Innovative aliphatic-aromatic biobased polyurethanes from different biomass - CERN Indico
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Innovative aliphatic-aromatic biobased
polyurethanes from different biomass.
Pr. Luc Avérous
BioTeam
ICPEES – UMR CNRS 7515
ECPM : École Européenne de Chimie, Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : luc.averous@unistra.fr
Website : www.BIODEG.NET
Twitter : LucAverous
BioTeam Members:
Ø Staff (3):
• Pr. Luc Avérous (BioTeam leader)
• Dr. Eric Pollet (A/Prof.)
• Pr. Jean Marc Jeltsch (Vice-President UniStra)
Ø Researchers:
Ø Post-Doct. (3):
• Dr. Zarah Walsh (European Project SYNPOL, 2015/2016)
• Dr. Chengcheng Gao (ANR, 2015/2016)
• Dr. Antoine Duval (European Project SYNPOL, 2015-2016)
Ø PhD Students (7):
• Stéphane Duchiron (Company, 2012-2016)
• Marie Reulier (CIFRE. 2012-2016)
• Thibaud Debuissy (European Project SYNPOL, 2013-2016)
• Amparo Jimenez-Quero (Government, 2013-2016)
• Pierre Furtwengler (Companies, 2014-3017)
• Pietro Bueno (Luxembourg FRC, 2014-2017)
• Audrey Magnin (European Project P4SB, 2015-2018)
… + Masters and invited researchers
BioTeam
General Topic (BioTeam):
► Biobased and/or Biodegradable Polymers,
for Environmental and Biomedical Applications.
Springer 2012
Wiley 2016
Biorefinery from different Biomasses
Polyesters: PHAs, PLA … Extraction
Fermentation
Fatty acids (TG)
Plants
Biobased Micro-algae
Starch
Fractionation
Thermosets
or
Mushroom, Thermoplastics
crustaceans … Thermoplastic
Polysaccharides
Chitin. Chitosan
Lignins. Tannins
Clay
BioMaterials Ligno-cellulose Nano-Biocomposites
(Fibers) …
Biocomposites
► Integration. from the biomass
to final objects
BioTeam
Integration « Biochemistry/Chemistry & Process »
Bio- Chemical Formulation
Production Synthesis Process
Characterization
Biomass: Final Objects:
Triglycerides, For automotive,
Ligno-cellulose, Building, Textile,
Tannins, Packaging,
Starch, Agriculture,
Chitin,
Academic international collaborations:
Funding – Cooperation - Partners Institutions, Academics: Companies:
3 Main Thematics
Biodegradable Polymers Materials (short-term applications & biomedical):
• Thermoplastic starch, thermoplastic chitosan,
• Bio(co)polyesters: PLA, PCL, PHAs, PBSA, PBS, PBAT ...
• Synthesis by Enzymatic Catalysis of biopolyesters (eROP, polycondensation, )
• Biosynthesis of building blocks (Liquid and Solid fermentations) towards polymers
elaboration.
Biobased and Durable Polymers Materials (long-term applications):
• New Vegetable oil-based polymers (from fatty acid, dimer …)
• New aromatic macromolecular architectures, based on lignins and tannins,
• Novative Biobased TPU, PU, NIPU & PA.
Specific Biomedical Developments:
• Wound dressings,
• Tissue Engineering, scaffolds developed by electrospinning,
• Biosensors, Drug Release ...
8
Biobased Polyurethanes
Pr. Luc Avérous
BioTeam
ICPEES – UMR CNRS 7515
ECPM : École Européenne de Chimie. Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : luc.averous@unistra.fr
Website : www.BIODEG.NET
Twitter : LucAverous
Biobased Polyurethanes
based on dimer fatty acid (DFA)
Pr. Luc Avérous
BioTeam
ICPEES – UMR CNRS 7515
ECPM : École Européenne de Chimie, Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : luc.averous@unistra.fr
Website : www.BIODEG.NET
Twitter : LucAverousNew TPU architectures based on DFA
Dr. Hablot
TPUs: Multiblock copolymers
Dr. Bueno Synthesis: Two-steps polymerization
Ferrer
1st step: Prepolymer synthesis (with Reactive Mixing)
2 OCN―R―NCO HO OH OCN―R―NHCOO OCONH―R―NCO
(Long Polyol) (Prepolymer)
- Polyol: Bio-based polyester polyol based on dimer fatty acids
from rapeseed oil [Mw 3000 g mol-1 ; OH value = 40 mg KOH g-1]
- Isocyanate: 4.4’-diphenylmethane diisocyanate (MDI) (80⁰C)
REACTI VE M I XI N G
Bueno-Ferrer C et al. Polym Degrad and Stab 2012. 97, 1964-1969; Macromol Mat & Eng 2012. 297, 777–784New TPU architectures based on DFA
Dr. Hablot
2nd step: Synthesis of High MW TPU
OCN―R―NHCOO OCONH―R―NCO HO―R’ ―OH (Chain extender)
Dr. Bueno
Ferrer ― CONHRNHCOO OCONHRNHCOO―R’―O―
n
• Add Chain extender (1.4 BD0): 180⁰C (Reactive mixing)
• Curing in oven: 70⁰C
• Compression-molding: 200⁰C
• Quenching
Different HS contents:
(MDI+BDO)
10 to 40 wt%
TPU10
TPU20
TPU30
• r = NCO/OH = 1 TPU40
• Mw: from 209.000 (10 wt%) to 33.000 (40 wt%)
Bueno-Ferrer C et al. Polym Degrad and Stab 2012. 97, 1964-1969; Macromol Mat & Eng 2012. 297, 777–784New TPU architectures based on DFA
Dr. Hablot
Uniaxial tensile tests
Dr. Bueno ⇒ Typical curves of TPE,
Ferrer at low HS content (< 30%)
HS Max Strengh Deformation Modulus
(wt%) (MPa) Break (%) (MPa)
⇒ HS/SS segregations 10 1.3 ± 0.1 > 500 0.7 ± 0.1
20 3.7 ± 0.1 > 500 2.5 ± 0.1
30 5.6 ± 0.3 428 ± 40 8.6 ± 0.5
DSC 40 1.5 ± 0.4 25 ± 7 11.1 ± 1.2
Bueno-Ferrer C et al. Polym Degrad and Stab 2012. 97, 1964-1969; Macromol Mat & Eng 2012. 297, 777–784 13Aromatic Biobased Polyurethanes
from lignins or tannins
Pr. Luc Avérous
BioTeam
ICPEES – UMR CNRS 7515
ECPM : École Européenne de Chimie. Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : luc.averous@unistra.fr
Website : www.BIODEG.NET
Twitter : LucAverousLignins: Chemical structure
Lignocelulosic Various chemical groups
biomass:
Wood. Straw. OH aliphatic
3
1
1
4
1 7
2
5
6
u Natural phenolic compounds, 1
Liaisons :
largely available 1 β-O-4
1 2 α-O-4
u Variability, according to the 1 3 5-5
ressource and the extraction 3
4 β-β
5 4-O-5
process 6 β-5
OH phenolic 7 β-1
Laurichesse S., Avérous L. Progress in Polymer Science 2014. 39, 1266-1290New PU architectures based on lignin
Dr.
Laurichesse
OHs present low reactivity and accessibility
Lignin must be modified to obtain an active macropolyol
Different strategies:
Synthesis of active macropolyols:
ε-caprolactone
Specific Lignins
Propylene
(Soda & Organosolv)
Oxyde
PU synthesis
Fatty acid
Laurichesse S. et al. Green Chem 2014. 16, 3958-3970; Polymer 2013. 54, 3882–3890New PU architectures based on lignin
and fatty acid
Dr.
Laurichesse u Chemical modification from oleic acid
Oleic acid C18H34O2
u Hydrophobic properties
Chloration
u Bring insaturation and carboxyl group
Esterification
Epoxydation
Ring opening
Laurichesse S. et al. Green Chem 2014. 16, 3958-3970New PU architectures based on lignin
and fatty acid
Dr.
Laurichesse u Chemical modification from oleic acid
Oleic acid C18H34O2
u Hydrophobic properties
Chloration
u Bring insaturation and carboxyl group
Esterification
Macropolyol 100% biobased
Epoxydation
Ring opening
Laurichesse S. et al. Green Chem 2014. 16, 3958-3970New PU architectures based on lignin
and fatty acid
Dr.
Laurichesse PU Synthesis:
PPG
Biobased content: till 90%
Laurichesse S. et al. Green Chem 2014. 16, 3958-3970Aromatic Biobased Polyurethanes
from lignins or tannins
Pr. Luc Avérous
BioTeam
ICPEES – UMR CNRS 7515
ECPM : École Européenne de Chimie, Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : luc.averous@unistra.fr
Website : www.BIODEG.NET
Twitter : LucAverousTannins: Chemical structures
OH phenolic
u Natural phenolic compounds, largely
available
u Variability of the chemical structure,
according to the ressource
u High OH content = MacroPOLYOL
Arbenz A., Avérous L. Green Chem 2015. 67, 2626-2646.New PU architectures based on tannins
and fatty acid
Dr. Arbenz
OHs present low reactivity and accessibility
⇒ Tannin must be modified to obtain an active macropolyol (OPT or OBT)
⇒ Oxyalkylation (OP, OB …):
Polyether Polyol (liquid)
Tannins
Tannins
= OH
Catalyser
(KOH) Oxyde 300
Réaction exothermique
25
250
20
200
Température en °C
Pression en bar
Under Pressure
15
u 150
10
u Fast kinetic 100 Consommation
de l’oxyde
5
From solid (powder) to liquid
50
u T°/ P
0 0
u Need purification (Homopolymer) 00:00 00:20 00:40 01:00 01:20 01:40
Durée en h:min
Arbenz A., Avérous L. Ind Crops and Prod 2015. 67, 295-304; RSC Adv 2015. 4, 61564 – 61572100% Biobased Polyurethanes
(with biobased polyisocyanates)
Pr. Luc Avérous
BioTeam
ICPEES – UMR CNRS 7515
ECPM : École Européenne de Chimie, Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : luc.averous@unistra.fr
Website : www.BIODEG.NET
Twitter : LucAverous100% biobased TPU
M. Charlon
• Soft Biobased Diisocyanate: 2-heptyl-3,4-bis(9-isocyanatononyl)-1-
pentylcyclohexane (DDI). Obtained from FDA by Cognis-BASF.
• Rigid Biobased Diols:
1,4 Butanediol (BDO):
Isosorbide (ISO):
• TPU structure:
Charlon M. et al. European Polymer Journal 2014. 61, 197–205 24100% biobased TPU
M. Charlon
• Thermal properties:
25% 50% 75%
TPU (Diol) 0% ISO 0% BDO
ISO ISO ISO
DSC: Tg s (°C) -15 -13 -8 2 -1
DSC: Tm (°C) 60 50 50 84 82
• Mechanical properties:
25% 50% 75%
TPU (Diol) 0% ISO 0% BDO
ISO ISO ISO
Elongation at break
700±200 350±100 100±10 150±20 30±20
(%)
Modulus (MPa) 40±4 20±2 12±2 12±2 16±2
⇒ No good HS/SS segregation to obtain a true TPE L
⇒ Striction under uniaxial tensile test
0% 25% 50% 75% 0%
TPU (Diol)
ISO ISO ISO ISO BDO
Mw 45,000 31,800 23,100 21,200 11,400
Ɖ 2.55 2.48 2.06 2.16 2.95
⇒ High dissymmetry mainly at low temperature (Petrovic et al. 2014)
and lower reactivity of the OH (second./primary) (ISO/BDO)
Charlon M. et al. European Polymer Journal 2014. 61, 197–205Biobased Polyurethanes
without isocyanates (NIPU)
Pr. Luc Avérous
BioTeam
ICPEES – UMR CNRS 7515
ECPM : École Européenne de Chimie, Polymères et Matériaux (ECPM)
Université de Strasbourg (UniStra)
email : luc.averous@unistra.fr
Website : www.BIODEG.NET
Twitter : LucAverousNIPUs: 3 main Pathways
The most dev.
PHU
Tomita, H., et al., J. Polym. Sci. A Polym. Chem., 2001, 39(6), pp. 851-859.
Deepa, P., et al., J. Polym. Sci. A Polym. Chem., 2008, 46(7), pp. 2445-2458.
Palaskar, D.V., et al., Biomacromolecules, 2010, 11(5), pp. 1202-1211.
27Short Conclusions
Biobased PU =
Ø A stimulating field
Ø A huge potential of chemical pathways
Ø Strong opportunities to develop innovative
macromolecular archit., to obtain new materials
prop., using a green chemistry
(No solvent, No catalyzer, Biobased compounds, )
Ø A durable developing market in connection with a
more sustainable development.
28Strasbourg (Alsace-France) Luc.averous@unistra.fr www.biodeg.NET
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