&EPA
United States
Environmental Protection
Agency
Presidential Green
Chemistry Challenge
Award Recipients
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United States EPA744-K-02-002
Environmental Protection June 2002
Agency www.epa.gov/greenchemistry
Office of Pollution Prevention and Toxics (7406M)
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Presidential Green
Chemistry Challenge
Award Recipients
Printed on paper that contains at least 50 percent postconsumer fiber.
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Contents
Introduction 1
2002 Winners
Academic Award: Professor Eric J. Beckman,
University of Pittsburgh 2
Small Business Award: SC Fluids, Inc. 4
Alternative Synthetic Pathways Award: Pfizer, Inc. 6
Alternative Solvents/Reaction Conditions Award:
Cargill Dow LLC 8
Designing Safer Chemicals Award: CSI 10
2001 Winners
Academic Award:
Professor Chao-Jun LI, Tulane University 12
Small Business Award: EDEN Bioscience Corporation 14
Alternative Synthetic Pathways Award:
Bayer Corporation and Bayer AC 16
Alternative Solvents/Reaction Conditions Award:
Novozymes North America, Inc. 18
Designing Safer Chemicals Award: PPG Industries 20
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2000 Winners
^Academic Award: Professor Chi-Huey Wong,
The Scripps Research Institute 22
Small Business Award: RevTech, Inc. 24
Alternative Synthetic Pathways Award: Roche Colorado
Corporation 26
Alternative Solvents/Reaction Conditions Award:
Bayer Corporation and Bayer AG 28
Designing Safer Chemicals Award:
Dow AgroSciences LLC JO
1999 Winners
Academic Award: Professor Terry Collins, Carnegie
Mellon University 32
Small Business Award: Bioftne, Inc. 34
Alternative Synthetic Pathways Award: Lilly Research
Laboratories _ 36
Alternative Solvents/Reaction Conditions Award:
Nalco Chemical Company 38
Designing Safer Chemicals Award:
Dow AgroSciences LLC 40
ii Contents
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1998 Winners
Academic /Awards.-
Professor Barry Al. Trosf, Stanford University 42
Dr. Karen M. Draths and Professor John H. Frost
Michigan State University 44
Small Business Award: PYROCOOL Technologies, Inc. 46
Alternative Synthetic Pathways Award:
F/exsvs America LP 48
Alternative Solvents/Reaction Conditions A\\ard:
Argonne National Laboratory 50
Designing Safer Chemicals Award: Rohm and
Haas Company 52
1997 Winners
Academic Award: Professor Joseph VI. DeSimone,
University of North Carolina at Chapel Hill
and North Carolina State University 54
Small Business Award: Legacy Systems, Inc. 56
Alternative Synthetic Pathways Award: BHC Company 58
Alternative Solents/Reaction Conditions .Award.- Imation... 60
Designing Safer Chemicals Award: Albright &
Wilson Americas 62
Conrents fff
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1996 Winners
Academic Award: Professor Mark Holtzapple,
Texas A&M University 64
Small Business Award: Donlar Corporation 66
Alternative Synthetic Pathways Award:
Monsanto Company 68
Alternative Solvents/Reaction Conditions Award:
The Dow Chemical Company 70
Designing Safer Chemicals Award: Rohm and
Haas Company 72
Program Information 74
Disclaimer 74
Index 75
Iv Contents
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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
catalysis/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 environ-
ment, 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 2002 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. The Presidential Green Chemistry Challenge Program is looking forward to
adding next year's winners to the growing list of chemists and chemical compa-
nies who are on the cutting edge of pollution prevention.
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8008 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 r>alkanes. leading to hopes that the chemical industry could
use CO2 as a "drop-in" replacement 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 COr including
heterogeneous polymerization, protein extraction, and homogeneous catalysis.
Although fluorinated amphiphiles allow new applications for CO,, their cost
(approximately $1 per gram) reduces the economic viability of CO2 processes.
particularly given that the use of CO2 requires high-pressure equipment. Further-
more, data have recently shown that fluoroalkyl materials persist in the environ-
ment leading to the withdrawal of certain consumer products from the market.
The drawbacks inherent to the use of fluorinated precursors, therefore, have
inhibited the commercialization of many new applications for COj. and the full
promise of CO2-based technologies has yet to be realized. To address this need.
Professor Eric Beckman and his group at the University of Pittsburgh have
developed materials that work well, exhibiting misdbility 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 CO2-philic materials should contain three primary
features: (Da relatively low glass transition temperature, (2'> a relatively low
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cohesive energy density, and (3) a number of Leu is base groups. Lou glass
transition temperature correlates to high free volume and high molecular
flexibility, which imparts a high entropy of mixing with CO, (or any solvent?. A
low cohesive energy density is primarily a result of weak solute-solute interac-
tions, a necessary feature given that CO2 is a rather feeble solvent. Finally,
because CO, is a Lewis acid, the presence of Lewis base groups should create
sites for specific favorable interactions with CO,.
Professor Beckman's simple heuristic model was demonstrated on three sets of
materials: functional silicones,- poMether-carbonates),- and acetate-functional
polyethers. PoMether-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 CO,-philes will
inevitably be discovered using this model, further broadening the applicability of
CO2 as a greener process solvent.
2002 Academic
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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 fabrication of inte-
grated circuits (ICs) relies heavily on photolithography to define the shape and
pattern of individual components. Current manufacturing practices use hazard-
ous chemicals and enormous amounts of purified water during this intermediate
step, which may be repeated up to 30 times for a single wafer. It is estimated
that a typical chip-fabrication plant generates 4 million gallons of 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
(particulate) residue from semiconductor wafers. The SCORR technology
outperforms conventional photoresist removal techniques in the areas of waste
minimization, water use, energy consumption, worker safety, feature size
compatibility, material compatibility, and cost. The key to the effectiveness of
SCORR is the use of supercritical CO2 in place of hazardous solvents and corro-
sive 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 dis-
charge permits. It thoroughly strips photoresists from the wafer surface in less
than half the time required for wet-stripping and far outperforms plasma,
resulting in increased throughput. It eliminates rinsing and drying steps during
the fabrication process, thereby simplifying and streamlining the manufacturing
process. It eliminates the need for ultra-pure deionized water, thus reducing
time, energy, and cost. Supercritical CO2 costs less than traditional solvents and
is recyclable.
4 2002 Award
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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 chemis-
tries 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 semicon-
ductor 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 Sma// Bus/ness Award 5
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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 implemented a substantive green chemistry
technology for a complex commercial process requiring extremely pure product.
As a result, Pfizer significantly improved both worker and environmental safety.
The new commercial process (referred to as the "combined" process) offers
substantial 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 tetralone, 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, which reduced the formation of impurities and the need for
reprocessing. 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 problematit reagent titanium
6 2002 Award
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tetrachloride. This process change eliminates of TOO 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 7
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Alternative Solvents/
Reaction Conditions Award
Carg.ni Dow LLC
TM
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 tradi-
tional 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 conven-
tional 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 residence. 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. The process
consists of three separate and distinct steps that lead to the production of lactic
acid, lactide, and PLA high polymer. Each of the process steps is free of organic
solvent: water is used in the 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 efficiency and
reduce energy consumption. Additionally, the lactic acid is derived from annually
renewable resources, PLA requires 20-50 percent less fossil resources than
comparable petroleum-based plastics, and PLA is fully biodegradable or readily
hydrolyzed into lactic acid for recycling back into the process.
While the technology to create PLA in the laboratory has been known for many
years, previous attempts at large-scale production were targeted solely at niche
8 2002 Award
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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 9
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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 approxi-
mately 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). Approximately 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 the 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 prevention
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 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,
10 2002 Award
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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 approximately $20 million to
increase its production capacity for ACQ to over 50 million active pounds. By
investing in ACQ technology, CSI has positioned itself and the wood preservation
industry to transition away from arsenic-based wood preservatives to a new
generation of preservative systems.
* RCRA - Resource Conservation and Recovery Act
2002 Des/gn/ng Safer Criem/cafc Award 11
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2001 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, poly-
mers, 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 condi-
tions in an air atmosphere.
The research of Professor Chao-Jun Li has focused on the development of
numerous transition-metal-catalyzed reactions both in air and 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 reaction 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 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 demonstrate unprecedented
chemoselectivity that eliminates byproduct formation and product separation.
Application of these new methodologies to natural product synthesis, including
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polyhydroxylated natural products, medium-sized rings, and macrocyclic com-
pounds, yields shorter reaction sequences.
Transition-metal catalyzed reactions in water and air offer many advantages.
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 transition-metal-mediated and -catalyzed reactions in air and water
offers an attractive alternative to the inert atmosphere and organic solvents
traditionally used in synthesis.
200? Academic Award 13
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Small Business Award
EDEN Bioscience 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 approach to crop production
that addresses these concerns.
EDEN's harpin technology is based on a new class of nontoxic, naturally occur-
ring 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 simultaneously activate certain plant
growth systems without altering the plant's DNA. When applied to crops, harpin
increases plant biomass, photosynthesis, nutrient uptake, and root development
and, ultimately, leads to greater crop yield and quality.
Unlike most agricultural chemicals, harpin-based products are produced in a
water-based fermentation system that uses no harsh solvents or reagents,
requires only modest energy inputs, and generates no hazardous chemical
wastes. Fermentation byproducts are fully biodegradable and safely disposable.
In addition, EDEN uses low-risk ingredients to formulate the harpin protein-based
end product. Approximately 70 percent of the dried finished product consists of
an innocuous food grade substance that is used as a carrier for harpin protein.
The result of this technology is an EPA-approved product called Messenger®, that
has been demonstrated on more than 40 crops to effectivelv stimulate plants to
14 2001 Award
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defend themselves against a broad spectrum of viral, fungal, and bacterial
diseases, including some for which there currently is no effective treatment. In
addition, Messenger* has been shoun 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 groundwater resources.
Deployment of harpin technology conserves resources and protects the environ-
ment by reducing total agricultural inputs and partially replacing many higher risk
products. Using environmentally benign harpin protein technology, growers for
the first time in the history of modern agriculture will be able to harness the
innate defense and growth systems of crops to substantially enhance yields,
improve crop quality, and reduce reliance on conventional agricultural chemicals.
2001 Small Business Award 15
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Alternative Synthetic
Pathways Award
Bayer Corporation and Bayer AC
Baypure™ CX: Iminodisucclnate
An Environmentally Friendly and Readily Biodegradable delating Agent
Chelating agents are used in a variety of applications, including detergents,
agricultural nutrients, and household and industrial cleaners. Most traditionally
used chelating agents, however, are poorly biodegradable. Some are actually
quite persistent and do not adsorb at the surface of soils in the environment or
at activated sludge in wastewater treatment plants. Because of this poor
biodegradability combined with high water 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 ecotoxicological standpoint. Sodium
iminodisuccinate is also an innovation in the design of chemicals that favorably
impact the environment. This accomplishment was realized not by "simple"
modification of molecular structures of currently used chelating agents, but
instead by the 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 environ-
mentally friendly, patented manufacturing process to provide this innovative
chelant commercially.
Sodium iminodisuccinate belongs to the aminocarboxylate class of chelating
agents. Nearly all aminocarboxylates in use today are acetic acid derivatives
produced from amines, formaldehyde, sodium hydroxide, and hydrogen
cyanide. The industrial use of thousands of tons of hydrogen cyanide is an
extreme toxicity hazard. In contrast, Bayer's sodium iminodisuccinate is pro-
duced from maleic anhydride (a raw material also produced by Bayer), water,
16 2001 Award
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sodium hydroxide, and ammonia. 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 dictating agents. For example, it can be used as a
builder and bleach stabilizer in laundry and dishwashing 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 photo-
graphic 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 applications
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, environ-
mentally friendly chelating agent that is also manufactured in a waste-free
process.
200; Alternative Synthetic Pathways Award 17
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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 subsequent textile finishing processes.
These water-intensive wet processing steps generate large volumes of wastes,
particularly from alkaline scouring 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 contaminants, 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, including reduced BOD/
COD and decreased water use. BioPreparation™ is an 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 (amylases, cellulases) used to improve the perfor-
mance properties of cotton fabrics.
18 2001 Award
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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 \\ere also demonstrated by combining
treatment steps. A recent statistical survey determined that 162 knitting mills
typically use 89 million mVvr of water in processing goods from scouring to
finishing; the BioPreparation™ approach \\ould save from 27-45 million nv/u
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 conservation 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.
200? Alternative Solvents/Reaction Conditions Anard ?9
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Designing Safer Chemicals Award
PPG Industries
Yttrium as a Lead Substitute in Cationic Electrodeposition Coatings
PPG Industries introduced the first cationic electrodeposition primer to the
automotive industry in 1976. During the succeeding years, this coating technol-
ogy became very widely used in the industry, such that today, essentially all
automobiles are given a primer coat using the chemistry and processing
methods developed by PPG. The major benefits of this technology are corrosion
resistance, high transfer efficiency (low waste), reliable automated application,
and very low organic emissions. 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 corrosion resistance grew,
lead was regularly exempted from regulation in electrocoat because there were
no cost-effective substitutes. This is especially important in moderately priced
cars and trucks where the high cost of using 100 percent zinc-coated (galva-
nized) 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.
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-containing products. In addition,
it has been found that as yttrium is deposited in an electrocoat film, it deposits
as the hydroxide. The hydroxide is converted to yttrium oxide during normal
baking of the electrocoat. The oxide is extraordinarily nontoxic by ingestion as
20 2001 Award
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indicated by the LDSO 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 environmen-
tal 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 pretreat-
ment 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-containing waste and, like lead, is also a
concern to recyclers of the finished vehicle. By using yttrium in the electrocoat
step, chrome can be completely eliminated using standard chrome-free rinses
and low-nickel or possibly nickel-free pretreatments, both of \\hich are commer-
cially available today. This should be possible without concern of compromising
long term vehicle corrosion performance. For PPG pretreatment customers,
this should result in the elimination of up to 25,000 pounds of chrome and
50,000 pounds of nickel annually from PPG products. As PPG customers imple-
ment yttrium over the next several years, approximately one million pounds of
lead (as lead metal) will be removed from the electrocoat applications of PPG
automotive customers.
2001 Des/gn/ng Safer Chemicals Award 21
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2000 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, catalysts, and processes have made
possible the synthesis of molecules with varying degrees of complexity. The
types of problems at which nonbiological organic synthesis has excelled, ranging
from stoichiometric reactions to catalysis with acids, bases, and metals, will
continue to be very important. New synthetic and catalytic methods are, how-
ever, necessary to deal with the new classes of compounds that are becoming
the key targets of molecular research and development.
Compounds with polytunctional 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 con-
cerns. 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 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 method-
ologies 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
22
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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 break-
through 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 contributions ranges from relatively
simple enzymatic processes (e.g., chiral resolutions and stereoselective synthe-
ses) to complex, multi-step enzymatic 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 glycosyltransferases coupled with in situ regeneration of
sugar nucleotides developed by Professor Wong has revolutionized the field of
carbohydrate chemistry and enabled the large-scale synthesis of complex
oligosaccharides for clinical evaluation. All of these new enzymatic reactions are
carried out in environmentally acceptable solvents, under mild reaction condi-
tions, at ambient temperature, and with minimum protection of functional
groups. The work of Professor Wong represents a new field of green chemistry
suitable for large-scale synthesis that is impossible or impractical to achieve by
nonenzymatic means.
2000 Academic Award 23
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Small Business Award
RevTec/i, Inc.
Envirogluv™: 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.
\\ost, 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 ha\e disad* antages. Paper labels are inexpensive, but can
be easily removed if the container is exposed to water or abrasion. 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 contain-
ers. \\ore 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 emironmental concerns. Moreover, the high-temperature
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 pleasing, durable, and obtained in a cost-
effective, environmentally friendly, and energy-efficient manner. Envirogluv™
technology fills that need. Envirogluv™ is a glass decorating technology that
directly silk screens radiation-curable inks onto glass, then cures the ink almost
instantly by exposure to UV light. The result is a crisp, clean label that is environ-
mentally sound, with a unit cost that is about half of that achieved with
traditional labeling.
24 2000 Award
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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 \\aste ink.
Furthermore, Envirogluv™ decorated glass containers eliminate the need for
extra packaging and are completely recyclable. Applications suitable for the
Envirogluv™ process include tableware, cosmetics containers, and plate glass.
2000 Small Business Award 25
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Alternative Synthetic
Pathways Award
Roche Colorado Corporation
An Efficient Process for the Production of Cytovene®,
A Potent Antiviral Agent
I he 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 pharmaceuti-
cal industry. Roche Colorado Corporation (RCC), in establishing management
and operational systems for the continuous improvement of environmental
quality in its business activities, has, in essence, adopted the Presidential Green
Chemistry Challenge Program's basic principles of green chemistry: the develop-
ment 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 immunocompromised patients,
including patients with AIDS, and also used for the prevention of CMV disease in
transplant recipients at risk for CMV.
In the early 1990s, Roche Colorado Corporation developed the first commercially
viable process for the production of Cytovene®. By 1993, chemists at RCC's
Boulder Technology Center designed a new and expedient process for the
production of Cytovene®, which at the time had an estimated commercial
demand of approximately 50 metric tons per year. Leveraging the basic principles
of green chemistry and molecular conservation into the design process, signifi-
cant improvements 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 solid waste
streams, eliminated 11 different chemicals from the hazardous liquid waste
streams, and efficiently recycled and reused four of the five ingredients not
incorporated into the final product. Inherent within the process improvements
demonstrated was the complete elimination of the need for operating and
monitoring three different potentially hazardous chemical reactions. Overall, the
26 2000 Award
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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 environmentally friendly syntheses,
including the development of alternative syntheses utilizing nonhazardous and
nontoxic feedstocks, reagents, and solvents,- elimination of waste at the source
(liquid waste: 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 27
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Alternative Solvents/
Reaction Conditions Awards
Bayer Corporation and Bayer AC
Two-Component Waterborne Polyurethane Coatings
I wocomponent (2K) waterborne poiyurethane coatings are an outstanding
example of the use of alternative reaction conditions for green chemistry. This
technology is achieved by replacing most or all of the volatile organic com-
pounds (VOCs) and hazardous air pollutants (HAPs) used in conventional 2K
solventborne poiyurethane 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
poiyurethane, it is not that straightforward.
Two-component solventborne poiyurethane 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 poiyurethane dispersions ameliorate this problem, but do not go far
enough.
An obvious solution to the deficiencies of 2K solventborne polyurethanes and
aqueous poiyurethane dispersions is a reactive 2K poiyurethane system with
water as the carrier. In order to bring 2K waterborne poiyurethane 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 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
environmental 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
28 2000 Award
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applications will also be reduced, and rugged interior coatings uith no solvent
smell will now be available.
Today, 2K waterborne polyurethane is being applied on industrial lines \\here
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 perfor-
mance criteria that include flat coatings with camouflage requirements, corro-
sion protection, chemical and chemical agent protection, flexibility, and exterior
durability, along with VOC reductions of approximately 50 percent.
2000 Alternative Solvents/Reaction Conditions 4v\ard 29
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Designing Safer Chemicals Award
Dow AgroSdences LLC
Sentricon™ Termite Colony Elimination System, A New Paradigm for
Termite Control
I he annual cost of termite treatments to the U.S. consumer is about $1.5 billion,
and each year as many as 1.5 million homeowners will experience a termite
problem and seek a control option. From the 1940s until 1995, the nearly
universal treatment approach for subterranean termite control involved the
placement of large volumes of insecticide dilutions into the soil surrounding a
structure to create a chemical barrier through which termites could not pen-
etrate. Problems with this approach include difficulty in establishing an uninter-
rupted barrier in the vast array of soil and structural conditions, use of large
volumes of insecticide dilution, p jtential hazards associated with accidental
misapplications, spills, off-target applications, and worker exposure. These
inherent problems associated with the use of chemical barrier approaches for
subterranean termite control created a need for a better method. The search for
a 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 character-
istics needed for a successful termite bait toxicant.
The unique properties of hexaflumuron made it an excellent choice for use in
controlling subterranean termite colonies. The Sentricon™ Termite Colony
Elimination System, developed by Dow AgroSciences in collaboration 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 threaten-
ing structures using a targeted approach, Sentricon™ delivers unmatched
technical performance, environmental compatibility, and reduced human risk.
The properties of hexaflumuron as a termite control agent are attractive from an
environmental and human risk perspective, but more important, the potential for
adverse effects is dramatically reduced because it is present only in very small
quantities in stations with termite activity. The comparisons to barrier methods
show significant reduction in the use of hazardous materials and substantial
reduction in potential impacts on human health and the environment.
30 2000 Award
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The discovery of hexaflumuron's activity with its unique fit and applicability for
use as a termite bait was a key milestone for the structural pest control industry
and Dow AgroSciences. The development and commercial launch of Sentricon'M
changed the paradigm for protecting structures from damage caused by
subterranean termites. The development of novel research methodologies, new
delivery systems, and the establishment of an approach that integrates monitor-
ing and baiting typify the innovation that has been a hallmark of the project.
More than 300,000 structures across the U.S. are nou being safeguarded through
application of this revolutionary technology, and adoption is growing rapidly.
2000 Designing Safer Chemicals Award 31
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1999 Winners
Academic Award
Professor Terry Collins
Carnegie Mellon University
TAML™ Oxidant Activators:
General Activation of Hydrogen Peroxide for Green Chemistry
I wenty years of research by Professor Terry Collins at Carnegie Mellon University
have led to the successful development of a series of environmentally friendly
oxidant activators based on iron. These TAML™ (tetraamido-macrocyclic ligand)
activators catalyze the reactions of oxidants in general. Their activation proper-
ties with hydrogen peroxide in water are of greatest environmental significance.
TAML™ activators arise from a design process invented by Professor Collins which
is complementary to that employed by Nature to produce powerful oxidizing
enzymes. The 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 industrial 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. The key
to quality papermaking is the selective removal of lignin from the white fibrous
polysaccharides, cellulose, and hemicellulose. Wood-pulp delignification has
traditionally relied on chlorine-based processes that produce chlorinated pollut-
ants. 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 technology for treating pulp. The new process moves the
elemental balance of 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
delignification 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 delignification technology based on chlorine
32
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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 more 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 TAML™-activated peroxide while they are
bound to a fabric. But in almost every case, 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 developed
including the use of TAML™- peroxide activators for water disinfection.
7999 Academic Award 33
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Small Business Award
Biofine, 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 CO, to the atmosphere,
conserves fossil fuels, and leads to a secure domestic supply of feedstocks
capable of making a huge array of chemical products. Biofine, Inc. has devel-
oped a high-temperature, dilute-acid hydrolysis 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 manu-
facturing 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 opportu-
nities 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 produced at $0.32/lb and converted into commodity
chemicals such as 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
34 1999 Award
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160 million Ib/yr of product. Fortunately, Biofine's technology is economical for a
broad range of plant sizes; even the one-ton-per-day demonstration 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
methyltetrahydrofuran (MTHF), a gasoline fuel additive,- 5-amino levulinic acid
(DALA), a broad-spectrum, nontoxic, and biodegradable pesticide; and new
biodegradable polymers.
1999 Small Business Award 35
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Alternative Synthetic
Pathways Award
Lilly Research Laboratories
Practical Application of a Biocatalyst in Pharmaceutical Manufacturing
I he synthesis of a pharmaceutical agent is frequently accompanied by the use
and generation of a large amount of hazardous substances. This 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 respon-
sible 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 disproportional quantities of
chromium waste compared to drug produced. These points provided compel-
ling 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 appropriately 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 stereocontrol in the asymmetric reduction of a dialkyl ketone. Imple-
mentation of the biocatalytic process was enabled on a large scale by employing
a novel, yet simple, three-phase reaction system. The protocol overcame 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 isola-
tion. 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.
36 1999 Award
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The new process was developed by combining innovations from chemistry,
microbiology, and engineering. The process circumvented the use of non-
recycled metal and significantly reduced solvent usage. For example, 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.
1999 Alternative Synthetic Pathways Award 37
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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 sus-
pended solids and contaminants and effecting separations. Conventionally, in
order to prepare such polymers in liquid form for safety and ease of handling,
the water-soluble monomers, water, and a hydrocarbon (oil) and surfactant
"carrier" mixture are combined in approximately a 1:1:1 ratio to form an emul-
sion. The monomers are then polymerized. Regrettably, the oil and surfactant
components of these inverse emulsions 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
environment (at the current consumption rates) as a consequence of their use.
Until now, there has been no alternative technology available to manufacture
liquid polymers without the obvious environmental disadvantages 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 manu-
facture of these widely used polymers as fine particles dispersed 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 medium and polymer carrier means that no oil or surfactants are
released into the environment when the polymers are used in the water treat-
ment application.
By choosing to manufacture water-based dispersions instead of water-in-oil
emulsions, Nalco has conserved over one million pounds of hydrocarbon
38 1999 Award
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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 ammonium
sulfate salt, a waste byproduct from the manufacture of caprolactam, 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 equip-
ment 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.
7999 Alternative Solvents/Reaction Conditions Award 39
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Designing Safer Chemicals Award
Dow AgroSc/ences LLC
Spinosad, A New Natural Product for Insect Control
Estimates of monetary losses in crops as a result of uncontrolled insect infesta-
tions 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 agricultural insect control, most
recently the advent of synthetic organic chemicals as insecticides. However, the
development of resistance has reduced the effectiveness of many of the
currently available insecticides, and more stringent environmental and toxicologi-
cal hurdles have restricted the use of others.
It was against this backdrop that researchers at Eli Lilly and Company introduced
high-volume testing of fermentation isolates in agricultural screens in the mid-
1980s. From this program, the microorganism Saccaropolyspora splnosa was
isolated from a Caribbean island soil sample, and the insecticidal activity of the
spinosyns, a family of unique macrocyclic lactones, was identified and devel-
oped by Dow AgroSciences as a highly selective, environmentally friendly
insecticide.
In Latin, "saccharopolyspora" means "sugar-loving, with many spores", and
"spinosa" refers to the spiny appearance of the spores. The microorganism 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 muscle contractions, eventually leading to paralysis and death.
Detailed investigations of the symptomology and electrophyslology have
indicated, however, that spinosad is not acting through any known mechanism.
It appears to affect insect nicotinic and Y-aminobutyric acid receptor function
through a novel mechanism.
40 1999 Award
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Splnosad 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, rela-
tively high margins of safety for avian and aquatic species translate into reduced
or nonexistent buffer zones and fewer regulated nontarget compliance mea-
sures. These advantages allow growers to control damaging crop pests with
fewer concerns about human or environmental safety and costly secondary 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. Additional registrations, intro-
duced as SpinTor™, Success™, Precise™, and Conserve™, have recently been
granted for insect control in vegetable and tree crops and in the urban environ-
ment for control of turf and ornamental plant nests.
1999 Designing Safer Chem/ca/s Award 41
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1998 Winners
Academic Award
Professor Barry M. Jrost
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 Pharmaceuticals. Econom-
ics generally dictates the feasibility of processes that are "practical". A criterion
that traditionally has not been explicitly recognized relates to the total quantity of
raw materials required for the process compared to the quantity of product
produced or, simply put, "how much of what you put into your pot ends up in
your product". In considering the question of what constitutes synthetic effi-
ciency. Professor Barry M. Trost has explicitly enunciated a new set of criteria by
which chemical processes should be evaluated. They fall under two categories-
selectivity and atom economy.
Selectivity and atom economy evolve from two basic considerations. First, the
vast majority of the synthetic organic chemicals in production derive from non-
renewable resources. It is self-evident that such resources should be used as
sparingly as possible. Second, all waste streams should be minimized. This
requires employment of reactions that produce minimal byproducts, either
through the intrinsic stoichiometry 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—chemo-
selectivity (differentiation among various functional groups in a polyfunctional
molecule), regioselectivity (orientational control), diastereoselectivity (control of
relative stereochemistry), and enantioselectivity (control of absolute stereochem-
istry). These considerations 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
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how much of the reactants ends up in the product, i.e., atom economy, tradition-
ally has been ignored. When Professor Trost's first paper on atom economy
appeared in the literature, the idea generally was not adopted by either
academia or industry. Many in 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 commercial
processes. In enunciating these principles. Professor Trost has set a challenge
for those involved in basic research to create new chemical processes that meet
the objectives. Professor Trost's efforts to meet this challenge involve the
rational invention of new chemical reactions that are either simple additions or,
at most, produce low-molecular-weight innocuous byproducts. A major applica-
tion of these reactions is in the synthesis of fine chemicals and Pharmaceuticals,
which, in general, 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 applications for which
such methodology may offer more efficient syntheses.
1998 Academic Award 43
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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 elaboration of
new, environmentally benign routes to existing chemicals. Alternatively, funda-
mental 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, hemicellulose, and
cellulose. In addition, water is used as the primary reaction 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 (BTX) fraction of petroleum
refining, as the starting material. In addition, the last step in the current manu-
facture 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 manufacture 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 acid using a single, genetically engineered microbe expressing a
biosynthetic pathway that does not exist in nature. This novel biosynthetic
pathway was assembled by isolating and amplifying the expression of genes
from different microbes including Klebsldla pneumonlae, Acinetobacter
calcoaceticus, and Escherichla coll. The c/s,c/s-muconic acid, which accumulates
extracellularly, is hydrogenated to afford adipic acid.
44 1998 Award
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Yet another example of the Draths-Frost strategy for synthesizing industrial
chemicals using biocatalysis and renewable feedstocks is their synthesis of
catechol. Approximately 21 million kg of catechol is produced 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 antioxidants (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 previ-
ously, 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 carbohydrate. 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.
1998 Academic Award 45
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Small Business Award
PYROCOOL Technologies, Inc.
Technology for the Third Millennium: The Development and Commercial
Introduction of an Environmentally Responsible Fire 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, however, have themselves created, in actual
use, potential long-term environmental 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
biodegradable 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 extinguish-
ment and cooling agent that would be effective in extinguishing fires and that
would greatly reduce the potential long-term environmental and health problems
associated with 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 biodegrad-
able nonionic surfactants, anionic surfactants, and amphoteric surfactants with a
46 1998 Award
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mixing ratio (with water) of 0.4 percent. In initial fire tests at the world's largest
fire-testing facility in The Netherlands, PYROCOOL F.E.F. was demonstrated to be
effective against a broad range of combustibles.
Since its development in 1993, PYROCOOL F.E.F. has been employed successfully
against numerous fires both in America and abroad. 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 employment 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 47
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Alternative Synthetic Pathways Award
Flexsys America L.P.
Elimination of Chlorine in the Synthesis of 4-Aminodiphenylamine-.
A New Process That Utilizes Nucleophilic Aromatic Substitution
for Hydrogen
1 he development of new environmentally favorable routes for the production of
chemical intermediates and products is an area of considerable interest to the
chemical processing industry. Recently, the use of chlorine in large-scale
chemical syntheses has come under intense scrutiny. Solutia, Inc. (formerly
Monsanto Chemical Company), one of the world's largest producers of chlori-
nated 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 Corporate 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 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
48 1998 Award
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reactions known as nucleophilic aromatic substitution of hydrogen (NASH).
Through a series of experiments designed to probe the mechanism of NASH
reactions, Flexsys realized a breakthrough in understanding this chemistry that
has led to the 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 mechanism of
the reaction between aniline and nitrobenzene have been recognized through-
out 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 innova-
tive and environmentally safe chemical processes.
1998 Alternative Synthetic Pathways Award 49
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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 process 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 retain-
ing the alcohol, acid, and ester. The ammonia is recovered and reused in
the fermentation to make ammonium lactate, eliminating the formation of
waste salt. The innovation overcomes major technical hurdles that had
made current production processes for lactate esters technically and eco-
nomically noncompetitive. The innovation will enable the replacement of
toxic solvents widely used by industry and consumers, expand the use of
renewable carbohydrate feedstocks, and reduce pollution and emissions.
Ethyl lactate has a good temperature performance range (boiling point:
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, perchloro-
ethylene, and chloroform) on a 1:1 basis. At current 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 petroleum-derived toxic solvents currently
used. The favorable economics of the ANL membrane process, therefore,
can lead to the widespread substitution of petroleum-delved toxic solvents
50 1998 Award
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by ethyl lactate in electronics manufacturing, paints and coatings, textiles,
cleaners and degreasers, adhesives, printing, de-inking, and many other indus-
trial, 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 fermentation-
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, oxygenated chemicals (e.g., propylene glycol
and acrylic acid), and specialty products. By improving purity and lowering costs,
the ANL process promises to make fermentation-derived organic acids an
economically viable alternative to many chemicals and products derived from
petroleum 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. A
10 million Ib/yr demonstration plant is being planned for early 1999, followed by
a 100 million Ib/yr full-scale plant.
1998 Alternative Solvents/Reaction Conditions Award 51
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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 dlacylhydrazines, 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 mechanisti-
cally novel, it effectively and selectively controls important caterpillar pests in
agriculture without posing significant risk to the applicator, the consumer, or
the ecosystem. It will replace many older, less effective, more hazardous
insecticides and has been classified by 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.
Since 20-hydroxy ecdysone neither occurs nor has any biological function in
most nonarthropods, CONFIRM™ is inherently safer than other insecticides 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 honey-
bees, lady beetles, parasitic wasps, predatory bugs, beetles, flies, and lacew-
ings, 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 secondary pests due to destruction of key natural
52 1998 Award
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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-oncogenic, nonmuta-
genic, and without adverse reproductive effects. Because of its high apparent
safety and relatively low use rates, CONFIRM™ poses no significant hazard to the
applicator or the food chain and does not 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 53
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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. Historically, the prime factor inhibiting the use of this
solvent replacement has been the low solubility of most materials in CO2, in both
its liquid and 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 identification
of *CO2-philic' materials from which to build amphiphiles. Although CO2 in both
its liquid and supercritical states dissolves many 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 dispersing high solids polymer latexes in both liquid and sc CO2
phases. The design criteria they developed for surfactants, which were capable
54
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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 C02 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 55
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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,
fiat 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. The active product is ozone, which safely decomposes
to oxygen in the presence of photoresist. Carbon dioxide, carbon monoxide,
oxygen, and water are formed, "mere 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 throughout 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 over
8,400 gallons of Piranha solutions used per year per silicon wet station and over
25,200 gallons used per year per flat panel display 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 corresponding water consumption in LSI's process is
4,200 gallons per year and there is no Piranha use.
56 1997 Award
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In 1995, the U.S. Patent Office granted LSI Patent 5,464,480 covering this technol-
ogy. The system has the lowest environmental impact of any wet-resist-strip
process, eliminating the need for thousands of gallons of Piranha chemicals and
millions of gallons of water a year.
1997 Small Business Award 57
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Alternative Synthetic Pathways Award
BHC Company
BHC Company Ibuprofen Process
DHC 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™. Commercialized 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 environmental excellence in chemical
processing technology. For its innovation, BHC was the recipient of the
Kirkpatrick Achievement Award for "outstanding advances in chemical engineer-
ing technology" in 1993.
The new technology involves only three catalytic steps, with approximately
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 hierar-
chy. Virtually all starting materials are either converted to product or reclaimed
byproduct or are completely recovered and recycled in the process. The genera-
tion 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 pharmaceutical
synthesis (i.e., how to avoid the large quantities of solvents and wastes associ-
ated with the traditional stoichiometric use of auxiliary chemicals for chemical
conversions). Large volumes of aqueous wastes (salts) normally associated with
such manufacturing are virtually eliminated. The anhydrous hydrogen fluoride
catalyst/solvent is recovered and recycled with greater than 99.9 percent effi-
ciency. No other solvent is needed in the process, simplifying product recovery
58 1997 Award
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and minimizing fugitive emissions. The nearly complete atom utilization of this
streamlined process truly makes it a waste-minimizing, environmentally friendly
technology.
1997 Alternative Synthetic Pathways Award 59
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1 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 operating 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, "me 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.
60 1997 Award
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DryView™ technology is applicable to all industries that process panchromatic
film products. The largest of these industries are medical radiography, printing,
industrial radiography, and military reconnaissance. DryView™ is valued by these
industries because it supports pollution prevention through source reduction.
1997 Alternative Solvents/Reaction Conditions Award 61
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Designing Safer Chemicals Award
Albright & Wilson Americas
THPS Biocides: 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 environment, leading to long-
term damage. To address this problem, a new and relatively benign class of
biocides, tetrakis(hydroxymethyl)phosphonium sulfate (THPS), has been discov-
ered by Albright & Wilson Americas. THPS biocides represent a completely new
class of antimicrobial chemistry that combines superior antimicrobial activity with
a relatively benign toxicology profile. THPS's benefits include low toxicity, low
recommended treatment level, rapid breakdown in the environment, and no
bioaccumulation. 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 treat-
ment level is below that which would be toxic to fish. In addition, THPS rapidly
breaks down in the environment through hydrolysis, oxidation,
photodegradation, and biodegradation. In many cases, it has already substan-
tially 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 com-
pounds (VOCs). Because THPS is halogen-free, it does not contribute to the
formation of dioxin or absorbable organic halides (AOX). Because of its low
overall toxicity and easier handling compared to alternative products, THPS
provides an opportunity to reduce the risk of health and safety incidents.
THPS has been applied to a range of industrial water systems for the successful
control of microorganisms. The United States industrial water treatment market
for nonoxidizing biocides alone is 42 million Ib/yr and growing at 6-8 percent
62 1997 Award
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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.
7997 Designing Safer Chemicals Award 63
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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, propi-
onate, 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 corre-
sponding alcohols such as isopropanol, isobutanol, and isopentanol.
The above technologies offer many benefits for human health and the environ-
ment. 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 economically from
waste biomass. Typically, waste biomass is landfilled or incinerated, which incurs
a disposal cost and contributes to land or air pollution. Through the production
of chemicals from biomass, nonrenewable resources, such as petroleum and
natural gas, are conserved for later generations. Because 50 percent of U.S.
petroleum consumption is now imported, displacing foreign oil will help reduce
the U.S. trade deficit.
64
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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 reduc-
ing factors that contribute to global warming.
1996 Academic Award 65
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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 economi-
cally viable, effective, and biodegradable alternative to PAC is thermal poly-
aspartate (TPA).
Donlar Corporation invented two highly efficient processes to manufacture 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 conversion 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 polymer-
ization, 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 minimiz-
ing waste.
Independent toxicity studies of commercially produced TPA have been con-
ducted using mammalian and environmental models. Results indicate that TPA is
nontoxic and environmentally safe. TPA biodegradability has also been tested by
an independent lab using established Organization for Economic Cooperation
and Development (OECD) methodology. Results indicate that TPA meets OECD
guidelines for Intrinsic Biodegradability. PAC cannot be classified as biodegrad-
able when tested under these same conditions.
66 7996 Award
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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 treatment, as well as in the detergent, oil,
and gas industries.
1996 Small Business Award 67
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Alternative Synthetic
Pathways Award
Monsanto Company
Catalytic Dehydrogenation of Diethanolamine
Disodium iminodiacetate (DSIDA) is a key intermediate in the production of
Monsanto's Roundup® herbicide, an environmentally friendly, nonselective
herbicide. Traditionally, Monsanto and others have manufactured DSIDA using
the Strecker process requiring ammonia, formaldehyde, hydrochloric acid, and
hydrogen cyanide. Hydrogen cyanide is acutely toxic and requires special
handling to minimize risk to workers, the community, and the environment.
Furthermore, the chemistry involves the exothermic generation of potentially
unstable intermediates, and special care must be taken to preclude the possibil-
ity 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 purification 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 formaldehyde, is safer to operate, produces higher overall yield, and has
fewer process steps.
The metal-catalyzed conversion of aminoalcohols to amino acid salts has been
known since 1945. Commercial application, however, was not known until
Monsanto developed a series of proprietary catalysts that made the chemistry
commercially feasible. Monsanto's patented improvements on metallic copper
catalysts afford an active, easily recoverable, highly selective, and physically
durable catalyst that has proven itself in large-scale use.
68 1996 Award
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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.
7996 Alternative Synthetic Pathways Award 69
-------
Alternative Solvents/
Reaction Conditions Award
The Dow Chemical Company
100 Percent Carbon Dioxide as a Blowing Agent for the Polystyrene Foam
Sheet Packaging Market
I n recent years the chlorofluorocarbon (CFC) blowing agents used to manufac-
ture polystyrene foam sheet have been associated with environmental 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 desirable properties has resulted in the growth of the polystyrene foam sheet
market in the United States to over 700 million pounds in 1995. Current applica-
tions 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.
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
70 7996 Award
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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 71
-------
Designing Safer Chemicals Award
Rohm and Haas Company
Designing an Environmentally Safe Marine Antifoulant
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 Antifoulant
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 alternative to
organotin compounds. Compounds from the 3-isothialozone class were chosen
as likely candidates and over 140 were screened for antifouling activity. The
4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-Nine™ antifoulant) was chosen as
the candidate for commercial development.
Extensive environmental testing compared Sea-Nine™ antifoulant to TBTO, the
current industry standard. Sea-Nine™ antifoulant degraded extremely rapidly
with a half-life of one day in seawater and one hour in sediment. Tin
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 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 AAAEC for TBTO was
0.002 ppb.
72 1996 Award
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Hundreds of ships have been painted with coatings containing Sea-Nine™
worldwide. Rohm and Haas Company obtained EPA registration for the use of
Sea-Nine™ antifoulant, the first new antifoulant registration in over a decade.
1996 Designing Safer Chemicals Award 73
-------
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 1996-2002 Presidential Green Chemistry Challenge Awards.
They were edited for space, stylistic consistency, and clarity, but they were
neither written nor officially endorsed by EPA. These summaries represent only a
fraction of the information that was provided in the entries received and, as
such, are intended to highlight the nominated projects, not describe them fully.
These summaries were not used in the judging process; judging was conducted
on all information contained in the entries. Claims made in these summaries
have not been verified by EPA.
74
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Index
acetic acid 18, 58, 60, 64
derivatives 16
acetone 64
acid rain 72
Acinetobacter calcoacetlcus 44
ACQ Preserve® 10-11
acrylic acid 34, 51
activators 32-33
adhesives 51
adipic acid 44-45
Advil™ 58
Agilent 5
agricultural chemicals
(agrochemicals) 12, 42, 69
catechols used to make 45
conventional 15
equipment 29
harpins 14-15
nutrients 16
residues 34, 64
agriculture 15,17, 52, 67
AIDS 26
Akzo Nobel 48
Albright & Wilson Americas 62
algae 15, 62
alkaline copper quaternary (ACQ)
wood preservative 10-11
alkanes, r>alkanes 2
amino acids 69
aminocarboxylates 16
4-aminodiphenylamine 48
5-amino levulinic acid (DALA) 35
ammonia 10,16-17, 50, 70
in Strecker process 68
ammonium
quaternary compound 10-11
sulfate 38-39
amphifiles, fluorinated 2
amphoteric surfactants 46
anaerobic fermentor 64
aniline 49
animal feed 64
anionic polymers 66
anionic surfactants 46
antifoulant, marine 72
antimicrobial 62
antioxidants 45
antiviral agent 26-27
AOX (absorbable organic haiides)... 62
apparel 8
applications
agricultural 17
automotive 29
commercial 51
consumer 8
electrocoat 20-21
flooring 29
household 51
industrial 51
interior 29, 66
manufacturing 37
military 29
packaging 8
process 42
specialty 50
aquatic organisms 15,41, 52, 62
aqueous wastes (salts) 58
Argonne National Laboratory 50
aromatic amines 48
Arroyo™ System 5
arsenic 10-11
aspartic acid 66
ATMI 5
atom economy/efficiency .... 42-43,48
atom utilization 58-59
automotive applications 29
automotive industry 20
avian species 15,41, 52
Index 75
-------
bacteria 62
Acinetobacter calcoaceticus 44
Escherichia coll 44
Klebsiella pneumoniae 44
Bayer Corporation 16-17, 28
Baypure™ 16
Beckman, EricJ 2
benzene 44-45, 48
BHC Company 58
bioaccumulation 62, 72
biocatalysis 11-12, 22, 36,44-45
biocides 62
biodegradability 16, 66
biodegradable 47
chelating agent 16-17
compostable 8-9
fermentation products 14
nonionic surfactants 46
pigments 24-25
polylactic acid 8-9
plastics 51
polymers 2, 35, 66
solvent 50
surfactants 46
biodegradation 12, 62
Biofine, Inc 34-35
biomass
cellulosic 34
lime-treated 64
plant 11,14
waste 34, 64-65
Biometics, Inc 34
BioPreparation™ 18-19
birds See.- avian species
bleaches, household 33
bleach stabilizer 17
blowing agent 70
BOD 18-19
bulk chemicals 34,42
butanediol 35
butyric acid 64
Y-butyrolactone 35
cadmium 24
caprolactam 39
carbohydrate 22-23, 44-45, 50
carbon dioxide (CO2)
blowing agent 70
CO2-philic materials 2-3, 54
environmental
emissions 34,45, 65
product of ozone use 56
solvent 10
stabilizer 10
supercritical 4, 54
surfactants for 54-55
carbon monoxide 56
carboxylic acid salts 69
Cargill DowLLC 8-9
Carnegie Mellon University 32
carpeting 8
catalysis 22,69
alternate synthetic pathways 11
biocatalysis 11-12, 22, 36, 44-45
copper 68
homogeneous 2
main group 43
transition metal 12-13,43
catalysts 8,44, 50,66
anhydrous hydrogen fluoride.... 58
enzymes 22-23
palladium 6
catechol 44-45
caterpillar control 52-53
caustic scours 19
cellulose 32, 34, 4445
CFC 50,70
CFG12 70
chelating agent(s) 16,18
chemical manufacturing 55
chemicals 11,16, 58,60
agricultural See.- agricultural
chemicals
bulk 9,34,42,69
commodity 9, 34,42, 69
conservation 19, 26
corrosive 4
elimination 19, 26
existing...: 44-45
76 Index
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fine 12,4243
hazardous 4
industrial 64
oxygenated 51
pharmaceutical
See.- pharmaceutical chemicals
Piranha 57
specialty 69
synthetic 40, 48
children, risk to 10
chlorinated aromatics 48
chlorine 32-33, 48
chlorine dioxide 33
chlorofluorocarbon (CFC) 50, 70
chloroform 50
chromated copper arsenate
(CCA) 10-11
chrome 21
chromium 21, 24, 36-37
hexavalent 10
chromium oxide 36
chronic toxicity 72
cleaners 16, 51
clothing 8
coal tar 45
coating industry See.- coatings
coatings 55
electrocoat 20
marine 73
paint and 51
polyurethane 28-29
waterborne 28
COD 18-19
cohesive energy density 3
Coldstrip™ 56
Collins, Terry 32
colloids 38
combustibles 47
commercial applications ..51, 68, 71-72
development 72
production 26-27, 31, 43-44
commercial products 70
advantages 33
coatings 20
containers 24
plants 34
commodity chemicals 9, 34, 42, 69
compostable material 8-9
CONFIRM™ Selective Caterpillar
Control Agent 52-53
Conserve'" 41
consumer products 2
consumers 5,14, 32, 50, 52
cooling systems 62
Cooperative Research and
Development Agreement 5
copper
catalyzed 68
bivalent complex in ACQ 10
corn 14, 64
corrosion resistance 20
cosmetics 25
cotton 8,18, 40-41
crops 14-15, 40-41, 52
crop yields 67
crude oil 47
CSI (Chemical Specialties, Inc.).... 10-11
cyanide, hydrogen 16, 68
cytomegalovirus (CMV) retinitis 26
Cytovene® 26-27
decks 10
degreasers 51
de-inking 51
delignification 32-33
depression 6
DeSimone, Joseph M 54
detergents 16-17, 67
dishwashing 17
diacylhydrazines 52
4,5-dichloro-2-fK)ctyl-4-
isothiazolin-3-one
(Sea-Nine™ antifoulant) 72-73
diethanolamine 68
diethyi ketone 64
diphenolic acid 34-35
disodium iminodiacetate 68
Donlar Corporation 66
Dow AgroSdences LLC 30-31, 40
Index 77
-------
Dow Chemical Company, The.... 70-71
Draths, Karen M 44-45
DryView™ Imaging Systems 60-61
dye 18-19,33
dye transfer 33
earthworms 52
ecdysone, 20-hydroxy 52
ecosystem 52-53
EDEN Bioscience Corporation 14
electrocoat, cationic See.- electro-
deposition coatings
electrodeposition coatings 20-21
electronics manufacturing 51
Eli Lilly and Company 40
energy conservation 4, 6, 8-9,19
energy-efficient 24, 54
Envirogluv™ 24-25
enzyme 18, 22-23, 32
keto-reductase 36
pectate lyase 18
Epic Ventures, Inc 34
Escherichia coli 44
ethanol 6
ethanolamine 10
fabric 18,33
farmers 52
fatty acid salts 54
feedstocks 11, 34, 36
nonhazardous 27
nontoxic 27
renewable 4445, 50-51
petroleum 8-9, 51
fermentation 8,14,40, 50-51
fermentor, anaerobic 64
fertilizers 64, 67
fibers, synthetic and natural 8
film products, panchromatic 61
fine chemicals 12, 42-43
fire extinguishment 46-47
fish 15,62
fix solution, photographic 60
flat panel display 56
flavors 42, 45
Flexsys America LP. 48-49
fluoroalkyl materials 2
fluorocarbons 46
fluoropolymers 2
foam products 70
food chain 53
formaldehyde 16, 68
fossil fuels 8, 34
fragrances 42
Frost, John W. 44-45
fruits 40
fuel consumption 72
fuels 34,64-65
fungi 62
garment care 55
gas
diffuser (ozone generator) 56
inert 12
chlorine 48
natural 64, 67, 70
phase 5
genetically engineered microbe 45
glass 24-25
decorating technology 24
transition temperature 3
global warming 65, 70, 72
glucose 44-45
glycol ethers 46, 50
glycol, polypropylene 51
guanine triester (GTE) process 26
halide, silver 60
halides, absorbable organic
(AOX) 62
halogenated 48, 50, 54-55
halogen-free 62
halon gases 46
harpin 14-15
hazardous air pollutants (HAPs) 28
HCFC-22 70
hemicellulose 32, 44-45
herbicides 64, 68
Hewlett Packard 5
hexaflumuron 30-31
hexane 6
high solids polymer latexes 54
78 index
-------
Holtzapple, Mark 64
household applications .. 16, 32-33, 51
hydrocarbons 38, 46
hydrochloric acid 7, 68
hydrofluoric acid 46
hydrogen cyanide 16, 68
hydrogen fluoride 58
hydrogen peroxide 32, 56
hydroquinone 60
IBM 5
ibuprofen 58
Imation 60
imine function 6
iminodisucdnate, sodium 16-17
industrial applications 29, 51
anionic polymers 66
chemicals 44-45, 64
cleaners 16
cooling systems 62
radiography 61
technology 54
water treatment 38, 62
wood pulp 32
inks 24-25
inorganic salts 48
inorganic waste 49
insect control 40-41, 52-53
insecticides 30, 40, 52-53
insects, beneficial 52
integrated circuits 4-5
integrated pest management... 30, 53
INTREPID™ 52
isobutanol 64
isopentanol 64
isopropanol 4, 64
keto-reductase 36
Kirkpatrick Achievement Award 58
Klebsiella pneumoniae 44
lactate 8, 50-51
lactate esters 50-51
lactic acid See.-lactate
lactide 8
lactones, macrocyclic 40
laser 60
latexes 54
laundry 17,32-33
lead 20-21,24
Legacy Systems, Inc 56
levulinic acid 34-35
Lewis base 2-3
Li, Chao-Jun 12
lignin 32-33
Lilly Research Laboratories 36
lime 64
lime-treated biomass 64
Los Alamos National Laboratory 4-5
MACH 2U1 52
mammalian toxicity 41
mammals 15, 40-41, 52-53, 66
mandelic acid salts 6
manure 64
marine antifoulant 72
medical
device fabrication 55
laser imagers 60
radiography 61
membranes, pervaporation 50
Messenger® 14-15
metal 29
ions 17
nonrecycled 37
pretreatments 21
metal-catalyzed conversion 12, 22, 68
metal, transition 12-13, 22, 36, 43
metals, heavy 24-25
methylene chloride 6,50
methyl ethyl ketone 64
methyltetrahydrofuran 35
Michigan State University 44
microbes 44, 64
genetically engineered 45
See also: bacteria
micromachining 56
microorganisms See.- microbes
military applications 29
military reconnaissance 61
monomethylamine 6
Monsanto 48, 68
lnde\ 79
-------
Motrin™ 58
muconic acid, cis.cis- 44
municipal solid waste 34, 64
Nalco Chemical Company 38-39
National Renewable Energy
Laboratory 35
natural gas 64, 70
Nature Works™ polylactic acid 8-9
Netherlands, The 47
New York State Energy Research
and Development Authority 34
nickel 21
nitric acid 44, 56
nitrobenzene 49
nitrous oxide 44
nonflammable chemicals 2, 39, 54, 70
nonionic surfactants 46, 54
nonoxidizing biocides 62
nonrenewable resources 64
nontoxic chemicals 27
6-amino levulinic acid (DALA).... 35
carbon dioxide solutions 54
glucose 44
harpins 14
lactate esters 50
sodium iminodisuccinate 17
thermal polyaspartic acid 66
yttrium oxide 20
North Carolina State University
(NCSU) 54
Novozymes North America, Inc 18
NTEC, Inc 51
Nucleophilic Aromatic Substitution
for Hydrogen (NASH) 48^9
oil 47, 64
crude 47
fields 62
industry 67
refining 42, 44
organic waste 49
Organization for Economic
Cooperation and Development
(OECD) 66
organometallic chemistry 12
organotin antifoulant 72
Organotin Antifoulant Paint
Control Act of 1998 72
ornamental plants 40-41
oxidation 32, 36, 44, 62
ozone
depletion 46, 50, 70
generator 56
layer 46
Pacific Northwest National
Laboratory 35
paints and coatings 51
papermaking 32
paper mill sludge 34
pectate lyase 18
perchloroethylene 50
perfluoropolyethers 3
peroxide 32-33, 56
pesticide applicator 52-53
pesticide(s) 14, 35, 64
traditional 14
reduced risk 30, 41, 52
See also: herbicides,- insecticides
petroleum
petrochemicals 8-9,12,34,
44-45, 50-51
nonrenewable resource 64
refining 44
Pfizer, Inc 6-7
pharmaceutical chemicals 22-23,
42-43, 45, 69
Cytovene® 26-27
ibuprofen 58-59
LY300164, a central nervous
system compound 36-37
synthesized by transition
metal catalysis 12
Zoloft® 6-7
photodegradation 62
photographic film 60
processing 17, 60
photolithography 4
photoresists 3, 56
photosynthesis 12,14
80 Index
-------
photothermography 60
picnic tables 10
Piranha solutions 56-57
plant nutrient 67
plasma, in integrated circuit
manufacture 4
plastic packaging materials 8
plastics 8,12,51
playground equipment 10
polyacrylic acid 66
polyaspartic acid, thermal 66
poly(ether-carbonates) 3
polyethers, acetate-functional 3
polylactic acid (PLA) 8-9
polymer latexes, high solids 54
polymerization
heterogeneous 2
inhibitors 45
polymers 12
acrylamide-based 38
anionic 66
biodegradable 35
feedstocks for synthesis of 51
water-based liquid dispersion 38-39
water-soluble 38
polystyrene foam sheet 70
polysucdnimide 66
polyurethane coatings 28-29
PPG Industries 20-21
Precise™ 41
precision cleaning 55
printing 24, 51, 61
propionic acid 64
propylene glycol 51
protein
extraction 2
harpin 14-15
pulp and paper industry 32-33
PYROCOOL Technologies, Inc. ... 46-47
PYROCOOL F.E.F. (Fire
Extinguishing Foam) 46-47
quaternary ammonium
compound 10
radiation-curable inks 24
radiography, medical and
industrial 61
RCRA (Resource Conservation and
Recovery Act) 11
reduced-risk pesticide .... 30, 41, 52, 62
reduction in waste 49
refrigerants 46
renewable
biomass 34
feedstocks 11, 4445, 50
resources 8
Rensselaer Polytechnic Institute 35
resources 15,42, 51, 64
fossil 8,34
renewable 8
Responsible Care' 16
RevTech, Inc 24
Roche Colorado Corporation 26
Rohm and Haas Company.... 52, 72-73
Roundup^ 68
ruminant animal feeds 64
runaway reaction 68
Saccaropolyspora spinosa 40
salts
amino acid 68
carboxylic acid 69
fatty acid 64
lead 20
mandelic acid 6
waste 18, 48, 50, 58
SC Fluids, Inc 4-5
SCORR 4-5
Sea-Nine™ antifoulant 72
Scripps Research Institute, The 22
selectivity 11-12, 42-43, 58
chemo- 42
diastereo- 42
enantio- 42
regio- 42
semiconductor 56
wafers 4
Sentricon™ Termite Colony
Elimination System 30-31
sertraline 6-7
Index 81
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service industry 55
sewage sludge 64
Shipley 5
shipping industry 72
silicones, functional 3
silicon wafer 4
silk 8
silver halide 60
sludge
paper mill 34
sewage 64
smog, ground-level 70
sodium hydroxide 16,18-19, 36
soft drink carbonation 70
solid waste, municipal 64
Solutia, Inc 48
solvents 11, 36-37, 51
ammonia 10
benign 6
biodegradable 50
carbon dioxide 2, 54
elimination 6-7, 37
ethanol 6
ethanoiamine 10
environmentally acceptable 23
halogenated 50, 54-55
hazardous 4
hexane 6
hydrocarbon 38
hydrogen fluoride 58
methylene chloride 6
nontoxic 27
organic 5,14, 22-23, 28-29,
54-55, 66
reduction 6-7, 37
supercritical CO2 4-5, 54
tetrahydrofuran 6
toluene 6
toxic 22,50
water 13,16, 4445
source reduction 58, 61
specialty chemicals 69
spinosad 40-41
spinosyns 40
SpinTor™ 41
stain removal 33
Stanford University 42
starch 44-45
stereoselective syntheses 23
Strecker process 68
Success™ 41
succinic acid 34-35
sulfuric acid 56
supercritical fluids 4-5
supercritical CO2 resist remover 4-5
surface active agents See.- surfactants
surface tension 5
surfactants 17-18, 38, 4647
systems for CO2 54-55
synthesis 11-13, 50
organic 22-23
pharmaceutical 58
polymer 54
tableware 25
TAML™ oxidant activators 32-33
termite control agent 30-31
tetraamido-macrocyclic ligand
(TAML™) 32-33
tetrahydrofuran (THF) 6, 35
tetrakis( hydroxymethyl)
phosphonium sulfate (THPS) 62
tetralone 6
Texas A&M University 64
textile mills 19
textiles 18, 33, 51
THPS biocides 62
tin 72
titanium dioxide 7
titanium tetrachloride 6-7
toluene 6, 44
toxicity
acute 72
chronic 72
mammalian 41
Tracer Naturalyte™ Insect Control... 41
transition metals 12-13, 22, 36,43
trees 40
tributyltin oxide (TBTO) 72
82 Index
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Trost, Barry M 42-43
Tulane University 12
turf 40-41,52
University of North Carolina
at Chapel Hill (UNO 54
University of Pittsburgh 2
U.S. Department of Energy 34
U.S. Environmental Protection Agency
(EPA) 14,30,41,52,58,72-74
U.S. Food and Drug Administration
(FDA) 27,50
U.S. Navy 46,72
U.S. Patent Office 57, 71
UV light 15,24-25
vapor cleaning technologies 5
vegetables 40
volatile organic compounds
(VOCs) 24-25, 28-29, 39, 62
wasps 41, 52
waste 11,14,16-18, 20-21
ammonium sulfate salt 39
biomass 34, 64-65
chromium 36-37
disposal 34
elimination 6-7, 27, 58
free 66
hazardous 11, 26-27, 68
inorganic 48-49
liquid 60
minimizing 4, 54, 59
municipal solid 34
organic 49
paper 34
RCRA 11
reduction 48-49, 58
salt(s) 18,48,50,58
streams 42
toxic 27,60
wood 34
zero 68
waste-free manufacturing
process 16, 66
wastewater 16, 39, 46, 49
treatment systems 16, 46
water
additives 46
byproduct 66
as carrier for dispersions 28-29
consumption 56
deionized 4
disinfection 33
drinking 16
feedstock 56
fermentation in 8,14, 40, 50-51
pollution 56
purified 4
removing labels with 24
saving 4,19,33
seawater 72
solvent... 12-14,16-17, 28, 32, 44-47
treatment 16, 38-39, 46, 62,67
use 4
waste .... 4,16, 18, 39, 46, 49-50, 60
waste (salts) 58
wet-resist-strip process 57
Wong, Chi-Huey 22-23
wood
finishes 29
preserved 10-11
pressure-treated 10-11
wool 8
worker safety 4-5, 36, 70
xylene 44
yeast-mediated reductions 36
yttrium 20-21
zero-waste 68
Zoloft® 6
ZyQosaccharomyces rouxii 36
index 83
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