1. Renewable Materials at Ashland
Joe Fox
Director, Emerging & External Technologies
Ashland Performance Materials
Delaware Sustainable Chemistry Summit
March 5, 2012
2. An Overview of Ashland Inc.
⢠A global, diversified specialty chemical company with $8B in sales
- No longer Ashland Oil!
⢠Strengthened by the acquisition of Hercules in 2008 and
International Specialty Products (ISP) in 2011
I am here
representing
Performance Materials
HQ = Dublin, OH
Consumer Markets Water Technologies Specialty Ingredients Performance Materials
Formulated Water Treatment Functional Adhesives &
Motor Oils Chemicals Additives Resins for Composites
2 DESCA Summit 03-05-12
3. How Each Division of Ashland Touches a Biorefinery
⢠Chemicals for a biorefinery
- Water Technologies (AWT)
⢠Pulping aids
⢠Corrosion, scale inhibitors
⢠Extraction aid for corn oil
⢠Chemicals from a biorefinery
I am here representing
- Performance Materials (APM)
Performance Materials (APM)
⢠Bio-based building blocks for resins
- Specialty Ingredients (ASI)
⢠High purity cellulose
⢠Nano-cellulose
- Consumer Markets (ACM)
⢠Biolubricants
3 DESCA Summit 03-05-12
4. Ashland Performance Materials
⢠Primary market focus Resins
- Transportation for
Composites
- Building & Construction
- Packaging & Converting
⢠Business-to-Business focus
⢠Major product lines High
Performance
- Resins for composites Adhesives
- High performance adhesives
⢠Structural adhesives
⢠Pressure-sensitive adhesives
⢠Products are based on thermoset resin chemistry
- Unsaturated polyesters, vinyl esters
- Urethanes
- Acrylics
- Hybrids
4 DESCA Summit 03-05-12
5. Ashland Products That Use Biorenewable Raw Materials
⢠Envirezâ˘: A family of bio-based resins.
Used in a variety of interior & exterior building products.
2008
Presidential
⢠Soyadâ˘: A formaldehyde-free, soy-based adhesive Green Chemistry
Award Winner
for plywood and particle board.
⢠Natrosolâ˘: A thickener for water-based paints
based on Hydroxyethyl Cellulose (HEC)
5 DESCA Summit 03-05-12
6. ENVIREZTM Bio-Based Resins
⢠Ashland has developed a family of unsaturated polyester (UPR) composite resins
that are formulated using renewably-sourced and/or recycled raw materials.
TRANSPORTATION
MARINE
BUILDING & CONSTRUCTION
6 DESCA Summit 03-05-12
7. Unsaturated Polyester Resins (a.k.a. UPRs or UPEs)
O
OH + OH
HO HO
Performance Materials O
buys monomers Diol Diacid
â (2n-1) H2O
O
O H
HO O
n
We convert them O
to oligomers Unsaturated Polyester
& formulate them
in our
manufacturing
plants
Our customers
Vinyl monomer complete the
(reactive diluent) polymerization
in their processes
Unsaturated Polyester Peroxide initiator Cured
Resin Cross-linking reaction Thermoset
7 DESCA Summit 03-05-12
8. Building Blocks for Envirez Resins
⢠Current:
- Bio-based raw materials:
⢠Ethanol
⢠Soybean oil
⢠Propylene glycol
⢠1,3 Propanediol
- Recycled raw materials:
⢠Recycled PET Terephthalic acid and ethylene glycol
⢠Desired renewable raw materials:
- Unsaturated di-acids: Fumaric acid, itaconic acid
- Glycols: Ethylene glycol
- Aromatic di-acids: Terephthalic acid, isophthalic acid
8 DESCA Summit 03-05-12
9. APMâs Partnering Strategy
⢠Performance Materials looks for both upstream and downstream partners
in the value chain.
Raw Intermediate Formulated Fabricated
Consumer
Material Materials Materials Product
Ashland looks Ashland Ashland looks
for partners here plays here for partners here
⢠Upstream partners
- Biorenewable raw materials
⢠Downstream partners
- Fabricators
- Channel-to-market
9 DESCA Summit 03-05-12
10. APMâs Partnering Strategy for Bio-Based Chemicals
Monomers Oligomers Formulated resins
Ashland plays here
Ashland looks for partners & suppliers here
ENVIREZTM Fiberglass Composites
Unsaturated for
1,3 PDO Polyester Agricultural Equipment
Resins & LEED Buildings
Soybean
Oil
Source: U.S. Department of Energy, âTop03-05-12 Chemicals From Biomassâ August, 2004
10 DESCA Summit Value Added
11. Vision for Chemical Production at an Ethanol Biorefinery
Agricultural
Biomass Ch
em
ica
lP
ro
du
cti
on
Fuel Sugar solution
Production Organism 1 Catalyst A Organism 2 Catalyst B
Glycol 1 Glycol 2 Acid 1 Acid 2
Ashland uses these monomeric
Ethanol building blocks to make its Envirez resins
⢠Message to the state of Ohio: Modification of a biorefinery to enable chemical
production would be less capital-intensive than a greenfield site and could lead to
faster job creation.
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12. Vision for Chemical Production at a Pulp & Paper Mill
Agricultural
Biomass Ch
em
ica
lP
ro
du
cti
âHardwareâ on
Pulp
& Sugar solution
Paper Organism 3 Catalyst C Organism 4 Catalyst D
Processing
âSoftwareâ
Glycol 1 Glycol 2 Acid 1 Acid 2
Ashland uses these monomeric
Pulp & Paper building blocks to make its Envirez resins
⢠Ashland does not intend to build or operate a biorefinery, but we represent a
strong downstream channel-to-market partner for bio-based chemicals.
⢠We look for partners that have the necessary âhardwareâ and/or âsoftwareâ.
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13. Ashlandâs Interest in Biorenewable Raw Materials
⢠Ashland is interested in using bio-based raw materials to make our products.
- For composite resins, adhesives, functional additives, lubricants, water treatment chemicals
⢠Motivation:
- Lower cost, greater price stability, greater accessibility relative to petroleum-based
raw materials
- Pull from our customers for green, sustainable products
Drop-In Strategy:
⢠In some instances, we are using (or hope to use) bio-derived versions of building
blocks that we already use. Examples:
- Bio-derived propylene glycol
- Bio-derived fumaric acid Driver = Green + Lower cost
- Bio-derived butyl acrylate
Exploratory Research:
⢠In other instances, we are trying to incorporate bio-based building blocks that arenât
currently used. Examples:
- Modified oils
- Reactive intermediates Driver = Green + Higher Performance
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14. Ashlandâs Interest in Biorenewable Materials
Higher New biorenewable
building blocks
Comparable Biorenewable versions of
existing raw materials
Performance relative to
petroleum-based products
Lower
Higher Comparable Lower Significantly
Lower
Cost relative to
petroleum-based products
14 DESCA Summit 03-05-12
15. Chemical Production from a Biorefinery
⢠Specific chemicals Performance Materials is interested in:
- Glycols:
⢠Ethylene glycol (EG), Propylene glycol (PG)
- Unsaturated di-acids
⢠Fumaric acid, Itaconic acid
- Acrylates
⢠Butyl acrylate, 2-Ethylhexylacrylate
- Aromatics
⢠Isophthalic acid, Terephthalic acid
⢠Replacements for Bis Phenol A
⢠Economics:
- Bio-based chemicals must be cost competitive with their petroleum-based
equivalents
⢠Technology gap:
- Enzymes /organisms for selective conversion of biomass to these chemicals
⢠Ashland does not have expertise in this area
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16. Summary of Our Message
⢠Ashland is interested in using existing and new bio-based building blocks
across its product lines.
⢠We are interested in working with organizations that have technology for the
selective conversion of biomass to chemicals
- Chemical conversion
- Biological conversion
⢠We are interested in partnering to secure funding for the production of
chemicals from a biorefinery
- Bioethanol refinery
- Pulp and paper mill
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17. Thank You !!
Joe Fox
614-790-3686
jfox@ashland.com
17 DESCA Summit 03-05-12
19. Ashland Performance Materials
⢠Primary market focus
- Transportation
- Building & Construction Resins
- Packaging & Converting for
Composites
⢠Business-to-Business focus
⢠Major product lines
- Resins for composites High
Performance
- High performance adhesives
Adhesives
⢠Structural adhesives
⢠Pressure-sensitive adhesives
Ashland Consumer Markets
⢠Strong brand recognition & marketing
- Valvoline
- Eagle One
⢠Business-to-Consumer products & services
- Lubricants
- Automotive chemicals
- Car care / appearance products
- Quick lube service
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20. Center for Biorenewable Chemicals (CBiRC)
⢠NSF Engineering Research Center (ERC) at Iowa State
⢠Iowa State, Wisconsin, Virginia, Rice, UC-Davis
⢠17 industrial members
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21. Evolution of ENVIREZ:
Green Building Blocks for Unsaturated Polyester Resins
Glycol Unsaturated Diacid Diacid Unsaturated
or Anhydride (optional) Polyester
O
heat O O
HO R OH + O + HO2C R1 CO2H HO R OC C C C O H
â H2O
O Add to reactive
Propylene Glycol Maleic Anhydride Phthalic Anhydride diluent
Ethylene Glycol Fumaric Acid Isophthalic Acid
Diethylene Glycol Adipic Acid
Neopentyl Glycol Terephthalic Acid
1,3-Propanediol Succinic Acid Styrene
Isosorbide
Unsaturated Polyester
Resin
Renewable / Recycled Building Blocks Include:
⢠âGreenâ versions of standard materials
â from renewable and / or recycled material
⢠Newly available / non-standard materials
DESCA Summit 03-05-12
21
Editor's Notes
Ashlandâs new structure, including the former Hercules businesses, is composed of five commerical units serving the worlds most essential needs and industries. Ashland Hercules Water Technologies â The #1 global producer of papermaking chemicals Ashland Performance Materials â The #1 global leader in unsaturated polyester resins and vinyl ester resins Ashland Aqualon Functional Ingredients â The #2 global producer of cellulose ethers Ashland Consumer Markets â The #3 passenger care motor oil and #2 quick-lube chain in the United States Ashland Distribution â The #2 plastics and #3 chemicals distributor in North America.
First, what is an unsaturated polyester resin and how do we make it? We first make the unsaturated polyester by condensation of a diol and diacid. The unsaturation in the polyester is generally from fumaric or maleic acid. In this example, we use fumaric acid and a simple diol, like ethylene glycol. The C=C double bonds remaining after the ester condensation reaction are capable of free radical polymerization to form a highly crosslinked network. Although we can use neat UPE, the more useful product (the unsaturated polyester resin) is generally made by combining the unsaturated polyester with a reactive monomer (such as styrene) This reduces the viscosity of the mixture and makes it easier to add the peroxide initiator and apply the resin. The combination is also more reactive. Upon addition of the initiator, free radical reaction ⌠...UPE is thermosetting resin matrix and some reinforcment and fillers are added⌠Plastics categoriesâŚ. Thermosets: Themoset plastics are solid material than cannot be returned to the uncured state. Thermoplastics: Thermoplastics are capable of repeatably softening when heated to change shape and hardening when cooled to keep shape.
Another opportunity that exists is that the availability of new renewable raw materials is increasingâŚwhich is of course in part due to new interest in this area. Ex w/DOE chart. Future for renewable resource-based UPRs or opportunities and challenges in UPR (we had a tough challenge in late 90s/early 2000 but new RRMs are online) see below ď availability of raw materials based on renewable resources
