VEGETABLE-BASED BUILDING BLOCKS FOR THE
SYNTHESIS OF RENEWABLE POLYURETHANES AND
POLYESTERS
Lise Maisonneuve,a Arvind More,a
Eric Cloutet,a Benoit Gadenne,b Carine Alfos,b and Henri Cramail a
a
b
Laboratoire de Chimie des Polymères Organiques, Bordeaux, France
Institut des corps gras (ITERG), Pessac France
SFEL 2012
A greener future for polymeric materials
Fats & Oils expertise
The Innovation Promise of Bio-Based Materials
Offering a step change for growth
Pipeline
Propanediol
PHA
PLA
PBS(X)
NOP
PA
APC
UPR
PTT
Epoxy
Succinic Acid
Lactic Acid
Vegetable oils
Hydroxy
Alkanoates
Isosorbide
other
PA46
Source : European bioplastics/ Probip 2009
SEFL – June 2012 – C.
Alfos
(ITERG)
DSM
NeoResins+
2
2
Bio-based raw materials
Fats & Oils expertise
Isosorbide
Methyl oleate
Starch
~90% in high oleic sunflower oil
Methyl ricinoleate
Between 85 and 95%
in castor oil
Progress in Polymer Science 2010, 35(5): 578-622.
Bio-based
raw materials
1,4-Diaminobutane
succinic acid
ChemSusChem 2011, 4(6): 785-791.
1,3-Propanediol
Methyl 10-undecenoate
Journal of the American Oil Chemist Society 1996, 73(9): 1109-1112.
SEFL – June 2012 – C. Alfos (ITERG)
Glycerol
Industrial & Engineering Chemistry Research
2003, 42(13): 2913-2923.
3
3
Bifunctional building blocks for polyurethanes
Fats & Oils expertise
Poly(ester urethane)s
Poly(amide urethane)s
Poly(ester amide urethane)s
SEFL – June 2012 – C. Alfos (ITERG)
4
4
Synthetic route to the fatty-based diols
Fats & Oils expertise
Transesterification and / or
Amidation
Thiol-ene reaction
SEFL – June 2012 – C. Alfos (ITERG)
5
5
Particular case of diamide diol
Fats & Oils expertise
Strategy :
Transesterification / Amidation
followed by thiol-ene reaction
(ppm)
EP patent 11306491 (2011), H. Cramail, L. Maisonneuve, T. Lebarbé, B. Gadenne, C. Alfos, E. Cloutet.
SEFL – June 2012 – C. Alfos (ITERG)
6
6
Structure of bio-based diols
Fats & Oils expertise
Bio-based
well-defined difunctional
building-blocks
Bio-based
Thermoplastic
polyurethanes &
polyesters
SEFL – June 2012 – C. Alfos (ITERG)
7
7
Bifunctional building blocks for polyurethanes
Fats & Oils expertise
Poly(ester urethane)s
Poly(amide urethane)s
Poly(ester amide urethane)s
SEFL – June 2012 – C. Alfos (ITERG)
Mn = 30 000 g.mol-1
Mw = 50 000 g.mol-1
D=1.6
8
8
Synthetic route to the poly(amide urethane)
Fats & Oils expertise
SEFL – June 2012 – C. Alfos (ITERG)
9
9
Amorphous polyurethanes
Fats & Oils expertise
Glass transitions from
-26.8°C to 51.5°C
DSC thermograms – Second cycle, 10°C.min-1
SEFL – June 2012 – C. Alfos (ITERG)
10
10
Semi-crystalline polyurethanes
Fats & Oils expertise
SEFL – June 2012 – C. Alfos (ITERG)
11
11
Semi-crystalline polyurethanes
Fats & Oils expertise
DSC thermograms – Second cycle, 10°C.min-1
SEFL – June 2012 – C. Alfos (ITERG)
Flexibility
High hydrogen bonding
12
12
Polyurethanes
Fats & Oils expertiseMechanical properties via tensile experiments
Samples
Young's modulus
(MPa)
Ultimate strength
(MPa)
Maximum strain
(%)
PU-dE-2
PU-EA-2
PU-dA-1
PU-dA-2
287 ± 35
314 ± 33
770 ± 68
775 ± 51
17.4 ± 2.4
23.2 ± 1.4
58.1 ± 3
48.3 ± 3
266 ± 24
269 ± 26
41 ± 2
44 ± 13
Ester → Amide
Tensile experiments : Tensile stress versus strain curves
SEFL – June 2012 – C. Alfos (ITERG)
13
13
Weight (%)
Deriv. weight (%/°C)
Fats & Oils expertise
2. Poly (ester/amide urethane)s
Thermal stability
Temperature (°C)
Temperature (°C)
TGA thermograms – N2, 10°C.min-1
 Typical multiple step degradations behavior
 Urethane functions, thiocarbon chains, ester and amide linkages
 Mostly T5% > 280°C
SEFL – June 2012 – C. Alfos (ITERG)
AOCS spring 2012
14
14
Fats & Oils expertise
Polyesters : Our strategy to more robust
fatty-acid based materials
Castor oil
SEFL – June 2012 – C. Alfos (ITERG)
Polyesters
Poly(ester-amide)s
-biodegradable
-Poor thermomechanical
properties
-biodegradable
-Good thermomechanical
properties
15
15
Our strategy to more robust fatty-acid based materials
Fats & Oils expertise
Polyesters
Poly(ester-amide)s
Bio-based
well-defined difunctional
building-blocks
Bio-based
Thermoplastic
polyesters &
poly(ester-amide)s
SEFL – June 2012 – C. Alfos (ITERG)
16
16
Polyesters using diol precursors
Fats & Oils expertise
Dynamic mechanical analysis
(compression mode)
Tan δ
Storage Modulus : E’
Loss Modulus : E’’
DSC – 10°C/min
Low increase of glass
transition ( 10°C) with
incorporation of Isosorbide
SEFL – June 2012 – C. Alfos (ITERG)
17
17
Fats & Oils expertise
Our strategy to more robust fatty-acid based
materials
Polyesters
Poly(ester-amide)s
Bio-based
well-defined difunctional
building-blocks
Bio-based
Thermoplastic
polyesters &
poly(ester-amide)s
SEFL – June 2012 – C. Alfos (ITERG)
18
18
Fats & Oils expertise
Poly(ester-amide)s :
promising bio-based materials
SEFL – June 2012 – C. Alfos (ITERG)
19
19
Fats & Oils expertise
Poly(ester-amide)s :
promising bio-based materials
Thermal degradation begins
between 300 and 350°C
TGA 10°C/min
Ester functions
degradation
SEFL – June 2012 – C. Alfos (ITERG)
Amide functions
degradation
20
20
Poly(ester-amide)s :
promising bio-based materials
Fats & Oils expertise
Modulated DSC
2°C/min
DSC
2nd
heating run 10°C/min
30min Annealing
10°C/min
High increase of melting point with
hydrogen bond density
36°C < Tm < 126°C
SEFL – June 2012 – C. Alfos (ITERG)
21
21
Fats & Oils expertise
Poly(ester-amide)s :
promising bio-based materials
Chemical structure comparable to Nylon
α form : hydrogen bonds between antiparallel chains
γ form : hydrogen bonds between parallel chains
Metastable pseudohexagonal structures which vary continuously in size, perfection,
and structural parameters
amide-amide intermolecular
H-bonded chains (~4.8 A)
van der Waals
packed sheets (~3.7A)
SEFL – June 2012 – C. Alfos (ITERG)
Disappearance of pseudohexagonal
reflection by heating
=
Melting of pseudohexagonal form
which crystallize in the α-form
22
22
Fats & Oils expertise
Poly(ester-amide)s :
promising bio-based materials
Tensile tests
Entry
PE1
PEA1
PEA2
PEA3
SEFL – June 2012 – C. Alfos (ITERG)
Young's Modulus (MPa)
93.0 ± 10.4
82.7 ± 15.2
131.5 ± 17.5
363.0 ± 89.1
Ultimate Strength (MPa)
2.9 ± 0.8
5.4 ± 1.2
3.5 ± 0.3
10.0 ± 3.5
Strain at break (%)
4.1 ± 1.3
11.1 ± 2.4
3.4 ± 0.7
3.3 ± 0.7
23
23
Conclusion
Fats & Oils expertise
POLYESTERS
AB TYPE
CONDENSATION
HYDROXYESTERS
POLY(ESTER-AMIDE)S WITH
IMPROVED THERMOMECHANICAL PROPERTIES
ESTER AND/OR
AMIDE DIOL
PRECURSORS
DIOL + DIESTER
CONDENSATION
POLY(ESTER-AMIDE)S
URETHANES WITH IMPROVED
THERMO-MECHANICAL
PROPERTIES
SEFL – June 2012 – C. Alfos (ITERG)
24 24
Acknowledgments
Fats & Oils expertise
Lise Maisonneuve
PhD 2A
Thomas lebarbé
PhD 2A
Henri Cramail
Benoit Gadenne
SEFL – June 2012 – C. Alfos (ITERG)
25
25