Transcript
Bio-based Non-isocyanate Polyurethanes
Maastricht UniversityFriday, June 19th 2020
Non isocyanate polyurethane in academic literature
Academic literature mostly reports one step synthesisLongest NIPU are made in harmful solvents
• Use of catalyst (DBU, TBD)
• Relatively low molecular weight <30 kg/mol in the melt
Prömpers, G., et al. (2005). "Polyurethanes with pendant hydroxy groups: polycondensation of D-mannitol-1,2:5,6-dicarbonate with diamines.“ Designed Monomers and Polymers 8(6): 547-569.
Schimpf, V., et al. (2017). "High Purity Limonene Dicarbonate as Versatile Building Block for Sustainable Non-Isocyanate Polyhydroxyurethane Thermosets and Thermoplastics." Macromolecules 50(3): 944-955.
1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) Triazabicyclodecene (TBD)
Melt synthesis
Solvent synthesis
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80 - 120°CCatalyst
Goal: fully sustainable bioNIPU
• Synthesis of biobased non-isocyanate polyurethanes• Replace toxic isocyanates by cyclic carbonates monomers
• Pressure from government for health reasons (ECHA restrictions)
• Use of biobased building blocks• Fossil vs. Biobased : Reduction of GHG emissions and preservation of petroleum feedstock
• “Greenest” possible conditions (solvent free or green solvents)
• Sustainable application and processing methods• Waterborne• High solids• Hot-cast
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• Lab-scale BioNIPU synthesis• Screening of NIPU properties
Project overview
WP1: Project management
WP2: Communication
activities
WP3: BioNIPU development
WP4: BioNIPU evaluation
WP5: BioNIPU synthesis upscaling
WP6: Industrial products
development
• Scientific publications• Presentations in congresses
• Evaluation of NIPU performances in formulations
• Application testing and properties tuning
• Upscaling of monomer synthesis
• Upscaling of resin synthesis• Upscaling of NIPU
formulations
• Semi-industrial coating application on substrate
• Semi-industrial elastomers hot-casting
• Project coordination• Communication on WP progression• Communication and diffusion of
BioNIPU results to a large audience
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Application goals: PHU resins
Thermoset coatings
Waterborne and high solidsLeather, textile, plastics, rubber
Elastomers
Hot-melt/hot-cast
Thermoplastic coatings
WaterborneFor textile
Mattress cover Rain clothing
Roll covering Wheel coveringLeather coating
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Application main requirements
• Aliphatic backbone
• Fast curing
• Mw= 100 kg/mol
• Solvent resistance (water, ethanol, MEK) 30 min
• Aromatic backbone
• Slow chain extension: pot-life> 5min
• Mn= 20-30 kg/mol
• Tg between -40°C and 15°C
• Tm lower than 100°C
• Oil, grease, solvent and water resistance (no swelling)
Thermoset coatingsHot-cast elastomers
Thermoplastic coatings• Fast curing
• Low Tg
• Hydrolysis resistance, waterproofness
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Solvent-free 2-step aliphaticbioNIPU synthesis for WB
coatings
Reactive extrusion• Bulk process• Better mixing
Standard PU process and NIPU process – WB coatings
II- Dispersion:Water or acetone process
Water/acetone
Bulk• Flask• Reactive extrusion
aliphatic
Reactive extrusion• Bulk process• Better mixing• Catalyst
I- Neutralization
cycloaliphaticSoft polyol Fatty-acid based
Two-step process enables a more precise control on PU structures than the one-step process
Neutralization into WB coating
Internal emulsifier
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Bulk or solvent (DMF, THF)
Zain N.M., Zubir S.A. (2016) Polyurethane-Based Smart Polymers. In: Hosseini M., Makhlouf A. (eds) Industrial Applications for Intelligent Polymers and Coatings. Springer, Cham
Monomer synthesis – BioNIPU coatings
Functionalization with glycerol carbonate
Use of commercially available bio based diamine
(Cyclo)aliphatic or fatty-acid based backboneAliphatic or fatty-acid based (Croda)
Priamine™
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Hot-melt elastomers: Fromaromatic diisocyanate based PU
to recyclable biobased NIPU
GalX-DiCC(hard segment)
Jeffamine(soft segment)
Bulk• Flask• Reactive extrusion
Curing step ?
(soft segment)(hard segment)
Reactive extrusion• Bulk process• Better mixing• Catalyst
Standard PU process and NIPU process – Hot-melt elastomers
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Our strategy – Targets for bioNIPU elastomers
Obtain a recyclable BioNIPU elastomer
Prepolymer synthesis in the melt : bulk synthesis
Chain extension in the melt : mold curing
Recyclability of NIPU scraps- Via degradation and monomer recovery- Via dynamic bonds exchange
GalX-DiCC(hard segment)
Jeffamine(soft segment)
Bulk• Flask• Reactive extrusion
Curing step ?
Reactive extrusion• Bulk process• Better mixing• Catalyst
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Monomer synthesis – BioNIPU elastomers
Functionalization with glycerol carbonateUse of commercially available diamine
Soft segment: Polyether diamine (Huntsman)• Jeffamine® ED-900 (95% primary amine)• Jeffamine® XTJ-582 (98% primary amine) Aromatic or cyclo-aliphatic rigid backbone to bring stiffness
and good phase separation
GalX (Cosun)
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DiCC DiamineRatio
CC/NH2
Reactiontime (h)
𝐌𝐧,target (g/mol)
𝐌𝐧 GPC(g/mol eq. PS)
Đ Tg (°C) Tm (°C) Remark
Flask reactor
C12 11
3.106 11,000 1.5 -3 28/47/81 Picture 1
C6 0.95 10,000 7000 1.9 -14 / Picture 2
Priamine™1075
1.37 4
3000
6000 1.7 -37 27/42 Picture 3
Priamine™1075
0.73 4 4000 1.9 -32 / Picture 4
Reactiveextrusion
Priamine™1075
1.37 2 10,000 2.2 -22 / Picture 5
Priamine™1075
0.73 2 9000 1.7 -33 / Picture 6
NIPU prepolymer (100 °C) – Firsts results
Max(Mn)= 11000 g/mol eq. PS after 1h, but crystalline
Real interest in two step polymerization, low Mn for prepolymer end chain extension into high molecular weight NIPU (small molecule)
Picture 1 Picture 2 Picture 3 Picture 4 Picture 5 Picture 6 14
Sebacic biscyclic carbonate
• Two-step synthesis- Prepolymer synthesis- Chain extension
Summary
• Melt process for BioNIPU coating synthesis to avoid the use of toxic solvent- If the use of solvent is mandatory, green solvent will be used- Aliphatic or fatty acid based monomer will be preferred
• Melt process for recyclable BioNIPU elastomer synthesis- Rigid monomer structures to bring stiffness and phase separation- Recyclability obtain via degradation or dynamic bound exchange
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Thank you for your attention
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