0. Coating Resins on Bio-based Raw Materials Reality or Distant Future?
Tosko Misev, Dirk Stanssens
DSM Resins bv, DSM Innovation Center

1. Introduction
Since existence of human beings, people have always used paints to express themselves
Early paints based on natural products were of inferior quality
Non-natural products were introduced to improve properties
alkyds, acrylics, polyurethanes, polyesters, epoxies, amino resins
Now we see a reverse movement
Oil reserves are limited and have a long cycle time (100 mln years)
Natural renewable resources are abundantly available with cycle time of 1 year
White biotechnology is developing with increasing speed

2. What is white (industrial) biotechnology?
Industrial applications
Market
penetration
Biofeedstock
Replacement of
fossil feedstock by
sugar and biomass
Pharma (red)
biotech
Bioprocesses
Use of natures toolbox
for industrial processes
(e.g., enzymes,bacteria)
White Biotech
Ag (green)
biotech
Bioproducts
Current and new bio
based products (e.g.,
fuel, materials)
Bioremediation
Use of biological
processes for environ
mental cleanup (e.g.,
waste water, oil pests)
Today
Time
Source: McKinsey

3. White (industrial) biotechnology
Biotechnology: The use of nature’s toolbox for industrial processes
Feedstock
Bioprocess
(cells / enzymes)
Products
White biotechnology is the modern use and application of biotechnology for the sustainable production of biochemicals, biomaterials and biofuels from renewable resources, using living cells and/or their enzymes. This results generally in cleaner processes with minimum waste generation and energy use. It can be differentiated from pharmaceutical (red) biotechnology or agricultural (green) biotechnology. “Red” biotechnology is confined to the healthcare sector, whereas “green” biotechnology is applied to the agro-food sector.
White biotechnology is a subject which is rapidly gaining priority on the agendas of those in industry, politics, academia and NGOs. Why? Because white biotechnology offers enormous opportunities, not just for the economy, but equally to our environment and to our society.
White biotechnology is mainly based on fermentation technology and biocatalysis. In a contained environment, genetically modified or non-GM micro-organisms (e.g. yeast, fungi and bacteria) or cell lines from animal or human origin, are cultivated in closed bioreactors to produce a variety of products. Likewise enzymes, which are derived from these (micro-) organisms, are applied to catalyze a conversion in order to generate the desired products.
It is important to note that although the biochemical conversion might be performed by genetically modified micro-organisms the products in itself are non-GMO chemicals, biomaterials or biofuels, since the products simply do not contain any genes.
Activities and opportunities in the field of white biotechnology are rapidly growing due to recent breakthroughs in genomics, molecular genetics, metabolic engineering, and catalysis. Promises are becoming reality and living cells can now be used as tiny micro-factories, which can be optimized with respect to productivity, safety and minimal environmental load.
Fermentable sugars
Specialties
Materials
Base chemicals
Fuel

4. Basic feedstock price developments
Over the last 10 years oil and sugar prices have followed quite opposite trends
CAGR 9,1%
Year
Price
CAGR -3,4%
Crude oil price
Raw sugar price (*) 0%
50%
100%
150%
200%
250%
1994 95 96 97 98 99
2000 01 02 03 04
Feedstock prices are expected to decrease further on with the conversion of wood and agricultural waste into fermentable sugar

5. Existing raw materials of petrochemical origin
Resin Raw Materials
Existing raw materials of petrochemical origin

6. Mineral oil - Natural gas Iso-or –n-butyraldehyde
Polycondensation Resins
Mineral oil - Natural gas
Reformate
Propylene
Methanol
Ethanol
Propylene
Iso-or –n-butyraldehyde
Formaldehyde
Acetaldehyde
Allyl Chloride
o,m,p-xylene
Epichlorohydrine
Phthalic acids
Neopentyl Glycol
Trimethylol Propane
Pentaerytritol
Glycerol
500 kT
200 kT
150 kT
Polyesters
Alkyds
1800 kT

7. Polymerization Resins
Mineral oil - Natural gas
Propylene
Alcohols
Acetone
Benzene
Ethylene
Methanol
Acetone cyanhydrine
Acetic acid
Acrolein
HCN
Ethylbenzene
H2SO4
Acrylic acid
Methacrylic esters
Acrylic esters
Styrene
Vinyl acetate
Acrylics, Styrene/Acrylics and Vinyl Acetate Copolymers
3200 kT

8. Upcoming bio-based building blocks

9. Biomass (straw, switchgrass) Citric acid, Oleochemicals
Building Blocks Through White Biotechnology
Sugar crops
Oil crops
Biomass (straw, switchgrass)
20 billion $
Pharma intermediates
Amino acids, Vitamins
Citric acid, Oleochemicals
Flavors, fragrances
Enzymes
Biological Feedstock
Biotechnological
and/or
Conventional Processes
Industrial Products
Fermentation
Bio-catalysis
1 billion $
Polylactic acid
Glycols
Ethylene
Acrylic acid
Bio-fuel
Biomaterials
Nutritional Ingredients
Specialty Chemicals
Commodity Chemicals

10. Conventional Processes
What can we count on ?
Sugar crops
Biological Feedstock
Oil crops
Sugars
Basic raw materials
Vegetable oils
Polyols
Polyacids
Monomers
Biotechnological
and/or
Conventional Processes
Polyols
Fatty Acids
Polyesters
Alkyd Resins
Polyurethanes
Epoxy Resins
Acrylic resins
Polyurethanes
Alkyd Resins
Polyamides
Epoxy Esters
Coating Resins

11. Use: Alkyd resins, Polyesters
What we already use
Vegetable oils:
Renewable
Non toxic
Biodegradable
Full environmental acceptance
Use: Alkyd resins
Glycerol:
Renewable
Non toxic
Biodegradable
Full environmental acceptance
Use: Alkyd resins, Polyesters

12. What is already available in the market
Soyol™ “biobased” polyols:
OH functionality: 2 – 3
Molecular weight:
Uses:
Seating foam furniture
Foam insulation
Carpet backing
Shoe soles
Roof coatings.
Effects:
Cost less than the petroleum polyols they replace.
Plant based, annually renewable resources.
Reduce demand and dependence on limited petroleum reserves.

13. What we can expect to come ?

14. One of the top 12 chemicals from biomass
What we expect to come HO OH O
Succinic Acid: C4H6O4
One of the top 12 chemicals from biomass
Potential use:
Diacid for polyesters
Diacid for alkyds
Intermediate for manufacturing of:
Maleic acid (polyesters)
Butanediol (polyesters)
Diaminobutane (polyamides)
Adipic acid (polyesters, polyamides)

15. Interrelation between the most relevant
1,4-bifunctional C4 building blocks.
The reactions from left to right require reduction (so the reverse require oxidation), whereas the ring-closures are dehydratation reactions.
HOOC -
CH=CH
COOH CH 2 OH
HOCH
Fumaric /
Maleic
acid
Succinic 4
Hydroxybutanoic
1,4
Butanediol
anhydride
gamma
Butyrolactone
Tetrahydrofuran O =O
O= =O

16. Commercial quantities: 2008/2009 Commercial quantities: 2007
What we expect to come
Isosorbide: C6H10O4 Via dehydration of sorbitol OH O
Difunctional polyol for:
Polyesters
Polycarbonates
Polyamides
Polyurethanes
Plasticizers
Commercial quantities: 2008/2009
Itaconic Acid: C5H6O4
Via fungal fermentation of glucose HO OH O
CH2
Potential use:
Polymerization monomer
(Meth)acrylic esters alternative
Hydrogels for superabsorption
Commercial quantities: 2007
3-Hydroxy Propionic Acid: C3H6O2
Feedstock for:
Acrylonitrile
Acrylic Acid
Acrylamide HO OH O
Technically feasible, but not yet cost effective

17. Polycondensation resins Polymerization resins
Summary of existing and potential opportunities
Acids:
Fatty acids
Succinic acid
Maleic acid
Fumaric acid
Adipic acid
Polyols:
Glycerol
Sorbitol
Isosorbide
Butane diol
Monomers:
Itaconic acid & esters
Acrylic acid & esters
Acrylonitrile
Acrylamide
Polycondensation resins
Alkyd resins
Polyesters
Polyurethanes
Polymerization resins
Acrylic resins
Alternatives to acrylic resins

18. Can the prices go even further down?
Energy crops: Miscanthus -1 years growth without replanting!
20 tons/acre? (
10-30 tons/acre (

19. Turning South Dakota into…
Biomass Will Make a Difference
Turning South Dakota into…
…a member of OPEC?!
Today
Tomorrow
Thousand barrels/day
Farm acres
44 Million
44 Million
Saudi Arabia
9,400 5 15
Iran
3,900
Tons/acre
South Dakota
3,429
Gallons/ton 25 80
Kuwait
2,600
Thousand barrels/day
857
3,429
Venezuela
2,500
UAE
2,500
Nigeria
2,200
Iraq
1,700
Libya
1,650
Algeria
1,380
Indonesia
925
Qatar
800
Source: Ceres Company Presentation

20. Biomass Will Make a Difference
The chemical industry is working hard to use ligno-cellulose as a feedstock
Ligno cellulose is much more available than e.g. crops.
A whole plant can be used.
Use of land not suitable for food or feed ( prairies-USA, pampas-Argentina)
No competition between making chemicals and supplying food.
Selection and\or genetically modified plants that grow very fast.
Environmentally friendly cultivation; plants that do not need fertilizers
The next step: bio-refinery
Switch-grass cultivation
Extraction of valuable products (proteins)
Chemical building blocks
Rest for Bio-fuel
The biomass as a feedstock will further reduce the prices of the chemicals

21. Not yet but will be soon Conclusion
Sugars
Vegetable oils
Mineral Oil
USD/barrel
USD/kg
Oil reserves are limited, not renewable. Oil price still volatile and has tripled in the past five years
Sugars/vegetable oils: Costs decreased with a tendency to stabilize.
Further progress in white biotechnology offers solutions based on even cheaper biomass feedstock
Coating Resins on Bio-based Raw Materials: Reality or Distant Future?
Not yet but will be soon