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