&EPA
United States
Environmental Protection
Agency
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United States 744K09002
Environmental Protection June 2009
Agency www.epa.gov
Office of Pollution Prevention and Toxics (7406M)
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The Presidential
Green Chemistry Challenge
Award Recipients
1996-2009
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Academic Award:
Professor Krzysztof Matyjaszewski,
Carnegie Mellon University 2
Small Business Award:
Virent Energy Systems, Inc. 4
Greener Synthetic Pathways Award:
Eastman Chemical Company 6
Greener Reaction Conditions Award:
CEM Corporation 8
Designing Greener Chemicals Award:
The Procter & Gamble Company, Cook Composites
and Polymers Company. 70
Academic Award:
Professors Robert E. Maleczka and
Milton R. Smith, III,
Michigan State University 72
Small Business Award:
SiGNa Chemisty, Inc 74
Greener Synthetic Pathways Award:
Battelle 76
Greener Reaction Conditions Award:
Nalco Company 78
Designing Greener Chemicals Award:
DowAgroSciences EEC 20
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Academic Anard:
Professor Michael j. Krische,
University of Texas at Austin 22
Small Business Award:
NovaSterilis Inc 24
Greener Synthetic Pathways Award:
Professor Kaichang Li, Oregon State University;
Columbia Forest Products; Hercules Incorporated
(nowAshland Inc.) 26
Greener Reaction Conditions Award:
Headwaters Technology Innovation 28
Designing Greener Chemicals Award:
Cargill, Incorporated 30
Academic Award:
Professor Galen j. Suppes,
University of Missouri-Columbia 32
Small Business Award:
Arkon Consultants, NuPro Technologies, Inc. (now
Eastman Kodak Company) 34
Greener Synthetic Pathways Award:
Merck & Co., Inc. 36
Greener Reaction Conditions Award:
Codexis, Inc. 38
Designing Greener Chemicals Award:
S.C.Johnson & Son, Inc 40
Academic Award:
Professor Robin D. Rogers,
The University of Alabama 42
lv Contents
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Small Business Award:
Metabolix, Inc 44
Greener Synthetic Pathways Awards:
Archer Daniels Midland Company, Novozymes 46
Merck & Co., Inc. 48
Greener Reaction Conditions Award:
BASF Corporation 50
Designing Greener Chemicals Award:
Archer Daniels Midland Company 52
-004 \\mrnis
Academic Award:
Professors Charles A. Eckert and Charles L. Liotta,
Georgia Institute of Technology 54
Small Business Award:
Jeneil Biosurfactant Company 56
Greener Synthetic Pathways Award:
Bristol-Myers Squibb Company 58
Greener Reaction Conditions Award:
Buckman Laboratories International, Inc 60
Designing Greener Chemicals Award:
Engelhard Corporation (now BASF Corporation) 62
:()():] \\ IIIIK:!',
Academic Award:
Professor Richard A. Gross,
Polytechnic University 64
Small Business Award:
AgraQuest, Inc. 66
Greener Synthetic Pathways Award:
Sud-Chemie Inc 68
Greener Reaction Conditions Award:
DuPont 70
Designing Greener Chemicals Award:
Shaw Industries, Inc 72
Contents v
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Academic Award:
Professor EricJ. Beckman,
University of Pittsburgh 74
Small Business Award:
SC Fluids, Inc 76
Greener Synthetic Pathways Award:
Pfizer, Inc. 78
Greener Reaction Conditions Award:
Cargill Dow LLC (now NatureWorks LLC) 80
Designing Greener Chemicals Award:
Chemical Specialties, Inc. (CSO(nowViance) 82
Academic Award:
Professor Chao-jun Li,
Tulane University 84
Small Business Award:
EDEN Bioscience Corporation 86
Greener Synthetic Pathways Award:
Bayer Corporation, Bayer AC (technology acquired by
LANXESS) 88
Greener Reaction Conditions Award:
Novozymes North America, Inc 90
Designing Greener Chemicals Award:
PPG Industries 92
Academic Award:
Professor Chi-Huey Wong,
The Scripps Research Institute 94
Small Business Award:
RevTech, Inc 96
Greener Synthetic Pathways Award:
Roche Colorado Corporation 98
vl Contents
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Greener Reaction Conditions Award:
Bayer Corporation, Bayer AC 700
Designing Greener Chemicals Award:
DowAgroSciences LLC 702
Academic Award:
Professor Terry Collins,
Carnegie Mellon University 704
Small Business Award:
Biofine, Inc. (nowBioMetics, Inc.) 706
Greener Synthetic Pathways Award:
Lilly Research Laboratories 708
Greener Reaction Conditions Award:
Nalco Chemical Company 770
Designing Greener Chemicals Award:
DowAgroSciences LLC 772
Academic Awards:
Professor Barry A/1. Trost,
Stanford University 774
Dr. Karen A/I. Draths and Professor John W. Frost,
Michigan State University 776
Small Business Award:
PYROCOOL Technologies, Inc 778
Greener Synthetic Pathways Award:
Flexsys America LP. 720
Greener Reaction Conditions Award:
Argonne National Laboratory 722
Designing Greener Chemicals Award:
Rohm and Haas Company (now The Dow Chemical
Company) 724
Contents vii
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Academic Award:
Professor Joseph A/1. DeSimone,
University of North Carolina at Chapel Hill and
North Carolina State University 726
Small Business Award:
Legacy Systems, Inc 728
Greener Synthetic Pathways Award:
BHC Company (now BASF Corporation) 130
Greener Reaction Conditions Award:
Imation (technology acquired by Eastman
Kodak Company) 732
Designing Greener Chemicals Award:
Albright & Wilson Americas (nowRhodia) 134
Academic Award:
Professor Mark Holtzapple,
Texas A&M University 136
Small Business Award:
Donlar Corporation (nowNanoChem
Solutions, Inc.) 138
Greener Synthetic Pathways Award:
Monsanto Company 740
Greener Reaction Conditions Award:
The Dow Chemical Company 742
Designing Greener Chemicals Award:
Rohm and Haas Company (now The Dow Chemical
Company) 744
viii Contents
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The Presidential Green Chemistry Challenge Awards Program is an opportunity for
individuals, groups, and organizations to compete for annual awards in recognition
of innovations in cleaner, cheaper, smarter chemistry. The Program provides national
recognition for outstanding chemical technologies that incorporate the principles of
green chemistry into chemical design, manufacture, and use. In addition, winning
technologies have been or can be used by industry to achieve its pollution prevention
goals. EPA typically honors five winners each year, one in each of the following
categories:
• Academia
• Small business
• Greener Synthetic Pathways, such as the use of innocuous and renewable feed-
stocks (e.g., biomass, natural oils); novel reagents or catalysts including biocatalysts
and microorganisms; natural processes including fermentation and biomimetic
syntheses,- atom-economical syntheses,- or convergent syntheses
• Greener Reaction Conditions, such as the replacement of hazardous solvents with
greener solvents,- solventless or solid-state reactions,- improved energy efficiency,-
novel processing methods,- or the elimination of energy- and material-intensive sepa-
rations and purifications
• Designing Greener Chemicals, such as chemicals that are less toxic than current
alternatives; inherently safer chemicals with regard to accident potential; chemicals
recyclable or biodegradable after use,- or chemicals safer for the atmosphere (e.g., do
not deplete ozone or form smog)
This booklet presents the 1996 through 2009 Presidential Green Chemistry Challenge
Award recipients and describes their award-winning technologies. Each winner demon-
strates a commitment to designing, developing, and implementing a green chemical
technology that is scientifically innovative, economically feasible, and less hazardous to
human health and the environment.
Collectively, these award-winning technologies have:
• Eliminated more than 1.3 billion pounds of hazardous chemicals and solvents,
• Saved over 42 billion gallons of water, and
• Eliminated nearly 460 million pounds of carbon dioxide releases to air.
The Presidential Green Chemistry Challenge Program is looking forward to adding
future years' winners to the growing list of scientists and companies who are on the
cutting edge of pollution prevention.
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2009 Winners
Atom Transfer Radical Polymerization: Low-impact Polymerization Using a
Copper Catalyst and Environmentally Friendly Reducing Agents
Hazardous chemicals are often required in the manufacture of important
polymers such as lubricants, adhesives, and coatings. Professor
Matyjaszewski developed an alternative process called "Atom Transfer
Radical Polymerization (ATRP)" for manufacturing polymers. The process
uses chemicals that are environmentally friendly, such as ascorbic acid
(vitamin C) as a reducing agent, and requires less catalyst. ATRP has been
licensed to manufacturers throughout the world, reducing risks from
hazardous chemicals.
-, • orldwide production of synthetic polymers is approximately 400 billion
pounds per year; approximately half of this involves free radical polymer-
ization. With the recent development of controlled radical polymerization
(CRP), it is now possible to make well-defined polymers with precisely
controlled molecular structures. Atom transfer radical polymerization
(ATRP) is one such technology; it is a transition-metal-mediated, con-
trolled polymerization process that was discovered at Carnegie Mellon
University (CMU) in 1995. Since then, Professor Matyjaszewski and his
group have published over 500 scientific papers on CRP; these papers
have been cited over 30,000 times, making Professor Matyjaszewski
the second-most cited researcher in all fields of chemistry in 2008. This
explosive interest in ATRP is due to its simplicity and ability to tailor-make
functional macromolecules for specialty applications. ATRP has become
the most versatile and robust of the CRP methods.
Professor Matyjaszewski has been working continually to increase the en-
vironmental friendliness of his process. During the last four years, he and
his team at CMU have developed new catalytic systems that dramatically
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decrease the concentration of transition metal, while preserving
good control over polymerization and polymer architecture. The latest im-
provements are activators generated by electron transfer (AGET, 2004), ac-
tivators regenerated by electron transfer (ARGET, 2005), and initiators for
continuous activator regeneration (ICAR, 2006). These methods allow the
preparation, storage, and use of the most active ATRP catalysts in their
oxidatively stable state as well as their direct use under standard industrial
conditions. The recent discovery of ARGET ATRP reduces the amount of
copper catalyst from over 1,000 ppm to around 1 ppm in the presence
of environmentally friendly reducing agents such as amines, sugars, or
ascorbic acid. AGET and ARGET ATRP provide routes to pure block copo-
lymers. The new processes allow oxidatively stable catalyst precursors to
be used in aqueous homogeneous, dispersed (miniemulsion, inverse
miniemulsion, microemulsion, emulsion, and suspension), and solvent-
less bulk polymerizations. Professor Matyjaszewski's work is opening new
"green" routes for producing many advanced polymeric materials.
ATRP has become an industrially important means to produce polymers.
Since 2003, ATRP has been licensed to 8 of the over 40 corporations fund-
ing the research at CMU (PPG, Dionex, Ciba, Kaneka, Mitsubishi, WEP,
ATRP Solutions, and Encapson). Licensees around the world have
begun commercial production of high-performance, less-hazardous, safer
materials including sealants, coatings, adhesives, lubricants, additives,
pigment dispersants, and materials for electronic, biomedical, health, and
beauty applications.
2009 Academic Award 3
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BioForming® Process: Catalytic Conversion of Plant Sugars into Liquid
Hydrocarbon Fuels
Virent's BioForming® process is a water-based, catalytic method to make
gasoline, diesel, or jet fuel from the sugar, starch, or cellulose of plants that
requires little external energy other than the plant biomass. The process is
flexible and can be modified to generate different fuels based on current
market conditions. It can compete economically with current prices for
conventionally produced petroleum-based fuels. Using plants as a
renewable resource helps reduce dependence on fossil fuels.
irent has discovered and is developing an innovative green synthetic
pathway to convert plant sugars into conventional hydrocarbon fuels and
chemicals. Virent's catalytic BioForming® process combines proprietary
aqueous-phase reforming (APR) technology with established petroleum
refining techniques to generate the same range of hydrocarbon mole-
cules now refined from petroleum. First, water-soluble carbohydrates are
catalytically hydrotreated. Next, in the APR process, resultant sugar alco-
hols react with water over a proprietary heterogeneous metal catalyst to
form hydrogen and chemical intermediates. Finally, processing with one
of multiple catalytic routes turns these chemicals into gasoline, diesel, or
jet fuel components. The technology also produces alkane fuel gases
and other chemicals. Virent's BioForming® platform can generate mul-
tiple end-products from a single feedstock and enable product optimiza-
tion based on current market conditions.
Compared to other biomass conversion systems, Virent's technology
broadens the range of viable feedstocks, provides more net energy, and
produces fuels compatible with today's infrastructure. The process uses
either food or non-food biomass; it is scalable to match feedstock sup-
ply. Unlike fermentation, Virent's robust process can use mixed sugar
streams, polysaccharides, and C5-and Cg- sugars derived from cellulosic
biomass. By using more plant mass per acre, the process provides
4 2009 Award
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better land use and higher value for farmers. The technology needs little
energy input and can be completely renewable. Virent's energy-dense
biofuels separate naturally from water; as a result, the process eliminates
the energy-intensive distillation to separate and collect biofuels required
by other technologies. The hydrocarbon biofuels from Virent's process
are interchangeable with petroleum products, matching them in compo-
sition, functionality, and performance; they work in today's engines, fuel
pumps, and pipelines. Preliminary analysis suggests that Virent's BioForm-
ing® process can compete economically with petroleum-based fuels and
chemicals at crude oil prices of $60 a barrel.
The BioForming® process can speed the use of non-food plant sugars
to replace petroleum as an energy source, thus both decreasing depen-
dence on fossil hydrocarbons and minimizing the impact on global water
and food supplies. Fuels derived from the process can have a
20-30 percent per Btu cost advantage over ethanol. The BioForming®
platform is near commercialization. During 2008, Virent produced over
40 liters of biogasoline for engine testing and began fabrication of its first
10,000-gallon-per-year pilot plant to produce biogasoline.
2009 Small Business Award 5
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A Solvent-Free Biocatalytic Process for Cosmetic and Personal Care
Ingredients
Esters are an important class of ingredients in cosmetics and personal care
products. Usually, they are manufactured by harsh chemical methods that
use strong acids and potentially hazardous solvents; these methods also
require a great deal of energy. Eastman's new method uses immobilized
enzymes to make esters, saving energy and avoiding both strong acids
and organic solvents. This method is so gentle that Eastman can use
delicate, natural raw materials to make esters never before available.
i he cosmetics and personal care market is a vast enterprise of formu-
lated specialty chemicals. Esters are an important class of cosmetic
ingredients, comprising emollients, emulsifiers, and specialty perfor-
mance ingredients. In 2006, the estimated North American consumption
of esters as emollients and emulsifiers was 50,000 metric tons. Usually,
such esters are manufactured using strong acid catalysts at high tempera-
tures; unfortunately, this produces undesirable byproducts that must be
removed by energy-intensive purifications. Other methods of producing
cosmetic esters require organic solvents that are potentially hazardous
to workers and the environment. The growing trend for natural ingredi-
ents and environmentally responsible processes in the cosmetics market
requires new manufacturing methods.
In 2005, scientists at Eastman began investigating enzymes as catalysts to
produce cosmetic esters. Eastman has now synthesized a variety of esters
via enzymatic esterifications at mild temperatures. The esterifications are
driven to high conversion by removing the coproduct, usually water from
esterification of an acid or a lower alcohol from transesterification of an
ester. The mild processing conditions do not lead to formation of unde-
sirable byproducts that may contribute color or odor. The immobilized
enzyme, such as lipase, is easily removed by filtration. The specificity of
6 2009 Award
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the enzymatic conversions and the relatively low reaction temperatures
minimize the formation of byproducts, increase yield, and save energy.
Eastman's process can use delicate raw materials such as unsaturated fat-
ty acids that would oxidize during conventional esterifications. Thus, East-
man can make ingredients never before available. It has manufactured
hundreds of such new esters by combining different alcohols and acids.
Biocatalysis can even yield new products that offer superior performance.
For example, two esters can be formed from 4-hydroxybenzyl alcohol
and acetic acid. One—esterification at the benzyl moiety—is only acces-
sible via the enzymatic route. This particular ester inhibits tyrosinase, a
key enzyme in melanin synthesis, and, therefore, is effective in reducing
undesirable skin pigmentation and providing a more uniform skin tone.
Eastman's biocatalytic process can save over ten liters of organic solvent
per kilogram of product. The ester product is often pure enough to
obviate post-reaction processing. An early lifecycle assessment identifies
Eastman's process as vastly improved over conventional processes, espe-
cially in energy use. Overall, this process improves quality, yield, cost, and
environmental footprint compared to conventional chemical syntheses.
Leading cosmetic companies are currently evaluating many of Eastman's
new esters, including emollient esters made from rice bran oil, glyceride
emulsifiers, and new ingredients that combat the visible signs of aging.
2009 Greener Synthetic Pathways Award 7
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Innovative Analyzer Tags Proteins for Fast, Accurate Results without
Hazardous Chemicals or High Temperatures
Each year, laboratories test millions of samples of food for the presence of
protein. Such tests generally use large amounts of hazardous substances
and energy. CEM has developed a fast, automated process that uses less
toxic reagents and less energy. The new system can eliminate 5.5 million
pounds of hazardous waste generated by traditional testing in the United
States each year. What's more, it differentiates between protein and other
chemicals used to adulterate food, such as melamine.
he recent use of melamine to masquerade as protein and adulterate
both baby formula in China and pet food in the United States makes
accurate testing for protein imperative. The standard Kjeldahl and com-
bustion tests for protein measure total nitrogen, however, and cannot
distinguish melamine from protein. Kjeldahl testing uses sulfuric acid,
sodium hydroxide, hydrochloric acid, and boric acid along with a cata-
lyst of copper sulfate, selenium, or mercury. U.S. companies generate
5.5 million pounds of hazardous waste annually from Kjeldahl testing.
Trained chemists are required to run these tests due to the hazardous
materials and high temperatures required.
The Sprint™ Rapid Protein Analyzer automates a technique that tags pro-
tein directly and provides fast, accurate results. CEM's proprietary iTAG™
solution actually tags protein by attaching only to histidine, arginine, and
lysine, the three basic amino acids commonly found in proteins. The
proprietary iTAG™ solution contains an acidic group that readily attaches
to the basic amino acids; iTAG™ also has an extensive aromatic group
that readily absorbs light and appears orange. The iTAG™ bound to the
protein is removed from solution by a filter and the remaining 1TAG™
is then measured by colorimetry. The Sprint™ System ignores any other
nitrogen that may be present, including the nitrogen in melamine. As a
8 2009 Award
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result, it enables food and pet food processors to be absolutely certain of
the bulk protein content of their ingredients and final products for quality
control, product safety, and nutritional labeling. Sprint™ may be used in
the laboratory, on the processing line, or as a rapid check for incoming
raw materials. The system does not require a trained chemist to obtain
accurate results.
Sprint™ uses a green chemistry method: its 1TAG™ solution is nontoxic,
nonreactive, and water-soluble. It eliminates all of the hazardous waste
created by Kjeldahl testing. In addition, Sprint™ does not require high
temperatures, making it a much safer method than Kjeldahl or combus-
tion techniques. It is easy to operate and can test most samples in 2-3
minutes, compared to 4 hours for a Kjeldahl analysis. It uses disposable
filters and recyclable sample cups and lids; all other parts of the system
that touch the sample are self-cleaning. Remarkably fast, accurate, cost-
effective, and safe, Sprint™ is poised to become the method of choice
for protein testing. The methods it automates are approved by AOAC
(Association of Analytical Communities) and AACC International (previ-
ously: American Association of Cereal Chemists). It was commercialized
in January 2008.
2009 Greener Reaction Conditions Award 9
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Chempol® MRS Resins and Sefose® Sucrose Esters Enable
High-Performance Low-VOC Alkyd Paints and Coatings
Conventional oil-based "alkyd" paints provide durable, high-gloss coatings
but use hazardous solvents. Procter & Gamble and Cook Composites and
Polymers are developing innovative Chempol® MPS paint formulations
using biobased Sefose® oils to replace petroleum-based solvents. Sefose®
oils, made from sugar and vegetable oil, enable new high-performance
alkyd paints with less than half the solvent. Paints with less hazardous
solvent will help improve worker safety, reduce fumes indoors as the paint
dries, and improve air quality.
' ;olvent-borne alkyd coatings are in demand because they are cost-effec-
tive and high-performing in many applications, including architectural
finishes, industrial metal, and equipment for agriculture and construction.
Millions of gallons of these paints and coatings are sold in the United
States and around the world. Conventional alkyd resin paints and coat-
ings require large amounts of volatile solvents to solubilize the organic
components and attain appropriate viscosities. These solvents contribute
to the formation of ground-level ozone and smog. Low-VOC alkyd coat-
ings exist, but suffer from inferior performance. Some take too long to
dry; others use substitute, VOC-exempt solvents that tend to be expen-
sive and often have an undesired odor or other inferior performance.
Low-VOC, waterborne acrylic latex paints are also available, but they have
performance trade-offs such as low gloss and reduced corrosion resis-
tance compared to solvent-borne alkyd coatings.
The Procter & Gamble Company (P&G) and Cook Composites and Poly-
mers Company (CCP) have collaborated to develop a new alkyd resin
technology that enables formulation of paints and coatings with less than
half the VOCs of solvent-borne alkyd coatings. These alkyd formulations
are enabled by Sefose® sucrose esters, which are prepared from renew-
10 2009 Award
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able feedstocks by esterifying sucrose with fatty acids in a patented,
solventless process. The molecular architecture and functional density
of Sefose® are controlled by selecting natural oil feedstocks with optimal
fatty acid chain length distribution, unsaturation level, and degree of
esterification. In applied paint films, Sefose® undergoes auto-oxidative
cross-linking with other constituents and becomes an integral part of
the coating films. Chempol® MRS alkyd resins are specially formulated
to deliver performance advantages such as fast drying, high gloss, film
toughness, and increased renewable content.
Replacement of conventional alkyd resins by Chempol® MRS could
(1) reduce VOCs equivalent to the emissions from 7,000,000 cars per year,
(2) reduce ground-level ozone by 215,000 tons per year, and (3) save
900,000 barrels per year of crude oil from the solvents and alkyd polymers
it replaces. Chempol® MRS is cost-competitive with conventional alkyds
on an equal-dry-film basis. In October 2008, CCP launched Chempol®
MRS and began actively sampling the coatings industry. P&G is also
evaluating and testing Sefose® oils as biobased alternatives to replace
petroleum-based lubricants.
2009 Designing Greener Chemicals Award 11
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2008 Winners
Green Chemistry for Preparing Boronic Esters
One way to build complex molecules, such as Pharmaceuticals and
pesticides, is with a Suzuki "coupling" reaction. This versatile coupling
reaction requires precursors with a carbon-boron bond. Making these
precursors, however, typically requires harsh conditions and generates
significant amounts of hazardous waste. Professors Maleczka and Smith
developed a new catalytic method to make these compounds under mild
conditions and with minimal waste and hazard. Their discovery allows the
rapid, green manufacture of chemical building blocks, including some that
had been commercially unavailable or environmentally unattractive.
Loupling" reactions are one way to build valuable molecules, such
as Pharmaceuticals, pesticides, and similar complex substances. Cou-
pling reactions connect two smaller molecules, usually through a new
carbon-carbon (C-C) bond. A particularly powerful coupling reaction is
the Suzuki coupling, which uses a molecule containing a carbon-boron
bond to make a larger molecule through a new C-C bond. In fact, the
Suzuki coupling is a well-established, mild, versatile method for construct-
ing C-C bonds and has been reported to be the third most common C-C
bond-forming reaction used to prepare drug candidates.
Chemical compounds with a carbon-boron bond are often prepared
from the corresponding halides by Grignard or lithiate formation followed
by reaction with trialkyl borate esters and hydrolytic workup. Miyaura
improved this reaction with a palladium catalyst, but even this new reac-
tion requires a halide precursor.
Several years ago, Professors Milton R. Smith, III and Robert E. Maleczka,
Jr. began collaborating to find a "halogen-free" way to prepare the aryl
and heteroaryl boronic esters that are the key building blocks for Su-
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zuki couplings. Their collaboration builds upon Smith's invention of the
first thermal, catalytic arene carbon-hydrogen bond (C-H) activation/
borylation reaction. This led to transformations using iridium catalysts that
are efficient, have high yields, and are tolerant of a variety of functional
groups (alkyl, halo-, carboxy, alkoxy-, amino, etc.). Sterics, not electronics
dictate the regiochemistry of the reactions. As a consequence, 1,3-subs-
tituted arenes give only 5-boryl (i.e., meta-substituted) products, even
when both the 1-and 3-substituents are ortho/para directing. Just as
significantly, the reactions are inherently clean as they can often be run
without solvent, and they occur with hydrogen being the only coproduct.
The success of these reactions has led Miyaura, Ishiyama, Hartwig, and
others to use them as well.
In brief, catalytic C-H activation/borylation allows the direct construction
of aryl boronic esters from hydrocarbon feedstocks in a single step, with-
out aryl halide intermediates, without the limitations of the normal rules
of aromatic substitution chemistry, and without many common functional
group restrictions. Moreover, due to its mildness, the borylation chemistry
combines readily in situ with subsequent chemical reactions.
This technology allows rapid, low-impact preparations of chemical build-
ing blocks that currently are commercially unavailable or only accessible
by protracted, costly, and environmentally unattractive routes. Indeed,
most recently, Michigan State University licensed the nominated tech-
nology to BoroPharm, Inc., which is using these catalytic borylations
to produce much of the company's product line. Thus, the nominated
technology is proving to be practical green chemistry beyond the labora-
tory bench.
2008 Academic Award 13
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New Stabilized Alkali Metals for Safer, Sustainable Syntheses
Alkali metals, such as sodium and lithium, are powerful tools in synthetic
chemistry because they are highly reactive. However, unless they are
handled very carefully, their reactivity also makes them both flammable
and explosive. SiGNa Chemistry developed a way to stabilize these
metals by encapsulating them within porous, sand-like powders, while
maintaining their usefulness in synthetic reactions. The stabilized metals
are much safer to store, transport, and handle. They may also be useful
for removing sulfur from fuels, storing hydrogen, and remediating a
variety of hazardous wastes.
'• Ikali metals have a strong propensity for donating electrons, which
makes these metals especially reactive. That reactivity has enormous po-
tential for speeding chemical reactions throughout science and industry,
possibly including new pathways to clean energy and environmental
remediation. Unfortunately, that same reactivity also makes them highly
unstable and dangerous to store and handle. In addition, increased risk
of supply-chain interruption and the expense of handling these metals
have made them unattractive to the chemical industry. Industries from
pharmaceutical to petroleum have developed alternative synthetic routes
to avoid using alkali metals, but these alternates require additional reac-
tants and reaction steps that lead to inefficient, wasteful manufacturing
processes.
SiGNa Chemistry addresses these problems with its technology for nano-
scale absorption of reactive alkali metals in porous metal oxides. These
new materials are sand-like powders. SiGNa's materials eliminate the dan-
ger and associated costs of using reactive metals directly but retain the
utility of the alkali metals. Far from their hazardous precursors, SiGNa's
materials react controllably with predictable activation that can be adapt-
ed to a variety of industry needs. By enabling practical chemical shortcuts
14 2008 Award
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and continuous flow processes, the encapsulated alkali metals create
efficiencies in storage, supply chain, manpower, and waste disposal.
For the pharmaceutical, petrochemical, and general synthesis industries,
SiGNa's breakthrough eliminates the additional steps that these indus-
tries usually take to avoid using the alkali metals and produces the de-
sired reaction in 80-90 percent less time. For the pharmaceutical industry
in particular, the materials can accelerate drug discovery and manufactur-
ing while bolstering worker safety.
Beyond greening conventional chemical syntheses, SiGNa's materials en-
able the development of entirely new areas of chemistry. In clean-energy
applications, the company's stabilized alkali metals safely produce record
levels of pure hydrogen gas for the nascent fuel cell sector. With yield
levels that already exceed the U.S. Department of Energy's targets for
2015, SiGNa's materials constitute the most effective means for process-
ing water into hydrogen. SiGNa's materials also allow alkali metals to be
safely applied to environmental remediation of oil contamination and the
destruction of PCBs and CFCs.
SiGNa's success in increasing process efficiencies, health, and environ-
mental safety and in enabling new chemical technologies has helped it
attract more than 50 major global pharmaceutical, chemical, and energy
companies as customers.
2008 Small Business Award 15
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Development and Commercialization of Biobased Toners
Laser printers and copiers use over 400 million pounds of toner each
year in the United States. Traditional toners fuse so tightly to paper that
they are difficult to remove from waste paper for recycling. They are
also made from petroleum-based starting materials. Battelle and its
partners, Advanced Image Resources and the Ohio Soybean Council, have
developed a soy-based toner that performs as well as traditional ones, but
is much easier to remove. The new toner technology can save significant
amounts of energy and allow more paper fiber to be recycled.
• lore than 400 million pounds of electrostatic dry toners based on
petroleum-derived resins are used in the United States annually to make
more than 3 trillion copies in photocopiers and printers. Conventional
toners are based on synthetic resins such as styrene acrylates and sty-
rene butadiene. These conventional resins make it difficult to remove
the toner during recycling, a process called de-inking. This makes paper
recycling more difficult. Although others have developed de-inkable ton-
ers, none of the competing technologies has become commercial due to
high costs and inadequate de-inking performance.
With early-stage funding from the Ohio Soybean Council, Battelle and
Advanced Image Resources (AIR) formed a team to develop and market
biobased resins and toners for office copiers and printers. This novel
technology uses soy oil and protein along with carbohydrates from
corn as chemical feedstocks. Battelle developed bioderived polyester,
polyamide, and polyurethane resins and toners from these feedstocks
through innovative, cost-effective chemical modifications and processing,
with the de-inking process in mind. By incorporating chemical groups that
are susceptible to degradation during the standard de-inking process,
Battelle created new inks that are significantly easier to remove from the
16 2008 Award
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paper fiber. AIR then scaled up the process with proprietary catalysts and
conditions to make the new resins.
The new technology offers significant advantages in recycling waste
office paper without sacrificing print quality. Improved de-inking of the
fused ink from waste copy paper results in higher-quality recovered ma-
terials and streamlines the recycling process. Preliminary life-cycle analy-
sis shows significant energy savings and reduced carbon dioxide (CO2)
emissions in the full value chain from resin manufacture using biobased
feedstocks to toner production and, finally, to the recovery of secondary
fibers from the office waste stream. At 25 percent market penetration in
2010, this technology could save 9.25 trillion British thermal units per year
(Btu/yr) and eliminate over 360,000 tons of CO2 emissions per year.
Overall, soy toner provides a cost-effective, systems-oriented, environ-
mentally benign solution to the growing problem of waste paper gener-
ated from copiers and printers. In 2006, AIR, the licensee of the technol-
ogy, successfully scaled up production of the resin and toners for use in
HP LaserJet 4250 Laser Printer cartridges. Battelle and AIR coordinated to
move from early-stage laboratory development to full-scale manufactur-
ing and commercialization. Their efforts have resulted in a cost-competi-
tive, highly marketable product that is compatible with current hardware.
The new toner will be sold under trade names BioRez®and Rezilution®.
Once commercial, it will provide users with seamless, environmentally
friendly printing and copying.
! Greener Synthetic Pathways Award 17
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3 DTRASAR® Technology
Cooling water touches many facets of human life, including cooling for
comfort in commercial buildings and cooling industrial processes. Cooling
systems require added chemicals to control microbial growth, mineral
deposits, and corrosion. Nalco developed 3 DTRASAR® technology to
monitor the condition of cooling water continuously and add appropriate
chemicals only when needed, rather than on a fixed schedule. The
technique saves water and energy, minimizes the use of water-treatment
chemicals, and decreases environmental damage from discharged water.
'• lost commercial buildings, including offices, universities, hospitals, and
stores, as well as many industrial processes, use cooling systems based
on water. These cooling systems can consume vast quantities of water.
Also, unless mineral scale and microbes are well-controlled, several prob-
lems can arise leading to increased water and energy consumption and
negative environmental impacts.
Mineral scale, which consists mostly of carbonates of calcium and mag-
nesium, forms on heat-exchange surfaces; this makes heat transfer ineffi-
cient and increases energy use. Similarly, microbial growth can lead to the
formation of biofilms on heat-exchange surfaces, decreasing exchange
efficiency. Conversely, high levels of biocide intended to prevent biofilm
cause several adverse effects including increased corrosion of system
components. Gradually, the integrity of the system becomes compro-
mised, increasing the risk of system leaks. The material from these leaks,
along with metal-containing byproducts of corrosion and the additional
biocide, are ultimately discharged with the cooling water. Every time wa-
ter is discharged, called "blowdown", pollutants are released in the waste-
water, and fresh water is used to replace the blowdown. Traditionally,
antiscalants and antimicrobials are added at regular intervals or, at best,
after manual or indirect measurements show scale or microbial buildup.
18 2008 Award
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In 2004, Nalco commercialized its 3D TRASAR® Cooling System Chemis-
try and Control technology. By detecting scaling tendency early, cooling
systems with Nalco's technology can operate efficiently; in addition, they
can use less water or use poor-quality water.
3D Scale Control, part of the 3D TRASAR® system, prevents the forma-
tion of mineral scale on surfaces, maintaining efficient heat transfer. The
system monitors antiscalant levels using a fluorescent-tagged, scale-
dispersant polymer and responds quickly when conditions favor scale
formation. In addition, 3D Bio-control, also part of the 3D TRASAR® sys-
tem, is the only online, real-time test for measuring planktonic and sessile
bacteria. It uses resazurin, another fluorescent molecule, which changes
its fluorescent signature when it interacts with respiring microbes. By add-
ing an oxidizing biocide in response to microbial activity, 3D Bio-control
generally reduces the use of biocide and also prevents biofilm from
building up on surfaces, maintaining efficient heat transfer.
A proprietary corrosion monitor and a novel corrosion inhibitor, phos-
phino succinic oligomer, provide improved corrosion protection. In 2006,
the 2,500 installations using the 3D TRASAR® system saved approximately
21 billion gallons of water. These installations have also significantly
reduced the discharge of water-treatment chemicals to water-treatment
plants or natural waterways.
2008 Greener Reaction Conditions Award 19
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Spinetoram: Enhancing a Natural Product for Insect Control
Spinosad biopesticide from Dow AgroSciences controls many insect
pests on vegetables, but is not particularly effective against certain key
pests of tree fruits. To solve this problem, Dow AgroSciences used an
"artificial neural network" to identify analogous molecules that might be
more effective against fruit-tree pests. They then developed a green
chemical synthesis for the new insecticide, called spinetoram.
Spinetoram retains the favorable environmental benefits of spinosad
while replacing organophosphate pesticides for tree fruits, tree nuts,
small fruits, and vegetables.
.'. -pinosad biopesticide won the Presidential Green Chemistry Challenge
Award for Designing Greener Chemicals in 1999. Spinosad, a combina-
tion of spinosyns A and D, is effective against insect pests on vegetables,
but there have been few green chemistry alternatives for insect-pest
control in tree fruits and tree nuts. Dow AgroSciences has now developed
spinetoram, a significant advancement over spinosad that extends the
success of spinosad to new crops.
The discovery of spinetoram involved the novel application of an artifi-
cial neural network (ANN) to the molecular design of insecticides. Dow
AgroSciences researchers used an ANN to understand the quantitative
structure-activity relationships of spinosyns and to predict analogues that
would be more active. The result is spinetoram, a mixture of 3'-O-ethyl-
5,6-dihydro spinosyn J and 3'-O-ethyl spinosyn L Dow AgroSciences
makes spinetoram from naturally occurring fermentation products
spinosyns J and L by modifying them with a low-impact synthesis in which
catalysts and most reagents and solvents are recycled. The biology and
chemistry of spinetoram have been extensively researched; the results
have been published in peer-reviewed scientific journals and presented
at scientific meetings globally.
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Spinetoram provides significant and immediate benefits to human health
and the environment over existing insecticides. Azinphos-methyl and
phosmet, two organophosphate insecticides, are widely used in pome
fruits (such as apples and pears), stone fruits (such as cherries and
peaches), and tree nuts (such as walnuts and pecans). The mammalian
acute oral toxicity of spinetoram is more than 1,000 times lower than that
of azinphos-methyl and 44 times lower than that of phosmet. The low
toxicity of spinetoram reduces the risk of exposures throughout the sup-
ply chain: in manufacturing, transportation, and application and to the
public.
Spinetoram has a lower environmental impact than do many current
insecticides because both its use rate and its toxicity to non-target species
are low. Spinetoram is effective at much lower rates than many compet-
ing insecticides. It is effective at use rates that are 10-34 times lower than
azinphos-methyl and phosmet. Spinetoram is also less persistent in the
environment compared with other traditional insecticides. In the United
States alone, Dow AgroSciences expects spinetoram to eliminate about
1.8 million pounds of organophosphate insecticides applied to pome
fruit, stone fruit, and tree nuts during its first five years of use. In 2007,
EPA granted pesticide registrations to the spinetoram products Radiant™
and Delegate™, and Dow AgroSciences began commercial sales.
2008 Designing Greener Chemicals Award 21
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2007 Winners
Hydrogen-Mediated Carbon—Carbon Bond Formation
A fundamental aspect of chemistry involves creating chemical bonds
between carbon atoms. Chemical processes commonly used to make
such bonds usually also generate significant amounts of waste. Professor
Krische developed a broad new class of chemical reactions that make
bonds between carbon atoms using hydrogen and metal catalysts. This
new class of reactions can be used to convert simple chemicals into
complex substances, such as Pharmaceuticals, pesticides, and other
important chemicals, with minimal waste.
eductions mediated by hydrogen, termed "hydrogenations", rank
among the most widely used catalytic methods employed industrially.
They are generally used to form carbon-hydrogen (C-H) bonds. Pro-
fessor Michael J. Krische and his coworkers at the University of Texas
at Austin have developed a new class of hydrogenation reactions that
form carbon-carbon (C-C) bonds. In these metal-catalyzed reactions,
two or more organic molecules combine with hydrogen gas to create a
single, more complex product. Because all atoms present in the starting
building-block molecules appear in the final product, Professor Krische's
reactions do not generate any byproducts or wastes. Hence, Professor
Krische's C-C bond-forming hydrogenations eliminate pollution at its
source.
Prior to Professor Krische's work, hydrogen-mediated C-C bond forma-
tions were limited almost exclusively to the use of carbon monoxide in
reactions such asalkene hydroformylation (1938) and the Fischer-Tropsch
reaction (1923). These prototypical hydrogen-mediated C-C bond for-
mations are practiced industrially on an enormous scale. Yet, despite
the importance of these reactions, no one had engaged in systematic
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research to develop related C-C bond-forming hydrogenations. Only a
small fraction of hydrogenation's potential as a method of C-C coupling
had been realized, and the field lay fallow for nearly 70 years.
Professor Krische's hydrogen-mediated couplings circumvent the use
of preformed organometallic reagents, such as Grignard and Oilman
reagents, in carbonyl and imine addition reactions. Such organometallic
reagents are highly reactive, typically moisture-sensitive, and sometimes
pyrophoric, meaning that they combust when exposed to air. Professor
Krische's coupling reactions take advantage of catalysts that avoid the
hazards of traditional organometallic reagents. Further, using chiral hydro-
genation catalysts, Professor Krische's couplings generate C-C bonds in a
highly enantioselective fashion.
Catalytic hydrogenation has been known for over a century and has
stood the test of time due its efficiency, atom economy, and cost-effec-
tiveness. By exploiting hydrogenation as a method of C-C bond forma-
tion, Professor Krische has added a broad, new dimension to one of
chemistry's most fundamental catalytic processes. The C-C bond-forming
hydrogenations developed by Professor Krische allow chemists to cre-
ate complex organic molecules in a highly selective fashion, eliminating
both hazardous starting materials and hazardous waste. Commercial
application of this technology may eliminate vast quantities of hazardous
chemicals. The resulting increases in plant and worker safety may enable
industry to perform chemical transformations that were too dangerous
using traditional reagents.
2007 Academic Award 23
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Environmentally Benign Medical Sterilization Using Supercritical Carbon
Dioxide
Sterilizing biological tissue for transplant is critical to safety and success in
medical treatment. Common existing sterilization techniques use ethylene
oxide or gamma radiation, which are toxic or have safety problems.
NovaSterilis invented a technology that uses carbon dioxide and a form
of peroxide to sterilize a wide variety of delicate biological materials such
as graft tissue, vaccines, and biopolymers. Their Nova 2200™ sterilizer
requires neither hazardous ethylene oxide nor gamma radiation.
'-• one of the common methods for medical sterilization is well-suited to
sterilizing delicate biological materials. The sterility of these materials is
critical. Distribution of contaminated donor tissues by tissue banks has
resulted in serious infections and illnesses in transplant patients. The two
most widely used sterilants (ethylene oxide and gamma radiation) also
raise toxicity and safety concerns. Ethylene oxide is a mutagenic, carci-
nogenic, volatile, flammable, reactive gas. Residues of ethylene oxide
remain in the sterilized material, increasing the risk of toxic side effects.
Gamma radiation is highly penetrating and is lethal to all cells. Neither
ethylene oxide nor gamma radiation can sterilize packaged biological
products without eroding their physical integrity.
NovaSterilis, a privately held biotechnology company in Ithaca, NY, has
successfully developed and commercialized a highly effective and envi-
ronmentally benign technique for sterilizing delicate biological materials
using supercritical carbon dioxide (CO2). NovaSterilis licensed a patent
for bacterial inactivation in biodegradable polymers that was issued to
Professor Robert S. Langer and his team at the Massachusetts Institute of
Technology. NovaSterilis then enhanced, expanded, and optimized the
technology to kill bacterial endospores. Their supercritical CO2 technol-
ogy uses low temperature and cycles of moderate pressure along with a
peroxide (peracetic acid) and small amounts of water. Their Nova 2200™
24 2007 Award
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sterilizer consistently achieves rapid (less than one hour) and total inacti-
vation of a wide range of microbes, including bacterial endospores. The
mechanism of bacterial inactivation is not well-understood, but does not
appear to involve bacterial cell lysis or wholesale degradation of bacterial
proteins.
The new technology is compatible with sensitive biological materials and
is effective for a wide range of important biomedical materials including:
(a) musculoskeletal allograft tissue (e.g., human bone, tendons, dermis,
and heart valves) for transplantation; (b) biodegradable polymers and re-
lated materials used in medical devices, instruments, and drugs; (c) drug
delivery systems; and (d) whole-cell vaccines that retain high antigenicity.
Besides being a green chemical technology, supercritical CO2 sterilization
achieves "terminal" sterilization, that is, sterilization of the final packaged
product. Terminal sterilization provides greater assurance of sterility than
traditional methods of aseptic processing. Sterilization of double-bagged
tissue allows tissue banks to ship terminally sterilized musculoskeletal
tissues in packages that can be opened in operating rooms by surgi-
cal teams immediately prior to use. NovaSterilis's patented technology
addresses the market need in tissue banks as well as other needs in
the biomedical, biologies, medical device, pharmaceutical, and vaccine
industries. By the end of 2006, NovaSterilis had sold several units to tissue
banks.
2007 Small Business Award 25
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Development and Commercial Application of Environmentally Friendly
Adhesives for Wood Composites
Adhesives used in manufacturing plywood and other wood composites
often contain formaldehyde, which is toxic. Professor Kaichang Li of
Oregon State University, Columbia Forest Products, and Hercules Incor-
porated developed an alternate adhesive made from soy flour. Their
environmentally friendly adhesive is stronger than and cost-competitive
with conventional adhesives. During 2006, Columbia used the new, soy-
based adhesive to replace more than 47 million pounds of conventional
formaldehyde-based adhesives.
' ;ince the 1940s, the wood composites industry has been using synthetic
adhesive resins to bind wood pieces into composites, such as plywood,
particleboard, and fiberboard. The industry has been the predominate
user of formaldehyde-based adhesives such as phenol-formaldehyde
and urea-formaldehyde (UF) resins. Formaldehyde is a probable human
carcinogen. The manufacture and use of wood composite panels bond-
ed with formaldehyde-based resins release formaldehyde into the air,
creating hazards for both workers and consumers.
Inspired by the superior properties of the protein that mussels use to
adhere to rocks, Professor Li and his group at Oregon State University
invented environmentally friendly wood adhesives based on abundant,
renewable soy flour. Professor Li modified some of the amino acids in
soy protein to resemble those of mussels' adhesive protein. Hercules
Incorporated provided a critical curing agent and the expertise to apply it
to commercial production of plywood.
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Oregon State University, Columbia Forest Products (CFP), and Hercules
have jointly commercialized soy-based adhesives to produce cost-com-
petitive plywood and particleboard for interior uses. The soy-based adhe-
sives do not contain formaldehyde or use formaldehyde as a raw mate-
rial. They are environmentally friendly, cost-competitive with the UF resin
in plywood, and superior to the UF resin in strength and water resistance.
All CFP plywood plants now use soy-based adhesives, replacing more
than 47 million pounds of the toxic UF resin in 2006 and reducing the
emission of hazardous air pollutants (HAPs) from each CFP plant by 50 to
90 percent. This new CFP plywood is sold under the PureBond™ name.
During 2007, CFP will replace UFat its particleboard plant; the company is
also seeking arrangements with other manufacturers to further the adop-
tion of this technology.
With this technology, those who make and use furniture, kitchen cabi-
netry, and other wood composite materials have a high-performing
formaldehyde-free alternative. As a result, indoor air quality in homes and
offices could improve significantly. This technology represents the first
cost-competitive, environmentally friendly adhesive that can replace the
toxic UF resin. The technology can greatly enhance the global competi-
tiveness of U.S. wood composite companies. In addition, by creating a
new market for soy flour, currently in over-supply, this technology pro-
vides economic benefits for soybean farmers.
2007 Greener Synthetic Pathways Award
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Direct Synthesis of Hydrogen Peroxide by Selective Nanocatalyst
Technology
Hydrogen peroxide is an environmentally friendly alternative to chlorine
and chlorine-containing bleaches and oxidants. It is expensive, however,
and its current manufacturing process involves the use of hazardous
chemicals. Headwaters Technology Innovation (HTI) developed an
advanced metal catalyst that makes hydrogen peroxide directly from
hydrogen and oxygen, eliminates the use of hazardous chemicals, and
produces water as the only byproduct. HTI has demonstrated their new
technology and is partnering with DegussaAG to build plants to produce
hydrogen peroxide.
; lydrogen peroxide (H2O2) is a clean, versatile, environmentally friendly
oxidant that can substitute for environmentally harmful chlorinated oxi-
dants in many manufacturing operations. However, the existing manufac-
turing process for H2O2is complex, expensive, and energy-intensive. This
process requires an anthraquinone working solution containing several
toxic chemicals. The solution is reduced by hydrogen in the presence of
a catalyst, forming anthrahydroquinone, which then reacts with oxygen
to release H2O2. The H2O2 is removed from the solution with an energy-
intensive stripping column and then concentrated by vacuum distillation.
The bulk of the working solution is recycled, but the process generates
a waste stream of undesirable quinone-derived byproducts that requires
environmentally acceptable disposal.
Headwaters Technology Innovation (HTI) has produced a robust catalyst
technology that enables the synthesis of H2O2 directly from hydrogen and
oxygen. This breakthrough technology, called NxCat™, is a palladium-plat-
inum catalyst that eliminates all the hazardous reaction conditions and
chemicals of the existing process, along with its undesirable byproducts.
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It produces H2O2 more efficiently, cutting both energy use and costs. It
uses innocuous, renewable feedstocks and generates no toxic waste.
NxCat™ catalysts work because of their precisely controlled surface mor-
phology. HTI has engineered a set of molecular templates and substrates
that maintain control of the catalyst's crystal structure, particle size, com-
position, dispersion, and stability. This catalyst has a uniform 4-nanometer
feature size that safely enables a high rate of production with a hydrogen
gas concentration below 4 percent in air (i.e., below the flammability limit
of hydrogen). It also maximizes the selectivity for H2O2 up to 100 percent.
The NxCat™ technology enables a simple, commercially viable H2O2
manufacturing process. In partnership with Degussa AG (a major H2O2
manufacturer), HTI successfully demonstrated the NxCat™ technology
and, in 2006, completed construction of a demonstration plant. This
demonstration plant will allow the partners to collect the data necessary
to design a full-scale plant and begin commercial production in 2009. The
NxCat™ process has the potential to cut the cost of H2O2 significantly,
generating a more competitively priced supply of H2O2 and increasing its
market acceptance as an industrial oxidant. Except for its historically high-
er price, H2O2 is an excellent substitute for the more frequently used—and
far more deleterious—chlorinated oxidants. The NxCat™ technology has
the benefit of producing an effective, environmentally preferable oxidant
(H2O2) without the waste or high cost associated with the traditional
process.
2007 Greener Reaction Conditions Award
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BiOH™ Polyols
Foam cushioning used in furniture or bedding is made from polyurethane,
a man-made material. One of the two chemical building blocks used to
make polyurethane is a "polyol." Polyols are conventionally manufactured
from petroleum products. Cargill's BiOH™ polyols are manufactured
from renewable, biological sources such as vegetable oils. Foams made
with BiOH™ polyols are comparable to foams made from conventional
polyols. As a result, each million pounds of BiOH™ polyols saves nearly
700,000 pounds of crude oil. In addition, Cargill's process reduces total
energy use by 23 percent and carbon dioxide emissions by 36 percent.
i olyols are key ingredients in flexible polyurethane foams, which are
used in furniture and bedding. Historically, polyurethane has been made
from petrochemical polyols. The idea of replacing these polyols with
biobased polyols is not new, but the poor performance, color, quality,
consistency, and odor of previous biobased polyols restricted them to
limited markets. Previous biobased polyols also suffer from poor chemical
reactivity, resulting in foam with inferior properties.
Cargill has successfully developed biobased polyols for several poly-
urethane applications, including flexible foams, which are the most
technically challenging. Cargill makes BiOH™ polyols by converting the
carbon—carbon double bonds in unsaturated vegetable oils to epoxide
derivatives and then further converting these derivatives to polyols using
mild temperature and ambient pressure. BiOH™ polyols provide excel-
lent reactivity and high levels of incorporation leading to high-performing
polyurethane foams. These foams set a new standard for consistent qual-
ity with low odor and color. Foams containing BiOH™ polyols retain their
white color longer without ultraviolet stabilizers. They also are superior
to foams containing only petroleum-based polyols in standard tests. In
large slabstock foams, such as those used in furniture and bedding, BiOH
5000 polyol provides a wide processing window, improved comfort factor,
30 2007 Award
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and reduced variations in density and load-bearing capacity. In molded
foams such as automotive seating and headrests, BiOH 2100 polyol can
enhance load-bearing or hardness properties relative to conventional
polyols.
Use of BiOH™ polyols reduces the environmental footprint relative to
today's conventional polyols for polyurethane production. BiOH™ polyols
"harvest" carbon that plants remove from the air during photosynthesis.
All of the carbon in BiOH™ polyols is recently fixed. In conventional poly-
ols, the carbon is petroleum-based. Replacing petroleum-based polyols
with BiOH™ polyols cuts total energy use by 23 percent including a
61 percent reduction in nonrenewable energy use, leading to a 36 per-
cent reduction in carbon dioxide emissions. For each million pounds of
BiOH™ polyol used in place of petroleum-based polyols, about 700,000
pounds (2,200 barrels) of crude oil are saved, thereby reducing the de-
pendence on petroleum. BiOH™ polyols diversify the industry's supply
options and help mitigate the effects of uncertainty and volatility of pe-
troleum supply and pricing. Cargill is the first company to commercialize
biobased polyols on a large scale in the flexible foam market. Formulators
can now use biobased polyols in flexible foam without compromising
product performance. That the top North American polyol users choose
BiOH™ polyols is validation of Cargill's accomplishment.
2007 Designing Greener Chemicals Award 31
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2006 Winners
Biobased Propylene Glycol and Monomers from Natural Glycerin
Professor Suppes developed an inexpensive method to convert waste
glycerin, a byproduct of biodiesel fuel production, into propylene glycol,
which can replace ethylene glycol in automotive antifreeze. This high-value
use of the glycerin byproduct can keep production costs down and help
biodiesel become a cost-effective, viable alternative fuel, thereby reducing
emissions and conserving fossil fuels.
Ulycerin isacoproduct of biodiesel production. The U.S. biodiesel in-
dustry is expected to introduce one billion pounds of additional glycerin
into a market that is currently only 600 million pounds. The economics of
biodiesel depend heavily on using its glycerin coproduct. A high-value
use for glycerin could reduce the cost of biodiesel by as much as 40C per
gallon. There is simply not enough demand for glycerin, however, to
make use of all the waste glycerin expected.
One solution is to convert the glycerin to propylene glycol. Approximately
2.4 billion pounds of propylene glycol are currently made each year,
almost exclusively from petroleum-based propylene oxide. Propylene
glycol is a less toxic alternative to ethylene glycol in antifreeze, but is
currently more expensive and, as a result, has a very small market share.
Professor Galen J. Suppes has developed a catalytic process that efficient-
ly converts crude glycerin to propylene glycol.
Professor Suppes's system couples a new copper-chromite catalyst with a
reactive distillation. This system has a number of advantages over previ-
ous systems that perform this conversion. The new process uses a lower
temperature and lower pressure than do previous systems (428 °F versus
500 °F and <145 psi versus >2,170 psi), converts glycerin to propylene
glycol more efficiently, and produces less byproduct than do similar
32
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catalysts. Propylene glycol made from glycerin by Professor Suppes's
method is also significantly cheaper than propylene glycol made from
petroleum.
Another solution is to convert glycerin to acetol (i.e., 1-hydroxy-2-pro-
panone or hydroxyacetone), a well-known intermediate and monomer
used to make polyols. When made from petroleum, acetol costs approxi-
mately $5 per pound, prohibiting its wide use. Professor Suppes's tech-
nology can be used to make acetol from glycerin at a cost of approxi-
mately 50C per pound, opening up even more potential applications and
markets for products made from glycerin.
Professor Suppes initiated this project in June 2003. The first commercial
facility, with a capacity of 50 million pounds per year, is under construc-
tion and is expected to be in operation by October 2006.
2006 Academic Award 33
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Environmentally Safe Solvents and Reclamation in the Flexographic
Printing Industry
Flexographic printing is used in a wide array of print jobs such as food
wrappers and boxes, but the process uses millions of gallons of solvents
each year. Arkon and NuPro developed a safer chemical processing system
that reduces the amounts of solvents needed for printing. The new system
eliminates hazardous solvents, reduces explosion potential and emissions
during solvent recycling, and increases worker safety in the flexographic
printing industry.
: lexographic printing is used on everything from food wrappers to sec-
ondary containers such as cereal boxes to shipping cartons. The photo-
polymerizable material on a flexographic printing plate cross-links when
exposed to light and captures an image. After exposure, flexographic
printing plates are immersed in a solvent to remove the unpolymerized
material. The developing, or washout, solvent is typically a mixture of
chloro, saturated cyclic, or acyclic hydrocarbons. Xylene is the most com-
mon solvent. Most traditional washout solvents are hazardous air pollut-
ants (HAPs) subject to stringent reporting requirements; they also raise
worker safety issues and create problems with recycling and disposal.
North America alone uses 2 million gallons of washout solvents each
year with a market value of $20 million. Many small printing plants use
these solvents.
Together, Arkon Consultants and NuPro Technologies have developed
a safer chemical processing system, including washout solvents and
reclamation/recycling machinery for the flexographic printing industry.
NuPro/Arkon have developed several new classes of washout solvents
with methyl esters, terpene derivatives, and highly substituted cyclic
hydrocarbons. The advantages include higher flash points and lower tox-
34 2006 Award
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icity, which reduce explosion potential, worker exposure, and regulatory
reporting. The methyl esters and terpene derivatives are biodegradable
and can be manufactured from renewable sources. All of their solvents
are designed to be recycled in their Cold Reclaim System™. In contrast to
traditional vacuum distillation, this combination of filtration and centrifu-
gation lowers exposures, decreases maintenance, and reduces waste.
The waste is a solid, nonhazardous polymeric material.
In the U.S. market, NuPro/Arkon are currently selling washout solvents
that are terpene ether- and ester-based or made with low-hazard cyclics.
They are marketing their methyl ester-based solvent in China and Japan.
Their first filtration-based Cold Recovery System™ is currently in use in
Menesha, Wl and is being marketed to larger U.S. users. Their centrifuga-
tion reclamation system for smaller users is in the final stages of develop-
ment.
Use of these solvents and systems benefits both human health and the
environment by lowering exposure to hazardous materials, reducing
explosion potential, reducing emissions, and, in the case of the terpene
and methyl ester-based solvents, using renewable resources. These sol-
vents and the reclamation equipment represent major innovations in
the safety of handling, exposure, and recovery. The reduced explosion
potential, reduced emissions, decreased worker exposure, and reduced
transport and maintenance costs translate into decreased cost and im-
proved safety in all aspects of flexographic printing processes.
2006 Small Business Award 35
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Novel Green Synthesis for p-Amino Acids Produces the Active Ingredient
in Januvia™
Merck discovered a highly innovative and efficient catalytic synthesis for
sitagliptin, which is the active ingredient in Januvia™, the company's new
treatment for type 2 diabetes. This revolutionary synthesis creates
220 pounds less waste for each pound of sitagliptin manufactured and
increases the overall yield by nearly 50 percent. Over the lifetime of
Januvia™, Merck expects to eliminate the formation of at least 330 million
pounds of waste, including nearly 110 million pounds of aqueous waste.
ianuvia™ is a new treatment for type 2 diabetes; Merck filed for regula-
tory approval in December 2005. Sitagliptin, achiral p-aminoacid deriva-
tive, is the active ingredient in Januvia™. Merck used a first-generation
synthesis of sitagliptin to prepare over 200 pounds for clinical trials. With
modifications, this synthesis could have been a viable manufacturing
process, but it required eight steps including a number of aqueous work-
ups. It also required several high-molecular-weight reagents that were not
incorporated into the final molecule and, therefore, ended up as waste.
While developing a highly efficient second-generation synthesis for
sitagliptin, Merck researchers discovered a completely unprecedented
transformation: the asymmetric catalytic hydrogenation of unprotected
enamines. In collaboration with Solvias, a company with expertise in
this area, Merck scientists discovered that hydrogenation of unprotected
enamines using rhodium salts of a ferrocenyl-based ligand as the catalyst
gives p-amino acid derivatives of high optical purity and yield. This new
method provides a general synthesis of p-amino acids, a class of mol-
ecules well-known for interesting biological properties. Merck scientists
and engineers applied this new method in a completely novel way: using
it in the final synthetic step to maximize the yield in terms of the valuable
chiral catalyst. The dehydro precursor to sitagliptin used in the asymmetric
hydrogenation is prepared in an essentially one-pot procedure. Following
36 2006 Award
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the hydrogenation, Merck recovers and recycles over 95 percent of the
valuable rhodium. The reactive amino group of sitagliptin is only revealed
in the final step; as a result, there is no need for protecting groups. The
new synthesis has only three steps and increases the overall yield by
nearly 50 percent.
This strategy is broadly applicable to other pharmaceutical syntheses;
Merck has used it to make several exploratory drug candidates. Imple-
menting the new route on a manufacturing scale has reduced the
amount of waste by over 80 percent and completely eliminated aqueous
waste streams. This second-generation synthesis will create 220 pounds
less waste for each pound of sitagliptin manufactured. Over the lifetime
of the drug, Merck expects to eliminate the formation of 330 million
pounds or more of waste, including nearly 110 million pounds of aque-
ous waste. Because Merck's new synthesis has reduced the amount
of raw materials, processing time, energy, and waste, it is a more cost-
effective option than the first-generation synthesis. The technology
discovered, developed, and implemented by Merck for the manufacture
of Januvia™ is an excellent example of scientific innovation resulting in
benefits to the environment.
2006 Greener Synthetic Pathways Award 37
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Directed Evolution of Three Biocatalysts to Produce the Key Chiral Building
Block for Atorvastatin, the Active Ingredient in Lipitor®
Codexis developed cutting-edge genetic methods to create "designer
enzymes". Codexis applied its methods to produce enzymes that greatly
improve the manufacture of the key building block for Lipitor®, one of
the world's best-selling drugs. The new enzymatic process reduces waste,
uses less solvent, and requires less processing equipment—marked im-
provements over processes used in the past. The process also increases
yield and improves worker safety.
\torvastatin calcium is the active ingredient of Lipitor®, a drug that
lowers cholesterol by blocking its synthesis in the liver. Lipitor® is the
first drug in the world with annual sales exceeding $10 billion. The key
chiral building block in the synthesis of atorvastatin is ethyl (£)-4-cyano-3-
hydroxybutyrate, known as hydroxynitrile (HN). Annual demand for HN is
estimated to be about 440,000 pounds. Traditional commercial processes
for HN require a resolution step with 50 percent maximum yield or syn-
theses from chiral pool precursors; they also require hydrogen bromide
to generate a bromohydrin for cyanation. All previous commercial HN
processes ultimately substitute cyanide for halide under heated alkaline
conditions, forming extensive byproducts. They require a difficult high-
vacuum fractional distillation to purify the final product, which decreases
the yield even further.
Codexis designed a green HN process around the exquisite selectivity of
enzymes and their ability to catalyze reactions under mild, neutral condi-
tions to yield high-quality products. Codexis developed three specific
enzymes using state-of-the-art, recombinant-based, directed evolution
technologies to provide the activity, selectivity, and stability required for a
practical and economic process. The bioengineered enzymes are so ac-
tive and stable that Codexis can recover high-quality product by extracting
the reaction mixture. In the first step, two of the enzymes catalyze the
38 2006 Award
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enantioselective reduction of a prochiral chloroketone (ethyl 4-chloroace-
toacetate) by glucose to form an enantiopure chlorohydrin. In the second
step, a third enzyme catalyzes the novel biocatalytic cyanation of the
chlorohydrin to the cyanohydrin under neutral conditions (aqueous,
pH ~7, 77-104 °F, atmospheric pressure). On a biocatalyst basis, the three
enzymes have improved the volumetric productivity of the reduction
reaction by approximately 100-fold and that of the cyanation reaction by
approximately 4,000-fold.
The process involves fewer unit operations than earlier processes, most
notably obviating the fractional distillation of the product. The process
provides environmental and human health benefits by increasing yield,
reducing the formation of byproducts, reducing the generation of waste,
avoiding hydrogen gas, reducing the need for solvents, reducing the
use of purification equipment, and increasing worker safety. The Codexis
process is operated by Lonza to manufacture HN for Pfizer's production
of atorvastatin calcium.
> Greener Reaction Conditions Award 39
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Greenlist™ Process to Reformulate Consumer Products
SC Johnson developed Greenlist™, a system that rates the environmental
and health effects of the ingredients in its products. SC Johnson is now
using Greenlist™ to reformulate many of its products. For example, SC
Johnson eliminated the use of nearly 4 million pounds of polyvinylidene
chloride (PVDC) annually after its "Greenlist" review of Saran Wrap®
revealed opportunities for changes.
'.•C Johnson (SCJ) formulates and manufactures consumer products
including a wide variety of products for home cleaning, air care, personal
care, insect control, and home storage. For more than a century, SCJ has
been guided by the belief that, because it is a family business, it must
consider the next generation when it makes current product decisions,
not merely the next fiscal quarter. The most recent initiative in SCJ's
long history of commitment to environmentally preferable products is
its Greenlist™ process, a system that rates the environmental footprint
of the ingredients in its products. Through Greenlist™, SCJ chemists and
product formulators around the globe have instant access to environmen-
tal ratings of potential product ingredients.
Starting in 2001, SCJ developed Greenlist™ according to the rigorous stan-
dards of scientific best practices. Greenlist™ uses four to seven specific
criteria to rate ingredients within 17 functional categories. SCJ enlisted
the help of suppliers, university scientists, government agencies, and
nongovernmental organizations (NGOs) to ensure that the rating criteria
were meaningful, objective, and valid. These criteria include vapor pres-
sure, octanol/water partition coefficient, biodegradability, aquatic toxicity,
human toxicity, European Union Classification, source/supply, and others,
as appropriate. The Greenlist™ process assigns an environmental classi-
fication (EC) score to each ingredient by averaging its scores for the crite-
ria in its category. EC scores range from Best (3) to Restricted Use Material
(0). SCJ lowers the EC score for chemicals with other significant concerns
40 2006 Award
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including PBT (persistence, bioaccumulation, and toxicity), endocrine
disruption, carcinogenicity, and reproductive toxicity. Today, Greenlist™
provides ratings for more than 90 percent of the raw materials SCJ uses,
including solvents, surfactants, inorganic acids and bases, chelants, pro-
pellants, preservatives, insecticides, fragrances, waxes, resins, nonwoven
fabrics, and packaging. Company scientists have also developed criteria
for dyes, colorants, and thickeners and are working on additional catego-
ries as well.
During fiscal 2000-2001, the baseline year, SCJ's EC average was 1.12. Their
goal was to reach an average EC of 1.40 during fiscal 2007-2008. The
company reached this goal three years early, with an average EC of 1.41
covering almost 1.4 billion pounds of raw materials.
In recent years, SCJ has used Greenlist™ to reformulate multiple prod-
ucts to make them safer and more environmentally responsible. In one
example, SCJ used the Greenlist™ process to replace polyvinylidene
chloride (PVDC) with polyethylene in Saran Wrap®. In another example,
SCJ applied Greenlist™ to remove a particular volatile organic compound
(VOC) from Windex®. They developed a novel new formula containing
amphoteric and anionic surfactants, a solvent system with fewer than
4 percent VOCs, and a polymer for superior wetting. Their formula cleans
30 percent better and eliminates over 1.8 million pounds of VOCs per
year.
> Designing Greener Chemicals Award 41
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2005 Winners
A Platform Strategy Using Ionic Liquids to Dissolve and Process Cellulose
for Advanced New Materials
Professor Rogers developed methods that allow cellulose from wood,
cloth, or even paper to be chemically modified to make new biorenew-
able or biocompatible materials. His methods also allow cellulose to be
mixed with other substances, such as dyes, or simply to be processed
directly from solution into a formed shape. Together, these methods can
potentially save resources, time, and energy.
'- \ajor chemical companies are currently making tremendous strides to-
wards using renewable resources in biorefineries. In atypical biorefinery,
the complexity of natural polymers, such as cellulose, is first broken down
into simple building blocks (e.g., ethanol, lactic acid), then built up into
complex polymers. If one could use the biocomplexity of natural poly-
mers to form new materials directly, however, one could eliminate many
destructive and constructive synthetic steps. Professor Robin D. Rogers
and his group have successfully demonstrated a platform strategy to
efficiently exploit the biocomplexity afforded by one of Nature's renew-
able polymers, cellulose, potentially reducing society's dependence on
nonrenewable petroleum-based feedstocks for synthetic polymers. No
one had exploited the full potential of cellulose previously, due in part to
the shift towards petroleum-based polymers since the 1940s, difficulty in
modifying the cellulose polymer properties, and the limited number of
common solvents for cellulose.
Professor Rogers's technology combines two major principles of green
chemistry: developing environmentally preferable solvents and using
biorenewable feedstocks to form advanced materials. Professor Rogers
has found that cellulose from virtually any source (fibrous, amorphous,
42
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pulp, cotton, bacterial, filter paper, etc.) can be dissolved readily and
rapidly, without derivatization, in a low-melting ionic liquid (IL), 1-butyl-3-
methylimidazolium chloride ([C4mim]CI), by gentle heating (especially
with microwaves). IL-dissolved cellulose can easily be reconstituted in
water in controlled architectures (fibers, membranes, beads, floes, etc.)
using conventional extrusion spinning or forming techniques. By incorpo-
rating functional additives into the solution before reconstitution, Profes-
sor Rogers can prepare blended or composite materials. The incorporated
functional additives can be either dissolved (e.g., dyes, complexants, oth-
er polymers) or dispersed (e.g., nanoparticles, clays, enzymes) in the IL
before or after dissolution of the cellulose. With this simple, noncovalent
approach, Professor Rogers can readily prepare encapsulated cellulose
composites of tunable architecture, functionality, and rheology. The IL can
be recycled by a novel salting-out step or by common cation exchange,
both of which save energy compared to recycling by distillation. Professor
Rogers's current work is aimed at improved, more efficient, and economi-
cal syntheses of [C4mim]CI, studies of the IL toxicology, engineering
process development, and commercialization.
Professor Rogers and his group are currently doing market research and
business planning leading to the commercialization of targeted materi-
als, either through joint development agreements with existing chemical
companies or through the creation of small businesses. Green chemistry
principles will guide the development work and product selection. For ex-
ample, targeting polypropylene- and polyethylene-derived thermoplastic
materials for the automotive industry could result in materials with lower
cost, greater flexibility, lower weight, lower abrasion, lower toxicity, and
improved biodegradability, as well as significant reductions in the use of
petroleum-derived plastics.
Professor Rogers's work allows the novel use of ILs to dissolve and recon-
stitute cellulose and similar polymers. Using green chemistry principles
to guide development and commercialization, he envisions that his
platform strategy can lead to a variety of commercially viable advanced
materials that will obviate or reduce the use of synthetic polymers.
2005 Academic Award 43
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Producing Nature's Plastics Using Biotechnology
Metabolix used new biotechnology methods to develop microorganisms
that produce polyhydroxyalkanoates (PHAs) directly. PHAs are natural
plastics with a range of environmental benefits, including reduced reliance
on fossil carbon, reduced solid waste, and reduced greenhouse gas
emissions. PHAs biodegrade to harmless products in the environment,
reducing the burden of plastic waste on landfills and the environment.
Metabolix hopes to develop plants that produce PHAs as well.
\ \etabolix is commercializing polyhydroxyalkanoates (PHAs), a broadly
useful family of natural, environmentally friendly, high-performing, bio-
based plastics. PHAs are based on a biocatalytic process that uses renew-
able feedstocks, such as cornstarch, cane sugar, cellulose hydrolysate,
and vegetable oils. PHAs can provide a sustainable alternative to petro-
chemical plastics in a wide variety of applications.
Metabolix uses biotechnology to introduce entire enzyme-catalyzed reac-
tion pathways into microbes, which then produce PHAs, in effect creating
living biocatalysts. The performance of these engineered microbes has
been fully validated in commercial equipment, demonstrating reliable
production of a wide range of PHA copolymers at high yield and repro-
ducibility. A highly efficient commercial process to recover PHAs has also
been developed and demonstrated. The routine expression of exog-
enous, chromosomally integrated genes coding for the enzymes used
in a non-native metabolic pathway is a tour de force in the application of
biotechnology. These accomplishments have led Metabolix to form an
alliance with Archer Daniels Midland Company, announced in November
2004, to produce PHAs commercially, starting with a 100-million-pound-
per-year plant to be sited in the U.S. Midwest.
These new natural PHA plastics are highly versatile, have a broad range of
physical properties, and are practical alternatives to synthetic petrochem-
44 2005 Award
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ical plastics. PHAs range from rigid to highly elastic, have very good
barrier properties, and are resistant to hot water and greases. Metabo-
lix has developed PHA formulations suitable for processing on existing
equipment and demonstrated them in key end-use applications such as
injection molding, thermoforming, blown film, and extrusion melt casting
including film, sheet, and paper coating.
Metabolix's PHA natural plastics will bring a range of environmental bene-
fits, including reduced reliance on fossil carbon and reduced greenhouse
gas emissions. PHAs are now made from renewable raw materials, such
as sugar and vegetable oils. In the future, they will be produced directly
in plants. In addition, PHAs will reduce the burden of plastic waste on
solid waste systems, municipal waste treatment systems, and marine and
wetland ecosystems: they will biodegrade to harmless products in a wide
variety of both aerobic and anaerobic environments, including soil, river
and ocean water, septic systems, anaerobic digesters, and compost.
Metabolix's PHA technology is the first commercialization of plastics
based on renewable resources that employs living biocatalysts in micro-
bial fermentation to convert renewable raw materials all the way to the
finished copolymer product. PHAs are also the first family of plastics that
combine broadly useful properties with biodegradability in a wide range
of environments, including marine and wetlands ecosystems. Replace-
ment of petrochemical plastics with PHAs will also have significant
economic benefits. Producing 50 billion pounds of PHA natural plastics
to replace about half of the petrochemical plastics currently used in the
United States would reduce oil imports by over 200-230 million barrels
per year, improving the U.S. trade balance by $6-9 billion per year,
assuming oil at $30-40 per barrel.
2005 Small Business Award 45
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NovaLipid™: Low Trans Fats and Oils Produced by Enzymatic
Interesterification of Vegetable Oils Using Lipozyme®
Archer Daniels Midland Company and Novozymes developed a way to
make edible fats and oils that contain no trans fatty acids. The improved
"interesterification" process they developed uses less resources. Potential
savings include hundreds of millions of pounds of soybean and other
vegetable oils, processing chemicals, and water resources each year.
i wo major challenges facing the food and ingredient industry are pro-
viding health-conscious products to the public and developing environ-
mentally responsible production technology. Archer Daniels Midland
Company (ADM) and Novozymes are commercializing enzymatic interest-
erification, a technology that not only has a tremendous positive impact
on public health by reducing tens fatty acids in American diet, but also
offers great environmental benefits by eliminating the waste streams
generated by the chemical interesterification process.
Triglycerides consist of one glycerol plus three fatty acids. Triglycerides
that contain mostly unsaturated fatty acids are liquid at room tempera-
ture. Manufacturers partially hydrogenate these fatty acids to make them
solids at room temperature. Trans fatty acids form during the hydrogena-
tion process; they are found at high concentrations in a wide variety of
processed foods. Unfortunately, consumption of trans fatty acids is also
a strong risk factor for heart disease. To reduce tens fats in the American
diet as much as possible, the FDA is requiring labeling of tens fats on all
nutritional fact panels by January 1, 2006. In response, the U.S. food and
ingredient industry has been investigating methods to reduce tens fats
in food.
Of the available strategies, interesterification is the most effective way to
decrease the tens fat content in foods without sacrificing the function-
46 2005 Award
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ality of partially hydrogenated vegetable oils. During interesterification,
triglycerides containing saturated fatty acids exchange one or two of their
fatty acids with triglycerides containing unsaturated fatty acids, resulting
in triglycerides that do not contain any trans fatty acids. Enzymatic inter-
esterification processes have many benefits over chemical methods, but
the high cost of the enzymatic process and poor enzyme stability had
prevented its adoption in the bulk fat industry.
Extensive research and development work by both Novozymes and ADM
has led to the commercialization of an enzymatic interesterification pro-
cess. Novozymes developed a cost-effective immobilized enzyme, and
ADM developed a process to stabilize the immobilized enzyme enough
for successful commercial production. The interesterified oil provides
food companies with broad options for zero and reduced fransfat food
products. Since the first commercial production in 2002, ADM has pro-
duced more than 15 million pounds of interesterified oils. ADM is current-
ly expanding the enzyme process at two of its U.S. production facilities.
Enzymatic interesterification positively affects both environmental and
human health. Environmental benefits include eliminating the use of
several harsh chemicals, eliminating byproducts and waste streams (solid
and water), and improving the use of edible oil resources. As one ex-
ample, margarines and shortenings currently consume 10 billion pounds
of hydrogenated soybean oil each year. Compared to partial hydrogena-
tion, the ADM/Novozymes process has the potential to save 400 million
pounds of soybean oil and eliminate 20 million pounds of sodium meth-
oxide, 116 million pounds of soaps, 50 million pounds of bleaching clay,
and 60 million gallons of water each year. The enzymatic process also
contributes to improved public health by replacing partially hydrogenated
oils with interesterified oils that contain no trans fatty acids and have
increased polyunsaturated fatty acids.
2005 Greener Synthetic Pathways Award 47
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A Redesigned, Efficient Synthesis of Aprepitant, the Active Ingredient in
Emend®: A New Therapy for Chemotherapy-Induced Emesis
Emend® is a drug that combats the nausea and vomiting often resulting
from chemotherapy treatment. Merck now makes Emend® using a new
process that requires much less energy, raw materials, and water than the
original process. With its new method, Merck eliminates approximately
41,000 gallons of waste per 1,000 pounds of the drug that it produces.
i mend® is a new therapy for chemotherapy-induced nausea and vomit-
ing, the most common side effects associated with the chemotherapeu-
tic treatment of cancer. Emend® has been clinically shown to reduce
nausea and vomiting when used during and shortly after chemotherapy.
Aprepitant is the active pharmaceutical ingredient in Emend®.
Aprepitant, which has two heterocyclic rings and three stereogenic cen-
ters, is a challenging synthetic target. Merck's first-generation commercial
synthesis required six synthetic steps and was based on the discovery
synthesis. The raw material and environmental costs of this route, how-
ever, along with operational safety issues compelled Merck to discover,
develop, and implement a completely new route to aprepitant.
Merck's new route to aprepitant demonstrates several important green
chemistry principles. This innovative and convergent synthesis assembles
the complex target in three highly atom-economical steps using four frag-
ments of comparable size and complexity. The first-generation synthesis
required stoichiometric amounts of an expensive, complex chiral acid
as a reagent to set the absolute stereochemistry of aprepitant. In con-
trast, the new synthesis incorporates a chiral alcohol as a feedstock; this
alcohol is itself synthesized in a catalytic asymmetric reaction. Merck uses
the stereochemistry of this alcohol feedstock in a practical crystallization-
induced asymmetric transformation to set the remaining stereogenic
centers of the molecule during two subsequent transformations.
48 2005 Award
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The new process nearly doubles the yield of the first-generation synthe-
sis. Much of the chemistry developed for the new route is novel and has
wider applications. In particular, the use of a stereogenic center that is
an integral part of the final target molecule to set new stereocenters with
high selectivity is applicable to the large-scale synthesis of other chiral
molecules, especially drug substances.
Implementing the new route has drastically improved the environmen-
tal impact of aprepitant production. Merck's new route eliminates all of
the operational hazards associated with the first-generation synthesis,
including those of sodium cyanide, dimethyl titanocene, and gaseous
ammonia. The shorter synthesis and milder reaction conditions have also
reduced the energy requirements significantly. Most important, the new
synthesis requires only 20 percent of the raw materials and water used
by the original one. By adopting this new route, Merck has eliminated
approximately 41,000 gallons of waste per 1,000 pounds of aprepitant that
it produces.
The alternative synthetic pathway for the synthesis of aprepitant as dis-
covered and implemented by Merck is an excellent example of minimiz-
ing environmental impact while greatly reducing production costs by
employing the principles of green chemistry. Merck implemented the
new synthesis during its first year of production of Emend®; as a result,
Merck will realize the benefits of this route for virtually the entire lifetime
of this product. The choice to implement the new route at the outset of
production has led to a huge reduction in the cost to produce aprepitant,
demonstrating quite clearly that green chemistry solutions can be aligned
with cost-effective ones.
2005 Greener Synthetic Pathways Award 49
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A UV-Curable, One-Component, Low-VOC Refinish Primer:
Driving Eco-Efficiency Improvements
BASF developed a new automobile paint primer that contains less than
half the amount of volatile organic compounds (VOCs) used in conven-
tional primers. The new primer is also free of diisocyanates, a major source
of occupational asthma. Use in repair facilities has shown that only one-
third as much of this primer is needed compared to conventional primer
and that waste is reduced from 20 percent to nearly zero.
he market for automotive refinish coatings in North America exceeds
$2 billion for both collision repairs and commercial vehicle applications.
Over 50,000 body shops in North America use these products. For more
than a decade, automotive refinishers and coating manufacturers have
dealt with increasing regulation of emissions of volatile organic com-
pounds (VOCs). At first, coating manufacturers were able to meet VOC
maximums with high-performance products such as two-component
reactive urethanes, which require solvents as carriers for their high-
molecular-weight resins. As thresholds for VOCs became lower, however,
manufacturers had to reformulate their reactive coatings, and the
resulting reformulations were slow to set a film. Waterborne coatings are
also available, but their utility has been limited by the time it takes the
water to evaporate. Continuing market pressures demanded faster film
setting without compromising either quality or emissions.
Through intense research and development, BASF has invented a new
urethane acrylate oligomer primer system. The resin cross-links with
monomer (added to reduce viscosity) into a film when the acrylate
double bonds are broken by radical propagation. The oligomers and
monomers react into the film's cross-linked structure, improving ad-
hesion, water resistance, solvent resistance, hardness, flexibility, and cure
speed. The primer cures in minutes by visible or near-ultraviolet (UV) light
from inexpensive UV-A lamps or even sunlight. BASF's UV-cured primer
50 2005 Award
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eliminates the need for bake ovens that cure the current primers, greatly
reducing energy consumption. BASF's primer performs better than the
current conventional urethane technologies: it cures ten times faster,
requires fewer preparation steps, has a lower application rate, is more
durable, controls corrosion better, and has an unlimited shelf life. BASF is
currently offering its UV-cured primers in its R-M® line as Flash Fill™ VP126
and in its Glasurit® line as 151-70.
BASF's primer contains only 1.7 pounds of VOCs per gallon, in contrast to
3.5-4.8 pounds of VOCs per gallon of conventional primers, a reduction
of over 50 percent. The primer meets even the stringent requirements
of South Coast California, whereas its superior properties ensure its
acceptance throughout the U.S. market. The one-component nature
of the product reduces hazardous waste and cleaning of equipment,
which typically requires solvents. Applications in repair facilities over the
past year have shown that only one-third as much primer is needed and
that waste is reduced from 20 percent to nearly zero. The BASF acrylate-
based technology requires less complex, less costly personal protective
equipment (PPE) than the traditional isocyanate-based coatings; this, in
turn, increases the probability that small body shops will purchase and
use the PPE, increasing worker safety.
This eco-efficient product is the first step in an automobile refinishing
coating system for which BASF plans to include the globally accepted
waterborne basecoat from BASF (sold under the Glasurit® brand as
line 90). In the near future, this system can be finished with the appli-
cation of a one-component, UV-A-curable clearcoat. The system will
deliver quality, energy efficiency, economy, and speed for the small
businessperson operating a local body shop, while respecting the health
and safety of the workers in this establishment and the environment in
which these products are manufactured and used. To fully support these
claims, BASF has conducted an eco-efficiency study with an independent
evaluation.
2005 Greener Reaction Conditions Award 51
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Archer RC™: A Nonvolatile, Reactive Coalescent for the Reduction of
VOCs in Latex Paints
Latex paints require coalescents to help the paint particles flow together
and cover surfaces well. Archer Daniels Midland developed Archer RC™, a
new biobased coalescent to replace traditional coalescents that are volatile
organic compounds (VOCs). This new coalescent has other performance
advantages as well, such as lower odor, increased scrub resistance, and
better opacity.
Mnce the 1980s, waterborne latex coatings have found increasingly
broad acceptance in architectural and industrial applications. Traditional
latex coatings are based on small-particle emulsions of a synthetic resin,
such as acrylate- and styrene-based polymers. They require substantial
quantities of a coalescent to facilitate the formation of a coating film as
water evaporates after the coating is applied. The coalescent softens
(plasticizes) the latex particles, allowing them to flow together to form a
continuous film with optimal performance properties. After film forma-
tion, traditional coalescents slowly diffuse out of the film into the atmo-
sphere. The glass transition temperature of the latex polymer increases as
the coalescent molecules evaporate and the film hardens. Alcohol esters
and ether alcohols, such as ethylene glycol monobutyl ether (EGBE) and
Texanol® (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), are com-
monly used as coalescents. They are also volatile organic compounds
(VOCs). Both environmental concerns and economics continue to drive
the trend to reduce the VOCs in coating formulations. Inventing new
latex polymers that do not require a coalescent is another option, but
these polymers often produce soft films and are expensive to synthesize,
test, and commercialize. Without a coalescent, the latex coating may
crack and may not adhere to the substrate surface when dry at ambient
temperatures.
52 2005 Award
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Archer RC™ provides the same function as traditional coalescing agents
but eliminates the unwanted VOC emissions. Instead of evaporating into
the air, the unsaturated fatty acid component of Archer RC™ oxidizes and
even cross-links into the coating. Archer RC™ is produced by interesteri-
fying vegetable oil fatty acid esters with propylene glycol to make the
propylene glycol monoesters of the fatty acids. Corn and sunflower oils
are preferred feedstocks for Archer RC™ because they have a high level
of unsaturated fatty acids and tend to resist the yellowing associated with
linolenic acid, found at higher levels in soybean and linseed oils. Because
Archer RC™ remains in the coating after film formation, it adds to the
overall solids of a latex paint, providing an economic advantage over
volatile coalescents.
The largest commercial category for latex paint, the architectural market,
was 618 million gallons in the United States in 2001. Typically, coalesc-
ing solvents constitute 2-3 percent of the finished paint by volume; this
corresponds to an estimated 120 million pounds of coalescing solvents in
the United States and perhaps three times that amount globally. Current-
ly, nearly all of these solvents are lost into the atmosphere each year.
Archer Daniels Midland Company has developed and tested a number
of paint formulations using Archer RC™ in place of conventional coalesc-
ing solvents. In these tests, Archer RC™ performed as well as commercial
coalescents such as Texanol®. Archer RC™ often had other advantages as
well, such as lower odor, increased scrub resistance, and better opacity.
Paint companies and other raw material suppliers have demonstrated
success formulating paints with Archer RC™ and their existing commer-
cial polymers. Archer RC™ has been in commercial use since March 2004.
2005 Designing Greener Chemicals Award 53
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2004 Winners
Benign Tunable Solvents Coupling Reaction and Separation Processes
Professors Eckert and Liotta found ways to replace conventional organic
solvents with benign solvents, such as supercritical CO2 or water "tuned"
by carefully selecting both temperature and pressure. These methods
combine reactions and separations, improving efficiency and reducing
waste in a variety of industrial applications.
; or any chemical process, there must be both a reaction and a separa-
tion. Generally, the same solvent is used for both but is optimized only
for the reaction. The separation typically involves 60-80 percent of the
cost, however, and almost always has a large environmental impact.
Conventional reactions and separations are often designed separately,
but Professors Charles A. Eckert and Charles L. Liotta have combined
them with a series of novel, benign, tunable solvents to create a para-
digm for sustainable development: benign solvents and improved perfor-
mance.
Supercritical CO2, nearcritical water, and CO2-expanded liquids are tun-
able benign solvents that offer exceptional opportunities as replacement
solvents. They generally exhibit better solvent properties than gases and
better transport properties than liquids. They offer substantial property
changes with small variations in thermodynamic conditions, such as
temperature, pressure, and composition. They also provide wide-ranging
environmental advantages, from human health to pollution prevention
and waste minimization. Professors Eckert, Liotta, and their team have
combined reactions with separations in a synergistic manner to use be-
nign solvents, minimize waste, and improve performance.
54
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These researchers have used supercritical CO2 to tune reaction equilibria
and rates, improve selectivities, and eliminate waste. They were the first
to use supercritical CO2 with phase transfer catalysts to separate prod-
ucts cleanly and economically. Their method allows them to recycle their
catalysts effectively. They have demonstrated the feasibility of a variety of
phase transfer catalysts on reactions of importance in the chemical and
pharmaceutical industries, including chiral syntheses. They have carried
out a wide variety of synthetic reactions in nearcritical water, replacing
conventional organic solvents. This includes acid- and base-catalysis us-
ing the enhanced dissociation of nearcritical water, negating the need
for any added acid or base and eliminating subsequent neutralization
and salt disposal. They have used CO2 to expand organic fluids to make
it easier to recycle homogeneous catalysts, including phase transfer
catalysts, chiral catalysts, and enzymes. Finally, they have used tunable
benign solvents to design syntheses that minimize waste by recycling
and demonstrate commercial feasibility by process economics.
The team of Eckert and Liotta has combined state-of-the-art chemistry
with engineering know-how, generating support from industrial sponsors
to facilitate technology transfer. They have worked with a wide variety of
government and industrial partners to identify the environmental and
commercial opportunities available with these novel solvents; their inter-
actions have facilitated the technology transfer necessary to implement
their advances.
2004 Academic Award 55
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Rhamnolipid Biosurfactant: A Natural, Low-Toxicity Alternative to Synthetic
Surfactants
Billions of pounds of surfactants are used each year to lubricate, clean, or
reduce undesired foaming in industrial applications. Jeneil Biosurfactant
Company developed biobased surfactants that are less toxic and more
biodegradable than conventional surfactants. Jeneil makes its biosur-
factants using a simple fermentation.
">urfactants are chemicals that reduce the surface tension of water.
Surfactants are widely used in soaps, laundry detergents, dishwashing
liquids, and many personal care products, such as shampoos. Other
important uses are in lubricants, emulsion polymerization, textile process-
ing, mining flocculates, petroleum recovery, and wastewater treatment.
Most currently used surfactants are derived from petroleum feedstocks.
The total worldwide chemical surfactant consumption in the year 2000
has been estimated to be approximately 36 billion pounds. Many of
these chemical surfactants pose significant environmental risks because
they form harmful compounds from incomplete biodegradation in water
or soil.
Jeneil Biosurfactant Company has successfully produced a series of rham-
nolipid biosurfactant products, making them commercially available and
economical for the first time. These biosurfactant products provide good
emulsification, wetting, detergency, and foaming properties, along with
very lowtoxicity. They are readily biodegradable and leave no harmful or
persistent degradation products. Their superior qualities make them suit-
able for many diverse applications.
Rhamnolipid biosurfactant is a naturally occurring extracellular glycolipid
that is found in the soil and on plants. Jeneil produces this biosurfactant
commercially in controlled, aerobic fermentations using particular strains
of the soil bacterium, Pseudomonas aeruginosa. The biosurfactant is
56 2004 Award
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recovered from the fermentation broth after sterilization and centrifuga-
tion, then purified to various levels to fit intended applications.
Rhamnolipid biosurfactants are a much less toxic and more environment-
ally friendly alternative to traditional synthetic or petroleum-derived sur-
factants. Rhamnolipid biosurfactants are also "greener" throughout their
life cycle. Biosurfactant production uses feedstocks that are innocuous
and renewable compared to those used for synthetic or petroleum-
derived surfactants. In addition, their production requires less resources,
employs processes that are less complex and less capital- and energy-
intensive, and does not require the use and disposal of hazardous
substances.
Some current uses of rhamnolipid biosurfactant are in consumer clean-
ing products, in solutions to clean contact lenses, and in an agricultural
fungicide as the active ingredient. These biosurfactants are also extreme-
ly effective in precluding harmful environmental impacts and remediat-
ing environmental pollution. For example, rhamnolipid biosurfactants
can facilitate removal of hydrocarbons or heavy metals from soil, clean
crude oil tanks, and remediate sludge; often they can facilitate recovery
of a significant amount of the hydrocarbons. In many applications, these
biosurfactants can replace less environmentally friendly synthetic or pe-
troleum-derived surfactants. Further, these biosurfactants have excellent
synergistic activity with many synthetic surfactants and, when formulated
together in a cosurfactant system, can allow a substantial reduction in the
synthetic surfactant component.
Although rhamnolipid biosurfactants have been the subject of consider-
able research, they had previously been produced only on a small scale
in laboratories. Jeneil Biosurfactant Company, in conjunction with its
associated company, Jeneil Biotech, Inc., has commercialized the rham-
nolipid technology by developing efficient bacterial strains, as well as
cost-effective processes and equipment for commercial-scale production.
Jeneil's facility in Saukville, Wl produces the surfactants.
2004 Small Business Award 57
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Development of a Green Synthesis for Taxol® Manufacture via Plant Cell
Fermentation and Extraction
Bristol-Myers Squibb manufactures paditaxel, the active ingredient in the
anticancer drug, Taxol®, using plant cell fermentation (PCF) technology.
PCF replaces the conventional process that extracts a paditaxel building
block from leaves and twigs of the European yew. During the first five
years of commercialization, PCF technology will eliminate an estimated
71,000 pounds of hazardous chemicals and materials, eliminate 10 solvents
and 6 drying steps, and save a significant amount of energy.
aclitaxel, the active ingredient in the anticancer drug Taxol®, was
first isolated and identified from the bark of the Pacific yew tree, Taxus
brevifolia, in the late 1960s by Wall and Wani under the auspices of the
National Cancer Institute (NCI). The utility of paditaxel to treat ovarian
cancer was demonstrated in clinical trials in the 1980s. The continuity of
supply was not guaranteed, however, because yew bark contains only
about 0.0004 percent paditaxel. In addition, isolating paditaxel required
stripping the bark from the yew trees, killing them in the process. Yews
take 200 years to mature and are part of a sensitive ecosystem.
The complexity of the paditaxel molecule makes commercial production
by chemical synthesis from simple compounds impractical. Published
syntheses involve about 40 steps with an overall yield of approximately
2 percent. In 1991, NCI signed a Collaborative Research and Develop-
ment Agreement with Bristol-Myers Squibb (BMS) in which BMS agreed
to ensure supply of paditaxel from yew bark while it developed a semi-
synthetic route (semisynthesis) to paditaxel from the naturally occurring
compound 10-deacetylbaccatin III (10-DAB).
10-DAB contains most of the structural complexity (8 chiral centers) of the
paditaxel molecule. It is present in the leaves and twigs of the European
yew, Taxus baccata, at approximately 0.1 percent by dry weight and can
58 2004 Award
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be isolated without harm to the trees. Taxus baccata is cultivated through-
out Europe, providing a renewable supply that does not adversely impact
any sensitive ecosystem. The semisynthetic process is complex, however,
requiring 11 chemical transformations and 7 isolations. The semisynthetic
process also presents environmental concerns, requiring 13 solvents
along with 13 organic reagents and other materials.
BMS developed a more sustainable process using the latest plant cell
fermentation (PCF) technology. In the cell fermentation stage of the pro-
cess, calluses of a specific taxus cell line are propagated in a wholly aque-
ous medium in large fermentation tanks under controlled conditions at
ambient temperature and pressure. The feedstock for the cell growth
consists of renewable nutrients: sugars, amino acids, vitamins, and trace
elements. BMS extracts paclitaxel directly from plant cell cultures, then pu-
rifies it by chromatography and isolates it by crystallization. By replacing
leaves and twigs with plant cell cultures, BMS improves the sustainability
of the paclitaxel supply, allows year-round harvest, and eliminates solid
biomass waste. Compared to the semisynthesis from 10-DAB, the PCF pro-
cess has no chemical transformations, thereby eliminating six intermedi-
ates. During its first five years, the PCF process will eliminate an estimated
71,000 pounds of hazardous chemicals and other materials. In addition,
the PCF process eliminates 10 solvents and 6 drying steps, saving a con-
siderable amount of energy. BMS is now manufacturing paclitaxel using
only plant cell cultures.
2004 Greener Synthetic Pathways Award 59
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Optimyze®: A New Enzyme Technology to Improve Paper Recycling
Paper mills traditionally use hazardous solvents, such as mineral spirits, to
remove sticky contaminants (stickles) from machinery. Optimyze® technol-
ogy uses a novel enzyme to remove stickles from paper products prior to
recycling, increasing the percentage of paper that can be recycled. Each
paper mill that switches to Optimyze® can reduce its hazardous solvent
use by 200 gallons daily, reduce its chemical use by approximately
600,000 pounds yearly, increase its production by more than 6 percent,
and save up to $1 million per year.
Kecycling paper products is an important part of maintaining our envi-
ronment. Although produced from renewable resources, paper is a major
contributor to landfilled waste. Paper can be recycled numerous times,
and much progress has been made: about one-half of the paper and
paperboard currently used in the United States is collected and reused.
Some papers, however, contain adhesives, coatings, plastics, and other
materials that form sticky contaminants, creating serious problems during
the paper recycling process. These contaminants, called "stickles" by the
paper industry, can produce spots and holes in paper goods made from
recycled materials, ruining their appearance and lowering their quality.
Stickles also waste significant manufacturing resources when production
must stop to clean the equipment. One source estimates the cost to
the industry from production downtime alone to be more than $500 mil-
lion annually. Further, this cleaning is traditionally done with chemical
solvents, typically mineral spirits, which can have health and safety prob-
lems, are obtained from nonrenewable, petroleum resources, and are not
readily recycled. These solvents are volatile organic compounds (VOCs)
that contribute to air pollution. As a result, some paper grades cannot be
recycled into reusable products.
60 2004 Award
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Optimyze® technology from Buckman Laboratories is a completely new
way to control the problems associated with stickles. It uses a novel
enzyme to eliminate common problems in the manufacture of paper
from recycled papers. A major component of the sticky contaminants in
paper is poly(vinyl acetate) and similar materials. Optimyze® contains an
esterase enzyme that catalyzes the hydrolysis of this type of polymer to
poly(vinyl alcohol), which is not sticky and is water-soluble. A bacterial
species produces large amounts of the Optimyze® enzyme by fermenta-
tion. As a protein, the enzyme is completely biodegradable, much less
toxic than alternatives, and much safer. Only renewable resources are
required to manufacture Optimyze®.
Optimyze® has been commercially available since May 2002. In that short
time, more than 40 paper mills have converted to Optimyze® for manu-
facturing paper goods from recycled papers. In one U.S. mill, conversion
to Optimyze® reduced solvent use by 200 gallons per day and chemical
use by about 600,000 pounds per year. Production increased by more
than 6 percent, which amounted to a $1 million benefit per year for this
mill alone.
This new enzyme technology has improved production of a broad range
of paper products, including tissue, paper toweling, corrugated cartons,
and many other materials. It improves the quality and efficiency of paper-
making, dramatically reducing downtime to clean equipment. As a result,
more paper is being recycled and grades of paper that were not recycla-
ble earlier are now being recycled. Paper mills adopting Optimyze® have
been able to greatly reduce the use of hazardous solvents.
In summary, Optimyze® makes it possible to recycle more grades of
paper, allows more efficient processing of recycled papers, and produces
higher-quality paper goods from recycled materials. The Optimyze®
technology comes from renewable resources, is safe to use, and is itself
completely recyclable.
2004 Greener Reaction Conditions Award 61
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Engelhard Rightfit™ Organic Pigments: Environmental Impact,
Performance, and Value
Rightfit™ azo pigments contain calcium, strontium, or barium; they replace
conventional heavy-metal-based pigments containing lead, hexavalent
chromium, or cadmium. Because of their low potential toxicity and very
low migration, most of the Rightfit™ azo pigments have received U.S.
Food and Drug Administration (FDA) and Canadian Health Protection
Branch (HPB) approval for indirect food contact applications. By 2004,
Engelhard expects to have replaced all 6.5 million pounds of its heavy-
metal-based pigments with Rightfit™ pigments.
; 'istorically, pigments based on lead, chromium(VI), and cadmium
have served the red, orange, and yellow color market. When EPA began
regulating heavy metals, however, color formulators typically turned to
high-performance organic pigments to replace heavy-metal-based pig-
ments. Although high-performance pigments meet performance require-
ments, they do so at the expense of the following: (1) their higher cost
often acts as a deterrent to reformulation; (2) their production uses large
volumes of organic solvents; (3) some require large quantities of poly-
phosphoric acid, resulting in phosphates in the effluent; and (4) some
are based on dichlorobenzidine or polychlorinated phenyls.
Engelhard has developed a wide range of environmentally friendly Right-
fit™ azo pigments that contain calcium, strontium, or sometimes barium
instead of heavy metals. True to their name, the Rightfit™ pigments have
the right environmental impact, right color space, right performance
characteristics, and right cost-to-performance value. Since 1995, when
Engelhard produced 6.5 million pounds of pigments containing heavy
metals, it has been transitioningto Rightfit™ azo pigments. In 2002, En-
gelhard produced only 1.2 million pounds of heavy-metal pigments; they
expect to phase them out completely in 2004.
62 2004 Award
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Rightfit™ pigments eliminate the risk to human health and the environ-
ment from exposure to heavy metals such as cadmium, chromium(VI),
and lead used in the manufacture of cadmium and chrome yellow pig-
ments. They are expected to have very low potential toxicity based on tox-
icity studies, physical properties, and structural similarities to many widely
used food colorants. Because they have low potential toxicity and very
low migration, most of the Rightfit™ pigments have been approved both
by the U.S. Food and Drug Administration (FDA) and the Canadian Health
Protection Branch (HPB) for indirect food contact applications. In addition,
these pigments are manufactured in aqueous medium, eliminating expo-
sure to the polychlorinated intermediates and organic solvents associated
with the manufacture of traditional high-performance pigments.
Rightfit™ pigments have additional benefits, such as good dispersibility,
improved dimensional stability, improved heat stability, and improved
color strength. Their higher color strength achieves the same color values
using less pigment. Rightfit™ pigments also cover a wide color range
from purple to green-shade yellow color. Being closely related chemically,
these pigments are mutually compatible, so two or more can combine to
achieve any desired intermediate color shade.
Rightfit™ pigments meet the essential performance characteristics at sig-
nificantly lower cost than high-performance organic pigments. Thus, for-
mulators get the right performance properties at the right cost, resulting
in a steadily increasing market for these pigments. Rightfit™ pigments
provide environmentally friendly, value-added color to packaging used in
the food, beverage, petroleum product, detergent, and other household
durable goods markets.
2004 Designing Greener Chemicals Award 63
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2003 Winners
New Options for Mild and Selective Polymerizations Using Lipases
Professor Gross developed a highly selective, more efficient way to make
polyesters using enzymes. This technique requires less energy and toxic
substances than conventional methods that typically use heavy metal
catalysts and hazardous solvents. This innovation also makes it possible to
manufacture new types of polyesters.
isolated Upases, harvested from living organisms, have been used as
catalysts for polymer synthesis in vitro. Professor Richard A. Gross's devel-
opments on lipase-catalyzed polymer synthesis have relied on the ability
of enzymes to reduce the activation energy of polymerizations and, thus,
to decrease process energy consumption, further, the regioselectivity of
Upases has been used to polymerize polyols directly. Alternative synthetic
pathways for such polymerizations require protection-deprotection chemi-
cal steps. The mild reaction conditions allow polymerization of chemically
and thermally sensitive molecules. Current alternative chemical routes
require coupling agents (e.g., carbodiimides) that would be consumed in
stoichiometric quantities relative to the reactants. fundamental studies of
these polymerizations have uncovered remarkable capabilities of Upases
for polymerization chemistry. Selected examples include: (1) Upases
catalyze transesterification reactions between high-molecular-weight
chains in melt conditions; (2) Upases will use non-natural nucleophiles
such as carbohydrates and monohydroxyl polybutadiene (Mn 19,000) in
place of water,- (3) the catalysis of ring-opening polymerization occurs
in a controlled manner without termination reactions and with predict-
able molecular weights; and (4) the selectivity of lipase-catalyzed step-
condensation polymerizations leads to nonstatistical molecular weight
distributions (polydispersities well below 2.0). These accomplishments
are elaborated on the next page.
64
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A series of polyol-containing polyesters was synthesized via a one-pot li-
pase-catalyzed condensation polymerization. By using various mixtures of
polyols (e.g., glycerol, sorbitol) with other diacid and diol building blocks,
the polyols are partially or completely solubilized, resulting in highly reac-
tive condensation polymerizations. By this method, organic solvents and
activated acids (e.g., divinyl esters) are not needed. The polymerization
reactions give high-molecular-weight products (/Vlw up to 200,000) with
narrow polydispersities (as low as 1.3). Further, the condensation reactions
with glycerol and sorbitol building blocks proceed with high regioselectiv-
ity. Although the polyols used have three or more hydroxyl groups, only
two of these hydroxyl groups are highly reactive in the polymerization.
Thus, instead of obtaining highly cross-linked products, the regioselectiv-
ity provided by the lipase leads to lightly branched polymers where the
degree of branching varies with the reaction time and monomer stoichi-
ometry. By using lipase as the catalyst, highly versatile polymerizations
result that can simultaneously polymerize lactones, hydroxyacids, cyclic
carbonates, cyclic anhydrides, amino alcohols, and hydroxylthiols. The
method developed offers simplicity, mild reaction conditions, and the abil-
ity to incorporate carbohydrates, such as sugars, into polyesters without
protection-deprotection steps.
Professor Gross's laboratory discovered that certain Upases catalyze
transesterification reactions between high-molecular-weight chains that
contain intrachain esters or have functional end-groups. Thus, Upases,
such as Lipase B from Candida antarctica, catalyze intrachain exchange
reactions between polymer chains as well as transesterification reactions
between a monomer and a polymer. For polymers that have melting
points below 100 °C, the reactions can be conducted in bulk. Transacyla-
tion reactions occur because the lipase has the ability to accommodate
large-molecular-weight substrates and to catalyze the breaking of ester
bonds within chains. Immobilized Candida antarctica Lipase B (Novozyme-
435) catalyzed transesterification reactions between aliphatic polyesters
that had Mn values in excess of 40,000 grams per mole. In addition to
catalyzing metal-free transesterifications at remarkably low temperatures,
Upases endow transesterification reactions with remarkable selectivity.
This feature allows the preparation of block copolymers that have selected
block lengths.
2003 Academic Award 65
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Serenade®: An Effective, Environmentally Friendly Biofungicide
Serenade® is a new biofungicide for fruits and vegetables based on a
naturally occurring strain of bacteria. Serenade® is nontoxic to beneficial
and other nontarget organisms, does not generate any hazardous chemi-
cal residues, and is safe for workers and groundwater. It is well-suited for
use in integrated pest management (IPM) programs and is listed with the
Organic Materials Review Institute (OMRI) for use in organic agriculture.
' .erenade® Biofungicide is based on a naturally occurring strain of
Bacillus subtilis QST-713, discovered in a California orchard by AgraQuest
scientists. Serenade® has been registered for sale as a microbial pesti-
cide in the United States since July 2000. It is also registered for use in
Chile, Mexico, Costa Rica, and New Zealand. Registration is pending in
the Philippines, Europe, Japan, and several other countries. The product
is formulated as a wettable powder, wettable granule, and liquid aque-
ous suspension. Serenade® has been tested on 30 crops in 20 countries
and is registered for use in the United States on blueberries, cherries,
cucurbits, grape vines, greenhouse vegetables, green beans, hops, leafy
vegetables, mint, peanuts, peppers, pome fruit, potatoes, tomatoes, and
walnuts. It is also registered for home and garden use. AgraQuest has
been issued four U.S. patents; several international patents are pending
on the QST-713 strain, associated antifungal lipopeptides, formulations,
and combinations with other pesticides.
Serenade® works through a complex mode of action that is manifested
both by the physiology of the bacteria and through the action of sec-
ondary metabolites produced by the bacteria. Serenade® prevents plant
diseases first by covering the leaf surface and physically preventing at-
tachment and penetration of the pathogens. In addition, Serenade® pro-
duces three groups of lipopeptides (iturins, agrastatins/plipastatins, and
surfactins) that act in concert to destroy germ tubes and mycelium. The
iturins and plipastatins have been reported to have antifungal properties.
66 2003 Award
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Strain QST-713 is the first strain reported to produce iturins, plipastatins,
and surfactins, as well as two new compounds with a novel cyclic peptide
moiety, the agrastatins. The surfactins have no activity on their own, but
low levels (25 ppm or less) in combination with the iturins or the agra-
statin/plipastatin group cause significant inhibition of spores and germ
tubes. In addition, the agrastatins and iturins have synergistic activities
towards inhibition of plant pathogen spores.
The Serenade® formulation is available as a wettable powder, wettable
granule, and aqueous suspension that is applied just like any other foliar
fungicide. It can be applied alone or tank mixed; it can also be alternated
with traditional chemical pesticides. Serenade® is not toxic to beneficial
and nontarget organisms, such as trout, quail, lady beetles, lacewings,
parasitic wasps, earthworms, and honey bees. Serenade® is exempt from
tolerance because there are no synthetic chemical residues and it is safe
to workers and ground water.
Serenade®'s wettable granule formulation is listed with the Organic
Materials Review Institute (OMRI) for use in organic agriculture and will
continue to be listed under the National Organic Standards, which were
enacted in the United States in October 2002.
Serenade®'s novel, complex mode of action, environmental friendliness,
and broad spectrum control make it well-suited for use in integrated pest
management (IPM) programs that utilize many tools, such as cultural
practices, classical biological control, and other fungicides. Serenade®
can be applied right up until harvest, providing needed pre- and post-har-
vest protection when there is weather conducive to disease development
around harvest time.
2003 Small Business Award 67
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A Wastewater-Free Process for Synthesis of Solid Oxide Catalysts
Sud-Chemie's new process to synthesize solid oxide catalysts used in pro-
ducing hydrogen and clean fuel has virtually zero wastewater discharge,
zero nitrate discharge, and no or little NOX emissions. Each 10 million
pounds of oxide catalyst produced by the new pathway eliminates approxi-
mately 760 million pounds of wastewater discharges, 29 million pounds of
nitrate discharges, and 7.6 million pounds of NOX emissions. The process
also saves water and energy.
';ome major achievements in pollution reduction have been made re-
cently through advancement of catalytic technologies. One such effort is
in the area of hydrogen and clean fuel production. However, the synthe-
sis of catalysts for such reactions is often accompanied by the discharge
of large amounts of wastewater and other pollutants, such as NOX, SOX,
and halogens.
As a result of their commitment to continuously develop and invest in
new and improved catalyst synthesis technologies, Sud-Chemie success-
fully developed and demonstrated a new synthetic pathway that is able
to achieve virtually zero wastewater discharge, zero nitrate discharge,
and no or little NOX emissions. Meantime, it substantially reduces the
consumption of water and energy, for example, it is estimated that about
760 million pounds of wastewater discharges, about 29 million pounds of
nitrate discharges, and about 7.6 million pounds of NOX emissions can be
eliminated for every 10 million pounds of oxide catalyst produced.
The new synthetic pathway is based on very simple chemistry. Instead of
acid-base precipitation typically using metal nitrate as raw material, the
new process starts with a clean metal that is readily and economically
available in commercial quantities. The synthesis proceeds by reaction of
the metal with a mild organic acid in the presence of an oxidation agent.
The function of the acid is to activate the metal and extract electrons
68 2003 Award
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to form the oxide precursor. With assistance of the oxidation agent (typi-
cally air), a porous solid oxide is synthesized in one step at ambient tem-
perature without any wastewater discharge. The other active ingredients
of the catalyst can be incorporated using the concept of wet-agglomera-
tion. In contrast, the precipitation process requires intensive washing and
filtration to remove nitrate and the other salts. Further, the new process
substantially reduces the consumption of water and energy for produc-
tion of solid oxide catalysts over conventional methods. The emission in
the entire process is only pure water vapor and a small amount of CO2
that is generated during spray-drying and afterburning of hydrogen.
This wastewater-free process for making solid oxide catalysts has been
demonstrated, and more than 300 kilograms of the metal oxide catalysts
have been produced. Patent protection is being sought for the develop-
ment. The catalysts made by the green process give superior perfor-
mance in the synthesis of clean fuels and chemicals. The market for such
solid oxide catalysts is estimated to be approximately $100 million. Sud-
Chemie is the first in the industry to use the green process for making a
catalyst for the synthesis of "green" fuels and chemicals.
2003 Greener Synthetic Pathways Award 69
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Microbial Production of 1,3-Propanediol
DuPont and Genencor International jointly developed a genetically
engineered microorganism to manufacture the key building block for
DuPont's Sorona® polyester. The process uses renewable cornstarch
instead of petroleum to make environmentally friendly, cost-competitive
textiles.
i .-'uPont is integrating biology in the manufacture of its newest polymer
platform, DuPont Sorona® polymer. Combining metabolic engineering
with polymer science, researchers are introducing a microbial process in
a business that, historically, has relied solely on traditional chemistry and
petrochemical feedstocks. This achievement, comprising biocatalytic pro-
duction of 1,3-propanediol from renewable resources, offers economic
as well as environmental advantages. The key to the novel biological pro-
cess is an engineered microorganism that incorporates several enzyme
reactions, obtained from naturally occurring bacteria and yeast, into an
industrial host cell line. For the first time, a highly engineered microor-
ganism will be used to convert a renewable resource into a chemical at
high volume.
The catalytic efficiency of the engineered microorganism allows replace-
ment of a petroleum feedstock, reducing the amount of energy needed
in manufacturing steps and improving process safety. The microbial pro-
cess is environmentally green, less expensive, and more productive than
the chemical operations it replaces. 1,3-Propanediol, a key ingredient
in the Sorona® polymers, provides advantageous attributes for apparel,
upholstery, resins, and nonwoven applications.
Scientists and engineers from DuPont and Genencor International, Inc.
redesigned a living microbe to produce 1,3-propanediol. Inserting biosyn-
thetic pathways from several microorganisms into an industrial host cell
line allows the direct conversion of glucose to 1,3-propanediol, a route
70 2003 Award
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not previously available in a single microorganism. Genes from a yeast
strain with the ability to convert glucose, derived from cornstarch, to glyc-
erol were inserted into the host. Genes from a bacterium with the ability
to transform glycerol to 1,3-propanediol were also incorporated. Addition-
ally, the reactions present naturally in the host were altered to optimize
product formation. The modifications maximize the ability of the organ-
ism to convert glucose to 1,3-propanediol while minimizing its ability to
produce biomassand unwanted byproducts. Coalescing enzyme reac-
tions from multiple organisms expands the range of materials that can be
economically produced by biological means.
For more than 50 years, scientists have recognized the performance
benefits of polyesters produced with 1,3-propanediol; however, the high
cost of manufacturing the ingredient using petroleum feedstock and tra-
ditional chemistry kept it from the marketplace. The biological process us-
ing glucose as starting material will enable cost-effective manufacture of
Sorona® polymer, which will offer consumer fabrics with softness, stretch
and recovery, easy care, stain resistance, and colorfastness. A unique kink
in the structure of the polymer containing 1,3-propanediol allows recov-
ery at a high rate when it is stretched. As a result, Sorona® improves fit
and comfort because the fabric quickly recovers its original shape when
stretched, for example, in knees or elbows. The resilience of Sorona® also
adds beneficial features to automotive upholstery and home textiles. In
resin applications, Sorona®'s barrier characteristics protect moisture, taste,
and odor.
Biology offers chemical manufacturers attractive options for the produc-
tion of chemicals while adhering to the principles of green chemistry.
This microbial production of a key polymer ingredient from renewable
sources is one example. By integrating biology with chemistry, physics,
and engineering, DuPont develops new solutions that enhance the envi-
ronment and improve upon existing materials.
2003 Greener Reaction Conditions Award 71
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EcoWorx™ Carpet Tile: A Cradle-to-Cradle Product
Conventional backings for carpet tiles contain bitumen, polyvinyl chloride
(PVC), or polyurethane. EcoWorx™ carpet tiles have a novel backing that
uses less toxic materials and has superior adhesion and dimensional sta-
bility. Because EcoWorx™ carpet tiles can be readily separated into carpet
fiber and backing, each component can be easily recycled.
istorically, carpet tile backings have been manufactured using bitumen,
polyvinyl chloride (PVC), or polyurethane (PU). While these backing
systems have performed satisfactorily, there are several inherently
negative attributes due to their feedstocks or their ability to be recycled.
Although PVC has, to date, held the largest market share of carpet tile
backing systems, it was Shaw's intent to design around PVC due to the
health and environmental concerns around vinyl chloride monomer,
chlorine-based products, plasticized PVC-containing phthalate esters, and
toxic byproducts of combustion of PVC, such as dioxin and hydrochloric
acid. While some claims are accepted by the Agency for Toxic Substances
and Disease Registry (ATSDR) and the EPA, those resulting from publicly
debated consumer perceptions provide ample justification for finding a
PVC alternative.
Due to the thermoset cross-linking of polyurethanes, they are extremely
difficult to recycle and are typically downcycled or landfilled at the end of
their useful life. Bitumen provides some advantages in recycling, but the
modified bitumen backings offered in Europe have failed to gain market
acceptance in the United States and are unlikely to do so.
Shaw selected a combination of polyolefin resins from Dow Chemical as
the base polymer of choice for EcoWorx™ due to the low toxicity of its
feedstocks, superior adhesion properties, dimensional stability, and its
ability to be recycled. The EcoWorx™ compound also had to be designed
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to be compatible with nylon carpet fiber. Although EcoWorx™ may be
recovered from any fiber type, nylon-6 provides a significant advantage.
Polyolefins are compatible with known nylon-6 depolymerization meth-
ods. PVC interferes with those processes. Nylon-6 chemistry is well-known
and not addressed in first-generation production.
From its inception, EcoWorx™ met all of the design criteria necessary to
satisfy the needs of the marketplace from a performance, health, and
environmental standpoint. Research indicated that separation of the fiber
and backing through elutriation, grinding, and air separation proved to be
the best way to recover the face and backing components, but an infra-
structure for returning postconsumer EcoWorx™ to the elutriation process
was necessary. Research also indicated that the postconsumer carpet tile
had a positive economic value at the end of its useful life. The cost of col-
lection, transportation, elutriation, and return to the respective nylon and
EcoWorx™ manufacturing processes is less than the cost of using virgin
raw materials.
With introduction in 1999 and an anticipated lifetime often to fifteen
years on the floor, significant quantities of EcoWorx™ will not flow back
to Shaw until 2006 to 2007. An expandable elutriation unit is now operat-
ing at Shaw, typically dealing with industrial EcoWorx™ waste. Recovered
EcoWorx™ is flowing back to the backing extrusion unit. Caprolactam re-
covered from the elutriated nylon-6 is flowing back into nylon compound-
ing. EcoWorx™ will soon displace all PVC at Shaw.
2003 Designing Greener Chemicals Award 73
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2002 Winners
Design of Non-Fluorous, Highly CCh-Soluble Materials
Carbon dioxide (CO2) is a nontoxic chemical that can be used as a solvent
in many industrial processes. Professor Beckman developed new deter-
gents that allow a broad range of substances to dissolve in CO2. Any pro-
cess that can now use CO2 may reduce or eliminate the use of hazardous
solvents.
L arbon dioxide (CO2), an environmentally benign and nonflammable
solvent, has been investigated extensively in both academic and indus-
trial settings. Solubility studies performed during the 1980s had sug-
gested that CO2's solvent power was similar to that of n-alkanes, leading
to hopes that the chemical industry could use CO2 as a "drop-in" replace-
ment for a wide variety of organic solvents. It was learned that these solu-
bility studies inflated the solvent power value by as much as 20 percent
due to the strong quadrupole moment of CO2 and that CO2 is actually a
rather feeble solvent compared to alkanes. As the 1980s drew to a close,
a number of research groups began to explore the design of CO2-philic
materials, that is, compounds that dissolve in CO2 at significantly lower
pressures than do their alkyl analogs. These new CO2-philes, primarily
fluoropolymers, opened up a host of new applications for CO2 including
heterogeneous polymerization, protein extraction, and homogeneous
catalysis.
Although fluorinated amphiphiles allow new applications for CO2, their
cost (approximately $1 per gram) reduces the economic viability of CO2
processes, particularly given that the use of CO2 requires high-pressure
equipment. Furthermore, data have recently shown that fluoroalkyl
materials persist in the environment, leading to the withdrawal of certain
consumer products from the market. The drawbacks inherent to the use
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of fluorinated precursors, therefore, have inhibited the commercializa-
tion of many new applications for CO2, and the full promise of CO2-based
technologies has yet to be realized. To address this need, Professor Eric
J. Beckman and his group at the University of Pittsburgh have developed
materials that work well, exhibiting miscibility pressures in CO2 that are
comparable or lower than fluorinated analogs and yet contain no fluo-
rine.
Drawing from recent studies of the thermodynamics of CO2 mixtures,
Professor Beckman hypothesized that CO2-philic materials should contain
three primary features: (1) a relatively low glass transition temperature;
(2) a relatively low cohesive energy density; and (3) a number of Lewis
base groups. Low glass transition temperature correlates to high free
volume and high molecular flexibility, which imparts a high entropy of
mixing with CO2 (or any solvent). A low cohesive energy density is primar-
ily a result of weak solute-solute interactions, a necessary feature given
that CO2 is a rather feeble solvent. Finally, because CO2 is a Lewis acid,
the presence of Lewis base groups should create sites for specific favor-
able interactions with CO2.
Professor Beckman's simple heuristic model was demonstrated on three
sets of materials: functional silicones; poly(ether-carbonates); and acetate-
functional polyethers. Poly(ether-carbonates) were found to exhibit lower
miscibility pressures in CO2 than perfluoropolyethers, yet are biodegrad-
able and 100 times less expensive to prepare. Other families of non-
fluorous CO2-philes will inevitably be discovered using this model, further
broadening the applicability of CO as a greener process solvent.
2002 Academic Award 75
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SCORR—Supercritical CO2 Resist Remover
SCORR (Supercritical CC>2 Resist Remover) technology cleans residues from
semiconductor wafers during their manufacture. SCORR improves on
conventional techniques: it minimizes hazardous solvents and waste, is
safer for workers, costs less, and uses less water and energy. SCORR also
eliminates rinsing with ultrapure water and subsequent drying.
i he semiconductor industry is the most successful growth industry in his-
tory, with sales totaling over $170 billion in the year 2000. The fabrication
of integrated circuits (ICs) relies heavily on photolithography to define
the shape and pattern of individual components. Current manufacturing
practices use hazardous chemicals and enormous amounts of purified
water during this intermediate step, which may be repeated up to
30 times for a single wafer. It is estimated that a typical chip-fabrication
plant generates 4 million gallons of wastewater and consumes thousands
of gallons of corrosive chemicals and hazardous solvents each day.
SC Fluids, in partnership with Los Alamos National Laboratory, has de-
veloped a new process, SCORR, that removes photoresist and post-ash,
-etch, and -CMP (particulate) residue from semiconductor wafers. The
SCORR technology outperforms conventional photoresist removal tech-
niques in the areas of waste minimization, water use, energy consump-
tion, worker safety, feature size compatibility, material compatibility, and
cost. The key to the effectiveness of SCORR is the use of supercritical
CO2 in place of hazardous solvents and corrosive chemicals. Neat CO2 is
also utilized for the rinse step, thereby eliminating the need for a deion-
ized water rinse and an isopropyl alcohol drying step. In the closed-loop
SCORR process, CO2 returns to a gaseous phase upon depressurization,
leaving the silicon wafer dry and free of residue.
SCORR is cost-effective for five principal reasons. It minimizes the use of
hazardous solvents, thereby minimizing costs required for disposal and
76 2002 Award
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discharge permits. It thoroughly strips photoresists from the wafer surface
in less than half the time required for wet-stripping and far outperforms
plasma, resulting in increased throughput. It eliminates rinsing and drying
steps during the fabrication process, thereby simplifying and streamlining
the manufacturing process. It eliminates the need for ultrapure deionized
water, thus reducing time, energy, and cost. Supercritical CO2 costs less
than traditional solvents and is recyclable.
SCORR will meet future, as well as current technology demands. To con-
tinue its astounding growth, the semiconductor industry must develop
ICs that are smaller, faster, and cheaper. Due to their high viscosity,
traditional wet chemistries cannot clean small feature sizes. Vapor clean-
ing technologies are available, but viable methods for particle removal in
the gas phase have not yet been developed. Using SCORR, the smallest
features present no barriers because supercritical fluids have zero surface
tension and a "gaslike" viscosity and, therefore, can clean features less
than 100 nm.The low viscosity of super-critical flu ids also allows particles
less than 100 nm to be removed. The end result is a technically enabling
"green" process that has been accepted by leading semiconductor manu-
facturers and equipment and material suppliers.
SCORR technology is being driven by industry in pursuit of its own accel-
erated technical and manufacturing goals. SCORR was initially developed
through a technical request from Hewlett Packard (now Agilent). A joint
Cooperative Research and Development Agreement between Los Alamos
National Laboratory and SC Fluids has led to the development of com-
mercial units (SC Fluids's Arroyo™ System). Other industry leaders, such
as IBM, ATMI, and Shipley, are participating in the development of this
innovative technology.
2002 Small Business Award 77
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Green Chemistry in the Redesign of the Sertraline Process
Pfizer dramatically improved its manufacturing process for sertraline, the
active ingredient in its popular drug, Zoloft®. The new process doubles
overall product yield, reduces raw material use by 20-60 percent, elimi-
nates the use or generation of approximately 1.8 million pounds of hazard-
ous materials, reduces energy and water use, and increases worker safety.
.'.^ertraline is the active ingredient in the important pharmaceutical,
Zoloft®. Zoloft® is the most prescribed agent of its kind and is used to
treat an illness (depression) that each year strikes 20 million adults in the
United States, and that costs society $43.7 billion (1990 dollars). As of
february 2000, more than 115 million Zoloft® prescriptions had been
written in the United States.
Applying the principles of green chemistry, Pfizer has dramatically im-
proved the commercial manufacturing process of sertraline. After
meticulously investigating each of the chemical steps, Pfizer implement-
ed a substantive green chemistry technology for a complex commercial
process requiring extremely pure product. As a result, Pfizer significantly
improved both worker and environmental safety. The new commercial
process (referred to as the "combined" process) offers substantial pollu-
tion prevention benefits including improved safety and material handling,
reduced energy and water use, and doubled overall product yield.
Specifically, a three-step sequence in the original manufacturing process
was streamlined to a single step in the new sertraline process. The new
process consists of imine formation of monomethylamine with a tetral-
one, followed by reduction of the imine function and in situ resolution of
the diastereomeric salts of mandelic acid to provide chirally pure sertra-
line in much higher yield and with greater selectivity. A more selective
palladium catalyst was implemented in the reduction step, which re-
duced the formation of impurities and the need for reprocessing. Raw
78 2002 Award
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material use was cut by 60 percent, 45 percent, and 20 percent for
monomethylamine, tetralone, and mandelic acid, respectively.
Pfizer also optimized its process using the more benign solvent ethanol
for the combined process. This change eliminated the need to use,
distill, and recover four solvents (methylene chloride, tetrahydrofuran,
toluene, and hexane) from the original synthesis. Pfizer's innovative use
of solubility differences to drive the equilibrium toward imine formation
in the first reaction of the combined steps eliminated approximately
310,000 pounds per year of the problematic reagent titanium tetrachlo-
ride. This process change eliminates 220,000 pounds of 50 percent
sodium hydroxide, 330,000 pounds of 35 percent hydrochloric acid waste,
and 970,000 pounds of solid titanium dioxide waste per year.
By eliminating waste, reducing solvents, and maximizing the yield of key
intermediates, Pfizer has demonstrated significant green chemistry inno-
vation in the manufacture of an important pharmaceutical agent.
2002 Greener Synthetic Pathways Award 79
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NatureWorks™ PLA Process
The NatureWorks™ process makes biobased, compostable, and recycla-
ble polylactic acid (PLA) polymers using 20-50 percent less fossil fuel
resources than comparable petroleum-based polymers. The synthesis of
PLA polymers eliminates organic solvents and other hazardous materials,
completely recycles product and byproduct streams, and efficiently uses
catalysts to reduce energy consumption and improve yield.
atureWorks™ polylactic acid (PLA) is the first family of polymers derived
entirely from annually renewable resources that can compete head-to-
head with traditional fibers and plastic packaging materials on a cost and
performance basis, for fiber consumers, this will mean a new option for
apparel and carpeting applications: a material that bridges the gap in
performance between conventional synthetic fibers and natural fibers
such as silk, wool, and cotton. Clothing made with NatureWorks™ fibers
features a unique combination of desirable attributes such as superior
hand, touch, and drape, wrinkle resistance, excellent moisture manage-
ment, and resilience. In packaging applications, consumers will have the
opportunity to use a material that is natural, compostable, and recyclable
without experiencing any tradeoffs in product performance.
The NatureWorks™ PLA process offers significant environmental benefits
in addition to the outstanding performance attributes of the polymer.
NatureWorks™ PLA products are made in a revolutionary new process
developed by Cargill Dow LLC that incorporates all 12 green chemistry
principles. The process consists of three separate and distinct steps that
lead to the production of lactic acid, lactide, and PLA high polymer. Each
of the process steps is free of organic solvent: water is used in the fer-
mentation while molten lactide and polymer serve as the reaction media
in monomer and polymer production. Each step not only has exception-
ally high yields (over 95 percent) but also utilizes internal recycle streams
to eliminate waste. Small (ppm) amounts of catalyst are used in both the
80 2002 Award
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lactide synthesis and polymerization to further enhance efficiency and
reduce energy consumption. Additionally, the lactic acid is derived from
annually renewable resources, PLA requires 20-50 percent less fossil
resources than comparable petroleum-based plastics, and PLA is fully
biodegradable or readily hydrolyzed into lactic acid for recycling back into
the process.
While the technology to create PLA in the laboratory has been known for
many years, previous attempts at large-scale production were targeted
solely at niche biodegradable applications and were not commercially
viable. Only now has Cargill Dow been able to perfect the NatureWorks™
process and enhance the physical properties of PLA resins to compete
successfully with commodity petroleum-based plastics. Cargill Dow is
currently producing approximately 8.8 million pounds of PLA per year
to meet immediate market development needs. Production in the first
world-scale 310-million-pound-per-year plant began November 1, 2001.
The NatureWorks™ process embodies the well-known principles of green
chemistry by preventing pollution at the source through the use of a
natural fermentation process to produce lactic acid, substituting annually
renewable materials for petroleum-based feedstock, eliminating the use
of solvents and other hazardous materials, completely recycling product
and byproduct streams, and efficiently using catalysts to reduce energy
consumption and improve yield. In addition, NatureWorks™ PLA products
can be either recycled or composted after use.
2002 Greener Reaction Conditions Award 81
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ACQ Preserve®: The Environmentally Advanced Wood Preservative
ACQ Preserve® is an environmentally advanced wood preservative de-
signed to replace chromated copper arsenate (CCA) wood preservatives,
which have been phased out because of their toxicity. ACQ Preserve® will
eliminate the use of 40 million pounds of arsenic and 64 million pounds of
hexavalent chromium each year. It also avoids the potential risks asso-
ciated with producing, transporting, using, and disposing of CCA wood
preservatives and CCA-treated wood.
he pressure-treated wood industry is a $4 billion industry, producing ap-
proximately 7 billion board feet of preserved wood per year. More than
95 percent of the pressure-treated wood used in the United States is cur-
rently preserved with chromated copper arsenate (CCA). Approximately
150 million pounds of CCA wood preservatives were used in the produc-
tion of pressure-treated wood in 2001, enough wood to build
435,000 homes. About 40 million pounds of arsenic and 64 million
pounds of chromium(VI) were used to manufacture these CCA wood
preservatives.
Over the past few years, scientists, environmentalists, and regulators
have raised concerns regarding the risks posed by the arsenic that is
either dislodged or leached from CCA-treated wood. A principal concern
is the risk to children from contact with CCA-treated wood in playground
equipment, picnic tables, and decks. This concern has led to increased
demand for and use of alternatives to CCA.
Chemical Specialties, Inc. (CSI) developed its alkaline copper quaternary
(ACQ) wood preservative as an environmentally advanced formula de-
signed to replace the CCA industry standard. ACQ formulations combine
a bivalent copper complex and a quaternary ammonium compound in a
2:1 ratio. The copper complex may be dissolved in either ethanolamine
82 2002 Award
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or ammonia. Carbon dioxide (CO2) is added to the formulation to im-
prove stability and to aid in solubilization of the copper.
Replacing CCA with ACQ is one of the most dramatic pollution prevention
advancements in recent history. Because more than 90 percent of the
44 million pounds of arsenic used in the United States each year is used
to make CCA, replacing CCA with ACQ will virtually eliminate the use of
arsenic in the United States. In addition, ACQ Preserve® will eliminate the
use of 64 million pounds of chromium(VI). Further, ACQ avoids the poten-
tial risks associated with the production, transportation, use, and disposal
of the arsenic and chromium(VI) contained in CCA wood preservatives
and CCA-treated wood. In fact, ACQ does not generate any RCRA (i.e., Re-
source Conservation and Recovery Act) hazardous waste from production
and treating facilities. The disposal issues associated with CCA-treated
wood and ash residues associated with the burning of treated wood will
also be avoided.
In 1996, CSI commercialized ACQ Preserve® in the United States. More
than one million active pounds of ACQ wood preservatives were sold in
the United States in 2001 for use by 13 wood treaters to produce over
100 million board feet of ACQ-preserved wood. In 2002, CSI plans to
spend approximately $20 million to increase its production capacity for
ACQ to over 50 million active pounds. By investing in ACQ technology,
CSI has positioned itself and the wood preservation industry to transi-
tion away from arsenic-based wood preservatives to a new generation of
preservative systems.
2002 Designing Safer Chemicals Award 83
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2001 Winners
Quasi-Mature Catalysis: Developing Transition Metal Catalysis in Air
and Water
Professor Li developed a novel method to carry out a variety of important
chemical reactions that had previously required both an oxygen-free
atmosphere and hazardous organic solvents. His reactions use metal
catalysts and run in open containers of water. His method is inherently
safer, requires fewer process steps, operates at lower temperatures, and
generates less waste.
he use of transition metals for catalyzing reactions is of growing impor-
tance in modern organic chemistry. These catalyses are widely used in
the synthesis of Pharmaceuticals, fine chemicals, petrochemicals, agri-
cultural chemicals, polymers, and plastics. Of particular importance is the
formation of C-C, C-O, C-N, and C-H bonds. Traditionally, the use of an
inert gas atmosphere and the exclusion of moisture have been essen-
tial in both organometallic chemistry and transition-metal catalysis. The
catalytic actions of transition metals in ambient atmosphere have played
key roles in various enzymatic reactions including biocatalysis, biodeg-
radation, photosynthesis, nitrogen fixation, and digestions, as well as
the evolution of bioorganisms. Unlike traditionally used transition-metal
catalysts, these "natural" catalytic reactions occur under aqueous condi-
tions in an air atmosphere.
The research of Professor Chao-Jun Li has focused on the development
of numerous transition-metal-catalyzed reactions both in air and wa-
ter. Specifically, Professor Li has developed a novel [3+2] cycloaddition
reaction to generate 5-membered carbocycles in water; a synthesis
of p-hydroxyl esters in water; a chemoselective alkylation and pinacol
coupling reaction mediated by manganese in water; and a novel alkyla-
tion of 1,3-dicarbonyl-type compounds in water. His work has enabled
84
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rhodium-catalyzed carbonyl addition and rhodium-catalyzed conjugate
addition reactions to be carried out in air and water for the first time. A
highly efficient, zinc-mediated Ullman-type coupling reaction catalyzed
by palladium in water has also been designed. This reaction is conducted
at room temperature under an atmosphere of air. In addition, a number
of Barbier-Grignard-type reactions in water have been developed; these
novel synthetic methodologies are applicable to the synthesis of a variety
of useful chemicals and compounds. Some of these reactions demon-
strate unprecedented chemoselectivity that eliminates byproduct forma-
tion and product separation. Application of these new methodologies to
natural product synthesis, including polyhydroxylated natural products,
medium-sized rings, and macrocyclic compounds, yields shorter reaction
sequences.
Transition-metal-catalyzed reactions in water and air offer many advantag-
es. Water is readily available and inexpensive; it is not flammable, explo-
sive, or toxic. Consequently, aqueous-based production processes are in-
herently safer with regard to accident potential. Using water as a reaction
solvent can save synthetic steps by avoiding protection and deprotection
processes that affect overall synthetic efficiency and contribute to solvent
emission. Product isolation may be facilitated by simple phase separation
rather than energy-intensive and organic-emitting processes involving
distillation of organic solvent. The temperature of reactions performed
in aqueous media is also easier to control since water has such a high
heat capacity. The open-air feature offers convenience in operations of
chemical synthesis involving small-scale combinatorial synthesis, large-
scale manufacturing, and catalyst recycling. As such, Professor Li's work in
developing transition-metal-mediated and -catalyzed reactions in air and
water offers an attractive alternative to the inert atmosphere and organic
solvents traditionally used in synthesis.
2001 Academic Award 85
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Messenger®: A Green Chemistry Revolution in Plant Production and
Food Safety
EDEN Bioscience Corporation discovered and commercialized harpins,
a new class of nontoxic, naturally occurring, biodegradable proteins, as
an alternative to traditional pesticides. Harpins activate a plant's defense
and growth mechanisms, thereby increasing crop yield and quality, and
minimizing crop losses. EDEN manufactures Messenger®, its commercially
available, harpin-containing, EPA-approved product, using a water-based
fermentation system.
In today's competitive agricultural environment, growers must maximize
crop productivity by enhancing yield and minimizing crop losses. The
Food and Agriculture Organization of the United Nations estimates that
annual losses to growers from pests reach $300 billion worldwide. In
addition to basic agronomic practices, growers generally have two alter-
natives to limit these economic losses and increase yields: (1) use tra-
ditional chemical pesticides; or (2) grow crops that are genetically engi-
neered for pest resistance. Each of these approaches has come under
increasing criticism from a variety of sources worldwide including environ-
mental groups, government regulators, consumers, and labor advocacy
groups. Harpin technology, developed by EDEN Bioscience Corporation,
provides growers with a highly effective alternative approach to crop
production that addresses these concerns.
EDEN's harpin technology is based on a new class of nontoxic, naturally
occurring proteins called harpins, which were first discovered by Dr.
Zhongmin Wei, EDEN's Vice President of Research, and his colleagues
during his tenure at Cornell University. Harpin proteins trigger a plant's
natural defense systems to protect against disease and pests and simulta-
neously activate certain plant growth systems without altering the plant's
DNA. When applied to crops, harpins increase plant biomass, photo-
86 2001 Award
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synthesis, nutrient uptake, and root development, and, ultimately, lead to
greater crop yield and quality.
Unlike most agricultural chemicals, harpin-based products are produced
in a water-based fermentation system that uses no harsh solvents or re-
agents, requires only modest energy inputs, and generates no hazardous
chemical wastes. Fermentation byproducts are fully biodegradable and
safely disposable. In addition, EDEN uses low-risk ingredients to formulate
the harpin protein-based end product. Approximately 70 percent of the
dried finished product consists of an innocuous, food-grade substance
that is used as a carrier for harpin protein.
The result of this technology is an EPA-approved product called Messen-
ger® that has been demonstrated on more than 40 crops to effectively
stimulate plants to defend themselves against a broad spectrum of viral,
fungal, and bacterial diseases, including some for which there currently
is no effective treatment. In addition, Messenger® has been shown
through an extensive safety evaluation to have virtually no adverse effect
on any of the organisms tested, including mammals, birds, honey bees,
plants, fish, aquatic invertebrates, and algae. Only 0.004-0.14 pounds
of harpin protein per acre per season is necessary to protect crops and
enhance yields. As with most proteins, harpin is a fragile molecule that is
degraded rapidly by UVand natural microorganisms and has no potential
to bioaccumulate or to contaminate surface or groundwater resources.
Deployment of harpin technology conserves resources and protects the
environment by reducing total agricultural inputs and partially replacing
many higher-risk products. Using environmentally benign harpin protein
technology, growers for the first time in the history of modern agriculture
will be able to harness the innate defense and growth systems of crops
to substantially enhance yields, improve crop quality, and reduce reliance
on conventional agricultural chemicals.
2001 Small Business Award 87
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Baypure™ CX (Sodium Iminodisuccinate): An Environmentally Friendly
and Readily Biodegradable Chelating Agent
Chelating agents are ingredients in a variety of products, such as deter-
gents, fertilizers, and household and industrial cleaners. Most traditional
chelating agents do not break down readily in the environment. Bayer Cor-
poration and Bayer AG developed a waste-free, environmentally friendly
manufacturing process for a new, biodegradable, nontoxic chelating
agent. This new process eliminates the use of formaldehyde and hydrogen
cyanide.
••• helating agents are used in a variety of applications, including deter-
gents, agricultural nutrients, and household and industrial cleaners. Most
traditional chelating agents, however, are poorly biodegradable. Some
are actually quite persistent and do not adsorb at the surface of soils in
the environment or at activated sludge in wastewater treatment plants.
Because of this poor biodegradability combined with high water solubil-
ity, traditional chelators are readily released into the environment and
have been detected in the surface waters of rivers and lakes and in make-
up water processed for drinking water.
As part of its commitment to Responsible Care®, Bayer Corporation man-
ufactures a readily biodegradable and environmentally friendly chelating
agent, D,L-aspartic-/V-(1,2-dicarboxyethyl) tetrasodium salt, also known as
sodium iminodisuccinate. This agent is characterized by excellent chela-
tion capabilities, especially for iron(lll), copper(ll), and calcium, and is
both readily biodegradable and benign from a toxicological and eco-
toxicological standpoint. Sodium iminodisuccinate is also an innovation
in the design of chemicals that favorably impact the environment. This
accomplishment was realized not by "simple" modification of molecular
structures of currently used chelating agents, but instead by the develop-
as 2001 Award
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merit of a wholly new molecule. Sodium iminodisuccinate is produced
by a 100 percent waste-free and environmentally friendly manufacturing
process. Bayer AG was the first to establish an environmentally friendly,
patented manufacturing process to provide this innovative chelant com-
mercially.
Sodium iminodisuccinate belongs to the aminocarboxylate class of
chelating agents. Nearly all aminocarboxylates in use today are acetic
acid derivatives produced from amines, formaldehyde, sodium hydroxide,
and hydrogen cyanide. The industrial use of thousands of tons of hydro-
gen cyanide is an extreme toxicity hazard. In contrast, Bayer's sodium
iminodisuccinate is produced from maleic anhydride (a raw material also
produced by Bayer), water, sodium hydroxide, and ammonia. The only
solvent used in the production process is water, and the only side prod-
uct formed, ammonia dissolved in water, is recycled back into sodium
iminodisuccinate production or used in other Bayer processes.
Because sodium iminodisuccinate is a readily biodegradable, nontoxic,
and nonpolluting alternative to other chelating agents, it can be used
in a variety of applications that employ chelating agents. For example, it
can be used as a builder and bleach stabilizer in laundry and dishwash-
ing detergents to extend and improve the cleaning properties of the
eight billion pounds of these products that are used annually. Specifically,
sodium iminodisuccinate chelates calcium to soften water and improve
the cleaning function of the surfactant. In photographic film processing,
sodium iminodisuccinate complexes metal ions and helps to eliminate
precipitation onto the film surface. In agriculture, chelated metal ions
help to prevent, correct, and minimize crop mineral deficiencies. Using
sodium iminodisuccinate as the chelating agent in agricultural applica-
tions eliminates the problem of environmental persistence common with
other synthetic chelating agents. In summary, Bayer's sodium iminodisuc-
cinate chelating agent offers the dual benefits of producing a biodegrad-
able, environmentally friendly chelating agent that is also manufactured
in a waste-free process.
2001 Greener Synthetic Pathways Award 89
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BioPreparation™ of Cotton Textiles: A Cost-Effective, Environmentally
Compatible Preparation Process
Novozymes North America developed BioPreparation™, a technology
to separate natural waxes, oils, and contaminants from cotton before it
is made into fabric. This technology uses enzymes instead of corrosive
chemicals and could save 7-12 billion gallons of water each year.
^n textiles, the source of one of the most negative impacts on the en-
vironment originates from traditional processes used to prepare cotton
fiber, yarn, and fabric. Fabric preparation consists of a series of various
treatments and rinsing steps critical to obtaining good results in subse-
quent textile finishing processes. These water-intensive, wet processing
steps generate large volumes of wastes, particularly from alkaline scour-
ing and continuous/batch dyeing. These wastes include large amounts
of salts, acids, and alkali. In view of the 40 billion pounds of cotton fiber
that are prepared annually on a global scale, it becomes clear that the
preparation process is a major source of environmentally harsh chemical
contribution to the environment.
Cotton wax, a natural component in the outer layer of cotton fibers, is
a major obstacle in processing textiles; it must be removed to prepare
the textile for dyeing and finishing. Conventional chemical preparation
processes involve treatment of the cotton substrate with hot solutions
of sodium hydroxide, chelating agents, and surface active agents, often
followed by a neutralization step with acetic acid. The scouring process is
designed to breakdown or release natural waxes, oils, and contaminants
and emulsify or suspend these impurities in the scouring bath. Typically,
scouring wastes contribute high biological oxygen demand (BOD) loads
during cotton textile preparation (as much as 50 percent).
Novozymes's BioPreparation™ technology is an alternative to sodium
hydroxide that offers many advantages for textile wet processing, includ-
90 2001 Award
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ing reduced biological and chemical oxygen demand (BOD/COD) and
decreased water use. BioPreparation™ is an enzymatic process for treat-
ing cotton textiles that meets the performance characteristics of alkaline
scour systems while reducing chemical and effluent load. Pectate lyase
is the main scouring agent that degrades pectin to release the entangled
waxes and other components from the cotton surface. The enzyme is
also compatible with other enzymatic preparations (amylases, cellulases)
used to improve the performance properties of cotton fabrics.
The practical implications that BioPreparation™ technology has on the
textile industry are realized in terms of conservation of chemicals, water,
energy, and time. Based on field trials, textile mills may save as much as
30-50 percent in water costs by replacing caustic scours or by combin-
ing the usually separate scouring and dyeing steps into one. This water
savings results because BioPreparation™ uses fewer rinsing steps than
required during a traditional caustic scour. Significant time savings were
also demonstrated by combining treatment steps. A recent statistical
survey determined that 162 knitting mills typically use 24 billion gallons
per year of water in processing goods from scouring to finishing; the
BioPreparation™ approach would save from 7-12 billion gallons per year
of water. In addition, field trials established that BOD and COD loads are
decreased by 25 and 40 percent, respectively, when compared to con-
ventional sodium hydroxide treatments. Furthermore, these conservation
measures translate directly into cost savings of 30 percent or more. As
such, this patented process provides an economical and environmentally
friendly alternative to alkaline scour systems currently used in the textile
industry.
2001 Greener Reaction Conditions Award 91
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Yttrium as a Lead Substitute in Cationic Electrodeposition Coatings
PPG Industries developed a novel metal primer that uses yttrium instead
of lead to resist corrosion in automobiles. The metal yttrium is far less toxic
to human health and the environment than is lead and is more effective
in preventing corrosion. PPG's primer should eliminate one million pounds
of lead from automobile manufacture over the next few years. In addition,
this primer does not require chromium- or nickel-based pretreatments,
potentially eliminating the use of 25,000 pounds of chromium and
50,000 pounds of nickel each year.
i 'PG Industries introduced the first cationic electrodeposition primer to
the automotive industry in 1976. During the succeeding years, this coat-
ing technology became very widely used in the industry such that today
essentially all automobiles are given a primer coat using the chemistry
and processing methods developed by PPG. The major benefits of this
technology are corrosion resistance, high transfer efficiency (low waste),
reliable automated application, and very low organic emissions. Unfortu-
nately, the high corrosion resistance property of electrocoat has always
been dependent on the presence of small amounts of lead salts or lead
pigments in the product. As regulatory pressure on lead increased and
consumer demand for improved corrosion resistance grew, lead was
regularly exempted from regulation in electrocoat because there were
no cost-effective substitutes. This is especially important in moderately
priced cars and trucks where the high cost of using 100 percent zinc-
coated (galvanized) steel could not be tolerated. Lead is very effective for
protecting cold-rolled steel, which is still a common material of construc-
tion in automobiles.
For more than 20 years, PPG and other paint companies have sought a
substitute for lead in this application. This search led to PPG's discovery
that yttrium can replace lead in cationic electrocoat without any sacrifice
in corrosion performance. Yttrium is a common element in the environ-
92 2001 Award
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ment, being widely distributed in low concentrations throughout the
earth's crust and more plentiful in the earth's crust than lead and silver.
Although yttrium is much less studied than lead, the available data on
yttrium indicate orders of magnitude lower hazard. As a dust hazard, yt-
trium is 100 times safer than lead at typical levels of use.
Numerous other benefits are realized when yttrium is used in electrocoat
applications. Yttrium is twice as effective as lead on a weight basis, allow-
ing the formulation of commercial coatings that contain half the yttrium
by weight relative to lead in comparably performing lead-containing
products. In addition, it has been found that as yttrium is deposited in an
electrocoat film, it deposits as the hydroxide. The hydroxide is converted
to yttrium oxide during normal baking of the electrocoat. The oxide is
extraordinarily nontoxic by ingestion as indicated by the LD50of over
10 grams per kilogram in rats, which is in stark contrast to lead. The ubiq-
uitous nature of yttrium in the environment and the insoluble ceramic-
like nature of the oxide combine to make it an unlikely cause of future
environmental or health problems.
An environmental side benefit of yttrium is its performance over low-
nickel and chrome-free metal pretreatments. In automotive production,
a metal pretreatment is always applied to the body prior to electrocoat,
which is designed to assist in adhesion and corrosion performance. This
process generates significant quantities of chromium-and nickel-contain-
ing waste and, like lead, is also a concern to recyclers of the finished ve-
hicle. By using yttrium in the electrocoat step, chrome can be completely
eliminated using standard chrome-free rinses and low-nickel or possibly
nickel-free pretreatments, both of which are commercially available today.
This should be possible without concern of compromising long-term
vehicle corrosion performance. For PPG pretreatment customers, this
should result in the elimination of up to 25,000 pounds of chrome and
50,000 pounds of nickel annually from PPG products. As PPG customers
implement yttrium over the next several years, approximately one million
pounds of lead (as lead metal) will be removed from the electrocoat ap-
plications of PPG automotive customers.
2001 Designing Greener Chemicals Award 93
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2000 Winners
Enzymes in Large-Scale Organic Synthesis
Professor Wong developed methods to replace traditional reactions requir-
ing toxic metals and hazardous solvents. His methods use enzymes,
environmentally acceptable solvents, and mild reaction conditions. His
methods also enable novel reactions that were otherwise impossible or
impractical on an industrial scale. Professor Wong's methods hold promise
for applications in a wide variety of chemical industries.
'. Jrganic synthesis has been one of the most successful of scientific
disciplines and has contributed significantly to the development of the
pharmaceutical and chemical industries. New synthetic reagents, catalysts,
and processes have made possible the synthesis of molecules with vary-
ing degrees of complexity. The types of problems at which nonbiological
organic synthesis has excelled, ranging from stoichiometric reactions to
catalysis with acids, bases, and metals, will continue to be very important.
New synthetic and catalytic methods are, however, necessary to deal with
the new classes of compounds that are becoming the key targets of mo-
lecular research and development.
Compounds with polyfunctional groups such as carbohydrates and related
structures pose particular challenges to nonbiological synthetic meth-
ods but are natural targets for biological methods. In addition, biological
methods are necessary to deal with increasing environmental concerns.
Transition metals, heavy elements, and toxic organic solvents are often
used in nonbiological processes. When these materials are used with great
care and efficiency, they may still be environmentally acceptable, but their
handling and disposal pose problems. The ability to use recombinant and
engineered enzymes to carry out environmentally acceptable synthetic
transformations that are otherwise impossible or impractical offers one of
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the best opportunities now available to chemistry and the pharmaceuti-
cal industry.
Professor Chi-Huey Wong at the Scripps Research Institute has pioneered
work on the development of effective enzymes and the design of novel
substrates and processes for large-scale organic synthesis. The methods
and strategies that Professor Wong has developed have made possible
synthetic transformations that are otherwise impossible or impractical,
especially in areas vitally important in biology and medicine, and have
pointed the way toward new green methodologies for use in large-scale
chemistry. A recent study by the Institute for Scientific Information ranked
Professor Wong in the top 15 of the most-cited chemists in the world for
the period 1994 to 1996. According to this study, he is also the most-cited
chemist worldwide working in the area of enzymes.
Some of the strategies and methods developed by Professor Wong are
breakthrough achievements that laid the framework for much of the
current use of enzymes as catalysts in large-scale organic synthesis. The
techniques and reagents developed in this body of pioneering work are
used widely today for research and development. The scope of contribu-
tions ranges from relatively simple enzymatic processes (e.g., chiral reso-
lutions and stereoselective syntheses) to complex, multistep enzymatic
reactions (e.g., oligosaccharide synthesis). For example, the irreversible
enzymatic transesterification reaction using enol esters in environmen-
tally acceptable organic solvents invented by Professor Wong represents
the most widely used method for enantioselective transformation of
alcohols in pharmaceutical development. The multi-enzyme system
based on genetically engineered glycosyltransferases coupled with in
situ regeneration of sugar nucleotides developed by Professor Wong has
revolutionized the field of carbohydrate chemistry and enabled the large-
scale synthesis of complex oligosaccharides for clinical evaluation. All of
these new enzymatic reactions are carried out in environmentally accept-
able solvents, under mild reaction conditions, at ambient temperature,
and with minimum protection of functional groups. The work of Professor
Wong represents a new field of green chemistry suitable for large-scale
synthesis that is impossible or impractical to achieve by nonenzymatic
means.
2000 Academic Award 95
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Envirogluv™: A Technology for Decorating Glass and Ceramicware with
Radiation-Curable, Environmentally Compliant Inks
RevTech developed the Envirogluv™ process to print top-quality labels di-
rectly on glass, replacing paper labels, decals, or applied ceramic labeling.
Envirogluv™ inks do not contain heavy metals, contain little to no volatile
organic compounds (VOCs), and are biodegradable. This technology saves
energy by replacing high-temperature ovens with ultraviolet light, saves
raw materials, wastes no ink, and produces decorated glass that is com-
pletely recyclable.
' illions of products are sold in glass containers in the United States
every year. Most, if not all, of these glass containers are labeled in some
fashion. Typically, decorative indicia are applied to glass using paper
labels, decals, or a process known as applied ceramic labeling (ACL). ACL
involves first printing the glass with an ink composition that contains vari-
ous heavy metals such as lead, cadmium, and chromium, then bonding
the ink to the glass by baking in an oven known as a lehr at temperatures
of 1,000 ° For more for several hours.
All of these processes have disadvantages. Paper labels are inexpensive
but can be easily removed if the container is exposed to water or abra-
sion. In addition, paper labels do not provide the aesthetics desired
by decorators who want rich, expensive-looking containers. Decals are
expensive and difficult to apply at the high line speeds that are required
in the decoration of most commercial containers. More important, decals
are made from materials that are not biodegradable, which causes seri-
ous problems in the recycling of glass containers that are decorated by
this method. The use and disposal of the heavy metals required in ACL
presents serious environmental concerns. Moreover, the high-tempera-
ture lehr ovens required in ACL decorating utilize substantial amounts of
energy and raise safety issues with respect to workers and plant facilities
that use this equipment. The inks used in ACL decorating also tend to
96 2000 Award
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contain high levels of volatile organic compounds (VOCs) that can lead to
undesirable emissions.
Clearly, there has been a need in the glass decorating industry for a deco-
rated glass container that is aesthetically pleasing, durable, and obtained
in a cost-effective, environmentally friendly, and energy-efficient manner.
Envirogluv™ technology fills that need. Envirogluv™ is a glass decorating
technology that directly silk-screens radiation-curable inks onto glass, then
cures the ink almost instantly by exposure to UV light. The result is a crisp,
clean label that is environmentally sound, with a unit cost that is about
half that of traditional labeling.
Envirogluv™ technology offers many human health and environmental
benefits. The ink compositions used in the Envirogluv™ process do not
contain any heavy metals and contain little to no VOCs. All Envirogluv™
pigments are biodegradable. The Envirogluv™ inks are cured directly on
the glass by exposure to UV radiation, eliminating the high-temperature
baking in a lehr oven that is associated with the ACL process. This pro-
vides additional safety and environmental benefits, such as reduced
energy consumption and reduced chance of worker injury. In addition,
the process uses less raw materials and does not generate any waste ink.
Furthermore, Envirogluv™ decorated glass containers eliminate the need
for extra packaging and are completely recyclable. Applications suitable
for the Envirogluv™ process include tableware, cosmetics containers, and
plate glass.
2000 Small Business Award 97
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An Efficient Process for the Production of Cytovene®, a Potent Antiviral
Agent
Roche Colorado developed an environmentally friendly way to synthesize
Cytovene®, a potent antiviral drug. Their process eliminates nearly 2.5 mil-
lion pounds of hazardous liquid waste and over 55,000 pounds of hazard-
ous solid waste each year. This process also increases the overall yield
more than 25 percent and doubles the production throughput.
i he design, development, and implementation of environmentally
friendly processes for the large-scale production of pharmaceutical prod-
ucts is one of the most technically challenging aspects of business opera-
tions in the pharmaceutical industry. Roche Colorado Corporation (RCC),
in establishing management and operational systems for the continuous
improvement of environmental quality in its business activities, has, in
essence, adopted the Presidential Green Chemistry Challenge Program's
basic principles of green chemistry: the development of environmentally
friendly processes for the manufacture of pharmaceutical products. In
particular, RCC has successfully applied these principles to the manufac-
ture of ganciclovir, the active ingredient in Cytovene®, a potent antiviral
agent. Cytovene® is used in the treatment of cytomegalovirus (CMV)
retinitis infections in immunocompromised patients, including patients
with AIDS, and also used for the prevention of CMV disease in transplant
recipients at risk for CMV.
In the early 1990s, Roche Colorado Corporation developed the first com-
mercially viable process for the production of Cytovene®. By 1993, chem-
ists at RCC's Boulder Technology Center designed a new and expedient
process for the production of Cytovene®, which at the time had an
estimated commercial demand of approximately 110,000 pounds per
year. Leveraging the basic principles of green chemistry and molecular
conservation into the design process, significant improvements were
demonstrated in the second-generation Guanine Triester (GTE) Process.
98 2000 Award
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Compared to the first-generation commercial manufacturing process, the
GTE Process reduced the number of chemical reagents and intermediates
from 22 to 11, eliminated the (only) two hazardous solid waste streams,
eliminated 11 different chemicals from the hazardous liquid waste
streams, and efficiently recycled and reused four of the five ingredients
not incorporated into the final product. Inherent within the process im-
provements demonstrated was the complete elimination of the need for
operating and monitoring three different potentially hazardous chemical
reactions. Overall, the GTE Process provided an expedient method for the
production of Cytovene®, demonstrating a procedure that provided an
overall yield increase of more than 25 percent and a production through-
put increase of 100 percent.
In summary, the new GTE Process for the commercial production of Cyto-
vene® clearly demonstrates the successful implementation of the gen-
eral principles of green chemistry: the development of environmentally
friendly syntheses, including the development of alternative syntheses
utilizing nonhazardous and nontoxic feedstocks, reagents, and solvents;
elimination of waste at the source (liquid waste: 2.5 million pounds per
year and solid waste: 56,000 pounds per year); and elimination of the
production of toxic wastes and byproducts. The process establishes new
and innovative technology for a general and efficient method for the
preparation of Cytovene® and other potent antiviral agents. It is regis-
tered with the U.S. Food and Drug Administration (FDA) as the current
manufacturing process for the world's supply of Cytovene®.
2000 Greener Synthetic Pathways Award 99
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Two-Component Waterborne Polyurethane Coatings
Bayer developed a series of high-performance, water-based, two-com-
ponent polyurethane coatings that eliminate most or all of the organic
solvents used in conventional polyurethane coatings. Bayer's water-based
polyurethane coatings reduce volatile organic compound (VOC) and haz-
ardous air pollutant (HAP) emissions by 50-90 percent.
i wo-component (2K) waterborne polyurethane coatings are an out-
standing example of the use of alternative reaction conditions for green
chemistry. This technology is achieved by replacing most or all of the
volatile organic compounds (VOCs) and hazardous air pollutants (HAPs)
used in conventional 2Ksolventborne polyurethane coatings with water
as the carrier, without significant reduction in performance of the result-
ing coatings. This may seem an obvious substitution, but, due to the
particular chemistry of the reactive components of polyurethane, it is not
that straightforward.
Two-component solventborne polyurethane coatings have long been
considered in many application areas to be the benchmark for high-
performance coatings systems. The attributes that make these systems so
attractive are fast cure under ambient or bake conditions, high-gloss and
mirror-like finishes, hardness or flexibility as desired, chemical and solvent
resistance, and excellent weathering. The traditional carrier, however, has
been organic solvent that, upon cure, is freed to the atmosphere as VOC
and HAP material. High-solids systems and aqueous polyurethane disper-
sions ameliorate this problem but do not go far enough.
An obvious solution to the deficiencies of 2K solventborne polyurethanes
and aqueous polyurethane dispersions is a reactive 2K polyurethane
system with water as the carrier. In order to bring 2K waterborne polyure-
thane coatings to the U.S. market, new waterborne and water-reducible
100 2000 Award
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resins had to be developed. To overcome some application difficulties,
new mixing/spraying equipment was also developed. For the technol-
ogy to be commercially viable, an undesired reaction of a polyisocyanate
cross-linker with water had to be addressed, as well as problems with the
chemical and film appearance resulting from this side reaction. The work
done on the 2K waterborne polyurethanes over the past several years
has resulted in a technology that will provide several health and environ-
mental benefits. VOCs will be reduced by 50-90 percent and HAPs by
50-99 percent. The amount of chemical byproducts evolved from films
in interior applications will also be reduced, and rugged interior coatings
with no solvent smell will now be available.
Today, 2K waterborne polyurethane is being applied on industrial lines
where good properties and fast cure rates are required for such varied
products as metal containers and shelving, sporting equipment, metal-
and fiberglass-reinforced utility poles, agricultural equipment, and paper
products. In flooring coatings applications where the market-driving force
is elimination of solvent odor, 2 K waterborne polyurethane floor coatings
provide a quick dry, high abrasion resistance, and lack of solvent smell
(<0.1 pound organic solvent per gallon). In wood applications, 2K water-
borne polyurethane coatings meet the high-performance wood finishes
requirements for kitchen cabinet, office, and laboratory furniture manu-
facturers while releasing minimal organic solvents in the workplace or
to the atmosphere. In the United States, the greatest market acceptance
of 2 K waterborne polyurethane is in the area of special-effect coatings
in automotive applications. These coatings provide the soft, luxurious
look and feel of leather to hard plastic interior automobile surfaces, such
as instrument panels and air bag covers. Finally, in military applications,
2K waterborne polyurethane coatings are being selected because they
meet the demanding military performance criteria that include flat coat-
ings with camouflage requirements, corrosion protection, chemical and
chemical agent protection, flexibility, and exterior durability, along with
VOC reductions of approximately 50 percent.
2000 Greener Reaction Conditions Award 101
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Sentricon™ Termite Colony Elimination System, A New Paradigm for
Termite Control
Dow's Sentricon™ System eliminates termite colonies with highly specific
bait applied only where termites are active; it replaces widespread appli-
cations of pesticide in the soil around houses and other structures. EPA has
registered Sentricon™ as a reduced-risk pesticide. Dow's system reduces
the use of hazardous materials and reduces potential impacts on human
health and the environment. By Iate1999, Sentricon™ was used for over
300,000 structures in the United States.
he annual cost of termite treatments to the U.S. consumer is about
$1.5 billion, and each year as many as 1.5 million homeowners will experi-
ence a termite problem and seeka control option. From the 1940s until
1995, the nearly universal treatment approach for subterranean termite
control involved the placement of large volumes of insecticide dilutions
into the soil surrounding a structure to create a chemical barrier through
which termites could not penetrate. Problems with this approach include
difficulty in establishing an uninterrupted barrier in the vast array of soil
and structural conditions, use of large volumes of insecticide dilution,
and potential hazards associated with accidental misapplications, spills,
off-target applications, and worker exposure. These inherent problems
associated with the use of chemical barrier approaches for subterranean
termite control created a need for a better method. The search for a bait-
ing alternative was the focus of a research program established by Dr.
Nan-Yao Su of the University of florida who, in the 1980s, had identified
the characteristics needed for a successful termite bait toxicant.
The unique properties of hexaflumuron made it an excellent choice for
use in controlling subterranean termite colonies. The Sentricon™ Termite
Colony Elimination System, developed by Dow AgroSciences in collabora-
tion with Dr. Su, was launched commercially in 1995 after receiving EPA
registration as a reduced-risk pesticide. Sentricon™ represents truly novel
102 2000 Award
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technology employing an Integrated Pest Management approach using
monitoring and targeted delivery of a highly specific bait. Because it elim-
inates termite colonies threatening structures using a targeted approach,
Sentricon™ delivers unmatched technical performance, environmental
compatibility, and reduced human risk. The properties of hexaflumuron
as a termite control agent are attractive from an environmental and
human risk perspective, but more important, the potential for adverse
effects is dramatically reduced because it is present only in very small
quantities in stations with termite activity. The comparisons to barrier
methods show significant reduction in the use of hazardous materials
and substantial reduction in potential impacts on human health and the
environment.
The discovery of hexaflumuron's activity with its unique fit and applica-
bility for use as a termite bait was a key milestone for the structural pest
control industry and Dow AgroSciences. The development and commer-
cial launch of Sentricon™ changed the paradigm for protecting structures
from damage caused by subterranean termites. The development of nov-
el research methodologies, new delivery systems, and the establishment
of an approach that integrates monitoring and baiting typify the innova-
tion that has been a hallmark of the project. More than 300,000 structures
across the United States are now being safeguarded through application
of this revolutionary technology, and adoption is growing rapidly.
) Designing Greener Chemicals Award 103
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1999 Winners
TAML™ Oxidant Activators: General Activation of Hydrogen Peroxide
for Green Oxidation Technologies
Professor Collins developed a series of activator chemicals that work with
hydrogen peroxide to replace chlorine bleaches. His TAML™ activators
have many potential uses that include preparing wood pulp for paper-
making and removing stains from laundry. This novel, environmentally
benign technology eliminates chlorinated byproducts from wastewater
streams and saves both energy and water.
^n nature, selectivity is achieved through complex mechanisms using a
limited set of elements available in the environment. In the laboratory,
chemists prefer a simpler design that utilizes the full range of the peri-
odic table. The problem of persistent pollutants in the environment can
be minimized by employing reagents and processes that mimic those
found in nature. By developing a series of activators effective with the
natural oxidant, hydrogen peroxide, Professor Terry Collins has devised
an environmentally-benign oxidation technique with widespread appli-
cations. TAML™ activators (tetraamido-macrocyclic ligand activators) are
iron-based and contain no toxic functional groups. These activators offer
significant technology breakthroughs in the pulp and paper industry and
the laundry field.
The key to quality papermaking is the selective removal of lignin from the
white fibrous polysaccharides, cellulose, and hemicellulose. Wood pulp
delignification has traditionally relied on chlorine-based processes that
produce chlorinated pollutants. Professor Collins has demonstrated that
TAML™ activators effectively catalyze hydrogen peroxide in the selective
delignification of wood pulp. This is the first low-temperature peroxide
oxidation technique for treating wood pulp, which translates to energy
savings for the industry. Environmental compliance costs may be expect-
104
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ed to decrease with this new approach because chlorinated organicsare
not generated in this totally chlorine-free process.
TAML™ activators may also be applied to the laundry field, where most
bleaches are based on peroxide. When bound to fabric, most commercial
dyes are unaffected by the TAML™-activated peroxide. However, random
dye molecules that "escape" the fabric during laundering are intercepted
and destroyed by the activated peroxide before they have a chance to
transfer to other articles of clothing. This technology prevents dye-transfer
accidents while offering improved stain-removal capabilities. Washing
machines that require less water will be practical when the possibility of
dye-transfer is eliminated.
An active area of investigation is the use of TAML™ peroxide activators for
water disinfection. Ideally, the activators would first kill pathogens in the
water sample, then destroy themselves in the presence of a small excess
of peroxide. This protocol could have global applications, from develop-
ing nations to individual households.
The versatility of the TAML™ activators in catalyzing peroxide has been
demonstrated in the pulp and paper and laundry industries. Environ-
mental benefits include decreased energy requirements, elimination of
chlorinated organics from the waste stream, and decreased water use.
The development of new activators and new technologies will provide
environmental advantages in future applications.
1999 Academic Award 105
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Conversion of Low-Cost Biomass Wastes to Levulinic Acid and Derivatives
Biofine developed a process to convert the waste cellulose in paper mill
sludge, municipal solid waste, unrecyclable waste paper, waste wood, and
agricultural residues into levulinic acid (LA). LA can be used as a building
block for many other useful chemicals. LA made from waste cellulose
reduces the use of fossil fuels and reduces the overall cost of LA from
$4-6 per pound to as little as $0.32 per pound.
'Replacing petroleum-based feedstocks with renewable ones is a crucial
step toward achieving sustainability. When considering alternatives to
traditional feedstocks, attention often focuses on plant-based materi-
als. Renewable biomass conserves our dwindling supplies of fossil fuels
and contributes no net CO2 to the atmosphere. Biofine has developed a
high-temperature, dilute-acid hydrolysis process that converts cellulosic
biomass to levulinic acid (LA) and derivatives. Cellulose is initially con-
verted to soluble sugars, which are then transformed to levulinic acid. By-
products in the process include furfural, formic acid, and condensed tar,
all of which have commercial value as commodities or fuel, feedstocks
used include paper mill sludge, municipal solid waste, unrecyclable waste
paper, waste wood, and agricultural residues.
Levulinic acid serves as a building block in the synthesis of useful
chemical products. Markets already exist for tetrahydrofuran, succinic
acid, and diphenolic acid, all of which are levulinic acid derivatives. The
use of diphenolic acid (DPA) as a monomer for polycarbonates and
epoxy resins is currently under investigation. An industry/government
consortium has conducted research on two additional derivatives with
commercial value: methyltetrahydrofuran (MTHF), a fuel additive, and
5-amino levulinic acid (DALA), a pesticide.
The conversion of levulinic acid to MTHF is accomplished at elevated
temperature and pressure using a catalytic hydrogenation process. MTHF
106 1999 Award
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is a fuel additive that is miscible with gasoline and hydrophobic, allowing
it to be blended at the refinery rather than later in the distribution proc-
ess. Using MTHF as a fuel additive increases the oxygenate level in gaso-
line without adversely affecting engine performance. MTHF also boasts a
high octane rating (87) and a lower vapor pressure, thereby reducing fuel
evaporation and improving air quality.
DALA can be obtained from levulinic acid in high yield using a three-step
process. DALA is a broad-spectrum pesticide that is nontoxic and bio-
degradable. Its activity is triggered by light, selectively killing weeds while
leaving most major crops unaffected. DALA also shows potential as an
insecticide.
Diphenolic acid is synthesized by reacting levulinic acid with phenol. DPA
has the potential to displace bisphenol-A, a possible endocrine disrupter,
in polymer applications. Brominated DPA shows promise as an environ-
mentally-acceptable marine coating, while dibrominated DPA may find
use as a fire retardant.
Currently, levulinic acid has a worldwide market of about one million
pounds per year at a price of $4-6 per pound. Large-scale commerciali-
zation of the Biofine process could produce levulinic acid for as little as
$0.32 per pound, spurring increased demand for LA and its derivatives.
Using the Biofine process, waste biomass can be transformed into valua-
ble chemical products. The ability to produce levulinic acid economically
from waste biomass and renewable feedstocks is the key to increased
commercialization of LA and its derivatives.
1999 Small Business Award 107
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Practical Application of a Biocatalyst in Pharmaceutical Manufacturing
Lilly Research Laboratories developed a novel, low-waste process for drug
synthesis. One key aspect uses yeast to replace a chemical reaction.
Applying its process, Lilly eliminates approximately 41 gallons of solvent
and 3 pounds of chromium waste for every pound of a drug candidate
that it manufactures. Lilly's process also improves worker safety and
increases product yield from 16 to 55 percent.
i he synthesis of a pharmaceutical agent is frequently accompanied by
the generation of a large amount of waste. This should not be surprising,
as numerous steps are commonly necessary, each of which may require
feedstocks, reagents, solvents, and separation agents. Lilly Research
Laboratories has redesigned its synthesis of an anticonvulsant drug can-
didate, LY300164. This pharmaceutical agent is being developed for the
treatment of epilepsy and neurodegenerative disorders.
The synthesis used to support clinical development of the drug candi-
date proved to be an economically viable process, although several steps
proved problematic. A large amount of chromium waste was generated,
an additional activation step was required, and the overall process re-
quired a large volume of solvent. Significant environmental improve-
ments were realized upon implementing the new synthetic strategy.
Roughly 9,000 gallons of solvent and 660 pounds of chromium waste
were eliminated for every 220 pounds of LY300164 produced. Only three
of the six intermediates generated were isolated, limiting worker expo-
sure and decreasing processing costs. The synthetic scheme proved more
efficient as well, with percent yield climbing from 16 to 55 percent.
The new synthesis begins with the biocatalytic reduction of a ketone to
an optically pure alcohol. The yeast Zygosaccharomyces rouxii demon-
strated good reductase activity but was sensitive to high product con-
centrations. To circumvent this problem, a novel three-phase reaction
108 1999 Award
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design was employed. The starting ketone was charged to an aqueous
slurry containing a polymeric resin, buffer, and glucose, with most of the
ketone adsorbed on the surface of the resin. The yeast reacted with the
equilibrium concentration of ketone remaining in the aqueous phase.
The resulting product was adsorbed onto the surface of the resin, sim-
plifying product recovery. All of the organic reaction components were
removed from the aqueous waste stream, permitting the use of conven-
tional wastewater treatments.
A second key step in the synthesis was selective oxidation to eliminate
the unproductive redox cycle present in the original route. The reaction
was carried out using dimethylsulfoxide, sodium hydroxide, and com-
pressed air, eliminating the use of chromium oxide, a possible carcino-
gen, and preventing the generation of chromium waste. The new proto-
col was developed by combining innovations from chemistry, microbiolo-
gy, and engineering. Minimizing the number of changes to the oxidation
state improved the efficiency of the process while reducing the amount
of waste generated. The alternative synthesis presents a novel strategy
for producing 5/-/-2,3-benzodiazepines. The approach is general and has
been applied to the production of other anticonvulsant drug candidates.
The technology is low-cost and easily implemented; it should have broad
applications within the manufacturing sector.
1999 Greener Synthetic Pathways Award 109
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The Development and Commercialization of ULTIMER®: The First of a
New Family of Water-Soluble Polymer Dispersions
The Nalco Chemical Company developed a novel way to synthesize the
polymers used to treat water in a variety of industrial and municipal opera-
tions. Nalco now manufactures these polymers in water, replacing the tra-
ditional water-in-oil mixtures and preventing the release of organic solvents
and other chemicals into the environment.
: ligh-molecular-weight polyacrylamides are commonly used as process
aids and water treatment agents in various industrial and municipal op-
erations. Annually, at least 200 million pounds of water-soluble, acrylam-
ide-based polymers are used to condition and purify water. These water-
soluble polymers assist in removing suspended solids and contaminants
and effecting separations. Traditionally, these polymers are produced as
water-in-oil emulsions. Emulsions are prepared by combining the mono-
mer, water, and a hydrocarbon oil-surfactant mixture in approximately
equal parts. Although the oil and surfactant are required for processing,
they do not contribute to the performance of the polymer. Consequently,
approximately 90 million pounds of oil and surfactant are released to the
environment each year. Nalco has developed a new technology that per-
mits production of the polymers as stable colloids in water, eliminating
the introduction of oil and surfactants into the environment.
The Nalco process uses a homogeneous dispersion polymerization tech-
nique. The water-soluble monomers are dissolved in an aqueous salt
solution of ammonium sulfatethen polymerized using a water-soluble,
free-radical initiator. A low-molecular-weight dispersant polymer is added
to prevent aggregation of the growing polymer chains. For end-use appli-
cations, the dispersion is simply added to water, thereby diluting the salt
and allowing the polymer to dissolve into a clear, homogeneous, poly-
mer solution. This technology has been successfully demonstrated with
110 1999 Award
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cationic copolymers of acrylamide, anionic copolymers of acrylamide,
and non-ionic polymers.
Development of water-based dispersion polymers provides three impor-
tant environmental benefits. First, the new process eliminates the use
of hydrocarbon solvents and surfactants required in the manufacture of
emulsion polymers. Dispersion polymers produce no VOCsand exhibit
lower biological oxygen demand (BOD) and chemical oxygen demand
(COD) than do emulsion polymers. Second, the salt used, ammonium
sulfate, is a waste byproduct from another industrial process, the produc-
tion of caprolactam. Caprolactam is the precursor in the manufacture of
nylon; 2.5-4.5 million pounds of ammonium sulfate are produced for ev-
ery million pounds of caprolactam, providing a ready supply of feedstock.
Finally, dispersion polymers eliminate the need for costly equipment and
inverter surfactants needed for mixing emulsion polymers. This techno-
logical advantage will make wastewater treatment more affordable for
small-and medium-sized operations.
Nalco's dispersion polymers contain the same active polymer component
as traditional emulsion polymers without employing oil and surfactant
carrier systems. The polymers are produced as stable colloids in water,
retaining ease and safety of handling while eliminating the release of oil
and surfactants into the environment. By adopting this new technology,
Nalco has conserved over one million pounds of hydrocarbon solvent
and surfactants since 1997 on two polymers alone. In 1998, the water-
based dispersions used 3.2 million pounds of ammonium sulfate, a by-
product from caprolactam synthesis that would otherwise be treated as
waste. Additional environmental benefits will be realized as the disper-
sion polymerization process is extended to the manufacture of other
polymers.
1999 Greener Reaction Conditions Award 111
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Spinosad: A New Natural Product for Insect Control
Dow developed spinosad, a highly selective, environmentally friendly
insecticide made by a soil microorganism. It controls many chewing insect
pests in cotton, trees, fruits, vegetables, turf, and ornamentals. Unlike
traditional pesticides, it does not persist in the environment; it also has low
toxicity to mammals and birds.
'. ontrolling insect pests is essential to maintaining high agricultural
productivity and minimizing monetary losses. Synthetic organic pesti-
cides, from a relatively small number of chemical classes, play a leading
role in pest control. The development of new and improved pesticides is
necessitated by increased pest resistance to existing products, along with
stricter environmental and toxicological regulations. To meet this need,
Dow AgroSciences has designed spinosad, a highly selective, environ-
mentally friendly insecticide.
High-volume testing of fermentation isolates in agricultural screens pro-
duced numerous leads, including the extracts of a Caribbean soil sample
found to be active on mosquito larvae. The microorganism, Saccharopoly-
spora spinosa, was isolated from the soil sample, and the insecticidal
activity of the spinosyns was identified. Spinosyns are unique macrocyclic
lactones, containing a tetracyclic core to which two sugars are attached.
Most of the insecticidal activity is due to a mixture of spinosyns A and D,
commonly referred to as spinosad. Products such as Tracer® Naturalyte®
Insect Control and Precise® contain spinosad as the active ingredient.
Insects exposed to spinosad exhibit classical symptoms of neurotoxicity:
lack of coordination, prostration, tremors, and other involuntary muscle
contractions leading to paralysis and death. Although the mode of action
of spinosad is not fully understood, it appears to affect nicotinic and
y-aminobutyric acid receptor function through a novel mechanism.
112 1999 Award
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Spinosad presents a favorable environmental profile. It does not leach,
bioaccumulate, volatilize, or persist in the environment. Spinosad will de-
grade photochemically when exposed to light after application. Because
spinosad strongly adsorbs to most soils, it does not leach through soil to
groundwater. Spinosad demonstrates low mammalian and avian toxicity.
No long-term health problems were noted in mammals, and a low poten-
tial for acute toxicity exists due to low oral, dermal, and inhalation toxicity.
This is advantageous, because low mammalian toxicity imparts reduced
risk to those who handle, mix, and apply the product. Although spinosad
is moderately toxic to fish, this toxicity represents a reduced risk to fish
when compared with many synthetic insecticides currently in use.
Spinosad has proven effective in controlling many chewing insect pests
in cotton, trees, fruits, vegetables, turf, and ornamentals. High selectivity
is also observed: 70-90 percent of beneficial insects and predatory wasps
are left unharmed. Spinosad features a novel molecular structure and
mode of action that provide the excellent crop protection associated with
synthetic products coupled with the low human and environmental risk
found in biological products. The selectivity and low toxicity of spinosad
make it a promising tool for integrated pest management.
1999 Designing Greener Chemicals Award 113
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1998 Winners
The Development of the Concept of Atom Economy
Professor Trost developed the concept of atom economy: chemical reac-
tions that do not waste atoms. Professor Trost's concept of atom economy
includes reducing the use of nonrenewable resources, minimizing the
amount of waste, and reducing the number of steps used to synthesize
chemicals. Atom economy is one of the fundamental cornerstones of
green chemistry. This concept is widely used by those who are working to
improve the efficiency of chemical reactions.
he general area of chemical synthesis covers virtually all segments of
the chemical industry—oil refining, bulk or commodity chemicals, and
fine chemicals, including agrochemicals, flavors, fragrances, pharmaceuti-
cals, etc. Economics generally dictates the feasibility of processes that are
"practical". A criterion that traditionally has not been explicitly recognized
relates to the total quantity of raw materials required for the process
compared to the quantity of product produced or, simply put, "how much
of what you put into your pot ends up in your product." In considering
the question of what constitutes synthetic efficiency, Professor Barry M.
Trost has explicitly enunciated a new set of criteria by which chemical
processes should be evaluated. They fall under two categories—selectivity
and atom economy.
Selectivity and atom economy evolve from two basic considerations.
First, the vast majority of the synthetic organic chemicals in production
derive from nonrenewable resources. It is self-evident that such resources
should be used as sparingly as possible. Second, all waste streams should
be minimized. This requires employment of reactions that produce mini-
mal byproducts, either through the intrinsic stoichiometry of a reaction or
114
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as a result of minimizing competing undesirable reactions (i.e., making
reactions more selective).
The issues of selectivity can be categorized under four headings—
chemoselectivity (differentiation among various functional groups in
a molecule), regioselectivity (locational), diastereoselectivity (relative
stereochemistry), and enantioselectivity (absolute stereochemistry). The
chemical community at large has readily accepted these considerations.
In too many cases, however, efforts to achieve the goal of selectivity
led to reactions requiring multiple components in stoichiometric quanti-
ties that are not incorporated into the product, thus creating significant
amounts of waste. How much of the reactants end up in the product
(i.e., atom economy) traditionally has been ignored. When Professor
Trost's first paper on atom economy appeared in the literature, the idea
generally was not adopted by either academia or industry. Many in indus-
try, however, were practicing this concept without explicitly enunciating it.
Others in industry did not consider the concept because it did not appear
to have any economic consequence. Today, all of the chemical industry
explicitly acknowledges the importance of atom economy.
Achieving the objectives of selectivity and atom economy encompasses
the entire spectrum of chemical activities—from basic research to com-
mercial processes. In enunciating these principles, Professor Trost has set
a challenge for those involved in basic research to create new chemical
processes that meet the objectives. Professor Trost's efforts to meet this
challenge involve the rational invention of new chemical reactions that
are either simple additions or, at most, produce low-molecular-weight
innocuous byproducts. A major application of these reactions is in the
synthesis of fine chemicals and Pharmaceuticals, which, in general, uti-
lize very atom-uneconomical reactions. Professor Trost's research involves
catalysis, largely focused on transition metal catalysis but also main group
catalysis. The major purpose of his research is to increase the toolbox of
available reactions to serve these industries for problems they encounter
in the future. However, even today, there are applications for which such
methodology may offer more efficient syntheses.
1998 Academic Award 115
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Use of Microbes as Environmentally Benign Synthetic Catalysts
Adipic acid, a building block for nylon, and catechol, a building block for
Pharmaceuticals and pesticides, are two chemicals of major industrial
importance. Using environmentally benign, genetically engineered
microbes, Dr. Draths and Professor Frost synthesized adipic acid and
catechol from sugars. These two chemicals are traditionally made from
benzene, a petroleum product; they can now be made with less risk to
human health and the environment.
i undamental change in chemical synthesis can be achieved by elabora-
tion of new, environmentally benign routes to existing chemicals. Alterna-
tively, fundamental change can follow from characterization and environ-
mentally benign synthesis of chemicals that can replace those chemicals
currently manufactured by environmentally problematic routes. Examples
of these design principles are illustrated by the syntheses of adipic acid
and catechol developed by Dr. Karen M. Draths and Professor John W.
Frost. The Draths-Frost syntheses of adipic acid and catechol use bioca-
talysis and renewable feedstocks to create alternative synthetic routes to
chemicals of major industrial importance. These syntheses rely on the
use of genetically manipulated microbes as synthetic catalysts. Nontoxic
glucose is employed as a starting material, which, in turn, is derived
from renewable carbohydrate feedstocks, such as starch, hemicellulose,
and cellulose. In addition, water is the primary reaction solvent, and the
generation of toxic intermediates and environment-damaging byproducts
is avoided.
In excess of 4.2 billion pounds of adipic acid are produced annually and
used in the manufacture of nylon 6,6. Most commercial syntheses of adi-
pic acid use benzene, derived from the benzene-toluene-xylene (BTX)
fraction of petroleum refining, as the starting material. In addition, the
last step in the current manufacture of adipic acid employs a nitric acid
oxidation resulting in the formation of nitrous oxide as a byproduct. Due
116 1998 Award
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to the massive scale on which it is industrially synthesized, adipic acid
manufacture has been estimated to account for some 10 percent of the
annual increase in atmospheric nitrous oxide levels. The Draths-Frost syn-
thesis of adipic acid begins with the conversion of glucose into c/s,c/s-mu-
conic acid using a single, genetically engineered microbe expressing a
biosynthetic pathway that does not exist in nature. This novel biosynthetic
pathway was assembled by isolating and amplifying the expression of
genes from different microbes including Klebsiella pneumoniae, Acineto-
bacter calcoaceticus, and Escherichia coli. The c/s,c7s-muconic acid, which
accumulates extracellularly, is hydrogenated to afford adipic acid.
Yet another example of the Draths-Frost strategy for synthesizing indust-
rial chemicals using biocatalysis and renewable feedstocks is their syn-
thesis of catechol. Approximately 46 million pounds of catechol are
produced globally each year. Catechol is an important chemical build-
ing block used to synthesize flavors (e.g., vanillin, eugenol, isoeugenol),
Pharmaceuticals (e.g., L-DOPA, adrenaline, papaverine), agrochemicals
(e.g., carbofuran, propoxur), and polymerization inhibitors and antioxi-
dants (e.g., 4-f-butylcatechol, veratrol). Although some catechol is distilled
from coal tar, petroleum-derived benzene is the starting material for most
catechol production. The Draths-Frost synthesis of catechol uses a single,
genetically engineered microbe to catalyze the conversion of glucose
into catechol, which accumulates extracellularly. As mentioned previously,
plant-derived starch, hemicellulose, and cellulose can serve as the renew-
able feedstocks from which the glucose starting material is derived.
In contrast to the traditional syntheses of adipic acid and catechol, the
Draths-Frost syntheses are based on renewable feedstocks, carbohydrate
starting materials, and microbial biocatalysis. As the world moves to
national limits on carbon dioxide (CO2) emissions, each molecule of a
chemical made from a carbohydrate may well be counted as a credit due
to the CO2 that is fixed by plants to form the carbohydrate. Biocatalysis
using intact microbes also allows the Draths-Frost syntheses to use water
as a reaction solvent, near-ambient pressures, and temperatures that typi-
cally do not exceed human body temperature.
1998 Academic Award 117
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Technology for the Third Millennium: The Development and Commercial
Introduction of an Environmentally Responsible Fire Extinguishment and
Cooling Agent
PYROCOOLTechnologies developed PYROCOOL F.E.F., afire extinguishing
foam that is nontoxic and highly biodegradable. PYROCOOF F.E.F. replaces
ozone-depleting gases and aqueous foams that release toxic and per-
sistent chemicals to the environment during use. PYROCOOF F.E.F. is
effective at approximately one-tenth the concentration of conventional fire
extinguishing chemicals.
Vdvances in chemical technology have greatly benefited firefighting
in this century. From the limitation of having only local water supplies
at their disposal, firefighters have been presented over the years with a
wide variety of chemical agents, as additives or alternatives to water, to
assist them. These advances in chemical extinguishment agents, how-
ever, have themselves created, in actual use, potential long-term envi-
ronmental and health problems that tend to outweigh their firefighting
benefits. PYROCOOL Technologies, Inc. developed PYROCOOL F.E.F. (Fire
Extinguishing Foam) as an alternative formulation of highly biodegrad-
able surfactants designed for use in very small quantities as a universal
fire extinguishment and cooling agent.
Halon gases, hailed as a tremendous advance when introduced, have
since proven to be particularly destructive to the ozone layer, having an
ozone depletion potential (OOP) value of 10-16 times that of common
refrigerants. Aqueous film-forming foams (AFFFs) developed by the U.S.
Navy in the 1960s to combat pooled-surface, volatile, hydrocarbon fires
release both toxic hydrofluoric acid and fluorocarbons when used. The
fluorosurfactant compounds that make these agents so effective against
certain types of fires render them resistant to microbial degradation,
often leading to contamination of groundwater supplies and failure of
wastewater treatment systems.
118 1998 Award
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In 1993, PYROCOOL Technologies initiated a project to create a fire extin-
guishment and cooling agent that would be effective in extinguishing
fires and that would greatly reduce the potential long-term environmental
and health problems associated with traditional products. To achieve this
objective, PYROCOOL Technologies first determined that the product
(when finally developed) would contain no glycol ethers or fluorosurfac-
tants. In addition, it decided that the ultimate formulation must be an
effective fire extinguishment and cooling agent at very low mixing ratios.
PYROCOOL F.E.F. is a formulation of highly biodegradable nonionic sur-
factants, anionic surfactants, and amphoteric surfactants with a mixing
ratio (with water) of 0.4 percent. In initial fire tests at the world's largest
fire-testing facility in the Netherlands, PYROCOOL F.E.F. was demonstrated
to be effective against a broad range of combustibles.
Since its development in 1993, PYROCOOL F.E.F. has been employed
successfully against numerous fires both in America and abroad. PYRO-
COOL F.E.F. carries the distinction of extinguishing the last large oil tanker
fire at sea (a fire estimated by Lloyd's of London to require 10 days to
extinguish) on board the Nassia tanker in the Bosphorous Straits in just
12.5 minutes, saving 80 percent of the ship's cargo and preventing
160 million pounds of crude oil from spilling into the sea.
As demonstrated by the PYROCOOL F.E.F. technology, selective employ-
ment of rapidly biodegradable substances dramatically enhances the
effectiveness of simple water, while eliminating the environmental and
toxic impact of other traditional fire extinguishment agents. Because
PYROCOOL F.E.F. is mixed with water at only 0.4 percent, an 87-93 per-
cent reduction in product use is realized compared to conventional extin-
guishment agents typically used at 3-6 percent. Fire affects all elements
of industry and society, and no one is immune from its dangers. PYRO-
COOL F.E.F. provides an innovative, highly effective, and green alternative
for firefighters.
1998 Small Business Award 119
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Elimination of Chlorine in the Synthesis of 4-Aminodiphenylamine:
A New Process That Utilizes Nucleophilic Aromatic Substitution
for Hydrogen
Flexsys developed a new method to eliminate waste from a critically impor-
tant reaction used to manufacture a wide range of chemical products. They
are using this method to manufacture 4-ADPA, a key, high-volume building
block for a rubber preservative. Converting just 30 percent of the world's
production capacity of this key building block to the Flexsys process would
reduce chemical waste by 74 million pounds per year and wastewater by
1.4 billion pounds per year.
i he development of new environmentally favorable routes for the produc-
tion of chemical intermediates and products is an area of considerable
interest to the chemical processing industry. Recently, the use of chlorine
in large-scale chemical syntheses has come under intense scrutiny. Solutia,
Inc. (formerly Monsanto Chemical Company), one of the world's largest
producers of chlorinated aromatics, has funded research over the years to
explore alternative synthetic reactions for manufacturing processes that
do not require the use of chlorine. It was clear that replacing chlorine in a
process would require the discovery of new atom-efficient chemical reac-
tions. Ultimately, it was Monsanto's goal to incorporate fundamentally new
chemical reactions into innovative processes that would focus on the elimi-
nation of waste at the source. In view of these emerging requirements,
Monsanto's Rubber Chemicals Division (now flexsys), in collaboration with
Monsanto Corporate Research, began to explore new routes to a variety
of aromatic amines that would not rely on the use of halogenated inter-
mediates or reagents. Of particular interest was the identification of novel
synthetic strategies to 4-aminodiphenylamine (4-ADPA), a key intermediate
in the Rubber Chemicals family of antidegradants. The total world volume
of antidegradants based on 4-ADPA and related materials is approximately
120 1998 Award
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300 million pounds per year, of which Flexsys is the world's largest pro-
ducer. (Flexsys is a joint venture of the rubber chemicals operations of
Monsanto and Akzo Nobel.)
Flexsys's current process to 4-ADPA is based on the chlorination of ben-
zene. Since none of the chlorine used in the process ultimately resides
in the final product, the pounds of waste generated in the process per
pound of product produced from the process are highly unfavorable. A
significant portion of the waste is in the form of an aqueous stream that
contains high levels of inorganic salts contaminated with organics that are
difficult and expensive to treat. Furthermore, the process also requires the
storage and handling of large quantities of chlorine gas. Flexsys found a
solution to this problem in a class of reactions known as nucleophilic aro-
matic substitution of hydrogen (NASH). Through a series of experiments
designed to probe the mechanism of NASH reactions, Flexsys realized a
breakthrough in understanding this chemistry that has led to the develop-
ment of a new process to 4-ADPA that utilizes the base-promoted, direct
coupling of aniline and nitrobenzene.
The environmental benefits of this process are significant and include a
dramatic reduction in waste generated. In comparison to the process
traditionally used to synthesize 4-ADPA, the Flexsys process generates
74 percent less organic waste, 99 percent less inorganic waste, and
97 percent less wastewater. In global terms, if just 30 percent of the
world's capacity to produce 4-ADPA and related materials were converted
to the Flexsys process, 74 million pounds less chemical waste would be
generated per year and 1.4 billion pounds less wastewater would be gen-
erated per year. The discovery of the new route to 4-ADPA and the elucida-
tion of the mechanism of the reaction between aniline and nitrobenzene
have been recognized throughout the scientific community as a break-
through in the area of nucleophilic aromatic substitution chemistry.
This new process for the production of 4-ADPA has achieved the goal for
which all green chemistry endeavors strive: the elimination of waste at the
source via the discovery of new chemical reactions that can be imple-
mented into innovative and environmentally safe chemical processes.
1998 Greener Synthetic Pathways Award 121
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Novel Membrane-Based Process for Producing Lactate Esters—
Nontoxic Replacements for Halogenated and Toxic Solvents
Argonne developed a novel process to synthesize organic solvents from
sugars. These solvents can replace a wide variety of more hazardous sol-
vents, such as methylene chloride. Argonne's process requires little energy,
is highly efficient, eliminates large volumes of salt waste, and reduces
pollution and emissions. These solvents can potentially replace 7.6 bil-
lion pounds of toxic solvents used annually by industry, commerce, and
households.
\rgonne National Laboratory (AND has developed a process based on
selective membranes that permits low-cost synthesis of high-purity ethyl
lactate and other lactate esters from carbohydrate feedstock. The process
requires little energy input, is highly efficient and selective, and elimi-
nates the large volumes of salt waste produced by conventional process-
es. ANL's novel process uses pervaporation membranes and catalysts. In
the process, ammonium lactate is thermally and catalytically cracked to
produce the acid, which, with the addition of alcohol, is converted to the
ester. The selective membranes pass the ammonia and water with high
efficiency while retaining the alcohol, acid, and ester. The ammonia is
recovered and reused in the fermentation to make ammonium lactate,
eliminating the formation of waste salt. The innovation overcomes major
technical hurdles that had made current production processes for lactate
esters technically and economically noncompetitive. The innovation will
enable the replacement of toxic solvents widely used by industry and
consumers, expand the use of renewable carbohydrate feedstocks, and
reduce pollution and emissions.
Ethyl lactate has a good temperature performance range (boiling point:
309 °F, melting point: 104 °F), is compatible with both aqueous and
organic systems, is easily biodegradable, and has been approved for food
by the U.S. Food and Drug Administration (FDA). Lactate esters (primarily
122 1998 Award
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ethyl lactate) can replace most halogenated solvents (including ozone-
depleting chlorofluorocarbons (CFCs), carcinogenic methylene chloride,
toxic ethylene glycol ethers, perchloroethylene, and chloroform) on a
1:1 basis. At 1998 prices ($1.60-2.00 per pound), the market for ethyl
lactate is about 20 million pounds per year for a wide variety of specialty
applications. The novel and efficient ANL membrane process will reduce
the selling price of ethyl lactate to $0.85-1.00 per pound and enable ethyl
lactate to compete directly with the petroleum-derived toxic solvents cur-
rently in use. The favorable economics of the ANL membrane process,
therefore, can lead to the widespread substitution of petroleum-derived
toxic solvents by ethyl lactate in electronics manufacturing, paints and
coatings, textiles, cleaners and degreasers, adhesives, printing, de-inking,
and many other industrial, commercial, and household applications.
More than 80 percent of the applications requiring the use of more than
7.6 billion pounds of solvents in the United States each year are suitable
for reformulation with environmentally friendly lactate esters.
The ANL process has been patented for producing esters from all fermen-
tation-derived organic acids and their salts. Organic acids and their esters,
at the purity achieved by this process, offer great potential as interme-
diates for synthesizing polymers, biodegradable plastics, oxygenated
chemicals (e.g., propylene glycol and acrylic acid), and specialty products.
By improving purity and lowering costs, the ANL process promises to
make fermentation-derived organic acids an economically viable alterna-
tive to many chemicals and products derived from petroleum feedstocks.
A U.S. patent on this technology has been allowed, and international pat-
ents have been filed. NTEC, Inc. has licensed the technology for lactate
esters and provided the resources for a pilot-scale demonstration of the
integrated process at ANL. The pilot-scale demonstration has produced
a high-purity ethyl lactate product that meets or exceeds all the process
performance objectives. A 10-million-pound-per-year demonstration plant
is being planned for early 1999, followed by a 100-million-pound-per-year,
full-scale plant.
1998 Greener Reaction Conditions Award 123
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Invention and Commercialization of a New Chemical Family of
Insecticides Exemplified by CONFIRM™ Selective Caterpillar Control
Agent and the Related Selective Insect Control Agents MACH 2™ and
INTREPID™
Rohm and Haas developed CONFIRM™, a novel insecticide for control-
ling caterpillar pests in turf and a variety of crops. CONFIRM™ is less toxic
than other insecticides to a wide range of nontarget organisms, poses no
significant hazard to farm workers or the food chain, and does not pres-
ent a significant spill hazard. EPA has classified CONFIRM™ as a reduced-
risk pesticide.
he value of crops destroyed worldwide by insects exceeds tens of
billions of dollars. Over the past fifty years, only a handful of classes of
insecticides have been discovered to combat this destruction. Rohm
and Haas Company has discovered a new class of chemistry, the diacyl-
hydrazines, that offers farmers, consumers, and society a safer, effective
technology for insect control in turf and a variety of agronomic crops.
One member of this family, CONFIRM™, is a breakthrough in caterpillar
control. It is chemically, biologically, and mechanistically novel. It ef-
fectively and selectively controls important caterpillar pests in agriculture
without posing significant risk to the applicator, the consumer, or the
ecosystem. It will replace many older, less effective, more hazardous
insecticides and has been classified by EPA as a reduced-risk pesticide.
CONFIRM™ controls target insects through an entirely new mode of ac-
tion that is inherently safer than current insecticides. The product acts by
strongly mimicking a natural substance found within the insect's body
called 20-hydroxy ecdysone, which is the natural "trigger" that induces
molting and regulates development in insects. Because of this "ecdy-
sonoid" mode of action, CONFIRM™ powerfully disrupts the molting
process in target insects, causing them to stop feeding shortly after
exposure and to die soon thereafter.
124 1998 Award
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Since 20-hydroxy ecdysone neither occurs nor has any biological function
in most nonarthropods, CONFIRM™ is inherently safer than other insec-
ticides to a wide range of nontarget organisms such as mammals, birds,
earthworms, plants, and various aquatic organisms. CONFIRM™ is also
remarkably safe to a wide range of key beneficial, predatory, and parasitic
insects such as honeybees, lady beetles, parasitic wasps, predatory bugs,
beetles, flies, and lacewings, as well as other predatory arthropods such
as spiders and predatory mites. Because of this unusual level of safety,
the use of these products will not create an outbreak of target or second-
ary pests due to destruction of key natural predators or parasites in the
local ecosystem. This should reduce the need for repeat applications of
additional insecticides and reduce the overall chemical load on both the
target crop and the local environment.
CONFIRM™ has low toxicity to mammals by ingestion, inhalation, and
topical application and has been shown to be completely non-oncogenic,
nonmutagenic, and without adverse reproductive effects. Because of its
high apparent safety and relatively low use rates, CONFIRM™ poses no
significant hazard to the applicator or the food chain and does not pres-
ent a significant spill hazard. CONFIRM™ has proven to be an outstand-
ing tool for control of caterpillar pests in many integrated pest manage-
ment (IPM) and resistance management situations. All of these attributes
make CONFIRM™ among the safest, most selective, and most useful
insect control agents ever discovered.
1998 Designing Greener Chemicals Award 125
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1997 Winners
Design and Application of Surfactants for Carbon Dioxide
Professor DeSimone developed new detergents that allow carbon dioxide
(CO2), a nontoxic gas, to be used as a solvent in many industrial applica-
tions. Using CO2 as a solvent allows manufacturers to replace traditional,
often hazardous chemical solvents and processes, conserve energy, and
reduce worker exposure to hazardous substances.
it has been a dilemma of modern industrial technology that the solvents
required to dissolve the environment's worst contaminants themselves
have a contaminating effect. Now, new technologies for the design and
application of surfactants for carbon dioxide (CO2), developed at UNC,
promise to resolve this dilemma.
Over 30 billion pounds of organic and halogenated solvents are used
worldwide each year as solvents, processing aids, cleaning agents, and
dispersants. Solvent-intensive industries are considering alternatives that
can reduce or eliminate the negative impact that solvent emissions can
have in the workplace and in the environment. CO2 in a solution state
has long been recognized as an ideal solvent, extractant, and separation
aid. CO2 solutions are nontoxic, nonflammable, energy-efficient, cost-
effective, waste-minimizing, reusable, and safe to work with. Historically,
the prime factor inhibiting the use of this solvent replacement has been
the low solubility of most materials in CO2, in both its liquid and supercriti-
cal states. With the discovery of CO2 surfactant systems, Professor Joseph
M. DeSimone and his students have dramatically advanced the solubility
performance characteristics of CO2 systems for several industries.
The design of broadly applicable surfactants for CO2 relies on the identifi-
cation of "CO,-philic" materials from which to build amphiphiles. Al-
126
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though CO2 in both its liquid and supercritical states dissolves many small
molecules readily, it is a very poor solvent for many substances at eas-
ily accessible conditions (T< 212 °Fand P< 4,350 psi). As an offshoot of
Professor DeSimone's research program on polymer synthesis in CO2, he
and his researchers exploited the high solubility of a select few CO2-
philic polymeric segments to develop nonionic surfactants capable of
dispersing high-solids polymer latexes in both liquid and supercritical CO2
phases. The design criteria they developed for surfactants, which were
capable of stabilizing heterogeneous polymerizations in CO2, have been
expanded to include CO2-insoluble compounds in general.
This development lays the foundation by which surfactant-modified CO2
can be used to replace conventional (halogenated) organic solvent sys-
tems currently used in manufacturing and service industries such as pre-
cision cleaning, medical device fabrication, and garment care, as well as
in the chemical manufacturing and coating industries.
1997 Academic Award 127
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Coldstrip™, A Revolutionary Organic Removal and Wet Cleaning
Technology
During manufacture, silicon-based semiconductors and flat-panel displays
require cleaning to remove manufacturing residues, usually with corrosive
acid solutions. Legacy Systems developed the Coldstrip™ process, which
uses only water and oxygen to clean silicon semiconductors. Coldstrip™
has the potential to cut the use of corrosive solutions by hundreds of
thousands of gallons and also save millions of gallons of water each year.
. or over 30 years, the removal of photoresists with Piranha solutions
(sulfuric acid, hydrogen peroxide, or ashers) has been the standard in the
semiconductor, flat panel display, and micromachining industries. Use
of Piranha solutions has been associated with atmospheric, ground, and
water pollution. Legacy Systems, Inc. (LSI) has developed a revolution-
ary wet processing technology, Coldstrip™, which removes photoresist
and organic contaminants for the semiconductor, flat panel display, and
micromachining industries.
LSI's Coldstrip™ process is a chilled-ozone process that uses only oxygen
and water as raw materials. The active product is ozone, which safely
decomposes to oxygen in the presence of photoresist. Carbon dioxide,
carbon monoxide, oxygen, and water are formed. There are no high tem-
peratures, no hydrogen peroxide, and no nitric acid, all of which cause
environmental issues.
The equipment required for the chilled-ozone process consists of a gas
diffuser, an ozone generator, a recirculating pump, a water chiller, and a
process vessel. The water solution remains clear and colorless through-
out the entire process sequence. There are no particles or resist flakes
shed from the wafer into the water; therefore, there are no requirements
for particle filtration.
128 1997 Award
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Using oxygen and water as raw materials replacing the Piranha solutions
significantly benefits the environment. One benefit is the elimination of
over 8,400 gallons of Piranha solutions used per year per silicon wet
station and over 25,200 gallons used per year per flat panel display sta-
tion. Additionally, the overall water consumption is reduced by over
3,355,800 gallons per year per silicon wafer wet station and over
5,033,700 gallons per year per flat panel display station. The correspond-
ing water consumption in LSI's process is 4,200 gallons per year and there
is no Piranha use.
In 1995, the U.S. Patent Office granted LSI Patent 5,464,480 covering this
technology. The system has the lowest environmental impact of any
wet-resist-strip process, eliminating the need for thousands of gallons of
Piranha chemicals and millions of gallons of water a year.
1997 Small Business Award 129
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BHC Company Ibuprofen Process
BHC Company developed an efficient method to make ibuprofen, a com-
monly used painkiller, using only three steps instead of six. BHC recovers
and recycles the waste byproduct from the manufacturing process and has
virtually eliminated large volumes of aqueous salt wastes. BASF Corpora-
tion, one of the BHC partners, uses this process in one of the largest
ibuprofen production plants in the world.
. HC Company has developed a new synthetic process to manufacture
ibuprofen, a well-known nonsteroidal anti-inflammatory painkiller mar-
keted under brand names such as Advil™ and Motrin™. Commercial-
ized since 1992 in BHC's 7.7-million-pound-per-year facility in Bishop, TX,
the new process has been cited as an industry model of environmental
excellence in chemical processing technology. For its innovation, BHC
was the recipient of the Kirkpatrick Achievement Award for "outstanding
advances in chemical engineering technology" in 1993.
The new technology involves only three catalytic steps with approximate-
ly 80 percent atom utilization (virtually 99 percent including the recovered
byproduct acetic acid) and replaces technology with six stoichiometric
steps and less than 40 percent atom utilization. The use of anhydrous
hydrogen fluoride as both catalyst and solvent offers important advan-
tages in reaction selectivity and waste reduction. As such, this chemistry
is a model of source reduction, the method of waste minimization that
tops EPA's waste management hierarchy. Virtually all starting materials
are either converted to product or reclaimed byproduct or are completely
recovered and recycled in the process. The generation of waste is practi-
cally eliminated.
The BHC ibuprofen process is an innovative, efficient technology that has
revolutionized bulk pharmaceutical manufacturing. The process provides
an elegant solution to a prevalent problem encountered in bulk pharma-
130 1997 Award
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ceutical synthesis (i.e., how to avoid the large quantities of solvents and
wastes associated with the traditional stoichiometric use of auxiliary
chemicals for chemical conversions). Large volumes of aqueous wastes
(salts) normally associated with such manufacturing are virtually elimi-
nated. The anhydrous hydrogen fluoride catalyst/solvent is recovered
and recycled with greater than 99.9 percent efficiency. No other solvent
is needed in the process, simplifying product recovery and minimizing
fugitive emissions. The nearly complete atom utilization of this stream-
lined process truly makes it a waste-minimizing, environmentally friendly
technology.
1997 Greener Synthetic Pathways Award 131
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DryView™ Imaging Systems
Imation's DryView™ Imaging Systems use a new type of photographic film
for medical imaging that uses heat instead of hazardous developer chemi-
cals. During 1996, Imation delivered more than 1,500 DryView™ Imaging
Systems worldwide. These units alone eliminate the annual disposal of
over half a million gallons of developer chemicals and 54.5 million gallons
of contaminated water and reduce workers' exposure to chemicals.
hotothermography is an imaging technology whereby a latent image,
created by exposing a sensitized emulsion to appropriate light energy,
is processed by the application of thermal energy. Photothermographic
films are easily imaged by laser diode imaging systems, with the resultant
exposed film processed by passing it over a heat roll. A heat roll operat-
ing at 250 °F in contact with the film will produce diagnostic-quality im-
ages in approximately 15 seconds. Based on photothermography technol-
ogy, Imation's DryView™ Imaging Systems use no wet chemistry, create
no effluent, and require no additional postprocess steps such as drying.
In contrast, silver halide photographic films are processed by being
bathed in a chemical developer, soaked in a fix solution, washed with
clean water, and finally dried. The developer and fix solutions contain
toxic chemicals such as hydroquinone, silver, and acetic acid. In the wash
cycle, these chemicals, along with silver compounds, are flushed from
the film and become part of the waste stream. The resulting effluent
amounts to billions of gallons of liquid waste each year.
Significant developments in photothermographic image quality have
been achieved that allow it to compete successfully with silver halide
technology. During 1996, Imation placed more than 1,500 DryView™
medical laser imagers, which represent 6 percent of the world's installed
base. These units alone have eliminated the annual disposal of
192,000 gallons of developer, 330,000 gallons of fixer, and 54.5 million
132 1997 Award
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gallons of contaminated water into the waste stream. As future systems
are placed, the reductions will be even more dramatic.
DryView™ technology is applicable to all industries that process pan-
chromatic film products. The largest of these industries are medical
radiography, printing, industrial radiography, and military reconnaissance.
DryView™ is valued by these industries because it supports pollution
prevention through source reduction.
1997 Greener Reaction Conditions Award 133
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THPS Biocides: A New Class of Antimicrobial Chemistry
Albright & Wilson discovered the antimicrobial properties of THPS and
developed it into a safer biocide that can be used to control the growth of
bacteria and algae in industrial water systems. THPS, or tetrakis(hydroxy-
methyDphosphonium sulfate, offers many advantages over other, tra-
ditional biocides because, for example, it is significantly less toxic to
nontarget organisms, is effective at much lower concentrations, and is
more biodegradable than other biocides.
••• .onventional biocides used to control the growth of bacteria, algae, and
fungi in industrial cooling systems, oil fields, and process applications are
highly toxic to humans and aquatic life and often persist in the environ-
ment, leading to long-term damage. To address this problem, a new and
relatively benign class of biocides, tetrakis(hydroxymethyl)phosphonium
sulfate (THPS), has been discovered by Albright & Wilson Americas. THPS
biocides represent a completely new class of antimicrobial chemistry
that combines superior antimicrobial activity with a relatively benign
toxicology profile. THPS's benefits include low toxicity, low recommended
treatment level, rapid breakdown in the environment, and no bioaccumu-
lation. When substituted for more toxic biocides, THPS biocides provide
reduced risks to both human health and the environment.
THPS is so effective as a biocide that, in most cases, the recommended
treatment level is below that which would be toxic to fish. In addition,
THPS rapidly breaks down in the environment through hydrolysis, oxi-
dation, photodegradation, and biodegradation. In many cases, it has
already substantially broken down before the treated water enters the
environment. The degradation products have been shown to possess a
relatively benign toxicology profile, furthermore, THPS does not bioaccu-
mulate and, therefore, offers a much-reduced risk to higher life forms.
134 1997 Award
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THPS biocides are aqueous solutions and do not contain volatile organic
compounds (VOCs). Because THPS is halogen-free, it does not contribute
to the formation of dioxin or absorbable organic halides (AOX). Because
of its low overall toxicity and easier handling compared to alternative
products, THPS provides an opportunity to reduce the risk of health and
safety incidents.
THPS has been applied to a range of industrial water systems for the
successful control of microorganisms. The U.S. industrial water treatment
market for nonoxidizing biocides alone is 42 million pounds per year and
growing at 6-8 percent annually. There are over 500,000 individual user
sites in this industry category. Because of its excellent environmental pro-
file, THPS has already been approved for use in environmentally sensitive
areas around the world and is being used as a replacement for higher
risk alternatives.
1997 Designing Greener Chemicals Award 135
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1996 Winners
Conversion of Waste Biomassto Animal Feed, Chemicals, and Fuels
Professor Holtzapple developed a family of technologies that convert
waste biomass, such as sewage sludge and agricultural wastes, into
animal feed products, industrial chemicals, or fuels, depending on the
technology used. Because these technologies convert waste biomass into
useful products, other types of basic resources, such as petroleum, can
be conserved. Also, the technologies can reduce the amount of biomass
waste going to landfills or incinerators.
\ family of technologies has been developed by Professor Mark Holz-
apple at Texas A&M University that converts waste biomass into animal
feed, industrial chemicals, and fuels. Waste biomass includes such
resources as municipal solid waste, sewage sludge, manure, and agricul-
tural residues. Waste biomass is treated with lime to improve digestibility.
Lime-treated agricultural residues (e.g., straw, stover, and bagasse) may
be used as ruminant animal feeds. Alternatively, the lime-treated biomass
can be fed into a large anaerobic fermentor in which rumen microor-
ganisms convert the biomass into volatile fatty acid (VFA) salts, such as
calcium acetate, propionate, and butyrate. The VFA salts are concentrated
and may be converted into chemicals or fuels via three routes. In one
route, the VFA salts are acidified, releasing acetic, propionic, and butyric
acids. In a second route, the VFA salts are thermally converted to ketones,
such as acetone, methyl ethyl ketone, and diethyl ketone. In a third route,
the ketones are hydrogenated to their corresponding alcohols such as
isopropanol, isobutanol, and isopentanol.
The technologies above offer many benefits for human health and the
environment. Lime-treated animal feed can replace feed corn, which is
approximately 88 percent of corn production. Growing corn exacerbates
136
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soil erosion and requires intensive inputs of fertilizers, herbicides, and
pesticides, all of which contaminate ground water.
Chemicals (e.g., organic acids and ketones) may be produced economi-
cally from waste biomass. Typically, waste biomass is landfilled or inciner-
ated, which incurs a disposal cost and contributes to land or air pollution.
Through the production of chemicals from biomass, non-renewable
resources, such as petroleum and natural gas, are conserved for later
generations. Because 50 percent of U.S. petroleum consumption is now
imported, displacing foreign oil will help reduce the U.S. trade deficit.
Fuels (e.g., alcohols) produced from waste biomass have the benefits
cited above (i.e., reduced environmental impact from waste disposal
and reduced trade deficit). In addition, oxygenated fuels derived from
biomass are cleaner-burning and do not add net carbon dioxide to the
environment, thereby reducing factors that contribute to global warming.
1996 Academic Award 137
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Production and Use of Thermal Polyaspartic Acid
Donlar developed TPA, a nontoxic, environmentally safe, biodegradable
polymer for use in agriculture, water treatment, and other industries.
Donlar manufactures TPA using a highly efficient process that eliminates
use of organic solvents, cuts waste, and uses less energy. TPA has been
used successfully in a variety of applications, such as improving fertilizer
uptake in plants, and improving the efficiency of oil and gas production.
''• Ullions of pounds of anionic polymers are used each year in many in-
dustrial applications. Polyacrylic acid (PAC) is one important class of such
polymers, but the disposal of PAC is problematic because it is not biode-
gradable. An economically viable, effective, and biodegradable alterna-
tive to PAC is thermal polyaspartate (TPA).
Donlar Corporation invented two highly efficient processes to manufac-
ture TPA for which patents have either been granted or allowed. The first
process involves a dry and solid polymerization converting aspartic acid
to polysuccinimide. No organic solvents are involved during the conver-
sion and the only byproduct is water. The process is extremely effi-
cient—a yield of more than 97 percent of polysuccinimide is routinely
achieved. The second step in this process, the base hydrolysis of polysuc-
cinimide to polyaspartate, is also extremely efficient and waste-free.
The second TPA production process involves using a catalyst during the
polymerization, which allows a lower heating temperature to be used.
The resulting product has improvements in performance characteristics,
lower color, and biodegradability. The catalyst can be recovered from the
process, thus minimizing waste.
Independent toxicity studies of commercially produced TPA have been
conducted using mammalian and environmental models. Results indicate
138 1996 Award
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that TPA is nontoxic and environmentally safe. TPA biodegradability has
also been tested by an independent lab using established Organization
for Economic Cooperation and Development (OECD) methodology. Re-
sults indicate that TPA meets OECD guidelines for Intrinsic Biodegradabil-
ity. PAC cannot be classified as biodegradable when tested under these
same conditions.
Many end-uses of TPA have been discovered, such as in agriculture to im-
prove fertilizer or nutrient management. TPA increases the efficiency of
plant nutrient uptake, thereby increasing crop yields while protecting the
ecology of agricultural lands. TPA can also be used for water treatment, as
well as in the detergent, oil, and gas industries.
1996 Small Business Award 139
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Catalytic Dehydrogenation of Diethanolamine
DSIDA is a key building block for the herbicide RoundUp®. Monsanto's
novel synthesis of DSIDA eliminates most of the manufacturing hazards
associated with the previous synthesis; it uses no ammonia, cyanide, or
formaldehyde. This synthesis is safer to operate, has a higher overall yield,
and has fewer process steps.
i . isodium iminodiacetate (DSIDA) is a key intermediate in the production
of Monsanto's Roundup® herbicide, an environmentally friendly, nonse-
lective herbicide. Traditionally, Monsanto and others have manufactured
DSIDA using the Strecker process requiring ammonia, formaldehyde,
hydrochloric acid, and hydrogen cyanide. Hydrogen cyanide is acutely
toxic and requires special handling to minimize risk to workers, the com-
munity, and the environment, furthermore, the chemistry involves the
exothermic generation of potentially unstable intermediates, and special
care must be taken to preclude the possibility of a runaway reaction. The
overall process also generates up to 1 pound of waste for every 7 pounds
of product, and this waste must be treated prior to safe disposal.
Monsanto has developed and implemented an alternative DSIDA process
that relies on the copper-catalyzed dehydrogenation of diethanolamine.
The raw materials have low volatility and are less toxic. Process operation
is inherently safer, because the dehydrogenation reaction is endother-
mic and, therefore, does not present the danger of a runaway reaction.
Moreover, this zero-waste route to DSIDA produces a product stream
that, after filtration of the catalyst, is of such high quality that no purifica-
tion or waste cut is necessary for subsequent use in the manufacture of
Roundup®. The new technology represents a major breakthrough in the
production of DSIDA, because it avoids the use of cyanide and formal-
dehyde, is safer to operate, produces higher overall yield, and has fewer
process steps.
140 1996 Award
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The metal-catalyzed conversion of amino-alcohols to amino acid salts
has been known since 1945. Commercial application, however, was not
known until Monsanto developed a series of proprietary catalysts that
made the chemistry commercially feasible. Monsanto's patented im-
provements on metallic copper catalysts afford an active, easily recover-
able, highly selective, and physically durable catalyst that has proven itself
in large-scale use.
This catalysis technology also can be used in the production of other
amino acids, such as glycine. Moreover, it is a general method for conver-
sion of primary alcohols to carboxylic acid salts; it is potentially applicable
to the preparation of many other agricultural, commodity, specialty, and
pharmaceutical chemicals.
1996 Greener Synthetic Pathways Award 141
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100 Percent Carbon Dioxide as a Blowing Agent for the Polystyrene Foam
Sheet Packaging Market
Dow developed a process for manufacturing polystyrene foam sheets
that uses carbon dioxide (CO2) as a blowing agent, eliminating 3.5 million
pounds per year of traditional blowing agents. Traditional blowing agents
deplete the ozone layer or contribute to ground-level smog. In addition,
Dow will obtain CO2 only from existing commercial and natural sources
that generate it as a byproduct, so this process will not contribute to global
CO2 levels.
^n recent years the chlorofluorocarbon (CFC) blowing agents used to
manufacture polystyrene foam sheet have been associated with environ-
mental concerns such as ozone depletion, global warming, and ground-
level smog. Due to these environmental concerns, The Dow Chemical
Company has developed a novel process for the use of 100 percent car-
bon dioxide (CO2). Polystyrene foam sheet is a useful packaging material
offering a high stiffness-to-weight ratio, good thermal insulation value,
moisture resistance, and recyclability. This combination of desirable prop-
erties has resulted in the growth of the polystyrene foam sheet market in
the United States to over 700 million pounds in 1995. Current applications
for polystyrene foam include thermoformed meat, poultry, and produce
trays; fast food containers; egg cartons; and serviceware.
The use of 100 percent CO2 offers optimal environmental performance
because CO2 does not deplete the ozone layer, does not contribute to
ground-level smog, and will not contribute to global warming because
CO2 will be used from existing byproduct commercial and natural sources.
The use of CO2 byproduct from existing commercial and natural sources,
such as ammonia plants and natural gas wells, will ensure that no net
increase in global CO2 results from the use of this technology. CO2 is also
nonflammable, providing increased worker safety. It is cost-effective and
142 1996 Award
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readily available in food-grade quality. CO2 also is used in such common
applications as soft drink carbonation and food chilling and freezing.
The Dow 100 percent CO2 technology eliminates the use of 3.5 mil-
lion pounds per year of hard CFC-12 and soft HCFC-22. This technology
has been scaled from pilot-line to full-scale commercial facilities. Dow has
made the technology available through a commercial license covering
both patented and know-how technology. The U.S. Patent Office granted
Dow two patents for this technology (5,250,577 and 5,266,605).
1996 Greener Reaction Conditions Award 143
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Designing an Environmentally Safe Marine Antifoulant
Rohm and Haas developed Sea-Nine™, a novel antifoulant to control the
growth of plants and animals on the hulls of ships. In 1995, fouling cost
the shipping industry approximately $3 billion a year in increased fuel
consumption. Sea-Nine™ replaces environmentally persistent and toxic
tin-containing antifoulants.
i ouling, the unwanted growth of plants and animals on a ship's surface,
costs the shipping industry approximately $3 billion a year, largely due to
increased fuel consumption to overcome hydrodynamic drag. Increased
fuel consumption contributes to pollution, global warming, and acid rain.
The main compounds used worldwide to control fouling are the organo-
tin antifoulants, such astributyltin oxide (TBTO). While effective, they
persist in the environment and cause toxic effects, including acute toxic-
ity, bioaccumulation, decreased reproductive viability, and increased shell
thickness in shellfish. These harmful effects led to an EPA special review
and to the Organotin Antifoulant Paint Control Act of 1988. This act man-
dated restrictions on the use of tin in the United States, and charged EPA
and the U.S. Navy with conducting research on alternatives to organotins.
Rohm and Haas Company searched for an environmentally safe alterna-
tive to organotin compounds. Compounds from the 3-isothiazolone class
were chosen as likely candidates and over 140 were screened for anti-
fouling activity. The 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-Nine™
antifoulant) was chosen as the candidate for commercial development.
Extensive environmental testing compared Sea-Nine™ antifoulant to
TBTO, the current industry standard. Sea-Nine™ antifoulant degraded
extremely rapidly with a half-life of one day in seawater and one hour in
sediment. Tin had bioaccumulation factors as high as 10,000-fold, where-
as Sea-Nine™ antifoulant's bioaccumulation was essentially zero. Both
144 1996 Award
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TBTO and Sea-Nine™ were acutely toxic to marine organisms, but TBTO
had widespread chronic toxicity, whereas Sea-Nine™ antifoulant showed
no chronic toxicity. Thus, the maximum allowable environmental concen-
tration (MAEC) for Sea-Nine™ antifoulant was 0.63 parts per billion (ppb)
whereas the MAEC for TBTO was 0.002 ppb.
Hundreds of ships have been painted with coatings containing Sea-
Nine™ worldwide. Rohm and Haas Company obtained EPA registration
for the use of Sea-Nine™ antifoulant, the first new antifoulant registration
in over a decade.
1996 Designing Greener Chemicals Award 145
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Additional information on the Presidential Green Chemistry Challenge
program is available from:
• The Green Chemistry Web site at
http://www.epa.gov/greenchemistryand
• The Industrial Chemistry Branch of EPA by e-mail at greenchemistry@
epa.gov or by telephone at 202-564-8740.
Note: The summaries provided in this document were obtained from
the entries received for the 1996-2009 Presidential Green Chemistry
Challenge Awards. They were edited for space, stylistic consistency, and
clarity, but they were neither written nor officially endorsed by EPA. These
summaries represent only a fraction of the information that was provided
in the entries received and, as such, are intended to highlight the
nominated projects, not describe them fully. These summaries were not
used in the judging process; judging was conducted on all information
contained in the entries.
146
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AgraQuest, Inc., 66-67
Albright & Wilson Americas (now
Rhodia), 134-135
Archer Daniels Midland Company
(ADM), 46-47, 52-53
Argonne National Laboratory (AND,
122-123
Arkon Consultants, 34-35
Ashland Inc, 26-27
BASF Corporation, 50-51, 62-63, 130-131
Battelle, 16-17
Bayer AC, 88-89, 100-101
Bayer Corporation, 88-89, 100-101
Beckman, EricJ., 74-75
BHC Company (now BASF Corpora-
tion), 130-131
Biofine, Inc., (now BioMetics, Inc.),
106-107
BioMetics, Inc., 106-107
Bristol-Myers Squibb Company (BMS),
58-59
Buckman Laboratories International,
Inc., 60-61
Cargill Dow LLC (now NatureWorks
LLC), 80-81
Cargill, Incorporated, 30-31
Carnegie Mellon University, 2-3, 104-
105
CEM Corporation, 8-9
Chemical Specialties, Inc. (CSI) (now
Viance), 82-83
Codexis, Inc., 38-39
Collins, Terry, 104-105
Columbia Forest Products, 26-27
Cook Composites and Polymers
Company, 10-11
DeSimone, Joseph M., 126-127
Donlar Corporation (now NanoChem
Solutions, Inc.), 138-139
Dow AgroSciences LLC, 20-21, 102-103,
112-113
Dow Chemical Company, The, 124-125,
142-143, 144-145
Draths, Karen M., 116-117
DuPont, 70-71
Eastman Chemical Company, 6-7
Eastman Kodak Company, 34-35,
132-133
Eckert, Charles A., 54-55
EDEN Bioscience Corporation, 86-87
Engelhard Corporation (now BASF
Corporation), 62-63
Flexsys America L.P., 130-131
Frost, John W., 116-117
Georgia Institute of Technology, 54-55
Gross, Richard A., 64-65
Headwaters Technology Innovation,
28-29
Hercules Incorporated (now Ashland
Inc.), 26-27
Holtzapple, Mark, 136-137
Imation, 132-133
Jeneil Biosurfactant Company, 56-57
Krische, Michael J., 22-23
Legacy Systems, Inc.(LSI), 128-129
Li, Chao-Jun, 84-85
Li, Kaichang, 26-27
Lilly Research Laboratories, 108-109
Liotta, Charles L, 54-55
147
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Maleczka, Robert E., Jr., 12-13
Matyjaszewski, Krzysztof, 2-3
Merck & Co, Inc., 36-37, 48-49
Metabolix, Inc., 44-45
Michigan State University, 12-13, 116-117
Monsanto Company, 140-141
Nalco Company, 18-19, 110-111
NanoChem Solutions, Inc., 138-139
Natureworks LLC, 80-81
North Carolina State University (NCSU),
126-127
NovaSterilislnc., 24-25
Novozymes, 46-47
Novozymes North America, Inc., 90-91
NuPro Technologies, Inc. (now East-
man Kodak Company), 34-35
Oregon State University, 26-27
Pfizer, Inc., 78-79
Polytechnic University, 64-65
PPG Industries, 92-93
Procter & Gamble Company, The, 10-11
PYROCOOL Technologies, lnc.,118-119
RevTech, Inc., 96-97
Rhodia, 134-135
Roche Colorado Corporation, 98-99
Rogers, Robin D., 42-43
Rohm and Haas Company (now
The Dow Chemical Company),
124-125, 144-145
SC Fluids, Inc., 76-77
S.C.Johnson & Son, Inc., 40-41
Scripps Research Institute, The, 94-95
Shaw Industries, Inc., 72-73
SiGNa Chemistry, Inc., 14-15
Smith, Milton R., Ill, 12-13
Stanford University, 114-115
Sud-Chemie Inc., 68-69
Suppes, Galen J., 32-33
Texas A&M University, 136-137
Trost, Barry M., 114-115
Tulane University, 84-85
University of Alabama, The, 42-43
University of Missouri-Columbia, 32-33
University of North Carolina at
Chapel Hill (UNO, 126-127
University of Pittsburgh, 74-75
University of Texas at Austin, 22-23
Viance, 82-83
Virent Energy Systems, Inc., 4-5
Wong, Chi-Huey, 94-95
148 Index
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