advances in bio-based polyurethane technology

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

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 Polymers

Sustainability-inspired technology for Leather processing







Renewable


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







Renewable Polymers


Polyurethane Dispersions

▪  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


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


Ingredients %

Polyol 60 -80 (on solids)

Isocyanate 10 -15 (on solids)

Solvent 5 – 10

Water 60 – 70

Additives 0 – 5 (on solids)

Renewables & Bio-Polyurethanes

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

Processing & Performance

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


Co-solvent

Bio-based polyols contribute to a lower pre-polymer viscosity.

Volatile Organic Content


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:

Bio-Polyurethanes: Film Performance after Hydrolysis

Future

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)

Land use for bioplastics 2014 and 2019

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


Soaking Degreasing Biodegradable Reduced COD




High Performance Polyurethanes based

on Renewables

Sustainable Leather Processing: Step by Step

If it can be imagined, it can be created

Thank you