advances in bio-based polyurethane technology
TRANSCRIPT
Advances in Bio-based Polyurethane Technology
Sustainability in the Leather Supply Chain Conference M. Costello, March 31st 2016, Hong Kong
▪ Introduction ▪ Technology for Leather Processing (Probiotics for Leather)
▪ Polyurethane Dispersions
▪ Renewables & Bio-Polyurethanes
▪ Processing & Performance
▪ Future
Advances in bio-based Polyurethanes
! 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
Raw Material to Wet Hide Dyeing & Finishing
Probiotic Technology Soaking & Degreasing
Biodegradable Reduced COD
Reduced Weight Reduced VOC Reduced COD
Retanning 4 5 Finishing 1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt Less Water Higher Yield
Renewable Polymers
Sustainability-inspired technology for Leather processing
Raw Material to Wet Hide Dyeing & Finishing
Probiotic Technology Soaking & Degreasing
Biodegradable Reduced COD
Reduced Weight Reduced VOC Reduced COD
Retanning 4 5 Finishing 1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt Less Water Higher Yield
Renewable
Sustainability-inspired technology for Leather processing
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
Raw Material to Wet Hide Dyeing & Finishing
Probiotic Technology Soaking & Degreasing
Biodegradable Reduced COD
Reduced Weight Reduced VOC Reduced COD
Retanning 4 5 Finishing 1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt Less Water Higher Yield
Renewable Polymers
Sustainability-inspired technology for Leather processing
▪ 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
HO-R-OH + OCN-R’-NCO HO-R [-O-C-N]-R’-NCO OH
Polyol Polyurethane Diisocyanate
■ Prepolymer phase: - Polyol + DMPA + Diisocyanate - Build polymeric structure
■ Dispersion phase: - Neutralization - Water dispersion - Diamine extension (build molecular weight)
Manufacturing Process
Polyurethane Dispersions
Typical Building Blocks
Typical Formula
HOO
O
O OHO
O
O
HOO
OO
OOH
OO
O
OHO
O
O
O
OOH
n
n
n
HOO
O
O OHO
O
O
HOO
OO
OOH
OO
O
OHO
O
O
O
OOH
n
n
n
HOO
O
O OHO
O
O
HOO
OO
OOH
OO
O
OHO
O
O
O
OOH
n
n
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)
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 …
nOH
O
nOH
OOH
On
Cat
nnOH
OOH
OOH OH
+m
- H2O
nnO
OO
OOH
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
Building Blocks
Typical Formula
Bio-based Polyester:
Isocyanate N=C=O
Bio-based Polyurethane Dispersions: Building Blocks
nnO
OO
OOH
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)
Sourcing: ▪ Canada
▪ China
▪ India
▪ Europe
▪ Australia
Current Usage: ▪ Animal feed
▪ Vegetable oils
▪ Biodiesel fuel
Canola oil Rapeseed example
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
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
■ 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:
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)
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
Raw Material to Wet Hide Dyeing & Finishing
Soaking Degreasing Biodegradable Reduced COD
Reduced Weight Reduced VOC Reduced COD
Retanning 4 5 Finishing 1 Raw Hides 2 Beamhouse 3 Tanning
Less Salt Less Water Higher Yield
High Performance Polyurethanes based
on Renewables
Sustainable Leather Processing: Step by Step