Sustainability in the Leather Supply Chain

1. Advances in Bio-based
Polyurethane Technology
Sustainability in the Leather Supply Chain Conference
M. Costello, March 31st 2016, Hong Kong

2. ▪ Introduction
▪ Technology for Leather Processing (Probiotics for Leather)
▪ Polyurethane Dispersions
▪ Renewables & Bio-Polyurethanes
▪ Processing & Performance
▪ Future
Advances in bio-based
Polyurethanes

3. ! Leading chemical supplier for leather processing
▪ Key player in the specialty coatings market
▪ 1800 employees
▪ 9 R&D Centres
▪ 38 applications labs/centres of excellence
▪ €600+ Million sales
▪ 6 Business units (4 in leather, 2 for coatings)
Introduction
Stahl

4. Technology
for Leather
Processing

5. Raw Material to Wet Hide Dyeing & Finishing
Probiotic Technology
Soaking & Degreasing
Biodegradable
Reduced COD
Reduced Weight
Reduced VOC
Reduced COD
Retanning4 5 Finishing1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt
Less Water
Higher Yield
Renewable
Polymers
Sustainability-inspired technology
for Leather processing

6. Raw Material to Wet Hide Dyeing & Finishing
Probiotic Technology
Soaking & Degreasing
Biodegradable
Reduced COD
Reduced Weight
Reduced VOC
Reduced COD
Retanning4 5 Finishing1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt
Less Water
Higher Yield
Renewable
Sustainability-inspired technology
for Leather processing

7. Key advantages
! Reduced chemical consumption
! Improved water waste
! Biodegradable
! Non-hazardous, non-toxic
! Reduced odour levels
Natural & Biodegradable
The Proviera® leather bio-chemicals are produced by a fermentation process
using probiotics cultures and natural raw materials.
Proviera®-Probiotics for Leather™
ProSpread and/or
ProSoak (0.1%-0.5%)
ProSpread and/or
ProSoak (0.2%-0.5%)
Replace surfactants, soaking,
agents and enzymes etc.
ProSpread (0.2%)
Rawhide > Prewash > Soaking > Liming + Unhairing >
ProDegreaze
(0.1%-0.4%)
Replace traditional
degreasing chemicals
Deliming >
ProDegreaze
0.1%-0.2% along
with bating enzyme
Bating >
ProSpread
0.2% to 1%
in tanning
Tanning >Pickle > Wet-Blue

8. Raw Material to Wet Hide Dyeing & Finishing
Probiotic Technology
Soaking & Degreasing
Biodegradable
Reduced COD
Reduced Weight
Reduced VOC
Reduced COD
Retanning4 5 Finishing1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt
Less Water
Higher Yield
Renewable
Polymers
Sustainability-inspired technology
for Leather processing

9. Polyurethane
Dispersions

10. ▪ Polyurethanes (water- and solvent-based)
▪ Nitrocellulose (topcoats, non automotive)
▪ Acrylic emulsions
▪ Butadiene (basecoats)
▪ Casein
Polyurethanes are typically used in high performance Leather Finishes:
▪ Durability
▪ Cold crack
▪ Weather resistance
Polymers for Leather
Finish formulating

11. Polyurethane Dispersions

12. Polyurethane Dispersions

13. HO-R-OH + OCN-R’-NCO HO-R [-O-C-N]-R’-NCO
OH
Polyol PolyurethaneDiisocyanate
■ Prepolymer phase:
- Polyol + DMPA + Diisocyanate
- Build polymeric structure
■ Dispersion phase:
- Neutralization
- Water dispersion
- Diamine extension (build molecular weight)
Manufacturing
Process
Polyurethane Dispersions

14. Typical Building BlocksTypical Formula
HO
O
O
O OH
O
O
O
HO
O
O
O
O
OH
O
O
O
O
HO
O
O
O
O
OH
n
n
n
HO
O
O
O OH
O
O
O
HO
O
O
O
O
OH
O
O
O
O
HO
O
O
O
O
OH
n
n
n
HO
O
O
O OH
O
O
O
O
O
O
HO
O
O
O
OH
n
Polyester
Polyether
Polycarbonate
Isocyanate N=C=O
Polyurethane Dispersions
Ingredients %
Polyol 60 -80 (on solids)
Isocyanate 10 -15 (on solids)
Solvent 5 – 10
Water 60 – 70
Additives 0 – 5 (on solids)

15. Renewables &
Bio-Polyurethanes

16. Polyols like polyethers and polyesters can be derived from both petroleum
based resources or renewable plant oils & bio-mass.
Polyurethane dispersions with 40% bio-content have already been achieved
with polyols derived from natural oils.
Cutting millions of years off lead times …

17. nOH
O
nOH
O
OH
O
n
Cat
nnOH
O
OH
O
OH OH
+
m
- H2O
nnO
O
O
O
OH
OH m m
The unsaturated fatty acid from the (eg: rapeseed) oil is dimerized:
Then polymerized with a diol, yielding a polyester with renewable content:
Renewable Resources

18. Building BlocksTypical Formula
Bio-based Polyester:
Isocyanate N=C=O
Bio-based Polyurethane Dispersions:
Building Blocks
nnO
O
O
O
OH
OH m m
Ingredients %
Polyol 60 -80 (on solids)
Isocyanate 10 -15 (on solids)
Solvent 5 – 10
Water 60 – 70
Additives 0 – 5 (on solids)

19. Sourcing:
▪ Canada
▪ China
▪ India
▪ Europe
▪ Australia
Current Usage:
▪ Animal feed
▪ Vegetable oils
▪ Biodiesel fuel
Canola oil
Rapeseed example

20. Processing &
Performance

21. HO-R-OH + OCN-R’-NCO HO-R [-O-C-N]-R’-NCO
OH
Polyol Polyurethane
(with Co-solvent)
Diisocyanate
■ Prepolymer phase:
- Polyol + DMPA + Diisocyanate
- Build polymeric structure
Pre-polymer viscosity is critical in determining the co-solvent
Amount in the final product.
Volatile Organic
Content
Polyurethane Dispersions
Co-solvent

22. Bio-based polyols contribute to a lower pre-polymer viscosity.
Volatile Organic
Content
Polyurethane Dispersions
Low Viscosity Pre-polymer Reduced co-solvent need.
Reduced V.O.C

23. ■ With the latest advances in biotechnology, improved properties have
been achieved for bio-based Polyurethane Dispersions
■ Touch, feel, appearance
■ Film durability performance after hydrolysis
Higher Performance
Bio-Polyurethanes:

24. Bio-Polyurethanes:
Film Performance after Hydrolysis

25. Future

26. Bright Future
Bio-based Polyurethanes
■ Even higher performance
■ Higher % bio-content
How?
■ New bio-polyols (soy, linseed, palm…)
■ Isocyanates (from biomass)
■ Co-solvents (plant-based becoming available)

27. Land use for bioplastics 2014 and 2019

28. Conclusions
Bio-based Polyurethanes
■ Performance is driving the introduction of bio-polymer technology
■ Bio-based polyurethane technology is advancing rapidly
■ Oil price fluctuations can temporarily cloud the long term reality

29. Raw Material to Wet Hide Dyeing & Finishing
Soaking Degreasing
Biodegradable
Reduced COD
Reduced Weight
Reduced VOC
Reduced COD
Retanning4 5 Finishing1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt
Less Water
Higher Yield
High Performance
Polyurethanes based
on Renewables
Sustainable Leather Processing:
Step by Step

30. If it can be imagined,
it can be created
Thank you