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1
Novel clean and selective processesfor starch modification
X. Coqueret1), C. Bliard2), P. Dole3), F. Cazaux4), S. Baumberger5) and C. Lapierre5)
1)UMR CNRS 6519, 2)FRE CNRS 2715, 3)UMR INRA FAREUniversité de Reims Champagne Ardenne - 51687 Reims
4)UMR CNRS 8009 LCOM, USTL - 59655 Villeneuve d’Ascq5)UMR 206 Chimie Biologique INRA INA PG - 78850 Thiverval-Grignon
Université de ReimsChampagne Ardenne
Université de Reims Champagne-Ardenne
UMR CNRS 6519 Réactions sélectives et applications
2
Pristine starch: a semi-crystalline polymer
Lipids AmyloseMW 2 105 – 106 g.mol-1
Amylopectin double helixMW 5 107 – 5 108 g.mol-1
cristallinity : 20-45%
O
O
OH
HO
HOCH2O
O
O
O
OO
O O
O
O
O
O
O
ca. 6% of ? (1? 6) linkage
? (1? 4) ; 6 AGU per pitch
anhydroglucose unit (AGU)
3
Food additives (16 %)? Sweeteners? Thickeners? Stabilizers? Humectants
Major non-food applications (84 %)
? Paper making industry (60%)? Construction Plaster wallboards?Adhesives
Industrial use of starch
? Pharmaceutical, galenics
? Textile sizing , Fabric finishing,? Printing industry (anti-set-off powder) ? Flocculating agents
4
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
Applications of starch
5
Vegetal origin + Clean processing = Greener chemistry
Processing
? Reactive extrusion? High-energy radiation
Chemical modification of starch
1. Cationization (quaternary ammonium)2. Enzymatic hydrolysis3. Radiation grafting of thermoplastic starch
Clean processes for starch modification
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
7
Etherification of AGU by trimethylammonium reagents
Cationization of starch
starchNaOH
water
Cl
OH
N+
CH3
CH3
H3C
Cl-
(I) HO
HON+
CH3
CH3
CH3Cl-
O
OO
O O
O
O
OH
O
OH
HO
HO
HO
HO
OH
OH
HON
Cl-
O N
(II)
Cl-
CH3
CH3
CH3
O
HON
HON
Cl-
Cl-
O
O
OH
HO
HOCH2O
+ someelimination
products
1,2-epoxypropyl trimethylammonium chloride
3-chloro-2-hydroxypropyl trimethylammonium chloride
8
1H NMR analysis of starch cationization
before reaction
after reaction
after washing
O
OO
O O
O
O
OH
O
OH
HO
HO
HO
HO
OH
OH
HON
Cl-
?? ((ppmppm))
3,03,0
HOD
3,43,43,83,84,24,24,64,65,05,05,45,45,85,8
H5H6,6’
H3
H4
H2
H
Consistent values of the degree of substitution (DS):NMR, elemental analysis, Kjeldhal, Cl- exchange 0,005 < DS < 0,2
9
Influence of [reactant] to [AGU] ratio on DS
5 min @ 120°C 5 min @ 120°C[reactant] / [NaOH] = 1 [reactant] / [NaOH] = 0,3
DS increases when [co-reactant] increases, but reaction yield decreases
[reactant I ] / [AGU]
0
0,02
0,04
0,06
0,08
0,1
0 0,1 0,2 0,3 0,4 0,5
20
40
60
80
Yield ( %)DS
0
0,01
0,02
0,03
0,04
0,05
0 0,02 0,04 0,06 0,08 0,1
20
40
60
80
100Yield (%)DS
100
[reactant II ] / [AGU]
Cl
OH
N+ CH3
CH3H3C
Cl-
(I)O N
(II)
Cl-
CH3
CH3
CH3
10
Influence of glycerol content on DS
5 min @ 120°C[reactant] / [AGU] = 0,05[reactant] / [NaOH] = 1
0,015
0,005
% % glycerolglycerol20 30 50
0,020
0,010
0 0
0,01
0,02
0,03
0,04
0,05
20 5030
(DS)
reactant [I]
(DS)
% % glycerolglycerol
reactant [II]
12
24
36
Yield (%)
30
60
90
Yield (%)
DS decreases when plasticizer content increases
11
Some other selected results
?Modeling of zation cationireaction
? Distribution of cationic functions
? Competing side reactions
? Relation between molecular structure and functional properties
Factors influencing cationization efficiency
A. Ayoub et al. Starch/Stärke (2004), 55 (7), 297-303A. Ayoub et al. Starch/Stärke (2004), 56 (11), 513-519.
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8Time (min)
Yie
ld(%
)
100°C120°C140°C
0200
400600800100012001400160018002000
Inte
nsity
5 9 13 17 21 25 29 33 37 41
2? [°]
12
Conventional methods
? Acidic hydrolysis ? Enzymatic? ? - or ? -amylase? liquefying or saccharifying enzymes
Drawback of current processes
? batch operations? wet chemistry? long reaction time
2 - Dextrinisation of starch
O
H
H O
O
O
OH
H
H
HO
O
O
O
H
H
H O
OO
O
O
OH
H
HO
OO
O
OH
HO
O
O
O
O H O
H
H O
O
O
O
O
H
H
H
H
H
H
O
O
OO
O
O
O
O
OH
H
HO
OO
O
O
H
H
H O
OO
O
O
OH
H
HO
OO
O
OH
HO
O
O
O
O
H
H
HO
OO
O
O
glucose syrup, dextrines …..
13
AMIVAL - C. Bliard, J.F. Lacoste
Dextrinisation of starch by reactive extrusion
native starch+ co-reactant (water)+ catalyst (enzyme)
- hydrolysis is faster- process is continuous- products are obtained
as a concentratehydration anddestructurization
hydrolysis
14
AMIVAL - C. Bliard, J.F. Lacoste
Dextrinisation of starch by reactive extrusion
-0,055
-0,045
-0,035
-0,025
-0,015
-0,005
0,005
5 10 15 20 25 30 35 40 45 50
t (min)
sign
al (
mC
)
JF 46 (DE 23)
Dormadry 21
SEC profiles of obtained oligosaccharides
Reference wet-technology
Reactive extrusion sample
15
Points under study
? Search for new thermally-mechanically resistant enzymes ?Multiparameter control of starch hydrolysis
(T°, power, water content, enzyme concentration)? Oriented hydrolysis towards target distributions
Confirmed advantages
? Low energy consumption? Single step process? Continuous production? Easy drying
Dextrinisation of starch by reactive extrusion
16
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
3 – Radiation grafting of starch
17
Lignins as additives for TPS
• A broad family of polyphenoliccompounds biodegradablesand hydrophobic
• Constituent of wood, secondin abundance after cellulose
• Large variety of structuresdepending on botanical originand industrial extraction process
• By-products of the pulp and paperindustry to be valorized
18
ObjectivesEvaluate the scope and limits of ionizing radiation for improving the existing materials and processes
ConceptUse 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
Radiation processing for improvingthe properties of thermoplastic starch
19
Radiation processing of starch-AU blends
- Physical stabilization effective- Multiple grafting demonstrated- MALDI TOF mass spectrometry
for the analysis of model blends
sample
electron curtain
irradiated film
Electron beam acceleratorHigh voltage : 175 kV5-800 kGy - in air
O
OH
O
HOOH
n
AGUAGU
AGUNH2
OC
NH
CH2
CHCH2O
OOH
HO
O
CH2 CH CH2 NH C NH2
O
+ starch
1) amorphization
2) EB-irradiation
D.D.RuckertRuckert, F. , F. CazauxCazaux, X. , X. CoqueretCoqueret J.J.ApplAppl..PolymPolym..SciSci. 1999, 73, 409. 1999, 73, 409--417417A.Olivier, C. A.Olivier, C. GorsGors, F. , F. CazauxCazaux, X. , X. CoqueretCoqueret, , BiomacromoleculesBiomacromolecules 2000, 1, 2822000, 1, 282--289289A.Olivier, F. A.Olivier, F. CazauxCazaux, and X. , and X. CoqueretCoqueret, , BiomacromoleculesBiomacromolecules 2001, 2, 12602001, 2, 1260--12661266
20
Properties of starch-lignin blends
Starch 70 wt-parts + Glycerol 30 wt-parts + Lignins 10-30 wt-parts:lignosulfonates (LS)wheat liginins (WL)bagasse lignins (BagL)
• Reduction of hydrophilicity Water sorption at 73 %RHT=25°C
Starch-Glycerol (no lignin) 21-23 % Starch-Glycerol-Bagasse lignins (20 phr) 13-16 %Starch-Glycerol-Wheat lignins (20 phr) 14-18 %Starch-Glycerol-Lignosulfonate (20-30 phr) 19-23 %
• Protective effect against radiation
21
Properties of starch-lignin blends
• Modification of wettability by water
0
10
20
30
40
50
60
70
Starch LS 20 LS 30 WL 20 WL 30 BagL 20 BagL 30
Con
tact
ang
le (
? 0°)
Native film
Irradiated film (400 kGy)
22
Maldi-ToF MS of maltodextrine Glucidex 19
Na+
OOH
O
OH OH
H
OH
n
m/z = (n x 162) + 18 + 23
n = 16
m/z
laser pulse
DHB* matrix
flight tube
*2,5-dihydroxybenzoic acid
model for starch
23
O
OO
OMeOH
OH
OH
OMe
O
OH
OH
O
MeO
OH
OH OMe
O
OH
OMe
O
OH OH
MeO O
OOH
OH
OMe
O
OH
OH
MeO
OH
OH
OMe
OMe
OHOH
O
OH
OMe
OH
OHO
OMe
OHOMe
OH OH
OH
MeO
OO
OMe
O
OH
OH
MeO
OH
OH
OMe
OMe
OH
OH
O
OHMeO
Models for lignins
24
Models for lignins
OH OH
OR
OH
OMe
OH OH
OH
OH
OH
? Phenols
? Benzyl alcohols
? Cinnamic derivatives and lignin monomers
OH OHO
OR
CH2OH
OH
CH2OH
OH
OMe
CH2OH
OH
MeO OMe
25
Reactivity of p-methoxybenzyl alcoholwith maltodextrine Glucidex 19
0
10
20
30
40
50
60
70
80
90
100
100 600 1100 1600 2100
malcohol = 138 Da
mhexamer = 1013 DaH-(UAG)6-OH
0
5
10
15
20
25
30
35
40
1000 1040 1080 1120 1160 1200
(UAG)6 + 120
1013,28 1175,32
1133,15
Observed adduct = 1133 Da
O
CH3
OH
Na+ mNa+ = 23 Da
Sum = 1154 Da
1606120 6
201 6 .)()(
)()( ?
??
?
?
mDPmDP
mDPadduct II
If
26
800 1200 1600 2000
0
10000
20000
30000
i
m/z
1100 1150
0i
m/z
OH
OMe
OH
OH
OH OH
+90+106
+118
+120
Hypothesis of a common mechanismfor the various benzylic derivatives
The benzyl alcohol function seems to be involved in the condensation process
Reactivity of various benzyl alcoholswith maltodextrine Glucidex 19
m/z m/z
27
Quantification of p-methoxybenzyl alcohol reactivity by 13C NMR analysis
? Maltodextrine G19 + p-methoxybenzyl alcohol (20 phr)? 13C NMR (gated decoupling) : integral of -CH2-OH to AGU CH-OH
0.4
41
0
1.0
00
8
In
te
gr
al
( p p m )
5 8 . 55 9 . 05 9 . 56 0 . 06 0 . 56 1 . 06 1 . 56 2 . 06 2 . 56 3 . 06 3 . 56 4 . 06 4 . 56 5 . 06 5 . 5
C 1 3 m é l a n g e 2 6 0 k G y B
0.2
29
0
1.0
00
0
In
te
gr
al
62
.5
48
6
60
.7
61
3
60
.2
59
8
( p p m )
5 8 . 55 9 . 05 9 . 56 0 . 06 0 . 56 1 . 06 1 . 56 2 . 06 2 . 56 3 . 06 3 . 56 4 . 06 4 . 56 5 . 06 5 . 5
C 1 3 m é l a n g e 2 6 2 0 0 k G y
B
G19
G19
OH
OMe
A2
A3
A2
A3
B
C
A4
A1
B
0.44
10
1.00
08
Inte
gral
(ppm)
58.559.059.560.060.561.061.562.062.563.063.564.064.565.065.5
O H
OM e
A 2
A 3
A 2
A 3
B
C
A 4
A 1
B
O
O
O H
H O
H O C H 2O
0
25
50
75
0 50 100 150 200 250
Dose (kGy)
Con
vers
ion
(%)
28
Formation of multiple adducts
? Maltodextrine G19 + p-methoxybenzyl alcohol - 400 kGy
? High grafting yield, and multiple grafting? Confirmation of free radical mechanism for grafting since there is
only a single site for acetalization per molecule
12 3 4 5 6 7 8 9 100%
10%
20%
30%
40%
50%
DP
Peak intensity in MALDI TOF mass spectra relative to parentoligomer of DP=x
1 addition (+120 Da)2 additions (+240 Da)3 additions (+360 Da)
29
Coupling mechanism for benzyl alcohols
• Radiolysis of constituants• UAG-UAG-UAG ? [UAG-UAG-UAG(-H)]° + H° • H2O ? H° + HO°• Ar-CR2-OH ? Ar-CR2° + HO°
• Secondary activation of polysaccharide by transferUAG-UAG-UAG + Rad°? [UAG-UAG-UAG(-H)]° + Rad-H
• Coupling by combination of free radical species[UAG-UAG-UAG(-H)]° + Ar-CR2°? [UAG-UAG-UAG(-H)(+CR2-Ar)]
30
0
10
20
30
40
50
60
70
80
90
100
500 550 600 650 700 750 800 850 900 950 1000
DP3 + 150
DP3 + 134
DP3 + 116 DP3 + 116 + 134
DP3 + 2*134
642,99
660,
676,98
777,
795,03
526,90
CH CH2 OHCH2
AGU AGU AGU
CH2CHCH
AGU AGU AGU
CH2CHCH
CH CH2CH2OH
AGU AGU AGU
CH2CHCH2
CH CH2CH2OH
OH
AGU AGU AGU
m/z
O
CH CH2 OHCH2
AGU AGUAGU
Grafting of Cinnamyl alcohol onto maltotriose(200 kGy dose)
MT
31
0
2
4
6
8
10
12
14
1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500
1129.44
1147,46
(UAG)-6 + 116
(UAG)-6 + 134
1263,51
1281,52
2*134 3*134
1415,59
134 + 2*116
134 + 116 2*134 + 116
1397,58116+134
1379,57
134 + 116
(UAG)-7 + 134
1309,5
1291,50
1343,5
2*134
(UAG)-7 + 116 116 + 1341101.45
(UAG)-5+116+134
(UAG)-5 + 2*134
(UAG)-5 +134+116
1235,54
1119,46
1217,451085,46
1253,543*134
2*134+116
134 + 2*116
Composition : G19 63%, H2O 16%, CML 5%, MeOH 16% - 400 kGy
Grafting of cinnamyl alcohol onto maltodextrine Glucidex 19 (400 kGy dose)
32
Quantification of cinnamyl alcohol reactivityby 1H NMR analysis
1.0
00
0
0.1
77
1
Inte
gra
l
7.3
95
57
.36
95
7.3
17
47
.29
30
7.2
67
0
7.2
14
97
.19
22
6.7
39
16
.71
79
6.5
41
4
6.4
88
5
6.3
79
56
.36
41
6.3
11
2
( p p m )
6 . 16 . 26 . 36 . 46 . 56 . 66 . 76 . 86 . 97 . 07 . 17 . 27 . 37 . 47 . 57 . 67 . 77 . 87 . 9
1 H m é l a n g e 2 1 2 5 k G y
1.0
00
0
0.1
16
3
Inte
gra
l
7.3
94
77
.36
87
7.3
16
67
.29
22
7.2
67
0
7.2
14
97
.19
05
6.7
35
06
.71
47
6.5
42
2
6.4
86
9
6.3
73
86
.36
33
6.3
09
6
6.2
33
1
( p p m )
6 . 16 . 26 . 36 . 46 . 56 . 66 . 76 . 86 . 97 . 07 . 17 . 27 . 37 . 47 . 57 . 67 . 77 . 87 . 9
1 H m é l a n g e 2 1 1 5 0 k G y
0 25 50 100150200
0,00
0,10
0,20
0,30
0,40
Con
verte
d C
inO
H
(mol
.kg-
1)
Dose (kGy)
Fractional conversion exceeds 50% at 200 kGy
[CinOH]0 = 0,08, 0,36, 0,68, 1,21 mol.kg-1
OH OH
H
5H
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)