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Coating Resins on Bio-based Raw Materials

Reality or Distant Future?

Tosko Misev, Dirk Stanssens

DSM Resins bv, DSM Innovation Center

DSM Coating Resins

2007/presentations/external/NVVT
 Introduction 1

• 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

DSM Coating Resins

2007/presentations/external/NVVT
 What is white (industrial) biotechnology? 2

Industrial applications
Market Biofeedstock
penetration Replacement of
fossil feedstock by
sugar and biomass
Pharma (red) Bioprocesses
biotech Use of natures toolbox
for industrial processes
White (e.g., enzymes,bacteria)
Biotech
Ag (green) Bioproducts
biotech 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
DSM Coating Resins
2007/presentations/external/NVVT
White (industrial) biotechnology 3

Biotechnology: The use of nature’s toolbox for industrial processes

Bioprocess
Feedstock Products
(cells / enzymes)

Fermentable
sugars Specialties
Materials
Base chemicals
Fuel

DSM Coating Resins

2007/presentations/external/NVVT
Basic feedstock price developments 4

Over the last 10 years oil and sugar prices have followed quite opposite trends

250%

Price
CAGR 9,1%
200%
Crude oil price

150%

100% Feedstock prices are

expected to decrease further
on with the conversion of
wood and agricultural waste
50% Raw sugar price (*) into fermentable sugar
CAGR -3,4%
Year
0%

DSM Coating Resins

2007/presentations/external/NVVT
Resin Raw Materials 5

Existing raw materials of petrochemical origin

DSM Coating Resins

2007/presentations/external/NVVT
Polycondensation Resins 6

Mineral oil - Natural gas

Reformate Propylene Methanol Ethanol Propylene

o,m,p-xylene Iso-or –n- Formaldehyde Acetaldehyde Allyl Chloride

butyraldehyde

Epichlorohydrine

Phthalic Neopentyl Trimethylol Pentaerytritol Glycerol

acids Glycol Propane
500 kT 200 kT
150 kT

Polyesters Alkyds

1800 kT
DSM Coating Resins
2007/presentations/external/NVVT
Polymerization Resins 7

Mineral oil - Natural gas

Propylene Alcohols Acetone Benzene Ethylene Methanol

Acrolein Acetone HCN Ethylbenzene Acetic acid

cyanhydrine

H2SO4
Acrylic acid

Acrylic esters Methacrylic Styrene Vinyl acetate

esters

Acrylics, Styrene/Acrylics and Vinyl Acetate Copolymers

3200 kT
DSM Coating Resins
2007/presentations/external/NVVT
 8

Upcoming bio-based building blocks

DSM Coating Resins

2007/presentations/external/NVVT
Building Blocks Through White Biotechnology 9

Sugar crops 20 billion $

Biological Feedstock Oil crops Pharma intermediates
Biomass (straw, switchgrass) Amino acids, Vitamins
Citric acid,
Oleochemicals

Biotechnological Flavors, fragrances

Fermentation
and/or Enzymes
Bio-catalysis
Conventional Processes

Bio-fuel 1 billion $
Biomaterials Polylactic acid
Industrial Products Nutritional Ingredients Glycols
Specialty Chemicals Ethylene
Commodity Chemicals Acrylic acid

DSM Coating Resins

2007/presentations/external/NVVT
What can we count on ? 10

Sugar crops Biological Feedstock Oil crops

Sugars Basic raw materials Vegetable oils

Polyols Biotechnological
Polyols
Polyacids and/or
Fatty Acids
Monomers Conventional Processes

Polyesters Polyurethanes
Alkyd Resins Alkyd Resins
Coating Resins
Polyurethanes Polyamides
Epoxy Resins Epoxy Esters
Acrylic resins

DSM Coating Resins

2007/presentations/external/NVVT
What we already use 11

Vegetable oils: Glycerol:

Renewable Renewable
Non toxic Non toxic
Biodegradable Biodegradable
Full environmental acceptance Full environmental acceptance

Use: Alkyd resins Use: Alkyd resins, Polyesters

DSM Coating Resins

2007/presentations/external/NVVT
What is already available in the market 12

Soyol™ “biobased” polyols:

OH functionality: 2 – 3
Molecular weight: 1000-2000

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.

DSM Coating Resins

2007/presentations/external/NVVT
 13

What we can expect to come ?

DSM Coating Resins

2007/presentations/external/NVVT
What we expect to come 14

O
Succinic Acid: C4H6O4
OH
One of the top 12 chemicals from biomass HO
O

Potential use:

• Diacid for polyesters

• Diacid for alkyds
• Intermediate for manufacturing of:
• Maleic acid (polyesters)
• Butanediol (polyesters)
• Diaminobutane (polyamides)
• Adipic acid (polyesters, polyamides)

DSM Coating Resins

2007/presentations/external/NVVT
Interrelation between the most relevant
1,4-bifunctional C4 building blocks. 15

The reactions from left to right require reduction (so the reverse require oxidation),
whereas the ring-closures are dehydratation reactions.

HOOC- CH=CH-COOH HOOC-CH2 -CH2 -COOH HOOC-CH2 -CH2 -CH2 OH HOCH2 -CH2 -CH2 -CH2 OH

Fumaric/Maleic acid Succinic acid 4- Hydroxybutanoic acid 1,4- Butanediol

Maleic anhydride Succinic anhydride gamma- Butyrolactone Tetrahydrofuran

O O O O
O= =O O= =O =O

DSM Coating Resins

2007/presentations/external/NVVT
What we expect to come 16

Isosorbide: C6H10O4 Itaconic Acid: C5H6O4 3-Hydroxy Propionic

Via dehydration of sorbitol Via fungal fermentation of glucose Acid: C3H6O2

OH O O
OH HO OH
HO
CH2 O O
O
OH

Difunctional polyol for: Feedstock for:

Potential use:
• Polyesters • Acrylonitrile
• Polymerization monomer
• Polycarbonates • (Meth)acrylic esters alternative • Acrylic Acid
• Polyamides • Hydrogels for superabsorption • Acrylamide
• Polyurethanes
• Plasticizers Technically
Commercial quantities: Commercial quantities: feasible, but not yet
2008/2009 2007 cost effective

DSM Coating Resins

2007/presentations/external/NVVT
Summary of existing and potential opportunities 17

Acids: Polyols: Monomers:

Fatty acids Glycerol Itaconic acid & esters
Succinic acid Sorbitol Acrylic acid & esters
Maleic acid Isosorbide Acrylonitrile
Fumaric acid Butane diol Acrylamide
Adipic acid

Polycondensation resins
Polymerization resins
Alkyd resins
Acrylic resins
Polyesters
Alternatives to acrylic resins
Polyurethanes

DSM Coating Resins

2007/presentations/external/NVVT
Can the prices go even further down? 18

Energy crops: Miscanthus -1 years growth without replanting!

20 tons/acre? (www.bical.net)
10-30 tons/acre (www.aces.uiuc.edu/DSI/MASGC.pdf)
DSM Coating Resins
2007/presentations/external/NVVT
 Biomass Will Make a Difference 19

Turning South Dakota into… …a member of OPEC?!

Today Tomorrow Thousand barrels/day

Farm acres 44 Million 44 Million Saudi Arabia 9,400

Tons/acre 5 15 Iran 3,900
South Dakota 3,429
Gallons/ton 25 80
Kuwait 2,600
Thousand 857 3,429
Venezuela 2,500
barrels/day
UAE 2,500
Nigeria 2,200
Iraq 1,700
Libya 1,650
Algeria 1,380
Indonesia 925
Qatar 800

DSM Coating Resins

Source:2007/presentations/external/NVVT
Ceres Company Presentation
Biomass Will Make a Difference 20

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

Extraction of Chemical Rest for

Switch-grass valuable products building Bio-fuel
cultivation (proteins) blocks

The biomass as a feedstock will further reduce the prices of the chemicals

DSM Coating Resins

2007/presentations/external/NVVT
 Conclusion 21

Mineral Oil Sugars Vegetable oils

80 0.6 0.7
70 0.68
0.5
60
USD/barrel USD/kg 0.66 USD/kg
50 0.4
0.64
40 0.3 0.62
30 0.6
0.2
20 0.58
10 0.1
0.56
0 0 0.54
2001 2002 2003 2004 2005 2006 2001 2002 2003 2004 2005 2006 2001 2002 2003 2004 2005 2006

• 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

DSM Coating Resins
2007/presentations/external/NVVT