimie Moleculaire de Reims, URCA Reims
xavier.coqueret@univ-reims.fr
Amylose: Linear polymer chain with a (1,4)
branching between
glucose monomer units.
Amylopectin: Polymer chain with a (1,4) and a (1,6) branching between glucose monomer units.
R1 = R2 = H p-Coumaryl Alcohol R1 = H, R2 = OMe Coniferyl Alcohol R1 = R2 = OMe Sinapyl Alcohol CH2OH OH R2 R1 O O O OMe O H OH OH OMe O O H O H O MeO O H O H OMe O O H OMe O O H OH MeO O O O H O H OMe O OH OH MeO O H OH OMe OMe O H O H O OH OMe OH OH O OMe O H OMe O H OH O H MeO O O O OMe O H OH OH OMe O O H O H O MeO O H O H OMe O O H OMe O O H OH MeO O O O H O H OMe O OH OH MeO O H OH OMe OMe O H O H O OH OMe OH OH O OMe O H OMe O H OH O H MeO OH OCH3 OCH3 O HO HO OH OH O Lignin Methoxyl Phenolic hydroxyl Benzyl alcohol
Surface and Mechanical Properties
0 10 20 30 40 50 60 70
Starch LS 20 LS 30 WL 20 WL 30 BagL 20 BagL 30
Co n ta ct a n g le ( q0 °) Native film
Irradiated film (400 kGy)
Starch : Glycerol : Lignins = 70 : 30 : 20 or 30 parts by wt
• Lignosulfonates (LS)
• Wheat liginins (WL)
• Bagasse lignins (BagL)
Echantillon natif Echantillon irradié 150-175 kV 10 MeV Sample for irradiation Irradiated Sample O O O O O O O O O O O O
Ionizing Radiation Structural Modifications From : Scission, Crosslinking, Grafting
O O O OMe O H OH OH OMe O O H O H O MeO O H O H OMe O O H OMe O O H OH MeO O O O H O H OMe O OH OH MeO O H OH OMe OMe O H O H O OH OMe OH OH O OMe O H OMe O H OH O H MeO CH2OH OH CH2OH OH OMe CH2OH OH MeO OMe OH OMe OH OH OH OH OH OH
Lignin Lignin Monomer Models
Starch Starch models
H OH O O O H OH O HO O OH O O H O OH OH OH H H n H OH O O O H OH O O O H OH O H O H O OH OH OH OH H H 5 µm 5 µm 5 µm XRD 5 10 15 20 25 0,0 5,0x103 1,0x104 1,5x104 2,0x104 2,5x104 U V Abs orbance 284 nm
Retention Time (minutes)
0 kGy 50 kGy 100 kGy 200 kGy 400 kGy
Award at IRaP 2010 conference, Bethesda MD
Invited conferences at IMRaP 2011, Tihany Radiation Conference 2011, Gordon Research Conference on Radiation Chemistry 2012
Baumberger et al., J. Agric Food Chem, 1998, 46, 2234-2240 Lepifre et al., Biomacromolecules, 2004, 5, 1678-1686
Khandal et al., Radiat. Phys. Chem. 2012, Vol 81, No. 8 (2012), 986-990 Khandal et al., Radiat. Phys. Chem., in press
3 other publications are in process of review or submission
Conferences and Publications
Modifications at Molecular Level
- Grafting of aromatic additives overcome chain scission
- Radiochemical yields G(S) and G(X) determined f ( [arom] ) - H-bonding and supramolecular interactions affect reactivity
