&EPA
United States
Environmental Protection
Agency
Presidential Green
Chemistry Challenge
Award Recipients
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vvEPA
United States 744-K-04-002
Environmental Protection June 2004
Agency www.epa.gov/greenchemistry
Office of Pollution Prevention and Toxics (7406M)
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Presidential Green
^Chemistry Challenge
Award Recipients
Recycled/Recyclable—Printed with vegetable oil based inks on 100%
(minimum 50% postconsumer) recycled paper.
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Contents
Introduction 1
2004 Winners
Academic Award:
Professors Charles A. Eckert and Charles L Liotta,
Georgia Institute of Technology 2
Small Business Award:
Jeneil Biosurfactant Company 4
Alternative Synthetic Pathways Award:
Bristol-Myers Squibb Company 6
Alternative Solvents/Reaction Conditions Award:
Buckman Laboratories International, Inc. 8
Designing Safer Chemicals Award:
Engelhard Corporation 10
2003 Winners
Academic Award:
Professor Richard A. Cross,
Polytechnic University 12
Small Business Award:
AgraQuest, Inc. 14
Alternative Synthetic Pathways Award:
Sud-Chemie Inc. 16
Alternative Solvents/Reaction Conditions Award:
DuPont 18
Designing Safer Chemicals Award:
Shaw Industries, Inc. 20
2002 Winners
Academic Award:
Professor ErlcJ. Beckman,
University of Pittsburgh 22
HI
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Small Business Award:
SC Fluids, Inc. 24
Alternative Synthetic Pathways Award:
Pfizer, Inc. 26
Alternative Solvents/Reaction Conditions Award:
Cargill Dow LLC 28
Designing Safer Chemicals Award:
CSI 30
2001 Winners
Academic Award:
Professor Chao-Jun Li,
Tulane University 32
Small Business Award:
EDEN Bioscience Corporation 34
Alternative Synthetic Pathways Award:
Bayer Corporation and Bayer AC 36
Alternative Solvents/Reaction Conditions Award:
Novozymes North America, Inc. 38
Designing Safer Chemicals Award:
PPG Industries 40
2000 Winners
Academic Award:
Professor Chi-Huey Wong,
The Scripps Research Institute 42
Small Business Award:
RevTech, Inc. 44
Alternative Synthetic Pathways Award:
Roche Colorado Corporation 46
Alternative Solvents/Reaction Conditions Award:
Bayer Corporation and Bayer AC 48
Designing Safer Chemicals Award:
DowAgroSciencesLLC 50
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1999 Winners
Academic Award:
Professor Terry Collins,
Carnegie Mellon University 52
Small Business Award:
Biofine. Inc. 54
Alternative Synthetic Pathways Award:
Lilly Research Laboratories 56
Alternative Solvents/Reaction Conditions Award:
Nalco Chemical Company 55
Designing Safer Chemicals Award:
DowAgroSciencesLLC 60
1998 Winners
Academic Awards:
Professor Barry M. Trost,
Stanford University, 62
Dr. Karen M. Draths and Professor John W. Frost,
Michigan State University 64
Small Business Award:
PYROCOOL Technologies, Inc. 66
Alternative Synthetic Pathways Award:
Flexsys America L.P. 68
Alternative Solvents/Reaction Conditions Award:
Argonne National Laboratory 70
Designing Safer Chemicals Award:
Rohm and Haas Company 72
1997 Winners
Academic Award:
Professor Joseph M. DeSimone,
University of North Carolina at Chapel Hill and
North Carolina State University 74
Small Business Award:
Legacy Systems, Inc. 76
Contents v
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Alternative Synthetic Pathways Award:
BHC Company 78
Alternative Solvents/Reaction Conditions Award:
Imation 80
Designing Safer Chemicals Award:
Albright & Wilson Americas 82
1996 Winners
Academic Award:
Professor Mark Holtzapple,
Texas A&M University 84
Small Business Award:
Donlar Corporation 86
Alternative Synthetic Pathways Award:
Monsanto Company (now Pharmacia) 88
Alternative Solvents/Reaction Conditions Award:
The Dow Chemical Company 90
Designing Safer Chemicals Award:
Rohm and Haas Company 92
Program Information 94
Disclaimer 94
Index 95
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Introduction
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 Challenge
Awards Program provides national recognition for outstanding chemical tech-
nologies that incorporate the principles of green chemistry into chemical design,
manufacture, and use, and that have been or can be utilized by industry to
achieve its pollution prevention goals. Five winners are typically honored each
year, one in each of the following categories:
• Academia.
• Small business.
• The use of alternative synthetic pathways for green chemistry, such as catal-
ysis/biocatalysis; natural processes, including photochemistry and biomimetic
synthesis; or alternate feedstocks that are more innocuous and renewable
(e.g., biomass).
• The use of alternative reaction conditions for green chemistry, such as the use
of solvents that have a reduced impact on human health and the environment
or increased selectivity and reduced wastes and emissions.
• The design of safer chemicals that are, for example, less toxic than current
alternatives or inherently safer with regard to accident potential.
This booklet presents the 1996 through 2004 Presidential Green Chemistry
Challenge Award recipients and describes their award^winning technologies. The
winners each demonstrate a commitment to designing, developing, and
implementing green chemical technologies that are scientifically innovative,
economically feasible, and less hazardous to human health and the environ-
ment. Collectively, these award-winning technologies have eliminated over
460 million pounds of hazardous chemicals and solvents, saved over 440 million
gallons of water, and eliminated over 170 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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2004 Winners
Academic Award
Professors Charles A. Eckert and Charles L Liotta
Georgia Institute of Technology
Benign Tunable Solvents Coupling Reaction and Separation Processes
For 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% of the cost,
however, and almost always has a large environmental impact. Conven-
tional reactions and separations are often designed separately, but
Professors Eckert and Liotta have combined them with a series of novel,
benign, tunable solvents to create a paradigm for sustainable develop-
ment: benign solvents and improved performance.
Supercritical CO2/ nearcritical water, and CO2-expanded liquids are tunable
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
benign solvents, minimize waste, and improve performance.
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 products
cleanly and economically. Their method allows them to recycle their
catalysts effectively. They have demonstrated the feasibility of a variety
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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 using the enhanced dissociation of nearcritical water, negating
the need for any added acid or base and eliminating subsequent neutral-
ization 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 spon-
sors to facilitate technology transfer. They have worked with a wide
variety of government and industrial partners to identify the environmen-
tal and commercial opportunities available with these novel solvents,-
their interactions have facilitated the technology transfer necessary to
implement their advances.
2004 Academic Award 3
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Small Business Award
Jeneil Biosurfactant Company
Rhamnolipid Biosurfactant - A Natural LowToxicity Alternative to
Synthetic Surfactants
Surfactants are chemicals that can 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 18 million tons. 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
rhamnolipid 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 low toxicity. They are readily biodegradable and leave no
harmful or persistent degradation products. Their superior qualities
make them suitable 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 aeruglnosa. The biosurfactant is
recovered from the fermentation broth after sterilization and centrifuga-
tion, then purified to various levels to fit intended applications.
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Rhamnolipid biosurfactants are a much less toxic and a more environ-
mentally friendly alternative to traditional synthetic or petroleum-derived
surfactants. Rhamnolipid biosurfactants are also "greener" throughout
their life cycle. Biosurfactant production uses feedstocks that are innocu-
ous 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 ex-
tremely effective in precluding harmful environmental impacts and
remediating 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 petroleum-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
rhamnolipid technology by developing efficient bacterial strains, as well
as cost-effective processes and equipment for commercial scale produc-
tion. JeneiPs facility in Saukville, Wisconsin produces the surfactants.
2004 Small Business Award 5
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Alternative Synthetic Pathways Award
Bristol-Myers Squibb Company
Development of a Green Synthesis for Taxol® Manufacture via Plant Cell
Fermentation and Extraction
Paclitaxel, 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 paclitaxel 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% paclitaxel. In addition, isolating paclitaxel 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 paclitaxel molecule makes commercial production
by chemical synthesis from simple compounds impractical. Published
syntheses involve about 40 steps with an overall yield of approximately
2%. In 1991, NCI signed a Collaborative Research and Development
Agreement with Bristol-Myers Squibb (BMS) in which BMS agreed to
ensure supply of paclitaxel from yew bark while it developed a semi-
synthetic route (semisynthesis) to paclitaxel from the naturally occurring
compound 10-deacetylbaccatin III (10-DAB).
10-DAB contains most of the structural complexity (8 chiral centers) of the
paclitaxel molecule. It is present in the leaves and twigs of the European
yew, Taxus baccata, at approximately 0.1% by dry weight and can be
isolated without harm to the trees. Taxus baccata is cultivated throughout
Europe, providing a renewable supply that does not adversely impact any
sensitive ecosystem. The semisynthetic process is complex however.
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requiring 11 chemical transformations and 7 isolations. The semi-
synthetic 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
process, calluses of a specific taxus cell line are propagated in a wholly
aqueous medium in large fermentation tanks under controlled condi-
tions 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 purifies it by chromatography and isolates it by crystalliza-
tion. 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 process has no chemical transformations, thereby
eliminating six intermediates. During its first five years, the PCF process
will eliminate an estimated 32 metric tons of hazardous chemicals and
other materials. In addition, the PCF process eliminates 10 solvents and
six drying steps, saving a considerable amount of energy. BMS is now
manufacturing paclitaxel using only plant cell cultures.
2004 Alternative Synthetic Pathways Award 7
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Alternative Solvents/
Reaction Conditions Award
Buckman Laboratories International, Inc.
Optimyze®: A New Enzyme Technology to Improve Paper Recycling
Recycling paper products is an important part of maintaining our envi-
ronment. Although produced from renewable resources, paper is a
major contributor to landfllled 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
"stickles1 by the paper industry, can produce spots and holes in paper
goods made from recycled materials, ruining their appearance and
lowering their quality.
Stickies 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 million
annually. Further, this cleaning is traditionally done with chemical
solvents, typically mineral spirits, which can have health and safety
problems, are obtained from nonrenewable, petroleum resources, and
are not readily recycled. These solvents are volatile organic compounds
that contribute to air pollution. As a result, some paper grades cannot be
recycled into reusable products.
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
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paper is polyvinyl acetate and similar materials. Optimyze® contains an
esterase enzyme that catalyzes the hydrolysis of this type of polymer to
polyvinyl 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 forty paper mills have converted to Optimyze® for
manufacturing 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%, 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
papermaking, dramatically reducing downtime to clean equipment. As a
result, more paper is being recycled and grades of paper that were not
recyclable 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. Ttie Optimyze®
technology comes from renewable resources, is safe to use, and is itself
completely recyclable.
2004 Alternative Solvents/Reaction Conditions Award 9
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Designing Safer Chemicals Award
Engelhard Corporation
Engelhard Rightfit™ Organic Pigments: Environmental Impact,
Performance and Value
Historically, pigments based on lead, chromium(VI), and cadmium have
served the red, orange, and yellow color market. When the U.S. EPA
began regulating heavy metals, however, color formulators typically
turned to high-performance organic pigments to replace heavy-metal-
based pigments. Although high performance pigments meet perform-
ance requirements, 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 polyphosphoric 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
Rightfit™ 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/performance value. Since
1995, when Engelhard produced 6.5 million pounds of pigments contain-
ing heavy metals, it has been transitioning to Rightfit™ azo pigments.
In 2002, Engelhard produced only 1.2 million pounds of heavy-metal
pigments,- they expect to phase them out completely in 2004.
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
pigments. They are expected to have very low potential toxicity based on
toxicity studies, physical properties, and structural similarities to many
widely used food colorants. Because they have low potential toxicity
W 2004 Award
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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 exposure 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
significantly lower cost than high-performance organic pigments. Thus,
formulators 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 packag-
ing used in the food, beverage, petroleum product, detergent, and other
household durable goods markets.
2004 Designing Safer Chemicals Award 7 7
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2003 Winners
Academic Award
Professor Richard A. Gross
Polytechnic University
New Options for Mild and Selective Polymerizations Using Upases
Isolated Upases, harvested from living organisms, have been used as
catalysts for polymer synthesis in vitro. Professor Richard 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
lipases has been used to polymerize polyols directly. Alternative synthetic
pathways for such polymerizations require protection-deprotection
chemical steps. The mild reaction conditions allow polymerization of
chemically and thermally sensitive molecules. Current alternative chemi-
cal routes require coupling agents (e.g., carbodiimides) that would be
consumed in stoichiometric quantities relative to the reactants. Funda-
mental studies of these polymerizations have uncovered remarkable
capabilities of lipases for polymerization chemistry. Selected examples
include-, (i) lipases catalyze transesterification reactions between high-
molecular-weight chains in melt conditions,- (ii) lipases will use non-
natural nucleophiles such as carbohydrates and monohydroxyl
polybutadiene (Mn 19,000) in place of water; (iii) the catalysis of ring-
opening polymerization occurs in a controlled manner without termina-
tion reactions and with predictable molecular weights,- and (iv) the
selectivity of lipase-catalyzed step-condensation polymerizations leads to
nonstatistical molecular weight distributions (well below 2.0). These
accomplishments are elaborated below.
A series of polyokontaining polyesters was synthesized via a one-pot
lipase-catalyzed condensation polymerization. By using various mixtures
of polyols (e.g., glycerol, sorbitol) with other diacid and diol building
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blocks, the poiyols are partially or completely solubillzed, resulting in
highly reactive 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 (Mw up to
200,000) with narrow polydispersities (as low as 1.3). Further, the con-
densation reactions with glycerol and sorbitol building blocks proceed
with high regioselectivity. Although the poiyols used have three or more
hydroxyl groups, only two of these hydroxyl groups are highly reactive in
the polymerization. Thus, instead of obtaining highly crosslinked prod-
ucts, the regioselectivity provided by the lipase leads to lightly branched
polymers where the degree of branching varies with the reaction time
and monomer stoichiometry. 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 ability to incorporate carbohydrates,
such as sugars, into polyesters without protection-deprotection steps.
Professor Gross's laboratory discovered that certain lipases catalyze trans-
esterification reactions between high-molecular-weight chains that
contain intrachain esters or have functional end groups. Thus, lipases,
such as Lipase B from Candida antarctlca, 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. Trans-
acylation reactions occur because the lipase has the ability to accommo-
date 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 g/mol. In addition to
catalyzing metal-free transesterifications at remarkably low temperatures,
lipases endow transesterification reactions with remarkable selectivity.
This feature allows the preparation of block copolymers that have se-
lected block lengths.
2003 Academic Award 13
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Small Business Award
AgraQuest, Inc.
Serenade®: An Effective, Environmentally Friendly Biofungictde
Serenade® Biofungicide is based on a naturally occurring strain of
Bacillus 5(;£>?///s 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 Phillippines, Europe, Japan, and several other countries. The product
is formulated as a wettable powder, wettable granule, and liquid aqueous
suspension. Serenade® has been tested on 30 crops in 20 countries and
is registered for use in the United States on blueberries, cherries, cucur-
bits, 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 and 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 second-
ary metabolites produced by the bacteria. Serenade® prevents plant
diseases first by covering the leaf surface and physically preventing
attachment and penetration of the pathogens. In addition, Serenade®
produces 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. Strain QST-713 is the first strain reported to produce iturins,
plipastatins, and surfactins and 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.yvjth the iturins or
14 2003 Award
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the agrastatin/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-
harvest protection when there is weather conducive to disease develop-
ment around harvest time.
2003 Small Business Award 75
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Alternative Synthetic Pathways Award
Sud-Chemie Inc.
A Wastewater-Free Process for Synthesis of Solid Oxide Catalysts
Some major achievements in pollution reduction have been made
recently through advancement of catalytic technologies. One such effort
is in the area of hydrogen and clean fuel production. However, the
synthesis 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 emission. Meantime, it substantially reduces the
consumption of water and energy. For example, it is estimated that
about 378,900 tons of wastewater discharges, about 14,300 tons of
nitrate discharges, and about 3,800 tons of NOx emissions can be elimi-
nated for every 5,000 tons 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 to
form the oxide precursor. With assistance of the oxidation agent (typically
air), a porous solid oxide Is synthesized in one step at ambient tempera-
ture without any wastewater discharge. The other active ingredients of
the catalyst can be incorporated using the concept of wet-agglomeration.
In contrast, the precipitation process requires intensive washing and
filtration to remove nitrate and the other salts. Further, the new process
16 2003 Award
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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 after-burning of hydrogen.
This wastewater-free process for making solid oxide catalysts has been
demonstrated and more than 300 kg of the metal oxide catalysts has
been produced. Patent protection is being sought for the development.
The catalysts made by the green process give superior performance 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 Alternative Synthetic Pathways Award 17
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Alternative Solvents/
Reaction Conditions Award
DuPont
Microbia! Production of 1,3-Propanediol
DuPont 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 feedstock. This achievement, comprising biocatalytic
production of 1,3-propanediol from renewable resources, offers eco-
nomic as well as environmental advantages. The key to the novel
biological process 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 engi-
neered microorganism 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
process is environmentally green, less expensive, and more productive
than the chemical operations it replaces. 1,3-Propanediol, a key ingredi-
ent 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
biosynthetic pathways from several microorganisms into an industrial
host cell line allows the direct conversion of glucose to 1,3-propanediol, a
route not previously available in a single microorganism. Genes from a
yeast strain with the ability to convert glucose, derived from cornstarch,
18 2003 Award
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to glycerol were inserted into the host. Genes from a bacterium with the
ability to transform glycerol to 1,3-propanediol were also incorporated.
Additionally, the reactions present naturally in the host were altered to
optimize product formation. The modifications maximize the ability of
the organism to convert glucose to 1,3-propanediol while minimizing its
ability to produce biomass and unwanted byproducts. Coalescing
enzyme reactions from multiple organisms expands the range of materi-
als 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
traditional chemistry kept it from the marketplace. The biological process
using glucose as starting material will enable cost-effective manufacture
of Sorona® polymer, which will offer consumers 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 recovery at a high rate when it is stretched. As a result, Sorona®
improves fit and comfort because a 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® 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
environment and improve upon existing materials.
2003 Alternative Solvents/Reaction Conditions Award 19
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Designing Safer Chemicals Award
Shaw Industries, Inc.
EcoWorx™ Carpet Tile: A Cradle-to-Cradle Product
Historically, 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 our 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 Sub-
stances and Disease Registry and the U.S. Environmental Protection
Agency, 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
to be compatible with nylon carpet fiber. Although EcoWorx™ may be
recovered from any fiber type, nylon-6 provides a significant advantage.
20 2003 Award
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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
infrastructure 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 collection, 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
recovered from the elutriated nylon-6 is flowing back into nylon com-
pounding. EcoWorx™ will soon displace all PVC at Shaw.
2003 Designing Safer Chemicals Award 21
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8003 Winners
Academic Award
Professor EricJ. Beckman
University of Pittsburgh
Design of Non-Fluorous, Highly CO2-Soluble Materials
Carbon dioxide, an environmentally benign and nonflammable solvent,
has been investigated extensively in both academic and industrial
settings. Solubility studies performed during the 1980s had suggested
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
solubility studies inflated the solvent power value by as much as
20 percent due to the strong quadrupole moment of CO2 and that
carbon dioxide 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 of fluorinated precursors, therefore, have inhibited the com-
mercialization of many new applications for CO2, and the full promise of
CO2-based technologies has yet to be realized. To address this need.
22
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Professor Eric Beckman and his group at the University of Pittsburgh have
developed materials that work well, exhibiting miscibility pressures in
carbon dioxide that are comparable or lower than fluorinated analogs
and yet contain no fluorine.
Drawing from recent studies of the thermodynamics of CO2 mixtures,
Professor Beckman hypothesized that CO,-philic materials should contain
three primary features: (Da 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
primarily 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
favorable interactions with CO2.
Professor Beckman's simple heuristic model was demonstrated on three
sets of materials: functional silicones; poly(ether-carbonates); and ace-
tate-functional polyethers. Poly(ether-carbonates) were found to exhibit
lower miscibility pressures in CO2 than perfluoropolyethers, yet are
biodegradable 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 CO2 as a greener process solvent.
2002 Academic Award 23
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Small Business Award
SC Fluids, Inc.
SCORR - Supercritical CO2 Resist Remover
The semiconductor industry is the most successful growth industry in
history, with sales totaling over $170 billion in the year 2000. The fabrica-
tion of integrated circuits (ICs) relies heavily on photolithography to
define the shape and pattern of individual components. Current manu-
facturing 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-fabrica-
tion plant generates 4 million gallons of waste water and consumes
thousands of gallons of corrosive chemicals and hazardous solvents
each day.
SC Fluids, in partnership with Los Alamos National Laboratory, has
developed a new process, SCORR, that removes photoresist and post-
ash, -etch, and -CMP (paniculate) residue from semiconductor wafers.
The SCORR technology outperforms conventional photoresist removal
techniques in the areas of waste minimization, water use, energy con-
sumption, worker safety, feature size compatibility, material compatibility,
and cost. The key to the effectiveness of SCORR is the use of super-
critical CO2 in place of hazardous solvents and corrosive chemicals. Neat
CO2 is also utilized for the rinse step, thereby eliminating the need for a
deionized water rinse and an isopropyl alcohol drying step. In the closed
loop SCORR process, CO2 returns to a gaseous phase upon depressuriza-
tion, 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
discharge permits. It thoroughly strips photoresists from the wafer
surface in less than half the time required for wet-stripping and far
24 2002 Award
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outperforms plasma, resulting in increased throughput. It eliminates
rinsing and drying steps during the fabrication process, thereby simplify-
ing and streamlining the manufacturing process. It eliminates the need
for ultra-pure 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
continue 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 cleaning 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 supercritical fluids 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 manufacturers and equipment and material suppliers.
SCORR technology is being driven by industry in pursuit of its own
accelerated 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 commercial units (SC Fluids' Arroyo™ System). Other
industry leaders, such as IBM, ATMI, and Shipley, are participating in the
development of this innovative technology.
2002 Small Business Award 25
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Alternative Synthetic
Pathways Award
Pfizer. Inc.
Green Chemistry in the Redesign of the Sertraline Process
Sertraline 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
U.S. and that costs society $43.7 billion (1990 dollars). As of February
2000, more than 115 million Zoloft® prescriptions had been written in
the U.S.
Applying the principles of green chemistry, Pfizer has dramatically
improved the commercial manufacturing process of sertraline. After
meticulously investigating of each of the chemical steps, Pfizer Imple-
mented a substantive green chemistry technology for a complex com-
mercial 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 pollution 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 tetra-
lone, followed by reduction of the imine function and in-situ resolution
of the diastereomeric salts of mandelic acid to provide chirally pure
sertraline in much higher yield and with greater selectivity. A more
selective palladium catalyst was implemented in the reduction step,
26 2002 Award
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which reduced the formation of impurities and the need for reprocess-
ing. Raw 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, 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
140 metric tons/yr of the problematic reagent titanium tetrachloride.
This process change eliminates of 100 metric tons of 50 percent NaOH
use, 150 metric tons of 35 percent HCI waste, and 440 metric tons of solid
titanium dioxide wastes per year.
By eliminating waste, reducing solvents, and maximizing the yield of key
intermediates, Pfizer has demonstrated significant green chemistry
innovation in the manufacture of an important pharmaceutical agent.
2002 Alternative Synthetic Pathways Award 27
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Alternative Solvents/
Reaction Conditions Award
Cargill Dow LLC
NatureWorks™ PLA Process
Nature Works™ 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 Nature Works™
fibers features a unique combination of desirable attributes such as
superior hand, touch, and drape, wrinkle resistance, excellent moisture
management, 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 Nature Works™ PLA process offers significant environmental benefit
in addition to the outstanding performance attributes of the polymer.
Nature Works™ PLA products are made in a revolutionary new process
developed by Cargill Dow LLC that incorporates all 12 green chemistry
principles, "me 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
fermentation while molten lactide and polymer serve as the reaction
media in monomer and polymer production. Each step not only has
exceptionally high yields (>95 percent), but also utilizes internal recycle
streams to eliminate waste. Small (ppm) amounts of catalyst are used in
both the lactide synthesis and polymerization to further enhance effi-
ciency and reduce energy consumption. Additionally, the lactic acid is
derived from annually renewable resources, PLA requires 20-50 percent
28 2002 Award
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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 Nature
Works™ process and enhance the physical properties of PLA resins to
compete successfully with commodity petroleum-based plastics. Cargill
Dow is currently producing approximately 4,000 metric tons of PLA per
year to meet immediate market development needs. Production in the
first world-scale 140,000 metric ton/yr plant began November 1, 2001.
The Nature Works™ 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, Nature Works™ PLA
products can be either recycled or composted after use.
2002 Alternative Solvents/Reaction Conditions Award 29
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Designing Safer Chemicals Award
csi
ACQ Preserve®: The Environmentally Advanced Wood Preservative
The pressure-treated wood industry is a $4 billion industry, producing
approximately 7 billion board feet of preserved wood per year. More
than 95 percent of the pressure-treated wood used in the United States is
currently preserved with chromated copper arsenate (CCA). Approxi-
mately 150 million pounds of CCA wood preservatives were used in the
production of pressure-treated wood in 2001, enough wood to build
435,000 homes. About 40 million pounds of arsenic and 64 million
pounds of hexavalent chromium 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
designed 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 or ammonia. Carbon dioxide (CO2) is added to the
formulation to improve stability and to aid in solubilization of the copper.
Replacing CCA with ACQ is one of the most dramatic pollution preven-
tion advancements in recent history. Because more than 90 percent of
the 44 million pounds of arsenic used in the U.S. each year is used to
30 2002 Award
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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 hexavalent chromium. Further, ACQ avoids
the potential risks associated with the production, transportation, use,
and disposal of the arsenic and hexavalent chromium contained in CCA
wood preservatives and CCA-treated wood. In fact, ACQ does not
generate any RCRA* 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 1 million active pounds of ACQ wood preservatives were sold in the
U.S. in 2001 for use by thirteen wood treaters to produce over 100 million
board feet of ACQ-preserved wood. In 2002, CSI plans to spend approxi-
mately $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 transition away
from arsenic-based wood preservatives to a new generation of preserva-
tive systems.
* RCRA - Resource Conservation and Recovery Act
2002 Designing Safer Chemicals Award 31
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8001 Winners
Academic Award
Professor Chao-Jun LI
Tulane University
Quasi-Nature Catalysis: Developing Transition Metal Catalysis in Air
and Water
The use of transition metals for catalyzing reactions is of growing
importance in modern organic chemistry. These catalyses are widely
used in the synthesis of Pharmaceuticals, fine chemicals, petrochemicals,
agricultural 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
essential 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,
biodegradation, 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
conditions 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 water.
Specifically, LI has developed a novel [3+2] cycloaddition reaction to
generate 5-membered carbocycles in water; a synthesis of beta-hydroxyl
esters in water; a chemo-selective alkylation and pinacol coupling reac-
tion mediated by manganese in water; and a novel alkylation of
1,3-dicarbonyl-type compounds in water. Li's work has enabled 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
32
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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 advan-
tages. Water is readily available and inexpensive, and is not flammable,
explosive, or toxic. Consequently, aqueous-based production processes
are inherently 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 tempera-
ture 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, the work of Li in developing tra'nsition-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 33
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Small Business Award
EDEN Biosclence Corporation
Messenger®: A Green Chemistry Revolution in Plant Production and
Food Safety
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
annual losses to growers from pests reach $300 billion worldwide. In
addition to basic agronomic practices, growers generally have two
alternatives to limit these economic losses and increase yields: (1) use
traditional chemical pesticides; or (2) grow crops that are genetically
engineered for pest resistance. Each of these approaches has come
under increasing criticism from a variety of sources worldwide including
environmental groups, government regulators, consumers, and labor
advocacy groups. Harpin technology, developed by EDEN Bioscience
Corporation, provides growers with a highly effective alternative ap-
proach 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, harpin increases plant biomass, photosyn-
thesis, nutrient uptake, and root development and, ultimately, leads to
greater crop yield and quality.
Unlike most agricultufal chemicals, harpin-based products are produced
in a water-based fermentation system that uses no harsh solvents or
reagents, requires only modest energy inputs, and generates no hazard-
34 2001 Award
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ous 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 a U.S. EPA-approved product called
Messenger®, that has been demonstrated on more than 40 crops to
effectively stimulate plants to defend themselves against a broad spec-
trum 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 to
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 UV and natural microorganisms and
has no potential to bioaccumulate or to contaminate surface or ground-
water 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.
2007 Sma// Business Award 35
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Alternative Synthetic
Pathways Award
Bayer Corporation and Bayer AC
Baypure™ CX: Iminodisuccinate
An Environmentally Friendly and Readily Biodegradable Chelating Agent
Chelating agents are used in a variety of applications, including deter-
gents, agricultural nutrients, and household and industrial cleaners.
Most traditionally used chelating agents, however, are poorly biodegrad-
able. Some are actually quite persistent and do not adsorb at the surface
of soils in the environment or at activated sludge in wastewater treat-
ment plants. Because of this poor biodegradability combined with high
water solubility, traditionally used 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 manufactures a
readily biodegradable and environmentally friendly chelating agent,
D,L-aspartic-N-(1,2-dicarboxyethyl) tetrasodium salt, also known as sodium
iminodisuccinate. This agent is characterized by excellent chelation
capabilities, especially for iron(lll), copper(ll), and calcium, and is both
readily biodegradable and benign from a toxicological and ecotoxico-
logical standpoint. Sodium iminodisuccinate is also an innovation in the
design of chemicals that favorably impact the environment. This accom-
plishment was realized not by "simple' modification of molecular struc-
tures of currently used chelating agents, but instead by the development
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
commercially.
36 2001 Award
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Sodium imlnodisuccinate belongs to the aminocarboxylate class of
chelating agents. Nearly all aminocarboxylates in use today are acetic
acid derivatives produced from amines, formaldehyde, sodium hydrox-
ide, and hydrogen cyanide. The industrial use of thousands of tons of
hydrogen 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 ammo-
nia. The only solvent used in the production process is water, and the
only side product 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 non-polluting 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 dish-
washing detergents to extend and improve the cleaning properties of the
8 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
iminodisuccinate chelating agent offers the dual benefits of producing
a biodegradable, environmentally friendly chelating agent that is also
manufactured in a waste-free process.
200 / Alternative Synthetic Pathways Award 37
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Alternative Solvents/
Reaction Conditions Award
Novozymes North America, Inc.
BioPreparation™ of Cotton Textiles: A Cost-Effective, Environmentally
Compatible Preparation Process
In textiles, the source of one of the most negative impacts on the
environment 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 and 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 break down or release natural waxes, oils, and contami-
nants, and emulsify or suspend these impurities in the scouring bath.
Typically, scouring wastes contribute high BOD loads during cotton textile
preparation (as much as 50 percent).
Novozymes' BioPreparation™ technology is an alternative to sodium
hydroxide that offers many advantages for textile wet processing, includ-
ing reduced BOD/COD and decreased water use. BioPreparation™ is an
38 2001 Award
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enzymatic process for treating 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 (amyiases, 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 combining
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 89 million m3/yr
of water in processing goods from scouring to finishing; the
BioPreparation™ approach would save from 27-45 million m3/yr
of water. In addition, field trials established that BOD and COD loads
are decreased by 25 and 40 percent, respectively, when compared to
conventional sodium hydroxide treatments. Furthermore, these conser-
vation measures translate directly into costs 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.
2007 Alternative Solvents/Reaction Conditions Award 39
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Designing Safer Chemicals Award
PPG Industries
Yttrium as a Lead Substitute in Catlonic Electrodeposltion Coatings
PPG Industries introduced the first cationic electrodeposition primer to
the automotive industry in 1976. During the succeeding years, this
coating 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 effi-
ciency (low waste), reliable automated application, and very low organic
emissions. Unfortunately, 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 corro-
sion 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 construction 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 lead can be replaced by yttrium in cationic electrocoat without any
sacrifice in corrosion performance. Yttrium is a common element in the
environment, 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,
yttrium is 100 times safer than lead at typical levels of use.
40 2001 Award
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Numerous other benefits are realized when yttrium is used in electrocoat
applications. Yttrium is twice as effective as lead on a weight basis,
allowing the formulation of commercial coatings that contain half the
yttrium by weight relative to lead in comparably performing lead-contain-
ing 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 LD50 of
>10g/kg in rats, which is in stark contrast to lead. The ubiquitous 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
vehicle. By using yttrium in the electrocoat step, chrome can be com-
pletely 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 compromis-
ing 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, approxi-
mately one million pounds of lead (as lead metal) will be removed from
the electrocoat applications of PPG automotive customers.
2007 Designing Safer Chemicals Award 41
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8000 Winners
Academic Award
Professor Chi-Huey Wong
The Scripps Research Institute
Enzymes In Large-Scale Organic Synthesis
Organic 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, catal-
ysts, and processes have made possible the synthesis of molecules with
varying degrees of complexity. The types of problems at which non-
biological 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 molecular research and development.
Compounds with polyfunctional groups, such as carbohydrates and
related structures, pose particular challenges to nonbiological synthetic
methods, but are natural targets for biological methods. In addition,
biological methods are necessary to deal with increasing constraints
imposed by 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 the best opportunities
now available to chemistry and the pharmaceutical industry.
Professor Chi-Huey Wong at the Scripps Research Institute has pioneered
work on the development of effective enzymes and the design of novel
42
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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
resolutions and stereoselective syntheses) to complex, multi-step enzy-
matic reactions (e.g., oligosaccharide synthesis). For example, the
irreversible enzymatic transesterification reaction using enol esters in
environmentally acceptable organic solvents invented by Wong repre-
sents the most widely used method for enantioselective transformation
of alcohols in pharmaceutical development. The multi-enzyme system
based on genetically engineered giycosyltransferases coupled with in situ
regeneration of sugar nucleotldes 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 Profes-
sor Wong represents a new field of green chemistry suitable for large-
scale synthesis that is impossible or impractical to achieve by nonenzy-
matic means.
2000 Academic Award 43
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Small Business Award
RevTech, Inc.
Envirogjuv™: A Technology for Decorating Glass and Ceramicware With
Radiation-Curable Environmentally Compliant Inks
Billions 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
various 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 °F or 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
serious 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
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
decorated glass container that is aesthetically pleasihg, durable, and
44 2000 Award
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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 of that achieved with 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 pigments used
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 associated with the ACL process. This provides additional
safety and environmental benefits, such as reduced energy consumption
and reduced chance of worker injury. In addition, there is less raw
material use and the process does not generate any waste ink. Further-
more, 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 45
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Alternative Synthetic
Pathways Award
Roche Colorado Corporation
An Efficient Process for the Production of Cytovene®, A Potent
Antiviral Agent
The design, development, and implementation of environmentally
friendly processes for the large-scale production of pharmaceutical
products is one of the most technically challenging aspects of business
operations in the pharmaceutical industry. Roche Colorado Corporation
(RCC), in establishing management and operational systems for the
continuous improvement of environmental quality in its business activi-
ties, has, in essence, adopted the Presidential Green Chemistry Chal-
lenge Program's basic principles of green chemistry: the development of
environmentally friendly processes for the manufacture of pharmaceuti-
cal products. In particular, RCC has successfully applied these principles
to the manufacture of Cytovene®, a potent antiviral agent used in the
treatment of cytomegalovirus (CMV) retinitis infections in immuno-
compromised 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
commercially viable process for the production of Cytovene®. By
1993, chemists at RCCs 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 50 metric
tons per year. Leveraging the basic principles of green chemistry and
molecular conservation into the design process, significant improve-
ments were demonstrated in the second-generation Guanine Triester
(GTE) Process. Compared to the first-generation commercial manufactur-
ing process, the GTE Process reduced the number of chemical reagents
and intermediates from 22 to 11, eliminated the (only) two hazardous
46 2000 Award
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solid waste streams, eliminated 11 different chemicals from the hazard-
ous liquid waste streams, and efficiently recycled and reused four of the
five ingredients not incorporated into the final product. Inherent within
the process improvements 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 throughput increase of 100 percent.
In summary, the new GTE Process for the commercial production of
Cytovene® clearly demonstrates the successful implementation of the
general principles of green chemistry: the development of environmen-
tally friendly syntheses, including the development of alternative synthe-
ses utilizing nonhazardous and nontoxic feedstocks, reagents, and
solvents; elimination of waste at the source (liquid waste: 1.12 million
kg/yr and solid waste: 25,300 kg/yr); 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 registered with the U.S.
Food and Drug Administration (FDA) as the current manufacturing
process for the world's supply of Cytovene®.
2000 Alternative Synthetic Pathways Award 47
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Alternative Solvents/
Reaction Conditions Awards
Bayer Corporation and Bayer AC
Two-Component Waterborne Polyurethane Coatings
Two-component (2K) waterborne polyurethane coatings are an outstand-
ing 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 2K solventborne polyurethane coatings with water
as the carrier, without significant reduction in performance of the
resulting 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 dispersions 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
resins had to be developed. To overcome some application difficulties,
new mixing/spraying equipment was also developed. For the technology
48 2000 Award
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to be commercially viable, an undesired reaction of a polyisocyanate
crosslinker 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, 2K waterborne polyurethane floor coatings
provide a quick dry, high abrasion resistance, and lack of solvent smell
(<0.1 Ib/gal organic solvent). In wood applications, 2K waterborne
polyurethane coatings meet the high-performance wood finishes
requirements for kitchen cabinet office, and laboratory furniture
manufacturers while releasing minimal organic solvents in the workplace
or to the atmosphere. In the U.S., the greatest market acceptance of
2K 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
coatings with camouflage requirements, corrosion protection, chemical
and chemical agent protection, flexibility, and exterior durability, along
with VOC reductions of approximately 50 percent.
2000 Alternative Solvents/Reaction Conditions Award 49
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Designing Safer Chemicals Award
Dow AgroSciences LLC
Sentricon™ Termite Colony Elimination System, A New Paradigm for
Termite Control
The 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
experience a termite problem and seek a control option. From the
1940s until 1995, the nearly universal treatment approach for subterra-
nean termite control Involved the placement of large volumes of insecti-
cide 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, potential hazards associated with accidental misappli-
cations, spills, off-target applications, and worker exposure. These
inherent problems associated with the use of chemical barrier ap-
proaches for subterranean termite control created a need for a better
method. The search for a baiting 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, "me Sentricon™ Termite
Colony Elimination System, developed by Dow AgroSciences in collabora-
tion with Dr. Su, was launched commercially in 1995 after receiving U.S.
EPA registration as a reduced-risk pesticide. Sentricon™ represents truly
novel technology employing an Integrated Pest Management approach
using monitoring and targeted delivery of a highly specific bait. Because
it eliminates termite colonies threatening structures using a targeted
approach, Sentricon™ delivers unmatched technical performance,
50 2000 Award
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environmental compatibility, and reduced human risk. The properties of
hexaflumuron as a termite control agent are attractive from an environ-
mental 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 applicabil-
ity 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
novel research methodologies, new delivery systems, and the establish-
ment of an approach that integrates monitoring and baiting typify the
innovation that has been a hallmark of the project. More than 300,000
structures across the U.S. are now being safeguarded through application
of this revolutionary technology, and adoption is growing rapidly.
2000 Designing Safer Chemicals Award 51
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1999 Winners
Academic Award
Professor Terry Collins
Carnegie Mellon University
TAAAL™ Oxidant Activators:
General Activation of Hydrogen Peroxide for Green Chemistry
Twenty years of research by Professor Terry Collins at Carnegie Mellon
University have led to the successful development of a series of environ-
mentally friendly oxidant activators based on iron. These TAML™
(tetraamido-macrocyclic ligand) activators catalyze the reactions of
oxidants in general. Their activation properties with hydrogen peroxide
in water are of greatest environmental significance. TAAAL™ activators
arise from a design process invented by Professor Collins which is
complementary to that employed by Nature to produce powerful oxidiz-
ing enzymes, "me activators promise extensive environmental benefits
coupled with superior technical performance and significant cost savings
across a broad-based segment of oxidation technology. Users of TAML™
peroxide activators will range from huge primary extractive-processing
industries to household consumers throughout the world. In laboratory
tests, the Collins activators have shown this potential in the major indus-
trial application of wood-pulp delignification and in the broad-based
consumer process of laundry cleaning.
Annually, bleached pulp has a global value of approximately $50 billion.
"me 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. It has been clearly demonstrated that
TAML™ activators can provide the Pulp and Paper Industry (P&PI) with the
first low-temperature hydrogen peroxide-based delignification technol-
ogy for treating pulp. The new process moves the elemental balance of
52
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pulp delignification closer to what Nature employs for degrading lignin, a
strategy reflected In the industry's recent development of totally chlorine
free (TCP) bleaching procedures. TAML™- activated peroxide delignifi-
cation proceeds rapidly and efficiently at 50 °C indicating that minimal
capital will be required to retrofit existing mills for its use. The new
technology is more selective than any other TCP process and, except at
low lignin content, is as selective as the current dominating delignifi-
cation technology based on chlorine dioxide. These parameters show
that the new technology can significantly reduce persistent pollutants
associated with chlorine-containing delignifying agents by enabling the
industry to use peroxide to remove the majority of lignin from kraft pulp
more selectively and rapidly.
In the laundry field of use, most household bleaches are based upon
peroxide. Here, TAML™ activators enable the most attractive dye transfer
inhibition processes ever developed. Almost all the approximately
80 dyes used on commercial textiles are safe from TAAAL™-activated
peroxide while they are bound to a fabric. But most cases, should a
dye molecule escape a fabric, the same TAML™-activated peroxide will
intercept and destroy it before it is able to transfer to other fabrics. This
attribute and the improved stain removal properties of TAML™-activated
peroxide offer significant commercial advantages for laundry products
producers. In addition, the combined features translate to both direct
and indirect environmental benefits by enabling laundering that replaces
stoichiometric with catalytic procedures and that requires less water.
Numerous other uses are anticipated; some are currently being devel-
oped including the use of TAML™- peroxide activators for water
disinfection.
7999 Academic Award 53
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Small Business Award
Bioflne, Inc.
Conversion of Low-Cost Biomass Wastes to Levulinic Acid
and Derivatives
Using biomass rather than petroleum to manufacture chemicals has
numerous advantages. Renewable biomass contributes no net CO2 to
the atmosphere, conserves fossil fuels, and leads to a secure domestic
supply of feedstocks capable of making a huge array of chemical prod-
ucts. Biofine, Inc. has developed a high-temperature, dilute-acid hydrol-
ysis process that converts cellulosic biomass to levulinic acid (LA) and
derivatives. Cellulose is initially converted to soluble sugars, which are
then transformed to levulinic acid. The process is economical even
without receiving waste disposal fees for feedstock, and wet feedstocks
can be used without drying, thereby saving energy.
In August 1997, Biofine, the U.S. Department of Energy, the New York
State Energy Research and Development Authority, and Biometics, Inc.
began manufacturing LA from paper mill sludge at a one-ton-per-day
demonstration plant at Epic Ventures, Inc. in South Glen Falls, New York.
Biofine's process had already been demonstrated on a smaller scale with
a variety of cellulosic feedstocks, including municipal solid waste,
unrecyclable municipal waste paper, waste wood, and agricultural
residues. Biofine hopes to serve the growing need for environmentally
acceptable waste disposal options.
LA niche markets provide excellent small-scale opportunities; large-scale
opportunities will open up as Biofine lowers the price of this highly
versatile chemical intermediate. LA's worldwide market is about one
million Ib/yr at a price of $4-6/lb. Full-scale commercial plants are
feasible at 50 dry ton/day of feedstock. At this scale, LA could be pro-
duced at $0.32/lb and converted into commodity chemicals such as
54 1999 Award
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succinic acid and diphenolic acid, which sell for $2/lb or less, or acrylic
acid, which sells for $0.50/lb. Eventually, Biofine hopes to build larger
plants to convert 1,000 dry ton/day of feedstock into LA at $0.04-0.05/lb.
The worldwide commercial market for LA and its derivatives could reach
1 trillion Ib/yr. Full-scale plant opportunities are being assessed for
several locations in the U.S. and worldwide. One full-scale commercial
plant using 1,000 dry ton/day of feedstock could manufacture more than
160 million Ib/yr of product. Fortunately, Biofine's technology is economi-
cal for a broad range of plant sizes; even the one-ton-per-day demonstra-
tion plant is self-sufficient at LA's existing price.
Because LA is a platform chemical, it need not be sold as a commodity
chemical. Derivatives are the key to marketability, and markets exist for
such LA derivatives as tetrahydrofuran, butanediol, y-butyrolactone,
succinic acid, and diphenolic acid. Fortunately, many economical
conversion processes are possible. The National Renewable Energy
Laboratory (NREL), Pacific Northwest National Laboratory (PNNL), and
Rensselaer Polytechnic Institute (RPI) are developing market applications
and production methods for other derivatives, including methyltetra-
hydrofuran (MTHF), a gasoline fuel additive,- 5-amino levulinic acid
(DALA), a broad-spectrum, nontoxic, and biodegradable pesticide,- and
new biodegradable polymers.
7999 Small Business Award 55
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Alternative Synthetic
Pathways Award
Lilly Research Laboratories
Practical Application of a Biocatalyst in Pharmaceutical Manufacturing
The synthesis of a pharmaceutical agent is frequently accompanied by
the use and generation of a large amount of hazardous substances, "mis
should not be surprising, as numerous steps are commonly necessary,
each of which may require feedstocks, reagents, solvents, and separation
agents. An example of an effort to reduce these hazards, employed by
Lilly Research Laboratories, is the use of an alternate synthetic pathway
designed for the environmentally responsible production of a LY300164, a
central nervous system compound in the early stages of development.
The original synthesis, which was employed to support early clinical
development, proved to be an economically viable manufacturing
process. The approach, however, involved several problematic steps.
The process required the use of large solvent volumes and chromium
oxide (a cancer suspect agent), which led to the generation of dispropor-
tional quantities of chromium waste compared to drug produced. These
points provided compelling incentive to pursue an alternate synthetic
approach.
The new synthetic pathway successfully increased worker safety and
limited environmental impact by offering a strategy that more appro-
priately controlled oxidation state adjustments. The new synthesis
involved the implementation of several inventive steps on large scale.
In particular, keto-reductase activity of a common microorganism,
Zygosaccharomyces rouxii, was discovered that led to excellent stereo-
control in the asymmetric reduction of a dialkyl ketone. Implementation
of the biocatalytic process was enabled on a large scale by employing a
novel, yet simple, three-phase reaction system. The protocol overcame
56 1999 Award
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long-standing limitations preventing the practical application of yeast-
mediated reductions by allowing high concentrations of the substrate to
be charged to the aqueous reaction medium and by providing a facile
method for product isolation. An unprecedented autoxidation reaction
of a C-1 aryl isochroman, which involved the treatment of the substrate
with air and sodium hydroxide, was also discovered that eliminated the
use of transition metal oxidants.
The new process was developed by combining innovations from chemis-
try, microbiology, and engineering. The process circumvented the use of
non-recycled metal and significantly reduced solvent usage. For ex-
ample, when conducted on a scale to generate 100 kg of LY300164, the
new process avoids the use of approximately 34,000 liters of solvent and
eliminates production of approximately 300 kg of chromium waste. In
addition, the synthetic scheme proved more efficient as well, with yield
climbing from 16 to 55 percent. The inventive steps of the process
represent low cost and easily implemented technology, which should
find broad manufacturing applications.
7999 Alternative Synthetic Pathways Award 57
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Alternative Solvents/
Reaction Conditions Award
Nalco Chemical Company
Water-Based Liquid Dispersion Polymers
Annually, at least 200 million pounds of water-soluble, acrylamide-based
polymers are used to condition and purify water in various industrial and
municipal operations. These water-soluble polymers assist in removing
suspended solids and contaminants and effecting separations. Conven-
tionally, in order to prepare such polymers in liquid form for safety and
ease of handling, the water-soluble monomers, water, and a hydrocar-
bon (oil) and surfactant 'carrier" mixture are combined in approximately a
1 -.1:1 ratio to form an emulsion. The monomers are then polymerized.
Regrettably, the oil and surfactant components of these inverse emul-
sions lend no value to the performance of the polymers,- they simply
allow their manufacture in liquid form. This means that approximately
90 million pounds of oil and surfactant are introduced into the environ-
ment (at the current consumption rates) as a consequence of their use.
Until now, there has been no alternative technology available to manu-
facture liquid polymers without the obvious environmental disadvan-
tages associated with the oil- and surfactant-based carrier systems.
In order to overcome the disadvantages of conventional liquid emulsion
polymers, Nalco has developed a series of new polymer products that
are produced through a unique polymerization technology that permits
the manufacture of these widely used polymers as fine particles dis-
persed in aqueous solutions of the inorganic salt ammonium sulfate.
Thus, while the chemistry of the active polymer component is the same,
the technology allows for the production of the polymers as stable
colloids in water. Since these dispersion polymers are liquid, they retain
the virtues of ease and safety of handling, but employing aqueous salt
solutions instead of hydrocarbons and surfactants as the reaction me-
ss 1999 Award
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dium and polymer carrier means that no oil or surfactants are released
into the environment when the polymers are used in the water treatment
application.
By choosing to manufacture water-based dispersions instead of water-in-
oil emulsions, Nalco has conserved over one million pounds of hydro-
carbon solvent and surfactants since 1997 on just two polymers in the
product line. There are also benefits over the water-in-oil emulsion
polymers for the users of these products as a consequence of their
water-based formulations. For example, as the products contain no oil,
they are safer to transport and use because they are nonflammable and
emit no volatile organic compounds (VOCs).
As mentioned, the water-based dispersion polymers make use of ammo-
nium sulfate salt, a waste byproduct from the manufacture of caprolac-
tam, the precursor to nylon. The preparation of water-based dispersion
polymers instead of water-in-oil emulsions allows Nalco to recycle and
make use of this byproduct from another industry for water treatment
and purification. Choosing to produce these polymers as water-based
dispersions instead of as water-in-oil emulsions allowed Nalco to utilize
over 3.2 million pounds of caprolactam-produced ammonium sulfate in
1998 alone.
Finally, because these new polymers are water-based, they dissolve
readily in water without the complex and relatively expensive mixing and
feeding equipment that is required for the use of water-in-oil polymers.
This distinct advantage provides new opportunities for medium- and
smaller-sized operations to treat wastewater streams cost-effectively.
1999 Alternative Solvents/Reaction Conditions Award 59
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Designing Safer Chemicals Award
DowAgroSciences LLC
Spinosad, A New Natural Product for Insect Control
Estimates of monetary losses In crops as a result of uncontrolled Insect
infestations are staggering, far in excess of the current $12 billion market
for insect control products. Man's continuing quest to control damaging
insect pests in crops or on property has spawned several eras of agricul-
tural insect control, most recently the advent of synthetic organic chemi-
cals as insecticides. However, the development of resistance has re-
duced the effectiveness of many of the currently available insecticides,
and more stringent environmental and toxicological hurdles have re-
stricted the use of others.
It was against this backdrop that researchers at Eli Lilly and Company
introduced higrwolume testing of fermentation isolates in agricultural
screens in the mid-1980s. From this program, the microorganism
Saccaropolyspora spinosa was isolated from a Caribbean island soil
sample, and the insecticidal activity of the spinosyns, a family of
unique macrocyclic lactones, was identified and developed by Dow
AgroSciences as a highly selective, environmentally friendly insecticide.
In Latin, "saccharopolyspora" means "sugar-loving, with many spores,"
and 'splnosa* refers to the spiny appearance of the spores. The microor-
ganism is an aerobic, gram-positive bacterium that is not acid fast, motile,
or filamentous. Most of the activity is produced by a mixture of spinosyn
A and spinosyn D, assigned the common name of spinosad. Spinosad
combines highly efficacious control of many chewing insect pests in
cotton, trees, fruits, vegetables, turf, and ornamentals with a superior
environmental profile, including mammalian and nontarget safety.
Insects exposed to spinosad exhibit classical symptoms of neurotoxicity,
including lack of coordination, prostration, tremors, and other involuntary
60 1999 Award
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muscle contractions, eventually leading to paralysis and death. Detailed
investigations of the symptomology and electrophysiology have indi-
cated, however, that spinosad is not acting through any known mecha-
nism. It appears to affect insect nicotinic and v-aminobutyric acid
receptor function through a novel mechanism.
Spinosad presents a favorable environmental profile. Spinosad does not
leach, bioaccumulate, volatilize, or persist in the environment. Hundreds
of innovative product development trials conducted over several years
have characterized the activity and determined that spinosad leaves
70-90 percent of beneficial insects and predatory wasps unharmed. The
low levels of mammalian toxicity result in reduced risk to those who
handle, mix, and apply the product. Similarly, relatively high margins of
safety for avian and aquatic species translate into reduced or nonexistent
buffer zones and fewer regulated nontarget compliance measures.
These advantages allow growers to control damaging crop pests with
fewer concerns about human or environmental safety and costly second-
ary pest outbreaks.
The first product containing spinosad (Tracer Naturalyte™ Insect Control)
received expedited review by the U.S. EPA and was granted registration
as a "reduced risk" insect control product for cotton in early 1997. Addi-
tional registrations, introduced as SpinTor™, Success™, Precise™, and
Conserve™, have recently been granted for insect control in vegetable
and tree crops and in the urban environment for control of turf and
ornamental plant nests.
1999 Des/gn/ng Safer Chemicals Award 61
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1998 Winners
Academic Award
Professor Barry M. Trost
Stanford University
The Development of the Concept of Atom Economy
The general area of chemical synthesis covers virtually all segments of
the chemical industry— oil refining, bulk or commodity chemicals, fine
chemicals, including agrochemicals, flavors, fragrances, etc., and Pharma-
ceuticals. Economics generally dictates the feasibility of processes that
are 'practical'. A criterion that traditionally has not been explicitly recog-
nized 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. Profes-
sor Barry M. Trost has explicitly enunciated a new set of criteria by which
chemical processes should be evaluated. They fall under two catego-
ries—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 non-renewable resources. It is self-evident that such re-
sources should be used as sparingly as possible. Second, all waste
streams should be minimized. This requires employment of reactions
that produce minimal byproducts, either through the intrinsic stoichiom-
etry of a reaction or 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
polyfunctional molecule), regioselectivity (orientational control),
diastereoselectivity (control of relative stereochemistry), and
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enantioselectivity (control of absolute stereochemistry). These consider-
ations have been readily accepted by the chemical community at large.
In approaching these goals, little attention traditionally has been paid to
the question of what is required. In too many cases, efforts to achieve
the goal of selectivity led to reactions requiring multiple components in
stoichiometric quantities that are not incorporated in the product or
reagents, thus intrinsically creating significant amounts of byproducts.
Consideration of how much of the reactants ends 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 gener-
ally was not adopted by either academia or industry. Many in industry,
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 chemi-
cal 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 gen-
eral, utilize 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 applica-
tions for which such methodology may offer more efficient syntheses.
1998 Academic Award 63
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Academic Award
Dr. Karen M. Draths and Professor John W. Frost
Michigan State University
Use of Microbes as Environmentally Benign Synthetic Catalysts
Fundamental change in chemical synthesis can be achieved by elabora-
tion of new, environmentally benign routes to existing chemicals.
Alternatively, fundamental change can follow from characterization and
environmentally 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
biocatalysis 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, hemi-
cellulose, and cellulose. In addition, water is used as the primary reac-
tion solvent, and the generation of toxic intermediates and environment-
damaging byproducts is avoided.
In excess of 1.9 billion kg of adipic acid is produced annually and used in
the manufacture of nylon 66. Most commercial syntheses of adipic acid
use benzene, derived from the benzene/toluene/xylene (BIX) 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 to the
massive scale on which it is industrially synthesized, adipic acid manufac-
ture has been estimated to account for some 10 percent of the annual
increase in atmospheric nitrous oxide levels. The Draths-Frost synthesis
of adipic acid begins with the conversion of glucose into c/s,c/s-muconic
64 1998 Award
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acid using a single, genetically engineered microbe expressing a biosyn-
thetic 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,
Acinetobacter calcoaceticus, and Escherichia coll. "me c/s,c/s-muconic
acid, which accumulates extracellularly, is hydrogenated to afford
adipic acid.
Yet another example of the Draths-Frost strategy for synthesizing indus-
trial chemicals using biocatalysis and renewable feedstocks is their
synthesis of catechol. Approximately 21 million kg of catechol is pro-
duced globally each year. Catechol is an important chemical building
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 renewable 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 the use of renewable feedstocks,
carbohydrate starting materials, and microbial biocatalysis. As the world
moves to national limits on carbon dioxide emissions, each molecule of
a chemical made from a carbohydrate may well be counted as a credit
due to the carbon dioxide that is fixed by plants to form the carbo-
hydrate. Biocatalysis using intact microbes also allows the Draths-Frost
syntheses to utilize water as a reaction solvent, near-ambient pressures,
and temperatures that typically do not exceed human body temperature.
7998 Academic Award 65
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Small Business Award
PYROCOOL Technologies, Inc.
Technology for the Third Millennium: The Development and Commercial
Introduction of an Environmentally Responsible Rre Extinguishment and
Cooling Agent
Advances 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 environ-
mental 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 (ODP) value of 10 to 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 ground water supplies and failure of
wastewater treatment systems.
In 1993, PYROCOOL Technologies initiated a project to create a fire
extinguishment and cooling agent that would be effective in extinguish-
ing fires and that would greatly reduce the potential long-term environ-
66 1998 Award
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mental and health problems associated with traditionally used products.
To achieve this objective, PYROCOOL Technologies first determined that
the product (when finally developed) would contain no glycol ethers or
fluorosurfactants. 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 surfactants, 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 Ttie 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.
PYROCOOL 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
78,000 tons 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 traditionally used fire extinguishment agents.
Because PYROCOOL F.E.F. is mixed with water at only 0.4 percent, an
87-93 percent reduction in product usage is realized compared to
conventional extinguishment agents typically used at 3-6 percent. Fire
affects all elements of industry and society and no one is immune from
its dangers. PYROCOOL F.E.F. provides an innovative, highly effective,
and green alternative for firefighters.
1998 Small Business Award 67
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Alternative Synthetic Pathways Award
Flexsys America LP.
Elimination of Chlorine in the Synthesis of 4-Aminodiphenylamine:
A New Process That Utilizes Nucleophilic Aromatic Substitution
for Hydrogen
The development of new environmentally favorable routes for the
production of chemical intermediates and products is an area of consid-
erable 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 atomically efficient chemical reactions. Ultimately, it was
Monsanto's goal to incorporate fundamentally new chemical reactions
into innovative processes that would focus on the elimination of waste at
the source. In view of these emerging requirements, Monsanto's Rubber
Chemicals Division (now Flexsys), in collaboration with Monsanto Corpo-
rate Research, began to explore new routes to a variety of aromatic
amines that would not rely on the use of halogenated intermediates 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
300 million Ib/yr, of which Flexsys is the world's largest producer. (Flexsys
is a joint venture of Monsanto's and Akzo Nobel's rubber chemicals
operations.)
Flexsys's current process to 4-ADPA is based on the chlorination of
benzene. Since none of the chlorine used in the process ultimately
68 1998 Award
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resides In the final product, the pounds of waste generated in the
process per pound of product produced from the process is 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 aromatic substitution of hydrogen
(NASH). Through a series of experiments designed to probe the mecha-
nism of NASH reactions, Flexsys realized a breakthrough in understand-
ing this chemistry that has led to the development 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 Ib/yr less chemical waste would be
generated and 1.4 billion Ib/yr less wastewater would be generated. The
discovery of the new route to 4-ADPA and the elucidation of the mecha-
nism of the reaction between aniline and nitrobenzene have been
recognized throughout the scientific community as a breakthrough 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
Implemented into innovative and environmentally safe chemical
processes.
7998 Alternative Synthetic Pathways Award 69
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Alternative Solvents/
Reaction Conditions Award
Argonne National Laboratory
Novel Membrane-Based Process for Producing Lactate Esters-
Nontoxic Replacements for Halogenated and Toxic Solvents
Argonne National Library (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 pro-
cess requires little energy input, is highly efficient and selective, and
eliminates the large volumes of salt waste produced by conventional
processes. 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 innova-
tion overcomes major technical hurdles that had made current produc-
tion processes for lactate esters technically and economically noncom-
petitive. 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:
154 °C, melting point: 40 °C), 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. Lactate esters (primarily
ethyl lactate) can replace most halogenated solvents (including ozone-
depleting CFCs, carcinogenic methylene chloride, toxic ethylene glycol
ethers, perchloroethylene, and chloroform) on a 1:1 basis. At current
70 1998 Award
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prices ($1.60-2.00/lb), the market for ethyl lactate is about 20 million Ib/yr
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/lb and enable ethyl lactate to compete directly with petro-
leum-derived toxic solvents currently used. The favorable economics of
the ANL membrane process, therefore, can lead to the widespread
substitution of petroleum-derived toxic solvents by ethyl lactate in elec-
tronics 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 3.8 million tons of solvents in
the U.S. 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
Intermediates for synthesizing polymers, biodegradable plastics, oxygen-
ated 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 alternative to many chemicals and products derived from petro-
leum feedstocks.
A U.S. patent on this technology has been allowed, and international
patents 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. A10 million Ib/yr demonstration
plant is being planned for early 1999, followed by a 100 million Ib/yr
full-scale plant.
7998 Alternative Solvents/Reaction Conditions Award 71
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Designing Safer Chemicals Award
Rohm and Haas Company
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™
The 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
diacylhydrazines, 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 effectively and selectively controls important caterpillar pests in
agriculture without posing significant risk to the applicator, the con-
sumer, or the ecosystem. It will replace many older, less effective, more
hazardous insecticides and has been classified by the U.S. EPA as a
reduced-risk pesticide.
CONFIRM™ controls target insects through an entirely new mode of
action 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
•ecdysonoid" 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.
72 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 insecti-
cides 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/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-onco-
genic, nonmutagenic, and without adverse reproductive effects. Be-
cause 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 present a significant spill hazard. CONFIRM™ has proven to be an
outstanding tool for control of caterpillar pests in many integrated pest
management (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 Safer Chemicals Award 73
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1997 Winners
Academic Award
Professor Joseph M. DeSimone
University of North Carolina at Chapel Hill (UNO
and North Carolina State University (NCSU)
Design and Application of Surfactants for Carbon Dioxide
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, safe to work with,
energy-efficient, cost-effective, waste-minimizing, and reusable. Histori-
cally, 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
supercritical (sc) states. With the discovery of CO2 surfactant systems.
Professor 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 iden-
tification of "CO2-philic" materials from which to build amphiphiles.
Although CO2 in both its liquid and supercritical states dissolves many
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small molecules readily, it is a very poor solvent for many substances at
easily accessible conditions (T< 100 °C and P< 300 bar). 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 dispers-
ing high solids polymer latexes in both liquid and sc 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
systems currently used in manufacturing and service industries such as
precision cleaning, medical device fabrication, and garment care, as well
as in the chemical manufacturing and coating industries.
1997 Academic Award 75
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Small Business Award
Legacy Systems, Inc.
Coldstrip™, A Revolutionary Organic Removal and Wet
Cleaning Technology
For 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 revolutionary
wet processing technology, Coldstrip™, which removes photoresist and
organic contaminants for the semiconductor, flat panel display, and
micromachining industries. Coldstrip™ uses only water and oxygen as
raw materials.
LSI's Coldstrip™ process is a chilled-ozone process that uses only oxygen
and water as raw materials. Ttie 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
temperatures, 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.
Using oxygen and water as raw materials replacing the Piranha solutions
significantly benefits the environment. One benefit is the elimination of
i over 8,400 gallons of Piranha solutions used per year per silicon wet
r
76 1997 Award
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station and over 25,200 gallons used per year per flat panel display
station. 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 corre-
sponding 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.
7997 Small Business Award 77
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Alternative Synthetic Pathways Award
BHC Company
BHC Company Ibuprofen Process
oHC Company has developed a new synthetic process to manufacture
ibuprofen, a well-known nonsteroidal anti-Inflammatory painkiller
marketed under brand names such as Advil™ and Motrin™. Commercial-
ized since 1992 in BHC's 3,500 metric-ton-per-year facility in Bishop,
Texas, the new process has been cited as an industry model of environ-
mental excellence in chemical processing technology. For its innovation,
BHC was the recipient of the Kirkpatrick Achievement Award for "out-
standing advances in chemical engineering technology" in 1993.
The new technology involves only three catalytic steps, with approxi-
mately 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 advantages in reaction selectivity and waste reduction. As
such, this chemistry is a model of source reduction, the method of waste
minimization that tops U.S. 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 practically 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-
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-
78 1997 Award
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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.
7997 Alternative Synthetic Pathways Award 79
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Alternative Solvents/
Reaction Conditions Award
Imation
DryView™ Imaging Systems
Photothermography 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
images in approximately 15 seconds. Based on photothermography
technology, 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
gallons of contaminated water into the waste stream. As future systems
are placed, the reductions will be even more dramatic.
80 1997 Award
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DryView™ technology is applicable to all industries that process pan-
chromatic film products. The largest of these industries are medical radi-
ography, printing, industrial radiography, and military reconnaissance.
DryView™ is valued by these industries because it supports pollution
prevention through source reduction.
1997 Alternative So/wenfcs/fieacf ton Conditions Award 81
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Designing Safer Chemicals Award
Albright & Wilson Americas
THPS Blocides: A New Class of Antimicrobial Chemistry
Conventional 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 toxicol-
ogy profile. THPS's benefits include lowtoxicity, low recommended
treatment level, rapid breakdown in the environment, and no bioaccu-
mulation. 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, oxida-
tion, 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
bioaccumulate and, therefore, offers a much-reduced risk to higher
life forms.
THPS biocides are aqueous solutions and do not contain volatile organic
compounds (VOCs). Because THPS is halogen-free, it does not contrib-
ute to the formation of dioxin or absorbable organic halides (AOX).
82 1997 Award
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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 United States industrial water
treatment market for nonoxidizing biocides alone is 42 million Ib/yr and
growing at 6-8 percent annually. There are over 500,000 individual use
sites in this industry category. Because of its excellent environmental
profile, THPS has already been approved for use in environmentally
sensitive areas around the world and is being used as a replacement for
the higher risk alternatives.
1997 Designing Safer Chemicals Award 83
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1996 Winners
Academic Award
Professor Mark Holtzapple
Texas A&M University
Conversion of Waste Biomass to Animal Feed, Chemicals, and Fuels
A family of technologies has been developed 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 agricultural residues. Waste biomass is
treated with lime to improve digestibility. Lime-treated agricultural
residues (e.g., straw, stover, bagasse) may be used as ruminant animal
feeds. Alternatively, the lime-treated biomass can be fed into a large
anaerobic fermentor in which rumen microorganisms 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 above technologies 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
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
incinerated, which incurs a disposal cost and contributes to land or air
84
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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 consump-
tion 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 85
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Small Business Award
Donlar Corporation
Production and Use of Thermal Polyaspartic Acid
Millions of pounds of anionic polymers are used each year in many
industrial applications. Polyacrylic acid (PAC) is one important class of
such polymers, but the disposal of PAC is problematic, because it is not
biodegradable. An economically viable, effective, and biodegradable
alternative 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 efficient—
a yield of more than 97 percent of polysuccinimide is routinely achieved.
The second step in this process, the base hydrolysis of polysuccinimide
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 that TPA is nontoxic and environmentally safe. TPA biodegrad-
ability has also been tested by an independent lab using established
Organization for Economic Cooperation and Development (OECD)
methodology. Results indicate that TPA meets OECD guidelines for
86 1996 Award
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Intrinsic Biodegradability. 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
improve 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 treat-
ment as well as in the detergent oil, and gas industries.
7996 Small Business Award 87
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Alternative Synthetic
Pathways Award
Monsanto Company (now Pharmacia)
Catalytic Dehydrogenation of Diethanolamine
Disodium iminodiacetate (DSIDA) is a key intermediate in the production
of Monsanto's Roundup® herbicide, an environmentally friendly, non-
selective herbicide. Traditionally, Monsanto and others have manufac-
tured DSIDA using the Strecker process requiring ammonia, formalde-
hyde, hydrochloric acid, and hydrogen cyanide. Hydrogen cyanide is
acutely toxic and requires special handling to minimize risk to workers,
the community, 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 kg of waste for every
7 kg 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 endothermic
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 formalde-
hyde, is safer to operate, produces higher overall yield, and has fewer
process steps.
The metal-catalyzed conversion of amino-alcohols to amino acid salts has
been known since 1945. Commercial application, however, was not
j
> ••
88 1996 Award
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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
conversion of primary alcohols to carboxylic acid salts, and is potentially
applicable to the preparation of many other agricultural, commodity,
specialty, and pharmaceutical chemicals.
1996 Alternative Synthetic Pathways Award 89
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Alternative Solvents/
Reaction Conditions Award
The Dow Chemical Company
100 Percent Carbon Dioxide as a Blowing Agent for the Polystyrene Foam
Sheet Packaging Market
In 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
carbon 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 desir-
able properties 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 readily available in food-grade quality. CO2 also is used in
such common applications as soft drink carbonation and food chilling
and freezing.
90 1996 Award
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The use of Dow 100 percent CO2 technology eliminates the use of
3.5 million Ib/yr of hard CFC-12 and/or 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 Alternative Solvents/Reaction Conditions Award 91
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Designing Safer Chemicals Award
Rohm and Haas Company
Designing an Environmentally Safe Marine Antifouiant
Fouling, 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
organotin antifoulants, such as tributyltin oxide (TBTO). While effective,
they persist in the environment and cause toxic effects, including acute
toxicity, bioaccumulation, decreased reproductive viability, and increased
shell thickness in shellfish. These harmful effects led to a U.S. EPA special
review and to the Organotin Antifouiant Paint Control Act of 1988. This
act mandated restrictions on the use of tin in the United States, and
charged the U.S. 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
antifouling activity. The 4,5-dichloro-2-/>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 bioaccumulated, with bioaccumulation factors as high as
10,000-fold, whereas Sea-Nine™ antifoulant's bioaccumulation was
essentially zero. Both TBTO and Sea-Nine™ were acutely toxic to marine
92 1996 Award
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organisms, but TBTO had widespread chronic toxicity, whereas Sea-Nine™
antifoulant showed no chronic toxicity. Thus, the maximum allowable
environmental concentration (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 registra-
tion for the use of Sea-Nine™ antifoulant, the first new antifoulant
registration in over a decade.
7996 Designing Safer Chemicals Award 93
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Program Information
Additional information on the Presidential Green Chemistry Challenge
program
is available from:
• EPA's Pollution Prevention Clearinghouse at 202-566-0799 or e-mail
ppic@epa.gov,
• Richard Engler of EPA at 202-564-8740 or engler.richard@epa.gov, and
• The Green Chemistry Web site at http://www.epa.gov/greenchemistry.
Disclaimer
Note: The summaries provided in this document were obtained from the
entries received for the 1996-2004 Presidential Green Chemistry Chal-
lenge 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 informa-
tion contained in the entries. Claims made in these summaries have not
been verified by EPA.
94
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Index
acetic acid, 38, 78, 80, 84
derivatives, 37
acetone, 84
acid rain, 92
Acinetobacter calcoaceticus, 65
ACQ Preserve®, 30-31
acrylic acid, 55, 71
acrylamide-based polymers, 58
activators, 52-53
adhesives, 8, 71
adipic acid, 64-65
Advil™, 78
Agency for Toxic Substances
and Disease Registry (ATSDR), 20
Agilent, 25
AgraQuest, Inc., 14
agrastatins, 14
agricultural chemicals (agrochemicals),
32, 62, 89
catechols used to make, 65
conventional, 35
harpins, 34-35
nutrients, 36
residues, 54,84
agriculture. 14-15, 35, 37. 72, 87
AIDS, 46
air, oxidation agent, 16
Akzo Nobel, 68
Albright & Wilson Americas, 82
algae, 35, 82
alkaline copper quaternary (ACQ)
wood preservative, 30-31 «
alkanes, n-alkanes, 22
amino acids, 89
amino alcohol polymerization. 13
amlnocarboxylates, 37
4-aminodiphenylamine, 68
6-arnino levullnic acid (DALA), 55
ammonia, 30, 37, 70.90
in Strecker process, 88
ammonium
quaternary compound, 30-31
sulfate, 58-59
amphiphiles, fluorinated, 22
amphoteric surfactants, 67
anaerobic fermentor, 84
aniline, 69
animal feed, 84
anionic polymers, 86
anionic surfactants, 67
antifoulant, marine, 92
antimicrobial, 82
antioxidants, 65
antiviral agent, 46-47
AOX (absorbable organic halides), 82
apparel, 18, 28
applications, 19, 4041, 49, 71
agricultural, 4-5,14-15,37
commercial, 20-21, 71, 89, 90-91
consumer, 19. 28
household, 14-15,19, 36, 52-53
industrial, 86
interior, 49
manufacturing, 57
packaging, 28
process, 62
specialty, 71
aquatic organisms, 35, 61, 73, 82
aqueous wastes (salts), 78
Argonne National Laboratory, 70-71
aromatic amines, 68
Arroyo™ System, 25
arsenic, 30-31
aspartic acid, 86
ATMI. 25
atom economy/efficiency, 62-63,68
atom utilization, 78-79
automotive applications, 19,49
automotive industry, 40
avian species, 14-15, 35, 61, 72
Index 95
-------
azo pigment 10
Bacillus subtilisQSJ-JK, 14
bacteria, 9,14,19, 65, 82
Pseudomonas aeruginosa, 4
barium. 10
Bayer Corporation. 36-37.48
Baypure™, 36
Beckman, EricJ., 22
benzene. 64-65, 68
BHC Company, 78
bioaccumulation, 82.92
biocatalysis. 18, 32-33.42, 56, 65
biocides, 82
biodegradability, 36. 86
biodegradable, 28-29, 66-67
chelating agent, 36-37
fermentation products, 34
pigments, 45
plastics, 71
polymers, 23, 55, 86
solvent, 70
surfactants, 4. 66
biodegradation, 32, 82
Biofine, Inc., 54-55
biofungicide, 4,14
biomass, 84-85
plant, 34
waste, 19, 54
Biometics. Inc., 54
BioPreparation™, 38-39
biosurfactant, 4-5
birds See: avian species
bitumen, 20
bleaches, household, 53
bleach stabilizer. 37
blowing agent, 90
BOD, 38-39
Bristol-Myers Squibb Company
(BMS), 6
Buckman Laboratories International,
Inc., 8
bulk chemicals, 29, 54.62,89
butanediol, 55
butyric acid, 84
Y-butyrolactone, 55
cadmium, 10.44
calcium. 10
Canadian Health Protection Branch
(HPB), 11
cancer, ovarian, 6
Candida Antarctica, 13
caprolactam, 21, 59
carbohydrate, 12,42-43,64-65, 70
carbon dioxide (CO2), 24, 30, 74-75
blowing agent, 90
CO2-philic materials, 22-23
environmental emissions. 16, 54.
65.85
expanded, 2
product of ozone use, 76
as solvent, 22,74
supercritical, 2
carbon monoxide. 76
carboxylic acid salts, 89
Cargill Dow LLC, 28-29
Carnegie Mellon University, 52
carpet, 20-21, 28
catalysis, 2,16, 29, 32-33.42, 63, 89
bio-, 18, 56. 65
copper, 88
homogeneous, 22
catalysts. 28. 64, 70,86
anhydrous hydrogen fluoride, 78
enzymes, 18, 32,42-43
homogeneous, 3
palladium, 26
phase transfer, 2
solid oxide, 16
catechol, 64-65
caterpillar control. 72-73
caustic scours. 39
cellulose, 52. 54, 64-65
CFC, 70, 90
chelatingagent(s), 36,38
96 Index
-------
chemical manufacturing, 75
chemicals, 18,31,36. 78,80
elimination of, 47
existing, 64
hazardous, 24
industrial, 64-65, 84
oxygenated, 71
Piranha solutions, 76-77
synthetic, 60, 68
See also, agricultural chemicals,
bulk chemicals, commodity
chemicals, pharmaceutical
chemicals
children, risk to, 30
chlorinated aromatics, 68
chlorine, 52-53, 68
chlorine-based products, 20
chlorine dioxide, 53
chlorofluorocarbon (CFC), 70.90
chloroform, 70
chromated copper arsenate (CCA),
30-31
chrome, 41
chromium, 41, 44, 56-57
(VI) hexavalent, 10,30
chromium oxide, 56
chronic toxicity, 93
clean fuel production, 16
cleaners, 4,36, 71
clothing, 28
CO2-expanded liquids, 2
coal tar, 65
coating industry See.- coatings
coatings, 75
electrocoat, 40
marine, 93
paint and, 71
paper, 8
waterbome polyurethane, 48-49
COD, 38-39
cohesive energy density. 23
Coldstrip™. 76
Collaborative Research and Develop-
ment Agreement (CRADA), 6
Collins, Terry, 52-53
colloids, 58
color space, 10
color strength, 11
colorants, food, 10
combustibles, 67
commercial applications, 20-21, 71, 89,
90-91
production of, 46-47, 51, 64-65
commercial products, 90
advantages, 53
coatings, 40
containers, 44
EcoWorx™ Carpet Tile, 20-21
plants, 54
commodity chemicals, 18-19, 29, 54,
62.89
compostable material, 28-29
condensation, polymerization, 12
CONFIRM™ Selective Caterpillar
Control Agent, 72-73
Conserve™, 61
consumer products, 4,18-19, 22
consumers, 34, 52, 70, 72
cooling systems, 82
Cooperative Research and Develop-
ment Agreement, 25
copolymers, block, 13
• copper
catalyzed, 88
bivalent complex in ACQ, 30
corn, 84
cornstarch, 18
corrosion resistance, 40
corrugated cartons, 9
cosmetics, 45
cotton, 28, 38, 60-61
coupling agents. 12
cradle-to-cradle, 20
crops, 14, 34-35, 60-61, 72
crop yields, 87
crude oil, 5,67
CSI (Chemical Specialties, Inc.), 30-31
cyanide, hydrogen, 37,88
Index 97
-------
cyclic anhydride polymerization, 13
cyclic carbonate polymerization, 13
cytomegalovirus (CAAV) retinitis, 46
Cytovene®, 46-47
10-deacetylbaccatin III (10-DAB), 6
decks, 30
degreasers. 71
de-inking, 71
deionized water, 24
deligniftcation, 52-53
depression, 26
DeSimone, Joseph M., 74-75
detergents, 4, 37,87
diacylhydrazines, 72
4,5-dichloro-2-rK>ctyl-4-isothiazolin-
3-one (Sea-Nine™ antifoulant), 92-93
dichlorobenzidine, 10
diethanolamine, 88
diethyl ketone, 84
dioxin, 20
diphenolic acid, 55
disodium iminodiacetate, 88
disposal of waste, 54
Donlar Corporation, 86
DowAgroSciences LLC, 50-51, 60
Dow Chemical Company, The, 20,90-
91
Draths. Karen M., 64-65
DryView™ Imaging Systems, 80-81
DuPont, 18
dye, 38-39, 53
dye transfer, 53
earthworms, 73
ecdysone, 20-hydroxy, 72
Eckert, Charles A., 2
ecosystem, 6, 72-73
EcoWorx™ Carpet Tile, 20-21
EDEN Bioscience Corporation, 34
electrocoat, cationic See electro-
deposition coatings
electrodeposition coatings, 40-41
electronics manufacturing, 71
Eli Lilly and Company, 60
emulsification, 4
energy conservation, 7,25.26,39
catalysts and, 16,18,28-29
energy-efficient, 5,45,74
Engelhard Corporation, 10
Envirogluv™, 4445
enzyme, 3, 8-9,18. 32, 39,4243, 52
keto-reductase, 56
Lipase B, 13
polymerization, 12-13
Epic Ventures, Inc., 54
Escherichia coll. 65
esters, divinyl, 13
ethanol, 27
ethanolamine, 30
fabric, 19, 38, 53
farmers, 72
fatty acid salts, 84
feedstocks, 5, 54,56
low toxiclty, 20
nontoxic, 47
renewable, 18-19, 64-65, 70-71
petroleum, 18,29, 71
fermentation, 9, 34,60,70-71
aerobic, 4
plant cell, 6-7
fermentor, anaerobic, 84
fertilizers, 84, 87
fibers, synthetic and natural, 20,28
film products, panchromatic, 81
fine chemicals, 32, 62
fire extinguishment, 66-67
fish, 15,35, 82
fix solution, photographic, 80
flat panel display, 76
flavors, 62,65
Flexsys America L.P., 68-69
flooring applications, 49
fluoroalkyl materials. 22
fluorocarbons, 66
fluoropolymers, 22
foam products, 90
98 Index
-------
food chain, 73
food colorants, 10
food contact applications, indirect, 11
formaldehyde. 37, 88
fossil fuels, 29, 54
fragrances, 62
Frost, John W., 64-65
fruits, 14, 60
fuel consumption, 92
fuels, 16, 54, 84-85
fungi, 82
fungicide, 5,14
garden. 14
garment care, 75
gas
diffuser (ozone generator), 76
inert, 32
chlorine, 52-53, 68
natural, 85, 87, 90
phase, 25
Genencor International, Inc., 18
genetically engineered microbe, 18-19,
65
glass, 44^5
transition temperature, 23
global warming, 85, 90, 92
glucose, 18, 64-65
glycerol, 12
glycol ethers, 67, 70
glycol, propylene, 71
glycolipid, extracellular, 4
Gross, Richard A., 12
guanine triester (GTE) process, 46
hallde, silver, 80
halides, absorbable organic (AOX), 82
halogenated, 68, 70,75
halogens, 16
halogen-free, 82
halon gases, 66
harpin, 34-35
hazardous air pollutants (HAPs), 48
HCFC-22, 91
Health Protection Branch (HPB), 11
hemicellulose, 52, 64-65
herbicides, 84, 88
Hewlett Packard, 25
hexaflumuron, 50-51
hexane, 27
high solids polymer latexes, 75
Holtzapple, Mark, 84
household applications, 14-15,19, 36,
52-53, 71
hydrocarbons, 5, 58, 66
hydrochloric acid, 20, 27, 88
hydrofluoric acid, 66
hydrogen production, 16
hydrogen cyanide, 37,88
hydrogen fluoride, 78
hydrogen peroxide, 52, 76
hydroquinone, 80
hydroxyacid polymerization, 13
hydroxylthiol polymerization, 13
IBM, 25
ibuprofen, 78
Imation, 80
imine function, 26
iminodisuccinate, sodium, 36-37
industrial applications, 49, 71
anionic polymers, 86
chemicals, 64-65, 84
cleaners, 36
radiography, 81
technology, 74
water treatment, 58-59, 82
wood pulp, 52
inks, 4M5
inorganic salts, 69
inorganic waste, 69
insect control, 60-61, 72-73
insecticides, 50,60, 72-73
insects, beneficial. 15,73
integrated circuits, 24-25
integrated pest management, 15,50,
73
Index 99
-------
INTREPID™, 72
iturins, 14
Jeneil Biosurfactant Company, 4
ketones, 84
keto-reductase, 56
Kirkpatrick Achievement Award, 78
Klebsiella pneumoniae, 65
lactate, 28, 70-71
lactate esters, 70-71
lactic acid See.-lactate
lactide, 28
lactones
macrocyclic, 60
polymerization, 13
landfilled waste, 8
laser, 80
latexes, 75
laundry, 37, 52-53
lead, 10. 4(M1,44
Legacy Systems, Inc., 76-77
levulinic acid, 54-55
Lewis base, 22-23
Li, Chao-Jun, 32
lignin, 52-53
Lilly Research Laboratories, 56-57
lime-treated biomass, 84
Liotta, Charles L. 2
lipases, 12-13
lipopeptides, antifungal, 14
Los Alamos National Laboratory, 24-25
MACH 2™, 72
main group catalysis, 63
mammals, 35, 61, 73, 86
mandelic acid salts, 26
manure, 84
marine antifoulant, 92
medical
device fabrication, 75
laser imagers, 80
radiography, 81
membranes, pervaporation, 70
Messenger®, 34-35
metabolic engineering, 18
metal, 49
ions, 37
nonrecycled, 57
pretreatments, 41
metal-catalyzed conversion, 32,42, 8i
metal nitrate, 16
metal, transition, 32-33, 42, 57, 63
metals, heavy. 5,10,44-45
methylene chloride, 27, 70
methyl ethyl ketone, 84
methyltetrahydrofuran, 55
Michigan State University, 64-65
microbes, 14, 64, 84
genetically engineered. 18-19, 65
See also: bacteria
micromachining, 76
microorganisms See.- microbes
military applications, 49
military reconnaissance, 81
monomethylamine, 26
Monsanto, 68, 88
Motrin™, 78
muconic acid, cis.cis-, 64
municipal solid waste, 54,84
Nalco Chemical Company, 58-59
National Cancer Institute (NCI), 6
National Organic Standards, 15
National Renewable Energy
Laboratory, 55
natural gas, 85, 90
Nature Works™ polylactic acid, 28-29
nearcritical water, 3
Netherlands, The, 67
New York State Energy Research and
Development Authority, 54
nickel, 41
nitrate, 16
nitric acid, 64r 76
nitrobenzene, 69
nitrous oxide, 64
700 Index
-------
NOx, 16
nonflammable chemicals, 22, 59, 74,
90
nonionlc surfactants, 66, 75
nonoxidizing biocides, 83
nonrenewable resources, 85
nontoxic chemicals, 47
6-amlno levulinic acid (DALA), 55
carbon dioxide solutions, 74
glucose, 18, 64-65
harpins, 34-35
lactate esters, 70-71
Serenade®, 14-15
sodium iminodisuccinate, 37
thermal polyaspartic acid, 86
yttrium, 40
North Carolina State University
(NCSU), 74-75
Novozyme435,13
Novozymes North America, Inc., 38-39
NTEC, Inc., 71
nucleophilic aromatic substitution for
hydrogen (NASH), 69
nuts, 14
nylon carpet fiber, 20
nylon-6 depolymerization, 21
oil, 5, 85
crude, 67
industry, 87
refining, 62,64
Optimyze®, 8-9
organic
agriculture, 15
pigments, 10
solvents, 3, 34, 4243, 49, 74-75
waste, 69
Organic Materials Review Institute,
(OMRI), 15
Organization for Economic Coopera-
tion and Development (OECD), 86
organometallic chemistry, 32
organotin antifoulant, 92
Organotin Antifoulant Paint Control Act
of 1988, 92
ornamental plants, 60-61
oxidation, 52, 56, 64, 82
oxidation agent, 16
ozone, 66
depletion, 70,90
generator, 76
Pacific Northwest National Laboratory,
55
paclitaxel, 6
paints and coatings, 71
paper, 9, 54
papermaking, 52
pathogen, plant, 15
pectate lyase, 39
perchloroethylene, 70
perfluoropolyethers, 23
peroxide, 52-53, 76
pesticide applicator, 14-15, 72-73
pestidde(s), 34, 55,84
microbial, 14
reduced risk, 50,61,72, 82
petrochemicals, 64-65
and feedstock, 18,29, 70-71
petroleum
nonrenewable resource, 8,85
refining, 64
See also-, petrochemicals
Pfizer, Inc., 26-27
pharmaceutical chemicals, 42-43,
62-63, 65, 89
Cytovene®, 46-47
ibuprofen, 78-79
LY300164, a central nervous system
compound, 56-57
paclitaxel, 6
synthesized by transition metal
catalysis, 32
Taxol®, 6
Zoloft®, 26-27
phosphates, 10
Index 101
-------
photodegradation, 82
photographic film, 80
processing, 37
photolithography, 24
photoresists, 24, 76
photosynthesis, 32, 34
photothermography, 80
phthalate esters, 20
picnic tables, 30
pigments, 10
Piranha solutions, 76-77
plant
biomass, 34
cell fermentation (PCF), 6-7
diseases, 14
nutrient uptake, 87
plasma, in integrated circuit
manufacture, 25
plastic, 8,18-19, 28, 32, 71
playground equipment, 30
plipastatins, 14
pollution, remediating, 5
polyacrylic acid, 86
polyaspartic acid, thermal, 86
polybutadiene, monohydroxyl, 12
polychlorinated intermediates, 10
polychlorinated phenyls, 10
polyesters, 13,19
poly(ether-carbonates), 23
polyethers, acetate-functional, 23
polylactic acid (PLA), 28-29
polymer latexes, high solids, 75
polymerization, 12-13
heterogeneous, 22
inhibitors, 65
polymers, 32
anionic, 86
biodegradable, 55
feedstocks for synthesis of, 71
Sorona®, 18
water-based liquid dispersion, 58-59
polyoleftn resins, 20
polyols, 12
polyphosphoric acid, 10
polystyrene foam sheet, 90
polysuccinimide, 86
Polytechnic University, 12
polyurethane, 20
coatings, 4849
polyvinyl acetate, 9
polyvinyl alcohol, 9
polyvinyl chloride (PVC), 20
postconsumer recycling, 21
PPG Industries, 40-41
Precise™, 61
precision cleaning, 75
printing, 44, 71, 81
1,3-propanediol, 18
propionic acid, 84
propylene glycol, 71
protein
extraction, 22
harpin, 34-35
Pseudomonas aeruginosa, 4
pulp and paper industry, 52-53
purified water, 24
PYROCOOL Technologies, Inc., 66-67
PYROCOOL F.E.F. (Fire Extinguishing
Foam), 66-67
quaternary ammonium compound, 30
radiation-curable inks, 45
radiography, medical and industrial, 81
RCRA (Resource Conservation and
Recovery Act), 31
recycling, 20-21
paper, 8-9
reduced-risk pesticide, 50,61, 72, 82
reduction
of solvents, 27, 57
source, 78,81
in waste, 7,69, 78
refrigerants, 66
regioselectivity, 12
renewable
biomass, 54
feedstocks, 5,18-19,64-65, 70-71
102 Index
-------
resources, 8,18, 28
Rensselaer Polytechnic Institute, 55
resins, 18
resources, 28, 35, 62, 71, 84
fossil, 54
renewable, 5,18
Responsible Care®, 36
RevTech, Inc., 44
rhamnolipid, 4
Rightfit™ pigments, 10-11
Roche Colorado Corporation, 46-47
Rohm and Haas Company, 72-73,92-93
Roundup®, 88
ruminant animal feeds, 84
runaway reaction, 88
Saccaropolyspora spinosa. 60
salts, 88-89
fatty acid, 84
lead, 40
mandelic acid, 26
waste, 3, 38, 68, 70, 78
SC Fluids, Inc., 24-25
SCORR, 24-25
Sea-Nine™ antifoulant, 92
Scripps Research Institute, The, 42
selectivity, 12, 32-33, 62-63, 78
semiconductor, 76
wafers, 24
semisynthetic route (semisynthesis), 6
Sentricon™ Termite Colony Elimination
System, 50-51
Serenade®, 14-15
sertraline, 26-27
service industry, 75
sewage sludge, 84
Shaw Industries, Inc., 20
Shipley, 25
shipping Industry, 92
silicone
functional, 23
wafer, 24
silk, 28
silver halide, 80
sludge
paper mill, 54
remediation, 5
sewage, 84
smog, ground-level, 90
SOx, 16
sodium hydroxide, 37, 38-39, 57
soft drink carbonation, 90
soil, remediation, 5
solid waste, municipal, 84
Solutia, Inc., 68
solvents, 8-9, 30-31, 57
benign, 2
biodegradable, 70
carbon dioxide, 22, 74
elimination of, 6-7, 26-27, 57
environmentally acceptable, 42
halogenated, 70, 75
hazardous, 7, 24
hydrocarbon, 5, 57, 58
hydrogen fluoride, 78
nontoxic, 47
supercritical CO2, 2, 24-25, 74
toxic, 42, 70
tunable, 2
water as, 10, 33, 36,48, 52, 64-65
See also, organic solvents
sorbitol, 12
Sorona®, 18
source reduction, 78,81
specialty chemicals, 89
spinosad, 60-61
spinosyns, 60
SpinTor™, 61
stabilizer, carbon dioxide, 30
stain removal, 53
Stanford University, 62
starch, 64-65
step-condensation, polymerization, 12
stereoselective syntheses, 43
sticky contaminants, 8
Strecker process, 88
Index 103
-------
strontium, 10
Success™, 61
succinic acid, 55
Sud-Chemie Inc., 16
sulfuric acid, 76
supercritical CO2, 2, 24-25, 74
surface active agents See.- surfactants
surface tension, 25
surfactants, 4-5, 37, 58, 66-67
systems for CO2, 74-75
surfactins, 14
synthesis, 32-33, 70
chiral, 3
organic, 42-43
pharmaceutical, 78
polymer, 12,75
synthetic efficiency, 62
tableware, 45
TAML™ oxidant activators, 52-53
Taxol®, 6-7
termite control agent, 50-51
tetraamido-macrocyclic ligand
(TAML™), 52-53
tetrahydrofuran (THF), 27, 55
tetrakls(hydroxymethyl)phosphonium
sulfate (THPS), 82
tetralone, 27
Texas A&M University, 84-85
textiles, 19, 38, 53, 71
mills, 39
thermoset cross-linking, 20
THPS biocides, 82
tin, 92
tissue, facial, 5
titanium dioxide, 27
titanium tetrachlorlde, 27
toluene, 27, 64
toxicity, 92
to organisms, 15
mammalian. 61
Tracer Naturalyte™ Insect Control, 61
traditional pesticides, 15
transacylation, 13
transesterification reactions, 12
transition metals, 32-33,42, 57, 63
trees, 6, 60
tributyltin oxide (TBTO), 92
Trost, Barry M., 62-63
Tulane University, 32
turf, 60, 72
University of North Carolina at Chapel
Hill (UNO, 74-75
University of Pittsburgh, 22
upholstery, 18
U.S. Department of Energy, 54
U.S, Environmental Protection Agency
(EPA), 20, 35, 72, 78, 92
registration, 50, 61, 93
U.S. Food and Drug Administration
(FDA), 11,47, 70
U.S. Navy, 66, 92
U.S. Patent Office, 77,91
UV light, 35, 45
vapor cleaning technologies, 25
vegetables, 14, 60
vinyl chloride, 20
volatile organic compounds (VOCs),
8, 4445, 48-49, 59, 82
Wall, Monroe E., 6
Wani, Mansukh C, 6
wasps, 15, 61, 72
waste, 35, 36-37, 4041, 54
ammonium sulfate salt, 59
biomass, 19, 54, 84-85
chromium, 56-57
elimination of, 2, 7, 26-27,47, 78
hazardous, 7, 31,46-47
landfilled, 8
liquid, 80
minimizing, 2, 24, 74, 79
reduction, 7,68-69, 78
salt(s), 3, 38, 68, 70, 78
104 Index
-------
streams, 62
toxic, 80
zero, 88
waste-free manufacturing process, 36,
86
wastewater, 16, 24, 59, 69,80
water, 24, 36-37, 76
as byproduct, 86
as carrier for dispersions, 48-49
consumption, 16
disinfection, 53
fermentation in, 28, 34,60,70-71
nearcrltical, 2
removing labels with, 44
saving, 39, 53
seawater, 92
as solvent, 10, 32-33, 48, 52, 64-65
treatment, 58-59, 82
waste, 16, 38, 59, 69, 80
water-based liquid dispersion, 59
waterborne coatings, 48-49
water-soluble, 58
wet-resist-strip process, 77
Wong, Chi-Huey, 42^3
wood, 30-31
finishes, 49
waste, 54
wool, 28
worker safety, 15, 26-27, 56, 90
xylene, 64
yeast-mediated reductions, 57
yeast, 18
Candida Antarctica, 13
yttrium, 40-41
zero-waste, 88
Zoloft®, 26-27
Zygosaccharomyces rouxii, 56
Index 105
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