Novel clean and selective processes for starch modification

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Université de Reims Champagne-Ardenne Université de Reims Champagne Ardenne UMR CNRS 6519 Réactions sélectives et applications Novel clean and selective processes for starch modification X.

1 Université de Reims Champagne-Ardenne Université de Reims Champagne Ardenne UMR CNRS 6519 Réactions sélectives et applications Novel clean and selective processes for starch modification X. Coqueret 1), C. Bliard 2), P. Dole 3), F. Cazaux 4), S. Baumberger 5) and C. Lapierre 5) 1) UMR CNRS 6519, 2) FRE CNRS 2715, 3) UMR INRA FARE Université de Reims Champagne Ardenne Reims 4) UMR CNRS 8009 LCM, USTL Villeneuve d Ascq 5) UMR 206 Chimie Biologique INRA INA PG Thiverval-Grignon 1

2 Pristine starch: a semi-crystalline polymer cristallinity : 20-45% HCH 2 H H anhydroglucose unit (AGU) Lipids Amylose MW g.mol -1 Amylopectin double helix MW g.mol -1? (1? 4) ; 6 AGU per pitch ca. 6% of? (1? 6) linkage 2

3 Industrial use of starch Food additives (16 %) Sweeteners Thickeners Stabilizers Humectants Pharmaceutical, galenics Major non-food applications (84 %) Paper making industry (60%) Construction Plaster wallboards Adhesives Textile sizing, Fabric finishing, Printing industry (anti-set-off powder) Flocculating agents 3

4 Applications of starch Foreseen market expansion or radically new applications Textiles - for weaving production lines and printing cloth plastics Construction: binders, antifreeze, retarding agents for concrete (gluconic ac.) Lubricants - in association with vegetable oils for manufacture of biolubricants Agrochemicals - binder for fertilizers, controlled release by encapsulation, seed coatings Super-absorbent products - grafted starches disposable nappies, root coating Thermoplastic material 4

5 Clean processes for starch modification Vegetal origin + Clean processing = Greener chemistry Processing Reactive extrusion High-energy radiation Chemical modification of starch 1. Cationization (quaternary ammonium) 2. Enzymatic hydrolysis 3. Radiation grafting of thermoplastic starch 5

6 1 - Cationization of starch Papermaking industry Different types of starches Up to 10 wt-% of starch in some papersheets Cationic starch for binding cellulose fibers 6

7 Cationization of starch Etherification of AGU by trimethylammonium reagents HCH 2 H starch H NaH H H H H H H H N Cl - H H H H 3 C CH 3 Cl N (I) Cl - + CH 3 3-chloro-2-hydroxypropyl trimethylammonium chloride water H H Cl - + N CH 3 CH 3 CH 3 (II) CH 3 Cl - N CH3 CH 3 H H N Cl - N Cl - + some elimination products 1,2-epoxypropyl trimethylammonium chloride 7

8 1 H NMR analysis of starch cationization before reaction HD H H H H H H H H N Cl - H H after reaction after washing H 3 H 5 H 6,6 H 4 H 2? (ppm) 5,8 5,4 Consistent values of the degree of substitution (DS): NMR, elemental analysis, Kjeldhal, Cl - exchange 0,005 < DS < 0,2 5,0 4,6 4,2 3,8 3,4 3,0 8

9 Influence of [reactant] to [AGU] ratio on DS C C [reactant] / [NaH] = 1 [reactant] / [NaH] = 0,3 (I) DS 0,1 0,08 0,06 0,04 0,02 0 Cl H H 3 C CH 3 N + Cl - CH3 0 0,1 0,2 0,3 0,4 0,5 Yield ( %) DS 0,05 0,04 0,03 0,02 0,01 0 (II) CH 3 Cl - N CH 3 CH 3 Yield (%) ,02 0,04 0,06 0,08 0, [reactant I ] / [AGU] [reactant II ] / [AGU] DS increases when [co-reactant] increases, but reaction yield decreases 9

10 Influence of glycerol content on DS C [reactant] / [AGU] = 0,05 [reactant] / [NaH] = 1 (DS) 0,020 0,015 Yield (%) 36 (DS) 0,05 0,04 Yield (%) 90 0,010 0, % glycerol ,03 0,02 0, % glycerol reactant [I] reactant [II] DS decreases when plasticizer content increases 10

11 Factors influencing cationization efficiency Some other selected results Modeling of zation cationireaction Distribution of cationic functions Competing side reactions Relation between molecular structure and functional properties A. Ayoub et al. Starch/Stärke (2004), 55 (7), A. Ayoub et al. Starch/Stärke (2004), 56 (11), Yield (%) Intensity C 120 C 140 C Time (min) ? [ ] 11

12 2 - Dextrinisation of starch Conventional methods Acidic hydrolysis H Enzymatic H H H? - or?-amylase liquefying or saccharifying enzymes H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H Drawback of current processes batch operations wet chemistry long reaction time glucose syrup, dextrines.. 12

destructurization AMIVAL - C. Bliard, J.F.

13 Dextrinisation of starch by reactive extrusion native starch + co-reactant (water) + catalyst (enzyme) hydration and destructurization AMIVAL - C. Bliard, J.F. Lacoste - hydrolysis is faster - process is continuous - products are obtained as a concentrate hydrolysis 13

14 Dextrinisation of starch by reactive extrusion SEC profiles of obtained oligosaccharides 0,005 t (min) ,005 Reactive JF 46 (DE 23) extrusion sample -0,015 Dormadry 21 signal (mc) -0,025-0,035-0,045-0,055 Reference wet-technology AMIVAL - C. Bliard, J.F. Lacoste 14

15 Dextrinisation of starch by reactive extrusion Points under study Search for new thermally-mechanically resistant enzymes Multiparameter control of starch hydrolysis (T, power, water content, enzyme concentration) riented hydrolysis towards target distributions Confirmed advantages Low energy consumption Single step process Continuous production Easy drying 15

16 3 Radiation grafting of starch Potentialities of thermoplastic starch (TPS) High MW polymer with interesting mechanical properties Biodegradable thermoplastic material Cheap, from renewable resources Some limitations to be overcome Retrogradation (recrystallization) High hydrophilicity (poor properties when wet) Limited compatibility between starch and organic additives Migration or phase separation of plasticizer upon ageing 16

17 Lignins as additives for TPS A broad family of polyphenolic compounds biodegradables and hydrophobic Constituent of wood, second in abundance after cellulose Large variety of structures depending on botanical origin and industrial extraction process By-products of the pulp and paper industry to be valorized 17

18 Radiation processing for improving the properties of thermoplastic starch Concept Use high energy irradiation to create covalent linkages between amorphized starch and organic additives (low to high MW compounds, natural or synthetic) Structural defects impeding starch retrogradation Forced compatibility between blends constituents No phase separation, absence of migration bjectives Evaluate the scope and limits of ionizing radiation for improving the existing materials and processes 18

19 Radiation processing of starch-au blends CH2 CH CH2 NH C NH2 + starch 1) amorphization 2) EB-irradiation Electron beam accelerator High voltage : 175 kv kgy - in air AGU H H AGU H H H CH 2 AGU irradiated film CH CH 2 NH C NH 2 n - Physical stabilization effective - Multiple grafting demonstrated - MALDI TF mass spectrometry for the analysis of model blends sample electron curtain D.Ruckert, F. Cazaux, X. Coqueret J.Appl.Polym.Sci , 73, A.livier, C. Gors, F. Cazaux, X. Coqueret, Biomacromolecules 2000, 1, A.livier, F. Cazaux, and X. Coqueret, Biomacromolecules 2001, 2,

20 Properties of starch-lignin blends Starch 70 wt-parts + Glycerol 30 wt-parts + Lignins wt-parts: lignosulfonates (LS) wheat liginins (WL) bagasse lignins (BagL) Reduction of hydrophilicity Water sorption at 73 %RH T=25 C Starch-Glycerol (no lignin) % Starch-Glycerol-Bagasse lignins (20 phr) % Starch-Glycerol-Wheat lignins (20 phr) % Starch-Glycerol-Lignosulfonate (20-30 phr) % Protective effect against radiation 20

21 Properties of starch-lignin blends Modification of wettability by water Contact angle (? 0 ) Native film Irradiated film (400 kgy) Starch LS 20 LS 30 WL 20 WL 30 BagL 20 BagL 30 21

22 Maldi-ToF MS of maltodextrine Glucidex 19 flight tube Na+ H H H H H n model for starch n = 16 laser pulse m/z = (n x 162) DHB* matrix *2,5-dihydroxybenzoic acid m/z 22

23 23 Me H H H Me H H Me H H Me H Me H H Me H H Me H H Me H H Me Me H H H Me H H Me H Me H H H Me Me H H Me H H Me Me H H H Me Models for lignins

24 Models for lignins Phenols H H R Benzyl alcohols H H H H Me Cinnamic derivatives and lignin monomers H H H H CH 2 H CH 2 H CH 2 H R H H Me Me H Me 24

25 Reactivity of p-methoxybenzyl alcohol with maltodextrine Glucidex , ,32 30 (UAG) , H-(UAG) 6 -H m hexamer = 1013 Da H m alcohol = 138 Da CH 3 Na + m + Na = 23 Da Sum = 1154 Da bserved adduct = 1133 Da f I ( mdp6? 120) ( adduct)?? I( mdp6? 120)? I( mdp6 )

26 Reactivity of various benzyl alcohols with maltodextrine Glucidex 19 Hypothesis of a common mechanism for the various benzylic derivatives H H H H H Me i i m/z m/z The benzyl alcohol function seems to be involved in the condensation process m/z 26

27 C13 mélange 26 0 kgy C13 mélange kgy (ppm) Quantification of p-methoxybenzyl alcohol reactivity by 13 C NMR analysis Maltodextrine G19 + p-methoxybenzyl alcohol (20 phr) 13 C NMR (gated decoupling) : integral of -CH 2 -H to AGU CH-H Integral B H A4 A3 A3 A2 A2 A1 M e C B B G19 Integral B B H A4 A3 A3 A2 A2 A1 Me C B (ppm) Integral H CH 2 H Conversion (%) G19 H Dose (kgy) (ppm) 27

28 Formation of multiple adducts Maltodextrine G19 + p-methoxybenzyl alcohol kgy 50% 40% 30% Peak intensity in MALDI TF mass spectra relative to parent oligomer of DP=x DP % 10% 0% 1 addition (+120 Da) 2 additions (+240 Da) 3 additions (+360 Da) High grafting yield, and multiple grafting Confirmation of free radical mechanism for grafting since there is only a single site for acetalization per molecule 28

29 Coupling mechanism for benzyl alcohols Radiolysis of constituants UAG-UAG-UAG [UAG-UAG-UAG(-H)] + H H 2 H + H Ar-CR 2 -H Ar-CR 2 + H Secondary activation of polysaccharide by transfer UAG-UAG-UAG + Rad [UAG-UAG-UAG(-H)] + Rad-H Coupling by combination of free radical species [UAG-UAG-UAG(-H)] + Ar-CR 2 [UAG-UAG-UAG(-H)(+CR 2 -Ar)] 29

30 Grafting of Cinnamyl alcohol onto maltotriose (200 kgy dose) AGU AGU AGU AGU AGU AGU AGU AGU AGU MT 526,90 CH CH CH 2 CH 2 CH CH 2 H CH 2 CH CH 2 H 80 H CH 2 CH CH DP DP DP3 + 2*134 DP DP , , , , 795,03 H CH 2 AGU AGU AGU CH CH 2 AGU AGU AGU CH CH 2 CH CH CH 2 CH 2 H m/z 30

31 Grafting of cinnamyl alcohol onto maltodextrine Glucidex 19 (400 kgy dose) Composition : G19 63%, H2 16%, CML 5%, MeH 16% kgy 14 (UAG) *134 3* , , * ,59 10 (UAG) , * , , (UAG) *134 (UAG)-5 + 2* ,46 3* , , (UAG) (UAG) * ,50 (UAG) , * , , ,

32 Quantification of cinnamyl alcohol reactivity by 1 H NMR analysis 1H mélange kgy Integral Integral , (ppm) H H H Converted CinH (mol.kg-1) 0,30 0,20 0,10 1H mélange kgy 0,00 5H Dose (kgy) (ppm) [CinH] 0 = 0,08, 0,36, 0,68, 1,21 mol.kg -1 Fractional conversion exceeds 50% at 200 kgy 32

33 Conclusion Tailored structure and properties of starch derivatives are obtained by applying appropriate treatment: chemical, enzymatic or radiation processing with better respect of green chemistry principles. Physical limitation to chemical reactivity: lack of mobility High energy irradiation induces selective chemistry, is not so complex and can be well-controlled LignoStarch project (ANR 2007) 33

Potential of Daughter Ion Mass Spectrometry (ESI-MS-CID) in the Analysis of Cationic and Methyl Starches

Potential of Daughter Ion Mass Spectrometry (ESI-MS-CID) in the Analysis of Cationic and Methyl Starches Petra Mischnick, Wiebke Tüting, Roland Adden TU Braunschweig Starch amorphous domain amorphous growth