1. A new way of creating cellular polyurethane materials: NIPU foams
Adrien CORNILLE
Ph.D Student
New cyclocarbonates building blocks reagents to room temperature, environmentally friendly for adhesives and sealants polyurethanes
UMR Institut de Chimie Moléculaire
et des Matériaux de Montpellier
Sylvain CAILLOL, Rémi AUVERGNE and Bernard BOUTEVIN
UMR 5253 – CNRS, UM, ENSCM

2. Latest polyurethane developments
Polyurethane historical1,2,3 :
1937: Polyurethane’s discovery by Otto Bayer in Germany
2015 : Polyurethanes find applications in almost everything we touch:
Dr. Otto Bayer (1937)
Chairs
Desks
Beds
Wall and roofing insulation
Paints
Glue
Elastomers
1O. Bayer, Angewandte Chemie, 1947, 59,
2L. Shen, et. al., Report of Utrecht University commisioned by European Polysaccgaride Network of Excellence and European Bioplastics, Utrecht University, 2009
3 C, Boujard, et. al., Panorama du marché du polyuréthane et état de l’art de ses techniques de recyclages, Report 1202C0079, ADEME, 2009

3. Latest polyurethane developments
Polyurethane market panorama
PU production in 2011 (kt)
Example to illustrate this production
Mousses rigides
Polyurethanes is an integral part of a car :
Flexible foams  car seats
Rigid foams  motor insulation
Coatings  paint
Elastomers  timing belt
Sealants  windshield sealants
6th polymer manufactured in the world
C., Boujard, et. al., Panorama du marché du polyuréthane et état de l’art de ses techniques de recyclages, Report 1202C0079, ADEME, 2009

4. Latest polyurethane developments
PU Segmentation of European production in 2011
Flexible foams
Rigid Foams
Furniture and Bedding
Car seats
Sound insulation
Insulating panels:
Building
Appliances
In 2011, flexible and rigid foams presented 2/3 of European polyurethane production
Raw material for polyurethane synthesis
Polyols for the material soft segments
Diisocyanates for rigid segments + + +
H2O
CO2
Excess
In the next few years, diisocyanates will be removed from PU formulations
C., Boujard, et. al., Panorama du marché du polyuréthane et état de l’art de ses techniques de recyclages, Report 1202C0079, ADEME, 2009

5. NIPU Synthesis and objective
Carbonate opening reaction with an amine: NIPU
Only unexpanded PHU materials1,2,3
Never for foams
Advantages:
Drawbacks:
Cyclic carbonates display low toward amines
PHU materials display low molar mass
No isocyanate use in PU formulations
Hydroxy groups improve the stability of PHU by hydrogen bonding
Objective:
How NIPU material can be expanded to obtain an isocyanate-free polyurethane foam ?
1C. Carre, L. Bonnet, L. Averous, RSC Adv. 2014, 4,
2L. Maisonneuve, A.-L. Wirotius, C. Alfos, E. Grau, H. Cramail, Polym. Chem. 2014, 5,

6. Cyclic carbonate reactivity
Endo’s study: difference of reactivity between C5 and C61
C6 are more reactive than their similar C5:
Total conversion of the C6 is reached in 80 hours of reaction
C6 is difficult to access: low yield or use of phosgene or derivatives phosgene (ethyl chloroformate)
A choice between C5 and C6 has to be made to find compromise between reactivity and precursors syntheses
1Endo, T. et al. J. Polym. Sci. Part A. Polym. Chem. 2001, 39,
2He, Y. et al. React. Funct. Polym. 2001, 71,
3Darensbourg, D.J., et al. Macromolecules, 2010, 43(14),
4Weilandt, K. D., et al Macromol. Chem. Phys., 1996, 197,

7. C5 syntheses
Several ways of C5 syntheses are described in literature :
Easy to handle
Use greenhouse gas: CO2
A Zhao, F.; Peop. Rep. China
B Aresta, M. et al. E. J. Supercrit. Fluids 2003, 25, 177
C Bhanage, B. M. et al. Green Chemistry 2003, 5, 429
D Tomita, H. et al. J. Pol. Sci. Part A: Pol. Chem. 2001, 39, 860
E Komura, H. et al. Bull. Chem. Soc. Jap. 1973, 46, 550
F Nishikubo, T. et al. Tetrahedron Lett. 1986, 27, 3741
G Weissermel, K. Industrial Organic Chemistry, 3rd Edition; Wiley-VCH, 1997

8. Epoxy carbonation Carbonates precursors
100% conversion (calculated by 1H NMR)
96% yield
Long aliphatic chain
 Brings the flexibility to materials
Carbonate
Epoxy
Epoxy

9. Epoxy carbonation Carbonates precursors
100% conversion (calculated by 1H NMR)
94% yield
Functionality of cyclocarbonate is 2.6
 To crosslink the materials and offset the low molar masses of PHU
Carbonate
Carbonate
Carbonate

10. Catalyst of carbonate/amine reaction
Increasing carbonate C5 reactivity: using catalytic system1
According to the time conversion curves, the TBD is the best catalyst
1R. H. Lambeth, T. J. Henderson: Organocatalytic synthesis of (poly)hydroxyurethanes from cyclic carbonates and amines, Polymer. 2013, 54,

11. Foaming of NIPU materials
Blowing agent for:
PU:
Formation of foams easily at room temperature
Epoxy:
1) NaHCO3: Decomposition at high temperature (180°C)1
2) Reaction between amine and poly(siloxane) at room temperature to release H22
NIPU:
No blowing agent described for NIPU foams therefore, by analogy with PU foams,
we are used poly(siloxane) for foaming NIPU materials
1E. Mazzon, A. Habas-Ulloa, J.-P. Habas, Eur. Polym. J. 2015, 68,
2P. M. Stefani, A. T. Barchi, J. Sabugal, A. Vazquez, Journal of Applied Polymer Science. 2003, 90,

12. Carbonates precursors Amines precursors
NIPU foams precursors
Carbonates precursors
Amines precursors
PRIAMINE 1073
Blowing agent
Catalyst
Cornille, A., et al, European Polymer Journal, 66, 2015,

13. NIPU foams formulations and characterizations
x TMP-Tri-C5 + y (PPO-Bis-C5) + 1,05 Amine + 0,05 MH ,05 TBD  NIPU Foams Δ
Only amount of TMP-Tri-C5 and PPO-Bis-C5 and the structure of amine are different
Amount of blowing agent and catalyst are the same
TMP-Tri-C5/EDR-148
TMP-Tri-C5/PPO-Bis-C5/EDR-148
TMP-Tri-C5/PPO-Bis-C5/Priamine
ρ= 300 kg.m-3
ρ= 250 kg.m-3
ρ= 200 kg.m-3
Aliphatic chain of PPO-Bis-C5 and Priamine increase the porosity and decrease the density compare to the foams with 100% TMP-Tri-C5
Cornille, A., et al, European Polymer Journal, 66, 2015,

14. 3 regions for flexible foams:
NIPU foams mechanical characterization
DMA: Stress vs. Strain  Determining the pressure to be applied to deform the foam
Densification
3 regions for flexible foams:
Linear elasticity: deformation of edge foam
Plateau: deformation of cells foam
Densification: crush of material after total crush of cells
Plateau
Linear Elasticity
Syntheses of a range of foams with different rigidity:
TMP-Tri-C5 cross-linker provides rigidity to foams
Aliphatic chain provides flexibility to foams
Cornille, A., et al, European Polymer Journal, 66, 2015,

15. NIPU foams mechanical characterization
DMA: NIPU foams resilience measurement  Time for the foam to return to its original state after compressed
NIPU foams present total resilience in 80 seconds
Cornille, A., et al, European Polymer Journal, 66, 2015,

16. NIPU foams thermal characterization
NIPU foams TGA and DSC analyzes
TMP / EDR-148
0,5TMP /
0,5PPO /
EDR-148
0,7TMP /
0,3PPO /
Priamine
DSC:
Variation of Tg as function of:
The crosslinker rate: Tg of 1st NIPU foam is higher
The aliphatic chain percentage:
2nde foam display lower Tg compare to 3rd foam: decrease PPO-Bis-C5 rate
4th and 5th foams display lower Tg compare to 2nde and 3rd: using Priamine 1073
TGA:
NIPU foams display similar thermal stability
Cornille, A., et al, European Polymer Journal, 66, 2015,

17. Conclusion and Outlooks
PU foam synthesis
NIPU foam synthesis
Outlooks :
Testing new blowing agent that do not release H2
NIPU foams formulation at room temperature
Flame retardant addition within foam formulations
Cornille, A., et al, European Polymer Journal, 66, 2015,

18. Thank you for your attention Do you have any questions ?
Acknowledgment
Pr. Bernard Boutevin
Pr. Dariusz Bogdal
Dr. Sylvain Caillol
Dr. Sylwia Dworakovska
Thank you for your attention
Do you have any questions ?