ICGM (Institut Charles Gerhardt de Montpellier)

Synthèse de building blocks biosourcés :
une approche plateforme pour l’élaboration
de polymères et matériaux
Dr Sylvain Caillol, Dr Rémi
Auvergne, Pr Bernard Boutevin
IAM
IAM
Research topic: Biobased polymers and
composites
 Double substitution : New biobased and less harmful building blocks
for polymers synthesis
 From molecules to materials
From MOLECULES…
…BUILDING
BLOCKS…
…TO MATERIALS
Vegetable oils
PUs, Epoxy,
Phenolic,
PEI…
Natural phenols
Polysaccharides
Synthèse de building blocks / approche
plate-forme sur les huiles végétales
IAM
Huile de pépins
de raisins
Huile de soja
Huile de colza
3
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Synthèse de building blocks / approche
plate-forme sur les huiles végétales
Macromolecules, 2011, 44, 2489–
2500
OCL, 2012, 1-7
Lipid Technology, 2014, 26, 35-38
Brevets FR 2962131, 2010 WO2012001315, 2012
4
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Synthèse de building blocks / approche
plate-forme sur les huiles végétales
5
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EJLST, 2012, 114, 1447
Synthèse de building blocks / approche
plate-forme sur les huiles végétales
6
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Synthèse de building blocks / approche
plate-forme sur les huiles végétales
Pol. Chem., 2012, 3, 450-457
EJLST, 2012, 114, 84-91
7
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Synthèse de building blocks / approche
plate-forme sur les huiles végétales
J. Pol. Sci. Part A: Pol. Chem., 2011, 49, 2434–2444
8
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Prog. Org. Coat., 2014, 77, 285– 291
Synthèse de building blocks / approche
plate-forme sur les huiles végétales
9
Biobased polyols for improved
Polyurethanes
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Tensile
strenght at
break (MPa)
Young
Modulus
N/mm2
Shore
Hardness
Desmophen 1150
10
64
A76
Polyol-lactate G2
24
954
D56
Polyol-glycolate G3
36
1284
D70
Polyol-acetate G4
24
977
D65
PU @ T=23°C / MDI
Force ru
MPa)
ptuure (
Improved mechanical
properties for biobased PUs
50
40
30
20
10
G4
G3
0
G1
3
Green Materials, 2013, 1, 16-26
T(° 2
C)
D1
150
Po
ly
0
-1
ol
G2
10
Context of Polyurethanes
IAM
Polyurethanes: 6th polymer in the world # 18Mt/y
diols
diisocyanates
Polyurethanes
Issues
• Petrobased and harmful
reactants (isocyanates)
• REACH: TDI and MDI (CMR)
in annex XVII
Blattmann, Mülhaupt, Macromol. Rapid Commun. 2014, 35, 1238−1254
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Objectifs
The Challenges of Non-Isocyanate
Polyurethanes
Synthèse de polyuréthanes, sans isocyanates (NIPUs)
Chimie basée sur la réaction cyclocarbonate + amine qui conduit
à la formation d’une liaison hydroxyuréthane
Propriétés
Adhésion similaire aux PUs
Stabilité thermique plus élevée que les PUs
Meilleure résistance à l’humidité
Enjeux
Faible réactivité
Masses molaires faibles
Endo, T. J. Pol. Sci. Part A. Polym. Chem. 2001, 39, 860867.
Figovsky, O. L., Macromol. Symp. 2002, 187, 325-332.
Figovsky, O. L., Surf. Coat. Int., Part B, 2004, 87, 3-90.
Diakoumakos, C. D., Macromol. Symp. 2004, 216, 37-46.
Webster, D. C., Prog. Org. Coat. 2000, 40, 275-282.
Webster, D. C.,. Prog. Org. Coat. 2003, 47, 77-86.
Synthèse de carbonates C5, C6 et Thio-C
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Butanol
Vanillin derived
Resorcinol
TMP
Gallic acid
limonene
Isosorbide
Polymer International, 2012, 61, 1666-1674
Polymer International, 2012, 61, 918–925
Reactive and Functional Polymers, 2013, 73, 588-594.
Polymer Chemistry, 2011, 2, 2661-2667
J. Pol. Sci. Part A: Polymer Chem., 2011, 49, 2677–2684
Lipid Technology, 2014, 26, 35-38
Polyether
Biobased NIPUS from isosorbide
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Isosorbide
+
NIPUs :
Tg from -8 to 60°C
Td # 250°C
Reactive and Functional Polymers, 2012, 3, 588-594
Thermal degradation
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Thermal degradation monitored by ATG/IR : no formation of NCO bonds
Td # 260°C
Degradation mechanism :
NIPUs not only synthesized without isocyanates
but don’t yield isocyanates by thermal degradation
Reactive and Functional Polymers, 2012, 3, 588-594
Variété des matériaux PUs et PHUS
synthétisés
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NIPU CO2
NIPU CO2
NIPU CO2
Cyclic carbonates
NIPU CO2
NIPU CO2
NIPU CO2
NIPU CO2
NIPU CO2
NIPU TEC
NIPU TEC
NIPU TEC
NIPU ester
NIPU ester
NIPU ester
NIPU ester
NIPU ester
NIPU ester
NIPU ester
Huile-acet
Huile-glyc
Huile-lact
Epoxidized oils
Ricin
TEC oils
Hydroform
Amide triol
Amide diol 8
Amide diol 2
Diester diol 6
Diester diol 4
Diester diol 2
Ester diol 6
Ester diol 4
Ester diol 2
Huile 3OH
-40
-20
0
Polym. Rev., 2012, 52, 38-79
20
40
Tg (°C)
60
80
100
120
16
Coatings PUs sans isocyanates
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Cross-linking with polyamines
Coatings formulation for paints
and varnishes
European Polymer Journal, 2014, 61, 133–144
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Mousses de NIPUs
ρ= 194 Kg.m-3
Tg= -13°C
ρ= 295 Kg.m-3
Tg= 19°C
ρ= 248 Kg.m-3
Tg= -12°C
Unsubmitted work
ρ= 242 Kg.m-3
Tg= -2°C
ρ= 197 Kg.m-3
Tg= -18°C
18
Approche plateforme sur les phénols
naturels
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 Monomer substitution
Tannins
Catechin
DGEBA
…TO MATERIALS
Gallic Acid
200kt/y
Bisphenol A
Phenol, formol
CNSL
900kt/y
Cardanol
Lignin
TDI, MDI…
Borregaard
Process
Vanillin
Chemical Reviews, 2014, 114, 1082–1115
Biobased building blocks from
natural phenols
IAM
Epoxided Catechine
Phosphorated
Phloroglucinol
Epoxided gallic
Polyphenols
Abietic
epoxided
Gallic
Carbonate
Epoxided
phloroglucinol
Allyl gallic
Abietic
epoxided
Green Chem., 2013, 15, 3091-3098
Gallique tetraamine
20
Platform molecule for new biobased
building blocks: Example of vanillin
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Lignin
Vanillin
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Platform molecule for new biobased
building blocks: Example of vanillin
Vanillin
Green Chemistry, 2014, 16, 1987-1998
22
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Platform molecule for new biobased
building blocks: Example of vanillin
Vanillin
Green Chemistry, 2014, 16, 1987-1998
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Platform molecule for new biobased
building blocks: Example of vanillin
Vanillin
Green Chemistry, 2014, 16, 1987-1998
24
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Platform molecule for new biobased
building blocks: Example of vanillin
Vanillin
Green Chemistry, 2014, 16, 1987-1998
25
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Platform molecule for new biobased
building blocks: Example of vanillin
Vanillin
Green Chemistry, 2014, 16, 1987-1998
26
Context: Epoxy resins
IAM
Epoxy resins : 2Mt/y - various applications
Amine or acid
curing
Issues
• Fossil resources reactants
• Harmful reactants
• Epoxy and Amines
Bisphenol A (BPA)
• CMR Repr. Cat. 2
• Endocrine disruptor
BADGE
(BPA diglycidyl ether)
Targets
• Biobased aromatic epoxy reactants
• From non toxic phenols
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Epoxy resins from commercial
cardanol
IAM
120°C
+
Epoxy resin
Epoxidized Cardanol prepolymer
(from Cardolite) – fonct° = 1.3


E’ (MPa)
Epoxided
Cardanol
Td (°C)
BADGE-IPDA
378
Card-IPDA
Card-Jeff400
Tα (°C)
20°C
Tα+60°C
158
1480
19.6
370
59
1218
3.2
366
9
7
2.6
Mechanical resistance due to the aromatic ring, flexibility due to longaliphatic chain that reduces Tg
Low Tg for coatings
EJLST, 2013, 116, 63–73
28
From epoxidized cardanol to vinyl
esters
IAM
Epoxidized Cardanol prepolymer
(from Cardolite) – fonct° = 1.3
E’ (MPa)
Cardanol/
Diluent 60/40
Td (°C)
BADGE-Sty
300
138
Card-Sty
265
Card-IBOMA
250


Tg (°C)
Tα (°C)
20°C
Tα+60°C
158
1270
17
69
86
1060
3.4
92
116
1050
5.6
IBOMA
Styrene
Vinyl ester
Good combination cardanol/IBOMA to reach interesting
properties
Use of IBOMA avoid the use of harmful and volatile
styrene
EJLST, 2014, 2014, 116, 928–939
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New aromatic multi-functional amine
from cardanol
IAM
Epoxy resin
1< l <10 ; 1< m <3 ; 0< p <10 ; 0< q <1
l+m+p+q = 15
E’ (MPa)
Epoxy Resin
Epoxided
Cardanol
and Card-NH2



Td (°C)
380
Tg (°C)
19
Tα (°C)
30
20°C
Tα+60°C
18
0.5
Synthesis of a reactive multi-functional amine with aromatic ring
Interesting epoxy hardener
Fully biobased epoxy resins
EJLST, 2014, accepted
30
Résines époxy base tanins –
substitution DGEBA
IAM
Green tea
natural extract
Tara
natural extract
Supplied by Innobat
Supplied by Silvateam
Catechin
Gallic acid
Tannins
Epoxidized
tannins
iPDA
Epoxy
Resins
Collaboration
Dr Hélène Fulcrand
Dr Chahinez Aouf
Ind. Crops and Products, 2014, 53, 296-307
Europ Pol J., 2014, 186-198
E’ (MPa)
Tα
(°C)
30°C
Tg+30°C
Td30
(°C)
BADGE-IPD
140
1.29 103
13.6
353
Catech-IPD
179
1.5 103
36.4
334
Tea-IPD
142
2.34 103
59.3
299
Tara-IPD
139
5.28 103
116.0
294
System

Similar Thermal resistance and
higher mechanical properties
Résines époxy base vanilline –
substitution DGEBA
IAM
220
200
Tα = 182°C
Tα = 166°C
180
Tα = 154°C
Temperature (°C)
160
100
Tg = 152°C
Tg = 132°C
140
120
Tg = 166°C
Tα = 106°C
Tg = 97°C
80
60
40
20
0
DGEVA-based polymer
DGEMHY-based polymer
DGEVAC-based polymer
DGEBA-based polymer
 Good thermo-mechanical properties, close to DGEBA-based materials.
 Tunability depending on the monomer used.
Europ. Pol. J., accepted
32
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ACKNOWLEDGEMENTS
ICGM - IAM
Myriam Desroches (PhD)
Dr Sofia Benyahya (Post-doc)
Dr Hélène Nouailhas (Post-doc)
Fanny Jaillet (PhD)
Emilie Darroman (PhD)
Maxence Fache (PhD)
Fatoumata Camara (PhD)
Marine Blain (PhD)
Dr Vincent Besse (Post-doc)
Adrien Cornille (PhD)
Sylvia Dvorakoska (PhD)
Dr Claire Negrell
Dr Rémi Auvergne
Pr Bernard Boutevin
ICBMS Lyon
THE PARTNERS
Pr Bruno Andrioletti
LCPO Bordeaux
Dr Ludivine Jean-Gérard
Pr Stéphane Carlotti
Pr Henri Cramail
Univ. Cracovie (Pol)
Pr Darek Bogdal
[email protected]
INSA Lyon
Pr Jean-Pierre Pascault
Pr Etienne Fleury
Dr Françoise Méchin
INRA Montpellier
Dr Hélène Fulcrand
Dr Chahinez Aouf