United States

Environmental Protection EPA Agency

The Presidential

Green Chemistry Challenge

Award Recipients

1996–2008
United States 744F08008

Environmental Protection June 2008

Agency www.epa.gov/greenchemistry EPA

Office of Pollution Prevention and Toxics (7406M)
The Presidential

Green Chemistry Challenge

Award Recipients

1996—2008

Contents

Introduction ....................................................................... 1

2008 Winners

Academic Award:

Professors Robert E. Maleczka, Jr. and

Milton R. Smith, III,

Michigan State University ............................................. 2

Small Business Award:

 SiGNa Chemistry, Inc. ........................................................ 4

Greener Synthetic Pathways Award:

Battelle ............................................................................... 6

Greener Reaction Conditions Award:

Nalco Company .................................................................. 8

Designing Greener Chemicals Award:

Dow AgroSciences LLC ..................................................... 10

2007 Winners

Academic Award:

Professor Michael J. Krische,

University of Texas at Austin ....................................... 12

Small Business Award:

NovaSterilis Inc. .............................................................. 14

Greener Synthetic Pathways Award:

Professor Kaichang Li, Oregon State University;

Columbia Forest Products; Hercules Incorporated .. 16

Greener Reaction Conditions Award:

Headwaters Technology Innovation .............................. 18

Designing Greener Chemicals Award:

Cargill, Incorporated ....................................................... 20

iii
iv Contents

2006 Winners

Academic Award:

Professor Galen J. Suppes,

University of Missouri-Columbia ............................... 22

Small Business Award:

Arkon Consultants, NuPro Technologies, Inc. .............. 24

Greener Synthetic Pathways Award:

Merck & Co., Inc. ............................................................. 26

Greener Reaction Conditions Award:

Codexis, Inc. .................................................................... 28

Designing Greener Chemicals Award:

S.C. Johnson & Son, Inc. ................................................. 30

2005 Winners

Academic Award:

Professor Robin D. Rogers,

The University of Alabama ......................................... 32

Small Business Award:

Metabolix, Inc. ................................................................ 34

Greener Synthetic Pathways Awards:

Archer Daniels Midland Company, Novozymes ........... 36

Merck & Co., Inc. ............................................................. 38

Greener Reaction Conditions Award:

BASF Corporation ............................................................ 40

Designing Greener Chemicals Award:

Archer Daniels Midland Company ................................. 42

2004 Winners

Academic Award:

Professors Charles A. Eckert and Charles L. Liotta,

Georgia Institute of Technology ................................ 44

Small Business Award:

Jeneil Biosurfactant Company ....................................... 46

Greener Synthetic Pathways Award:

Bristol-Myers Squibb Company ...................................... 48
Contents v

Greener Reaction Conditions Award:

Buckman Laboratories International, Inc. .................... 50

Designing Greener Chemicals Award:

Engelhard Corporation (now BASF Corporation) ......... 52

2003 Winners

Academic Award:

Professor Richard A. Gross,

Polytechnic University ................................................ 54

Small Business Award:

AgraQuest, Inc. ............................................................... 56

Greener Synthetic Pathways Award:

Süd-Chemie Inc. .............................................................. 58

Greener Reaction Conditions Award:

DuPont ............................................................................. 60

Designing Greener Chemicals Award:

Shaw Industries, Inc. ....................................................... 62

2002 Winners

Academic Award:

Professor Eric J. Beckman,

University of Pittsburgh ............................................. 64

Small Business Award:

SC Fluids, Inc. .................................................................. 66

Greener Synthetic Pathways Award:

Pfizer, Inc. ........................................................................ 68

Greener Reaction Conditions Award:

Cargill Dow LLC (now NatureWorks LLC) ...................... 70

Designing Greener Chemicals Award:

Chemical Specialties, Inc. (now Viance) ....................... 72
vi Contents

2001 Winners

Academic Award:

Professor Chao-Jun Li,

Tulane University ........................................................ 74

Small Business Award:

EDEN Bioscience Corporation ....................................... 76

Greener Synthetic Pathways Award:

Bayer Corporation, Bayer AG ......................................... 78

Greener Reaction Conditions Award:

Novozymes North America, Inc. .................................... 80

Designing Greener Chemicals Award:

PPG Industries ................................................................. 82

2000 Winners

Academic Award:

Professor Chi-Huey Wong,

The Scripps Research Institute .................................. 84

Small Business Award:

RevTech, Inc. ................................................................... 86

Greener Synthetic Pathways Award:

Roche Colorado Corporation ........................................ 88

Greener Reaction Conditions Award:

Bayer Corporation, Bayer AG ......................................... 90

Designing Greener Chemicals Award:

Dow AgroSciences LLC ................................................... 92

1999 Winners

Academic Award:

Professor Terry Collins,

Carnegie Mellon University ....................................... 94

Small Business Award:

Biofine, Inc. (now BioMetics, Inc.) ............................... 96

Greener Synthetic Pathways Award:

Lilly Research Laboratories ............................................ 98
Contents vii

Greener Reaction Conditions Award:

Nalco Chemical Company ............................................ 100

Designing Greener Chemicals Award:

Dow AgroSciences LLC ................................................. 102

1998 Winners

Academic Awards:

Professor Barry M. Trost,

Stanford University ................................................... 104

Dr. Karen M. Draths and Professor John W. Frost,

Michigan State University ........................................ 106

Small Business Award:

PYROCOOL Technologies, Inc. ..................................... 108

Greener Synthetic Pathways Award:

Flexsys America L.P. ........................................................110

Greener Reaction Conditions Award:

Argonne National Laboratory .......................................112

Designing Greener Chemicals Award:

Rohm and Haas Company .............................................114

1997 Winners

Academic Award:

Professor Joseph M. DeSimone,

University of North Carolina at Chapel Hill and

North Carolina State University ................................116

Small Business Award:

Legacy Systems, Inc. ......................................................118

Greener Synthetic Pathways Award:

BHC Company (now BASF Corporation) ...................... 120

Greener Reaction Conditions Award:

Imation ........................................................................... 122

Designing Greener Chemicals Award:

Albright & Wilson Americas (now Rhodia) ....................124
viii Contents

1996 Winners

Academic Award:

Professor Mark Holtzapple,

Texas A&M University ............................................... 126

Small Business Award:

Donlar Corporation (now NanoChem

Solutions, Inc.) .......................................................... 128

Greener Synthetic Pathways Award:

Monsanto Company ..................................................... 130

Greener Reaction Conditions Award:

The Dow Chemical Company ....................................... 132

Designing Greener Chemicals Award:

Rohm and Haas Company ............................................. 134

Program Information .................................................... 136

Disclaimer ...................................................................... 136
1

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 Program provides national

recognition for outstanding chemical technologies that incorporate the principles of green

chemistry into chemical design, manufacture, and use. In addition, winning technologies

have been or can be used by industry to achieve its pollution prevention goals. The U.S.

EPA typically honors five winners each year, one in each of the following categories:

• Academia

• Small business

• Greener Synthetic Pathways, Greener Synthetic Pathways such as the use of innocuous and renewable feedstocks (e.g., biomass, natural oils); novel reagents or catalysts including biocatalysts

and microorganisms; natural processes including fermentation and biomimetic

syntheses; atom-economical syntheses; or convergent syntheses

• Greener Reaction Conditions, Greener Reaction Conditions such as the replacement of hazardous solvents with

greener solvents; solventless or solid-state reactions; improved energy efficiency; novel

processing methods; or the elimination of energy- and material-intensive separations

and purifications

• Designing Greener Chemicals, Designing Greener Chemicals such as chemicals that are less toxic than current

alternatives; inherently safer chemicals with regard to accident potential; chemicals

recyclable or biodegradable after use; or chemicals safer for the atmosphere (e.g., do

not deplete ozone or form smog)

Award Winners

This booklet presents the 1996 through 2008 Presidential Green Chemistry Challenge

Award recipients and describes their award-winning technologies. Each winner demonstrates a commitment to designing, developing, and implementing a green chemical

technology that is scientifically innovative, economically feasible, and less hazardous to

human health and the environment.

Environmental Results

 Collectively, these award-winning technologies have:

• Eliminated more than 1.1 billion pounds of hazardous chemicals and solvents,

• Saved over 21 billion gallons of water, and

• Eliminated nearly 400 million pounds of carbon dioxide releases to air.

The Presidential Green Chemistry Challenge Program is looking forward to adding future

years’ winners to the growing list of scientists and companies who are on the cutting

edge of pollution prevention.
2 2008 Award

2008 Winners

Academic Award

Professors Robert E. Maleczka, Jr. and Milton R. Smith, III

Michigan State University

Green Chemistry for Preparing Boronic Esters

”Coupling" reactions are one way to build valuable molecules, such as

pharmaceuticals, pesticides and similar complex substances. Coupling

reactions connect two smaller molecules, usually through a new

carbon–carbon (C–C) bond. A particularly powerful coupling reaction is

the Suzuki coupling, which uses a molecule containing a carbon–

boron bond to make a larger molecule through a new C–C bond. In

fact, the Suzuki coupling is a well-established, mild, versatile method

for constructing C–C bonds and has been reported to be the third most

common C–C bond-forming reaction used to prepare drug candidates.

Chemical compounds with a carbon–boron bond are often prepared

from the corresponding halides by Grignard or lithiate formation

followed by reaction with trialkyl borate esters and hydrolytic workup.

Miyaura improved this reaction with a palladium catalyst, but even this

new reaction requires a halide precursor.

Innovation and Benefits

One way to build complex molecules, such as pharmaceuticals and

pesticides, is with a Suzuki “coupling” reaction. This versatile coupling

reaction requires precursors with a carbon–boron bond. Making these

precursors, however, typically requires harsh conditions and generates

significant amounts of hazardous waste. Professors Maleczka and Smith

developed a new catalytic method to make these compounds under

mild conditions and with minimal waste and hazard. Their discovery

allows the rapid, green manufacture of chemical building blocks,

including some that had been commercially unavailable or

environmentally unattractive.
2008 Academic Award 3

Several years ago, Professors Milton R. Smith, III and Robert E.

Maleczka, Jr. began collaborating to find a “halogen-free” way to

prepare the aryl and heteroaryl boronic esters that are the key building

blocks for Suzuki couplings. Their collaboration builds upon Smith’s

invention of the first thermal, catalytic arene carbon–hydrogen bond

(C–H) activation/borylation reaction. This led to transformations using

iridium catalysts that are efficient, have high yields, and are tolerant of

a variety of functional groups (alkyl, halo-, carboxy, alkoxy-, amino, etc.).

Sterics, not electronics dictate the regiochemistry of the reactions. As a

consequence, 1,3-substituted arenes give only 5-boryl (i.e., metasubstituted) products, even when both the 1- and 3-substituents are

ortho/para directing. Just as significantly, the reactions are inherently

clean as they can often be run without solvent, and they occur with

hydrogen being the only coproduct. The success of these reactions has

led Miyaura, Ishiyama, Hartwig, and others to use them as well.

In brief, catalytic C–H activation/borylation allows the direct construction

of aryl boronic esters from hydrocarbon feedstocks in a single step,

without aryl halide intermediates, without the limitations of the normal

rules of aromatic substitution chemistry, and without many common

functional group restrictions. Moreover, due to its mildness, the

borylation chemistry combines readily in situ with subsequent chemical

reactions.

This technology allows rapid, low-impact preparations of chemical

building blocks that currently are commercially unavailable or only

accessible by protracted, costly, and environmentally unattractive

routes. Indeed, most recently, Michigan State University licensed the

nominated technology to BoroPharm, Inc., which is using these

catalytic borylations to produce much of the company’s product line.

Thus, the nominated technology is proving to be practical green

chemistry beyond the laboratory bench.
4 2008 Award

Small Business Award

SiGNa Chemistry, Inc.

New Stabilized Alkali Metals for Safer, Sustainable Syntheses

Alkali metals have a strong propensity for donating electrons, which

makes these metals especially reactive. That reactivity has enormous

potential for speeding chemical reactions throughout science and

industry, possibly including new pathways to clean energy and environmental remediation. Unfortunately, that same reactivity also makes

them highly unstable and dangerous to store and handle. In addition,

increased risk of supply-chain interruption and the expense of handling

these metals have made them unattractive to the chemical industry.

Industries from pharmaceutical to petroleum have developed alternative synthetic routes to avoid using alkali metals, but these alternates

require additional reactants and reaction steps that lead to inefficient,

wasteful manufacturing processes.

SiGNa Chemistry addresses these problems with its technology for

nanoscale absorption of reactive alkali metals in porous metal oxides.

These new materials are sand-like powders. SiGNa’s materials eliminate the danger and associated costs of using reactive metals directly

but retain the utility of the alkali metals. Far from their hazardous

precursors, SiGNa’s materials react controllably with predictable activaInnovation and Benefits

Alkali metals, such as sodium and lithium, are powerful tools in synthetic

chemistry because they are highly reactive. However, unless they are

handled very carefully, their reactivity also makes them both flammable

and explosive. SiGNa Chemistry developed a way to stabilize these

metals by encapsulating them within porous, sand-like powders, while

maintaining their usefulness in synthetic reactions. The stabilized metals

are much safer to store, transport, and handle. They may also be useful

for removing sulfur from fuels, storing hydrogen, and remediating a

variety of hazardous wastes
2008 Small Business Award 5

tion that can be adapted to a variety of industry needs. By enabling

practical chemical shortcuts and continuous flow processes, the encapsulated alkali metals create efficiencies in storage, supply chain,

manpower, and waste disposal.

For the pharmaceutical, petrochemical, and general synthesis industries, SiGNa’s breakthrough eliminates the additional steps that these

industries usually take to avoid using the alkali metals and produces

the desired reaction in 80–90 percent less time. For the pharmaceutical

industry in particular, the materials can accelerate drug discovery and

manufacturing while bolstering worker safety.

Beyond greening conventional chemical syntheses, SiGNa’s materials

enable the development of entirely new areas of chemistry. In cleanenergy applications, the company’s stabilized alkali metals safely

produce record levels of pure hydrogen gas for the nascent fuel cell

sector. With yield levels that already exceed the U.S. Department of

Energy’s targets for 2015, SiGNa’s materials constitute the most effective means for processing water into hydrogen. SiGNa’s materials also

allow alkali metals to be safely applied to environmental remediation of

oil contamination and the destruction of PCBs and CFCs.

SiGNa’s success in increasing process efficiencies, health, and environmental safety and in enabling new chemical technologies has helped it

attract more than 50 major global pharmaceutical, chemical, and

energy companies as customers.
6 2008 Award

Greener Synthetic

Pathways Award

Battelle

Development and Commercialization of Biobased Toners

More than 400 million pounds of electrostatic dry toners based on

petroleum-derived resins are used in the United States annually to

make more than 3 trillion copies in photocopiers and printers. Conventional toners are based on synthetic resins such as styrene acrylates

and styrene butadiene. These conventional resins make it difficult to

remove the toner during recycling, a process called de-inking. This

makes paper recycling more difficult. Although others have developed

de-inkable toners, none of the competing technologies has become

commercial due to high costs and inadequate de-inking performance.

With early-stage funding from the Ohio Soybean Council, Battelle and

Advanced Image Resources (AIR) formed a team to develop and

market biobased resins and toners for office copiers and printers. This

novel technology uses soy oil and protein along with carbohydrates

from corn as chemical feedstocks. Battelle developed bioderived

polyester, polyamide, and polyurethane resins and toners from these

feedstocks through innovative, cost-effective chemical modifications

Innovation and Benefits

Laser printers and copiers use over 400 million pounds of toner each

year in the United States. Traditional toners fuse so tightly to paper that

they are difficult to remove from waste paper for recycling. They are also

made from petroleum-based starting materials. Battelle and its partners,

Advanced Image Resources and the Ohio Soybean Council, have

developed a soy-based toner that performs as well as traditional ones,

but is much easier to remove. The new toner technology can save

significant amounts of energy and allow more paper fiber to be

recycled.
2008 Greener Synthetic Pathways Award 7

and processing, with the de-inking process in mind. By incorporating

chemical groups that are susceptible to degradation during the standard de-inking process, Battelle created new inks that are significantly

easier to remove from the paper fiber. AIR then scaled up the process

with proprietary catalysts and conditions to make the new resins.

The new technology offers significant advantages in recycling waste

office paper without sacrificing print quality. Improved de-inking of the

fused ink from waste copy paper results in higher-quality recovered

materials and streamlines the recycling process. Preliminary life-cycle

analysis shows significant energy savings and reduced carbon dioxide

(CO2) emissions in the full value chain from resin manufacture using

biobased feedstocks to toner production and, finally, to the recovery of

secondary fibers from the office waste stream. At 25 percent market

penetration in 2010, this technology could save 9.25 trillion British

thermal units per year (Btu/yr) and eliminate over 360,000 tons of CO2

emissions per year.

Overall, soy toner provides a cost-effective, systems-oriented, environmentally benign solution to the growing problem of waste paper

generated from copiers and printers. In 2006, AIR, the licensee of the

technology, successfully scaled up production of the resin and toners

for use in HP LaserJet 4250 Laser Printer cartridges. Battelle and AIR

coordinated to move from early-stage laboratory development to fullscale manufacturing and commercialization. Their efforts have resulted

in a cost-competitive, highly marketable product that is compatible with

current hardware. The new toner will be sold under trade names

BioRez® and Rezilution®. Once commercial, it will provide users with

seamless, environmentally friendly printing and copying.
8 2008 Award

Greener Reactions Conditions Award

Nalco Company

3D TRASAR® Technology

Most commercial buildings, including offices, universities, hospitals,

and stores, as well as many industrial processes, use cooling systems

based on water. These cooling systems can consume vast quantities of

water. Also, unless mineral scale and microbes are well-controlled,

several problems can arise leading to increased water and energy

consumption and negative environmental impacts.

Mineral scale, which consists mostly of carbonates of calcium and

magnesium, forms on heat-exchange surfaces; this makes heat

transfer inefficient and increases energy use. Similarly, microbial growth

can lead to the formation of biofilms on heat-exchange surfaces,

decreasing exchange efficiency. Conversely, high levels of biocide

intended to prevent biofilm cause several adverse effects including

increased corrosion of system components. Gradually, the integrity of

the system becomes compromised, increasing the risk of system leaks.

The material from these leaks, along with metal-containing byproducts

of corrosion and the additional biocide, are ultimately discharged with

the cooling water. Every time water is discharged, called “blowdown”,

pollutants are released in the wastewater, and fresh water is used to

Innovation and Benefits

Cooling water touches many facets of human life, including cooling for

comfort in commercial buildings and cooling industrial processes.

Cooling systems require added chemicals to control microbial growth,

mineral deposits, and corrosion. Nalco developed 3D TRASAR®

technology to monitor the condition of cooling water continuously and

add appropriate chemicals only when needed, rather than on a fixed

schedule. The technique saves water and energy, minimizes the use of

water-treatment chemicals, and decreases environmental damage from

discharged water.
2008 Greener Reaction Conditions Award 9

replace the blowdown. Traditionally, antiscalants and antimicrobials are

added at regular intervals or, at best, after manual or indirect measurements show scale or microbial buildup.

In 2004, Nalco commercialized its 3D TRASAR® Cooling System Chemistry and Control technology. By detecting scaling tendency early, cooling

systems with Nalco’s technology can operate efficiently; in addition,

they can use less water or use poor-quality water.

3D Scale Control, part of the 3D TRASAR® system, prevents the formation of mineral scale on surfaces, maintaining efficient heat transfer.

The system monitors antiscalant levels using a fluorescent-tagged,

scale-dispersant polymer and responds quickly when conditions favor

scale formation. In addition, 3D Bio-control, also part of the

3D TRASAR® system, is the only online, real-time test for measuring

planktonic and sessile bacteria. It uses resazurin, another fluorescent

molecule, which changes its fluorescent signature when it interacts

with respiring microbes. By adding an oxidizing biocide in response to

microbial activity, 3D Bio-control generally reduces the use of biocide

and also prevents biofilm from building up on surfaces, maintaining

efficient heat transfer.

A proprietary corrosion monitor and a novel corrosion inhibitor,

phosphino succinic oligomer, provide improved corrosion protection. In

2006, the 2,500 installations using the 3D TRASAR® system saved

approximately 21 billion gallons of water. These installations have also

significantly reduced the discharge of water-treatment chemicals to

water-treatment plants or natural waterways.
10 2008 Award

Designing Greener Chemicals Award

Dow AgroSciences LLC

Spinetoram: Enhancing a Natural Product for Insect Control

Spinosad biopesticide won the Presidential Green Chemistry Challenge

Award for Designing Greener Chemicals in 1999. Spinosad, a combination of spinosyns A and D, is effective against insect pests on

vegetables, but there have been few green chemistry alternatives for

insect-pest control in tree fruits and tree nuts. Dow AgroSciences has

now developed spinetoram, a significant advancement over spinosad

that extends the success of spinosad to new crops.

The discovery of spinetoram involved the novel application of an

artificial neural network (ANN) to the molecular design of insecticides.

Dow AgroSciences researchers used an ANN to understand the quantitative structure-activity relationships of spinosyns and to predict analogues that would be more active. The result is spinetoram, a mixture

of 3’-O-ethyl-5,6-dihydro spinosyn J and 3’-O-ethyl spinosyn L. Dow

AgroSciences makes spinetoram from naturally occurring fermentation

products spinosyns J and L by modifying them with a low-impact

synthesis in which catalysts and most reagents and solvents are

recycled. The biology and chemistry of spinetoram have been extenInnovation and Benefits

Spinosad biopesticide from Dow AgroSciences controls many insect

pests on vegetables, but is not particularly effective against certain key

pests of tree fruits. To solve this problem, Dow AgroSciences used an

“artificial neural network” to identify analogous molecules that might be

more effective against fruit-tree pests. They then developed a green

chemical synthesis for the new insecticide, called spinetoram.

Spinetoram retains the favorable environmental benefits of spinosad

while replacing organophosphate pesticides for tree fruits, tree nuts,

small fruits, and vegetables.
2008 Designing Greener Chemicals Award 11

sively researched; the results have been published in peer-reviewed

scientific journals and presented at scientific meetings globally.

Spinetoram provides significant and immediate benefits to human

health and the environment over existing insecticides. Azinphos-methyl

and phosmet, two organophosphate insecticides, are widely used in

pome fruits (such as apples and pears), stone fruits (such as cherries

and peaches), and tree nuts (such as walnuts and pecans). The mammalian acute oral toxicity of spinetoram is more than 1,000 times lower

than that of azinphos-methyl and 44 times lower than that of phosmet.

The low toxicity of spinetoram reduces the risk of exposures throughout the supply chain: in manufacturing, transportation, and application

and to the public.

Spinetoram has a lower environmental impact than do many current

insecticides because both its use rate and its toxicity to non-target

species are low. Spinetoram is effective at much lower rates than many

competing insecticides. It is effective at use rates that are 10–34 times

lower than azinphos-methyl and phosmet. Spinetoram is also less

persistent in the environment compared with other traditional insecticides. In the United States alone, Dow AgroSciences expects

spinetoram to eliminate about 1.8 million pounds of organophosphate

insecticides applied to pome fruit, stone fruit, and tree nuts during its

first five years of use. In 2007, EPA granted pesticide registrations to the

spinetoram products RadiantTM and DelegateTM, and Dow AgroSciences

began commercial sales
12 2007 Award

2007 Winners

Academic Award

Professor Michael J. Krische

University of Texas at Austin

Hydrogen-Mediated Carbon—Carbon Bond Formation

Innovation and Benefits

A fundamental aspect of chemistry involves creating chemical bonds

between carbon atoms. Chemical processes commonly used to make such

bonds usually also generate significant amounts of waste. Professor

Krische developed a broad new class of chemical reactions that make

bonds between carbon atoms using hydrogen and metal catalysts. This

new class of reactions can be used to convert simple chemicals into

complex substances, such as pharmaceuticals, pesticides, and other

important chemicals, with minimal waste.

Reductions mediated by hydrogen, termed “hydrogenations”, rank

among the most widely used catalytic methods employed industrially.

They are generally used to form carbon–hydrogen (C–H) bonds.

Professor Michael J. Krische and his coworkers at the University of Texas

at Austin have developed a new class of hydrogenation reactions that

form carbon–carbon (C–C) bonds. In these metal-catalyzed reactions,

two or more organic molecules combine with hydrogen gas to create a

single, more complex product. Because all atoms present in the

starting building-block molecules appear in the final product, Professor

Krische’s reactions do not generate any byproducts or wastes. Hence,

Professor Krische’s C–C bond-forming hydrogenations eliminate

pollution at its source.

Prior to Professor Krische’s work, hydrogen-mediated C–C bond formations were limited almost exclusively to the use of carbon monoxide in

reactions such as alkene hydroformylation (1938) and the FischerTropsch reaction (1923). These prototypical hydrogen-mediated C–C

bond formations are practiced industrially on an enormous scale. Yet,

despite the importance of these reactions, no one had engaged in
2007 Academic Award 13

systematic research to develop related C–C bond-forming hydrogenations. Only a small fraction of hydrogenation’s potential as a method

of C–C coupling had been realized, and the field lay fallow for nearly

70 years.

Professor Krische’s hydrogen-mediated couplings circumvent the use of

preformed organometallic reagents, such as Grignard and Gilman

reagents, in carbonyl and imine addition reactions. Such organometallic

reagents are highly reactive, typically moisture-sensitive, and sometimes pyrophoric, meaning that they combust when exposed to air.

Professor Krische’s coupling reactions take advantage of catalysts that

avoid the hazards of traditional organometallic reagents. Further, using

chiral hydrogenation catalysts, Professor Krische’s couplings generate

C–C bonds in a highly enantioselective fashion.

Catalytic hydrogenation has been known for over a century and has

stood the test of time due its efficiency, atom economy, and costeffectiveness. By exploiting hydrogenation as a method of C–C bond

formation, Professor Krische has added a broad, new dimension to one

of chemistry’s most fundamental catalytic processes. The C–C bondforming hydrogenations developed by Professor Krische allow chemists

to create complex organic molecules in a highly selective fashion,

eliminating both hazardous starting materials and hazardous waste.

Commercial application of this technology may eliminate vast quantities

of hazardous chemicals. The resulting increases in plant and worker

safety may enable industry to perform chemical transformations that

were too dangerous using traditional reagents.
14 2007 Award

Small Business Award

NovaSterilis Inc.

Environmentally Benign Medical Sterilization Using Supercritical Carbon

Dioxide

Innovation and Benefits

Sterilizing biological tissue for transplant is critical to safety and success in

medical treatment. Common existing sterilization techniques use

ethylene oxide or gamma radiation, which are toxic or have safety

problems. NovaSterilis invented a technology that uses carbon dioxide

and a form of peroxide to sterilize a wide variety of delicate biological

materials such as graft tissue, vaccines, and biopolymers. Their Nova

2200TM sterilizer requires neither hazardous ethylene oxide nor gamma

radiation.

None of the common methods for medical sterilization is well-suited

to sterilizing delicate biological materials. The sterility of these materials

is critical. Distribution of contaminated donor tissues by tissue banks

has resulted in serious infections and illnesses in transplant patients.

The two most widely used sterilants (ethylene oxide and gamma

radiation) also raise toxicity and safety concerns. Ethylene oxide is a

mutagenic, carcinogenic, volatile, flammable, reactive gas. Residues of

ethylene oxide remain in the sterilized material, increasing the risk of

toxic side effects. Gamma radiation is highly penetrating and is lethal

to all cells. Neither ethylene oxide nor gamma radiation can sterilize

packaged biological products without eroding their physical integrity.

NovaSterilis, a privately held biotechnology company in Ithaca, NY, has

successfully developed and commercialized a highly effective and

environmentally benign technique for sterilizing delicate biological

materials using supercritical carbon dioxide (CO2

). NovaSterilis licensed

a patent for bacterial inactivation in biodegradable polymers that was

issued to Professor Robert S. Langer and his team at the Massachusetts

Institute of Technology. NovaSterilis then enhanced, expanded, and

optimized the technology to kill bacterial endospores. Their
2007 Small Business Award 15

supercritical CO2 technology uses low temperature and cycles of

moderate pressure along with a peroxide (peracetic acid) and small

amounts of water. Their Nova 2200TM sterilizer consistently achieves

rapid (less than one hour) and total inactivation of a wide range of

microbes, including bacterial endospores. The mechanism of bacterial

inactivation is not well-understood, but does not appear to involve

bacterial cell lysis or wholesale degradation of bacterial proteins.

The new technology is compatible with sensitive biological materials

and is effective for a wide range of important biomedical materials

including: (a) musculoskeletal allograft tissue (e.g., human bone,

tendons, dermis, and heart valves) for transplantation; (b) biodegradable polymers and related materials used in medical devices, instruments, and drugs; (c) drug delivery systems; and (d) whole-cell vaccines

that retain high antigenicity. Besides being a green chemical technology, supercritical CO2

 sterilization achieves “terminal” sterilization, that

is, sterilization of the final packaged product. Terminal sterilization

provides greater assurance of sterility than traditional methods of

aseptic processing. Sterilization of double-bagged tissue allows tissue

banks to ship terminally sterilized musculoskeletal tissues in packages

that can be opened in operating rooms by surgical teams immediately

prior to use. NovaSterilis’s patented technology addresses the market

need in tissue banks as well as other needs in the biomedical,

biologics, medical device, pharmaceutical, and vaccine industries. By

the end of 2006, NovaSterilis had sold several units to tissue banks.
16 2007 Award

Greener Synthetic Pathways Award

Professor Kaichang Li, Oregon State University; Columbia Forest

Products; Hercules Incorporated

Development and Commercial Application of Environmentally Friendly

Adhesives for Wood Composites

Innovation and Benefits

Adhesives used in manufacturing plywood and other wood composites

often contain formaldehyde, which is toxic. Professor Kaichang Li of

Oregon State University, Columbia Forest Products, and Hercules

Incorporated developed an alternate adhesive made from soy flour. Their

environmentally friendly adhesive is stronger than and cost-competitive

with conventional adhesives. During 2006, Columbia used the new, soybased adhesive to replace more than 47 million pounds of conventional

formaldehyde-based adhesives.

Since the 1940s, the wood composites industry has been using synthetic adhesive resins to bind wood pieces into composites, such as

plywood, particleboard, and fiberboard. The industry has been the

predominate user of formaldehyde-based adhesives such as phenol–

formaldehyde and urea–formaldehyde (UF) resins. Formaldehyde is a

probable human carcinogen. The manufacture and use of wood

composite panels bonded with formaldehyde-based resins release

formaldehyde into the air, creating hazards for both workers and

consumers.

Inspired by the superior properties of the protein that mussels use to

adhere to rocks, Professor Li and his group at Oregon State University

invented environmentally friendly wood adhesives based on abundant,

renewable soy flour. Professor Li modified some of the amino acids in

soy protein to resemble those of mussels’ adhesive protein. Hercules

Incorporated provided a critical curing agent and the expertise to apply

it to commercial production of plywood.
2007 Greener Synthetic Pathways Award 17

Oregon State University, Columbia Forest Products (CFP), and Hercules

have jointly commercialized soy-based adhesives to produce costcompetitive plywood and particleboard for interior uses. The soy-based

adhesives do not contain formaldehyde or use formaldehyde as a raw

material. They are environmentally friendly, cost-competitive with the UF

resin in plywood, and superior to the UF resin in strength and water

resistance. All CFP plywood plants now use soy-based adhesives,

replacing more than 47 million pounds of the toxic UF resin in 2006 and

reducing the emission of hazardous air pollutants (HAPs) from each CFP

plant by 50 to 90 percent. This new CFP plywood is sold under the

PureBondTM name. During 2007, CFP will replace UF at its particleboard

plant; the company is also seeking arrangements with other manufacturers to further the adoption of this technology.

With this technology, those who make and use furniture, kitchen

cabinetry, and other wood composite materials have a high-performing

formaldehyde-free alternative. As a result, indoor air quality in homes

and offices could improve significantly. This technology represents the

first cost-competitive, environmentally friendly adhesive that can replace

the toxic UF resin. The technology can greatly enhance the global

competitiveness of U.S. wood composite companies. In addition, by

creating a new market for soy flour, currently in over-supply, this technology provides economic benefits for soybean farmers.
18 2007 Award

Greener Reaction Conditions Award

Headwaters Technology Innovation

Direct Synthesis of Hydrogen Peroxide by Selective Nanocatalyst

Technology

Innovation and Benefits

Hydrogen peroxide is an environmentally friendly alternative to chlorine

and chlorine-containing bleaches and oxidants. It is expensive, however,

and its current manufacturing process involves the use of hazardous

chemicals. Headwaters Technology Innovation (HTI) developed an

advanced metal catalyst that makes hydrogen peroxide directly from

hydrogen and oxygen, eliminates the use of hazardous chemicals, and

produces water as the only byproduct. HTI has demonstrated their new

technology and is partnering with Degussa AG to build plants to produce

hydrogen peroxide.

Hydrogen peroxide (H2O2) is a clean, versatile, environmentally friendly

oxidant that can substitute for environmentally harmful chlorinated

oxidants in many manufacturing operations. However, the existing

manufacturing process for H2

O2 is complex, expensive, and energyintensive. This process requires an anthraquinone working solution

containing several toxic chemicals. The solution is reduced by hydrogen

in the presence of a catalyst, forming anthrahydroquinone, which then

reacts with oxygen to release H2

O2. The H2O2 is removed from the

solution with an energy-intensive stripping column and then concentrated by vacuum distillation. The bulk of the working solution is

recycled, but the process generates a waste stream of undesirable

quinone-derived byproducts that requires environmentally acceptable

disposal.

Headwaters Technology Innovation (HTI) has produced a robust catalyst

technology that enables the synthesis of H2

O2 directly from hydrogen

and oxygen. This breakthrough technology, called NxCatTM, is a palladium-platinum catalyst that eliminates all the hazardous reaction

conditions and chemicals of the existing process, along with its undesir-
2007 Greener Reaction Conditions Award 19

able byproducts. It produces H2O2 more efficiently, cutting both energy

use and costs. It uses innocuous, renewable feedstocks and generates

no toxic waste.

NxCatTM catalysts work because of their precisely controlled surface

morphology. HTI has engineered a set of molecular templates and

substrates that maintain control of the catalyst’s crystal structure,

particle size, composition, dispersion, and stability. This catalyst has a

uniform 4-nanometer feature size that safely enables a high rate of

production with a hydrogen gas concentration below 4 percent in air

(i.e., below the flammability limit of hydrogen). It also maximizes the

selectivity for H2

O2 up to 100 percent.

The NxCatTM technology enables a simple, commercially viable H2

O2

manufacturing process. In partnership with Degussa AG (a major H2O2

manufacturer), HTI successfully demonstrated the NxCatTM technology

and, in 2006, completed construction of a demonstration plant. This

demonstration plant will allow the partners to collect the data necessary

to design a full-scale plant and begin commercial production in 2009.

The NxCatTM process has the potential to cut the cost of H2

O2 significantly, generating a more competitively priced supply of H2

O2 and

increasing its market acceptance as an industrial oxidant. Except for its

historically higher price, H2

O2 is an excellent substitute for the more

frequently used—and far more deleterious—chlorinated oxidants. The

NxCatTM technology has the benefit of producing an effective, environmentally preferable oxidant (H2

O2) without the waste or high cost

associated with the traditional process.
20 2007 Award

Designing Greener Chemicals Award

Cargill, Incorporated

BiOHTM Polyols

Innovation and Benefits

Foam cushioning used in furniture or bedding is made from polyurethane,

a man-made material. One of the two chemical building blocks used to

make polyurethane is a “polyol.” Polyols are conventionally manufactured

from petroleum products. Cargill’s BiOHTM polyols are manufactured

from renewable, biological sources such as vegetable oils. Foams made

with BiOHTM polyols are comparable to foams made from conventional

polyols. As a result, each million pounds of BiOHTM polyols saves nearly

700,000 pounds of crude oil. In addition, Cargill’s process reduces total

energy use by 23 percent and carbon dioxide emissions by 36 percent.

Polyols are key ingredients in flexible polyurethane foams, which are

used in furniture and bedding. Historically, polyurethane has been

made from petrochemical polyols. The idea of replacing these polyols

with biobased polyols is not new, but the poor performance, color,

quality, consistency, and odor of previous biobased polyols restricted

them to limited markets. Previous biobased polyols also suffer from

poor chemical reactivity, resulting in foam with inferior properties.

Cargill has successfully developed biobased polyols for several polyurethane applications, including flexible foams, which are the most

technically challenging. Cargill makes BiOHTM polyols by converting the

carbon—carbon double bonds in unsaturated vegetable oils to epoxide

derivatives and then further converting these derivatives to polyols

using mild temperature and ambient pressure. BiOHTM polyols provide

excellent reactivity and high levels of incorporation leading to highperforming polyurethane foams. These foams set a new standard for

consistent quality with low odor and color. Foams containing BiOHTM

polyols retain their white color longer without ultraviolet stabilizers.

They also are superior to foams containing only petroleum-based
2007 Designing Greener Chemicals Award 21

polyols in standard tests. In large slabstock foams, such as those used

in furniture and bedding, BiOH 5000 polyol provides a wide processing

window, improved comfort factor, and reduced variations in density and

load-bearing capacity. In molded foams such as automotive seating

and headrests, BiOH 2100 polyol can enhance load-bearing or hardness

properties relative to conventional polyols.

Use of BiOHTM polyols reduces the environmental footprint relative to

today’s conventional polyols for polyurethane production. BiOHTM

polyols “harvest” carbon that plants remove from the air during photosynthesis. All of the carbon in BiOHTM polyols is recently fixed. In

conventional polyols, the carbon is petroleum-based. Replacing

petroleum-based polyols with BiOHTM polyols cuts total energy use by

23 percent including a 61 percent reduction in nonrenewable energy

use, leading to a 36 percent reduction in carbon dioxide emissions. For

each million pounds of BiOHTM polyol used in place of petroleumbased polyols, about 700,000 pounds (2,200 barrels) of crude oil are

saved, thereby reducing the dependence on petroleum. BiOHTM

polyols diversify the industry’s supply options and help mitigate the

effects of uncertainty and volatility of petroleum supply and pricing.

Cargill is the first company to commercialize biobased polyols on a

large scale in the flexible foam market. Formulators can now use

biobased polyols in flexible foam without compromising product

performance. That the top North American polyol users choose BiOHTM

polyols is validation of Cargill’s accomplishment.
22

2006 Winners

Academic Award

Professor Galen J. Suppes

University of Missouri-Columbia

Biobased Propylene Glycol and Monomers from Natural Glycerin

Innovation and Benefits

Professor Suppes developed an inexpensive method to convert waste

glycerin, a byproduct of biodiesel fuel production, into propylene glycol,

which can replace ethylene glycol in automotive antifreeze. This highvalue use of the glycerin byproduct can keep production costs down and

help biodiesel become a cost-effective, viable alternative fuel, thereby

reducing emissions and conserving fossil fuels.

Glycerin is a coproduct of biodiesel production. The U.S. biodiesel

industry is expected to introduce one billion pounds of additional

glycerin into a market that is currently only 600 million pounds. The

economics of biodiesel depend heavily on using its glycerin coproduct.

A high-value use for glycerin could reduce the cost of biodiesel by as

much as 40¢ per gallon. There is simply not enough demand for

glycerin, however, to make use of all the waste glycerin expected.

One solution is to convert the glycerin to propylene glycol. Approximately 2.4 billion pounds of propylene glycol are currently made each

year, almost exclusively from petroleum-based propylene oxide.

Propylene glycol is a less toxic alternative to ethylene glycol in antifreeze, but is currently more expensive and, as a result, has a very

small market share. Professor Galen J. Suppes has developed a catalytic

process that efficiently converts crude glycerin to propylene glycol.

Professor Suppes’s system couples a new copper-chromite catalyst

with a reactive distillation. This system has a number of advantages

over previous systems that perform this conversion. The new process

uses a lower temperature and lower pressure than do previous

systems (428 °F versus 500 °F and <145 psi versus >2,170 psi), converts
2006 Academic Award 23

glycerin to propylene glycol more efficiently, and produces less

byproduct than do similar catalysts. Propylene glycol made from

glycerin by Professor Suppes’s method is also significantly cheaper

than propylene glycol made from petroleum.

Another solution is to convert glycerin to acetol (i.e., 1-hydroxy-2-

propanone or hydroxyacetone), a well-known intermediate and monomer used to make polyols. When made from petroleum, acetol costs

approximately $5 per pound, prohibiting its wide use. Professor

Suppes’s technology can be used to make acetol from glycerin at a

cost of approximately 50¢ per pound, opening up even more potential

applications and markets for products made from glycerin.

Professor Suppes initiated this project in June 2003. The first commercial facility, with a capacity of 50 million pounds per year, is under

construction and is expected to be in operation by October 2006.
24 2006 Award

Small Business Award

Arkon Consultants

NuPro Technologies, Inc.

Environmentally Safe Solvents and Reclamation in the Flexographic

Printing Industry

Innovation and Benefits

Flexographic printing is used in a wide array of print jobs such as food

wrappers and boxes, but the process uses millions of gallons of solvents

each year. Arkon and NuPro developed a safer chemical processing system

that reduces the amounts of solvents needed for printing. The new system

eliminates hazardous solvents, reduces explosion potential and emissions

during solvent recycling, and increases worker safety in the flexographic

printing industry.

Flexographic printing is used on everything from food wrappers to

secondary containers such as cereal boxes to shipping cartons. The

photopolymerizable material on a flexographic printing plate crosslinks when exposed to light and captures an image. After exposure,

flexographic printing plates are immersed in a solvent to remove the

unpolymerized material. The developing, or washout, solvent is

typically a mixture of chloro, saturated cyclic, or acyclic hydrocarbons.

Xylene is the most common solvent. Most traditional washout solvents

are hazardous air pollutants (HAPs) subject to stringent reporting

requirements; they also raise worker safety issues and create problems

with recycling and disposal. North America alone uses 2 million gallons

of washout solvents each year with a market value of $20 million. Many

small printing plants use these solvents.

Together, Arkon Consultants and NuPro Technologies have developed

a safer chemical processing system, including washout solvents and

reclamation/recycling machinery for the flexographic printing industry.

NuPro/Arkon have developed several new classes of washout solvents

with methyl esters, terpene derivatives, and highly substituted cyclic

hydrocarbons. The advantages include higher flash points and lower
2006 Small Business Award 25

toxicity, which reduce explosion potential, worker exposure, and

regulatory reporting. The methyl esters and terpene derivatives are

biodegradable and can be manufactured from renewable sources. All

of their solvents are designed to be recycled in their Cold Reclaim

SystemTM. In contrast to traditional vacuum distillation, this combination

of filtration and centrifugation lowers exposures, decreases maintenance, and reduces waste. The waste is a solid, nonhazardous polymeric material.

In the U.S. market, NuPro/Arkon are currently selling washout solvents

that are terpene ether- and ester-based or made with low-hazard

cyclics. They are marketing their methyl ester-based solvent in China

and Japan. Their first filtration-based Cold Recovery SystemTM is currently in use in Menesha, WI and is being marketed to larger U.S.

users. Their centrifugation reclamation system for smaller users is in

the final stages of development.

Use of these solvents and systems benefits both human health and

the environment by lowering exposure to hazardous materials, reducing explosion potential, reducing emissions, and, in the case of the

terpene and methyl ester-based solvents, using renewable resources.

These solvents and the reclamation equipment represent major

innovations in the safety of handling, exposure, and recovery. The

reduced explosion potential, reduced emissions, decreased worker

exposure, and reduced transport and maintenance costs translate into

decreased cost and improved safety in all aspects of flexographic

printing processes.
26 2006 Award

Greener Synthetic Pathways Award

Merck & Co., Inc.

Novel Green Synthesis for β-Amino Acids Produces the Active

Ingredient in JanuviaTM

Innovation and Benefits

Merck discovered a highly innovative and efficient catalytic synthesis for

sitagliptin, which is the active ingredient in JanuviaTM, the company's new

treatment for type 2 diabetes. This revolutionary synthesis creates

220 pounds less waste for each pound of sitagliptin manufactured and

increases the overall yield by nearly 50 percent. Over the lifetime of

JanuviaTM, Merck expects to eliminate the formation of at least 330 million

pounds of waste, including nearly 110 million pounds of aqueous waste.

JanuviaTM is a new treatment for type 2 diabetes; Merck filed for

regulatory approval in December 2005. Sitagliptin, a chiral β-amino acid

derivative, is the active ingredient in JanuviaTM. Merck used a firstgeneration synthesis of sitagliptin to prepare over 200 pounds for

clinical trials. With modifications, this synthesis could have been a

viable manufacturing process, but it required eight steps including a

number of aqueous work-ups. It also required several high-molecularweight reagents that were not incorporated into the final molecule

and, therefore, ended up as waste.

While developing a highly efficient second-generation synthesis for

sitagliptin, Merck researchers discovered a completely unprecedented

transformation: the asymmetric catalytic hydrogenation of unprotected

enamines. In collaboration with Solvias, a company with expertise in

this area, Merck scientists discovered that hydrogenation of unprotected enamines using rhodium salts of a ferrocenyl-based ligand as

the catalyst gives β-amino acid derivatives of high optical purity and

yield. This new method provides a general synthesis of β-amino acids,

a class of molecules well-known for interesting biological properties.

Merck scientists and engineers applied this new method in a completely novel way: using it in the final synthetic step to maximize the
2006 Greener Synthetic Pathways Award 27

yield in terms of the valuable chiral catalyst. The dehydro precursor to

sitagliptin used in the asymmetric hydrogenation is prepared in an

essentially one-pot procedure. Following the hydrogenation, Merck

recovers and recycles over 95 percent of the valuable rhodium. The

reactive amino group of sitagliptin is only revealed in the final step; as

a result, there is no need for protecting groups. The new synthesis has

only three steps and increases the overall yield by nearly 50 percent.

This strategy is broadly applicable to other pharmaceutical syntheses;

Merck has used it to make several exploratory drug candidates.

Implementing the new route on a manufacturing scale has reduced

the amount of waste by over 80 percent and completely eliminated

aqueous waste streams. This second-generation synthesis will create

220 pounds less waste for each pound of sitagliptin manufactured.

Over the lifetime of the drug, Merck expects to eliminate the formation of 330 million pounds or more of waste, including nearly

110 million pounds of aqueous waste. Because Merck’s new synthesis

has reduced the amount of raw materials, processing time, energy,

and waste, it is a more cost-effective option than the first-generation

synthesis. The technology discovered, developed, and implemented

by Merck for the manufacture of JanuviaTM is an excellent example of

scientific innovation resulting in benefits to the environment.
28 2006 Award

Greener Reaction Conditions Award

Codexis, Inc.

Directed Evolution of Three Biocatalysts to Produce the Key Chiral

Building Block for Atorvastatin, the Active Ingredient in Lipitor®

Innovation and Benefits

Codexis developed cutting-edge genetic methods to create “designer

enzymes”. Codexis applied its methods to produce enzymes that greatly

improve the manufacture of the key building block for Lipitor®, one of the

world's best-selling drugs. The new enzymatic process reduces waste,

uses less solvent, and requires less processing equipment – marked improvements over processes used in the past. The process also increases

yield and improves worker safety.

Atorvastatin calcium is the active ingredient of Lipitor®, a drug that

lowers cholesterol by blocking its synthesis in the liver. Lipitor® is the

first drug in the world with annual sales exceeding $10 billion. The key

chiral building block in the synthesis of atorvastatin is ethyl (R)-4-cyano3-hydroxybutyrate, known as hydroxynitrile (HN). Annual demand for

HN is estimated to be about 440,000 pounds. Traditional commercial

processes for HN require a resolution step with 50 percent maximum

yield or syntheses from chiral pool precursors; they also require

hydrogen bromide to generate a bromohydrin for cyanation. All

previous commercial HN processes ultimately substitute cyanide for

halide under heated alkaline conditions, forming extensive

byproducts. They require a difficult high-vacuum fractional distillation to

purify the final product, which decreases the yield even further.

Codexis designed a green HN process around the exquisite selectivity

of enzymes and their ability to catalyze reactions under mild, neutral

conditions to yield high-quality products. Codexis developed three

specific enzymes using state-of-the-art, recombinant-based, directed

evolution technologies to provide the activity, selectivity, and stability

required for a practical and economic process. The bioengineered

enzymes are so active and stable that Codexis can recover high-quality
2006 Greener Reaction Conditions Award 29

product by extracting the reaction mixture. In the first step, two of the

enzymes catalyze the enantioselective reduction of a prochiral

chloroketone (ethyl 4-chloroacetoacetate) by glucose to form an

enantiopure chlorohydrin. In the second step, a third enzyme catalyzes the novel biocatalytic cyanation of the chlorohydrin to the cyanohydrin under neutral conditions (aqueous, pH ~7, 77–104 °F, atmospheric pressure). On a biocatalyst basis, the three enzymes have

improved the volumetric productivity of the reduction reaction by

approximately 100-fold and that of the cyanation reaction by approximately 4,000-fold.

The process involves fewer unit operations than earlier processes,

most notably obviating the fractional distillation of the product. The

process provides environmental and human health benefits by increasing yield, reducing the formation of byproducts, reducing the generation of waste, avoiding hydrogen gas, reducing the need for solvents,

reducing the use of purification equipment, and increasing worker

safety. The Codexis process is operated by Lonza to manufacture HN

for Pfizer’s production of atorvastatin calcium.
30 2006 Award

Designing Greener Chemicals Award

S.C. Johnson & Son, Inc.

GreenlistTM Process to Reformulate Consumer Products

Innovation and Benefits

SC Johnson developed GreenlistTM, a system that rates the environmental

and health effects of the ingredients in its products. SC Johnson is now

using GreenlistTM to reformulate many of its products. For example, SC

Johnson eliminated the use of nearly 4 million pounds of polyvinylidene

chloride (PVDC) annually after its “Greenlist” review of Saran Wrap®

revealed opportunities for changes.

SC Johnson (SCJ) formulates and manufactures consumer products

including a wide variety of products for home cleaning, air care,

personal care, insect control, and home storage. For more than a

century, SCJ has been guided by the belief that, because it is a family

business, it must consider the next generation when it makes current

product decisions, not merely the next fiscal quarter. The most recent

initiative in SCJ’s long history of commitment to environmentally

preferable products is its GreenlistTM process, a system that rates the

environmental footprint of the ingredients in its products. Through

GreenlistTM, SCJ chemists and product formulators around the globe

have instant access to environmental ratings of potential product

ingredients.

Starting in 2001, SCJ developed GreenlistTM according to the rigorous

standards of scientific best practices. GreenlistTM uses four to seven

specific criteria to rate ingredients within 17 functional categories. SCJ

enlisted the help of suppliers, university scientists, government

agencies, and nongovernmental organizations (NGOs) to ensure that

the rating criteria were meaningful, objective, and valid. These criteria

include vapor pressure, octanol/water partition coefficient, biodegradability, aquatic toxicity, human toxicity, European Union Classification,

source/supply, and others, as appropriate. The GreenlistTM process

assigns an environmental classification (EC) score to each ingredient by
2006 Designing Greener Chemicals Award 31

averaging its scores for the criteria in its category. EC scores range from

Best (3) to Restricted Use Material (0). SCJ lowers the EC score for

chemicals with other significant concerns including PBT (persistence,

bioaccumulation, and toxicity), endocrine disruption, carcinogenicity,

and reproductive toxicity. Today, GreenlistTM provides ratings for more

than 90 percent of the raw materials SCJ uses, including solvents,

surfactants, inorganic acids and bases, chelants, propellants, preservatives, insecticides, fragrances, waxes, resins, nonwoven fabrics, and

packaging. Company scientists have also developed criteria for dyes,

colorants, and thickeners and are working on additional categories as

well.

During fiscal 2000-2001, the baseline year, SCJ’s EC average was 1.12.

Their goal was to reach an average EC of 1.40 during fiscal 2007–2008.

The company reached this goal three years early, with an average EC

of 1.41 covering almost 1.4 billion pounds of raw materials.

In recent years, SCJ has used GreenlistTM to reformulate multiple

products to make them safer and more environmentally responsible.

In one example, SCJ used the GreenlistTM process to replace polyvinylidene chloride (PVDC) with polyethylene in Saran Wrap®. In

another example, SCJ applied GreenlistTM to remove a particular volatile

organic compound (VOC) from Windex®. They developed a novel new

formula containing amphoteric and anionic surfactants, a solvent

system with fewer than 4 percent VOCs, and a polymer for superior

wetting. Their formula cleans 30 percent better and eliminates over

1.8 million pounds of VOCs per year.
32

2005 Winners

Academic Award

Professor Robin D. Rogers

The University of Alabama

A Platform Strategy Using Ionic Liquids to Dissolve and Process

Cellulose for Advanced New Materials

Innovation and Benefits

Professor Rogers developed methods that allow cellulose from wood,

cloth, or even paper to be chemically modified to make new biorenewable or biocompatible materials. His methods also allow cellulose to be

mixed with other substances, such as dyes, or simply to be processed

directly from solution into a formed shape. Together, these methods can

potentially save resources, time, and energy.

Major chemical companies are currently making tremendous strides

towards using renewable resources in biorefineries. In a typical

biorefinery, the complexity of natural polymers, such as cellulose, is

first broken down into simple building blocks (e.g., ethanol, lactic

acid), then built up into complex polymers. If one could use the

biocomplexity of natural polymers to form new materials directly,

however, one could eliminate many destructive and constructive

synthetic steps. Professor Robin D. Rogers and his group have successfully demonstrated a platform strategy to efficiently exploit the

biocomplexity afforded by one of Nature’s renewable polymers,

cellulose, potentially reducing society’s dependence on nonrenewable

petroleum-based feedstocks for synthetic polymers. No one had

exploited the full potential of cellulose previously, due in part to the

shift towards petroleum-based polymers since the 1940s, difficulty in

modifying the cellulose polymer properties, and the limited number of

common solvents for cellulose.

Professor Rogers’s technology combines two major principles of green

chemistry: developing environmentally preferable solvents and using

biorenewable feedstocks to form advanced materials. Professor
2005 Academic Award 33

Rogers has found that cellulose from virtually any source (fibrous,

amorphous, pulp, cotton, bacterial, filter paper, etc.) can be dissolved

readily and rapidly, without derivatization, in a low-melting ionic liquid

(IL), 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), by gentle

heating (especially with microwaves). IL-dissolved cellulose can easily

be reconstituted in water in controlled architectures (fibers, membranes, beads, flocs, etc.) using conventional extrusion spinning or

forming techniques. By incorporating functional additives into the

solution before reconstitution, Professor Rogers can prepare blended

or composite materials. The incorporated functional additives can be

either dissolved (e.g., dyes, complexants, other polymers) or dispersed

(e.g., nanoparticles, clays, enzymes) in the IL before or after dissolution of the cellulose. With this simple, noncovalent approach, Professor

Rogers can readily prepare encapsulated cellulose composites of

tunable architecture, functionality, and rheology. The IL can be recycled

by a novel salting-out step or by common cation exchange, both of

which save energy compared to recycling by distillation. Professor

Rogers’s current work is aimed at improved, more efficient, and

economical syntheses of [C4mim]Cl, studies of the IL toxicology,

engineering process development, and commercialization.

Professor Rogers and his group are currently doing market research

and business planning leading to the commercialization of targeted

materials, either through joint development agreements with existing

chemical companies or through the creation of small businesses.

Green chemistry principles will guide the development work and

product selection. For example, targeting polypropylene- and polyethylene-derived thermoplastic materials for the automotive industry could

result in materials with lower cost, greater flexibility, lower weight,

lower abrasion, lower toxicity, and improved biodegradability, as well as

significant reductions in the use of petroleum-derived plastics.

Professor Rogers’s work allows the novel use of ILs to dissolve and

reconstitute cellulose and similar polymers. Using green chemistry

principles to guide development and commercialization, he envisions

that his platform strategy can lead to a variety of commercially viable

advanced materials that will obviate or reduce the use of synthetic

polymers.
34 2005 Award

Small Business Award

Metabolix, Inc.

Producing Nature’s Plastics Using Biotechnology

Innovation and Benefits

Metabolix used new biotechnology methods to develop microorganisms

that produce polyhydroxyalkanoates (PHAs) directly. PHAs are natural

plastics with a range of environmental benefits, including reduced

reliance on fossil carbon, reduced solid waste, and reduced greenhouse

gas emissions. PHAs biodegrade to harmless products in the environment,

reducing the burden of plastic waste on landfills and the environment.

Metabolix hopes to develop plants that produce PHAs as well.

Metabolix is commercializing polyhydroxyalkanoates (PHAs), a broadly

useful family of natural, environmentally friendly, high-performing,

biobased plastics. PHAs are based on a biocatalytic process that uses

renewable feedstocks, such as cornstarch, cane sugar, cellulose

hydrolysate, and vegetable oils. PHAs can provide a sustainable

alternative to petrochemical plastics in a wide variety of applications.

Metabolix uses biotechnology to introduce entire enzyme-catalyzed

reaction pathways into microbes, which then produce PHAs, in effect

creating living biocatalysts. The performance of these engineered

microbes has been fully validated in commercial equipment, demonstrating reliable production of a wide range of PHA copolymers at high

yield and reproducibility. A highly efficient commercial process to

recover PHAs has also been developed and demonstrated. The

routine expression of exogenous, chromosomally integrated genes

coding for the enzymes used in a non-native metabolic pathway is a

tour de force in the application of biotechnology. These accomplishments have led Metabolix to form an alliance with Archer Daniels

Midland Company, announced in November 2004, to produce PHAs

commercially, starting with a 100-million-pound-per-year plant to be

sited in the U.S. Midwest.
2005 Small Business Award 35

These new natural PHA plastics are highly versatile, have a broad range

of physical properties, and are practical alternatives to synthetic petrochemical plastics. PHAs range from rigid to highly elastic, have very

good barrier properties, and are resistant to hot water and greases.

Metabolix has developed PHA formulations suitable for processing on

existing equipment and demonstrated them in key end-use applications such as injection molding, thermoforming, blown film, and

extrusion melt casting including film, sheet, and paper coating.

Metabolix’s PHA natural plastics will bring a range of environmental

benefits, including reduced reliance on fossil carbon and reduced

greenhouse gas emissions. PHAs are now made from renewable raw

materials, such as sugar and vegetable oils. In the future, they will be

produced directly in plants. In addition, PHAs will reduce the burden of

plastic waste on solid waste systems, municipal waste treatment

systems, and marine and wetland ecosystems: they will biodegrade to

harmless products in a wide variety of both aerobic and anaerobic

environments, including soil, river and ocean water, septic systems,

anaerobic digesters, and compost.

Metabolix’s PHA technology is the first commercialization of plastics

based on renewable resources that employs living biocatalysts in

microbial fermentation to convert renewable raw materials all the way

to the finished copolymer product. PHAs are also the first family of

plastics that combine broadly useful properties with biodegradability in

a wide range of environments, including marine and wetlands ecosystems. Replacement of petrochemical plastics with PHAs will also have

significant economic benefits. Producing 50 billion pounds of PHA

natural plastics to replace about half of the petrochemical plastics

currently used in the United States would reduce oil imports by over

200–230 million barrels per year, improving the U.S. trade balance by

$6–9 billion per year, assuming oil at $30–40 per barrel.
36 2005 Award

Greener Synthetic Pathways Award

Archer Daniels Midland Company

Novozymes

NovaLipidTM: Low Trans Fats and Oils Produced by Enzymatic

Interesterification of Vegetable Oils Using Lipozyme®

Innovation and Benefits

Archer Daniels Midland Company and Novozymes developed a way to

make edible fats and oils that contain no trans fatty acids. The improved

“interesterification” process they developed uses less resources. Potential

savings include hundreds of millions of pounds of soybean and other

vegetable oils, processing chemicals, and water resources each year.

Two major challenges facing the food and ingredient industry are

providing health-conscious products to the public and developing

environmentally responsible production technology. Archer Daniels

Midland Company (ADM) and Novozymes are commercializing enzymatic interesterification, a technology that not only has a tremendous

positive impact on public health by reducing trans fatty acids in American diet, but also offers great environmental benefits by eliminating

the waste streams generated by the chemical interesterification

process.

Triglycerides consist of one glycerol plus three fatty acids. Triglycerides

that contain mostly unsaturated fatty acids are liquid at room temperature. Manufacturers partially hydrogenate these fatty acids to make

them solids at room temperature. Trans fatty acids form during the

hydrogenation process; they are found at high concentrations in a

wide variety of processed foods. Unfortunately, consumption of trans

fatty acids is also a strong risk factor for heart disease. To reduce trans

fats in the American diet as much as possible, the FDA is requiring

labeling of trans fats on all nutritional fact panels by January 1, 2006. In

response, the U.S. food and ingredient industry has been investigating methods to reduce trans fats in food.
2005 Greener Synthetic Pathways Award 37

Of the available strategies, interesterification is the most effective way

to decrease the trans fat content in foods without sacrificing the

functionality of partially hydrogenated vegetable oils. During

interesterification, triglycerides containing saturated fatty acids exchange one or two of their fatty acids with triglycerides containing

unsaturated fatty acids, resulting in triglycerides that do not contain any

trans fatty acids. Enzymatic interesterification processes have many

benefits over chemical methods, but the high cost of the enzymatic

process and poor enzyme stability had prevented its adoption in the

bulk fat industry.

Extensive research and development work by both Novozymes and

ADM has led to the commercialization of an enzymatic

interesterification process. Novozymes developed a cost-effective

immobilized enzyme, and ADM developed a process to stabilize the

immobilized enzyme enough for successful commercial production.

The interesterified oil provides food companies with broad options for

zero and reduced trans fat food products. Since the first commercial

production in 2002, ADM has produced more than 15 million pounds

of interesterified oils. ADM is currently expanding the enzyme process

at two of its U.S. production facilities.

Enzymatic interesterification positively affects both environmental and

human health. Environmental benefits include eliminating the use of

several harsh chemicals, eliminating byproducts and waste streams

(solid and water), and improving the use of edible oil resources. As

one example, margarines and shortenings currently consume 10 billion

pounds of hydrogenated soybean oil each year. Compared to partial

hydrogenation, the ADM/Novozymes process has the potential to save

400 million pounds of soybean oil and eliminate 20 million pounds of

sodium methoxide, 116 million pounds of soaps, 50 million pounds of

bleaching clay, and 60 million gallons of water each year. The enzymatic process also contributes to improved public health by replacing

partially hydrogenated oils with interesterified oils that contain no trans

fatty acids and have increased polyunsaturated fatty acids.
38 2005 Award

Greener Synthetic Pathways Award

Merck & Co., Inc.

A Redesigned, Efficient Synthesis of Aprepitant, the Active Ingredient

in Emend®: A New Therapy for Chemotherapy-Induced Emesis

Innovation and Benefits

Emend® is a drug that combats the nausea and vomiting often resulting

from chemotherapy treatment. Merck now makes Emend® using a new

process that requires much less energy, raw materials, and water than the

original process. With its new method, Merck eliminates approximately

41,000 gallons of waste per 1,000 pounds of the drug that it produces.

Emend® is a new therapy for chemotherapy-induced nausea and

vomiting, the most common side effects associated with the chemotherapeutic treatment of cancer. Emend® has been clinically shown to

reduce nausea and vomiting when used during and shortly after

chemotherapy. Aprepitant is the active pharmaceutical ingredient in

Emend®.

Aprepitant, which has two heterocyclic rings and three stereogenic

centers, is a challenging synthetic target. Merck’s first-generation

commercial synthesis required six synthetic steps and was based on

the discovery synthesis. The raw material and environmental costs of

this route, however, along with operational safety issues compelled

Merck to discover, develop, and implement a completely new route to

aprepitant.

Merck’s new route to aprepitant demonstrates several important green

chemistry principles. This innovative and convergent synthesis assembles the complex target in three highly atom-economical steps

using four fragments of comparable size and complexity. The firstgeneration synthesis required stoichiometric amounts of an expensive,

complex chiral acid as a reagent to set the absolute stereochemistry of

aprepitant. In contrast, the new synthesis incorporates a chiral alcohol

as a feedstock; this alcohol is itself synthesized in a catalytic asymmet-
2005 Greener Synthetic Pathways Award 39

ric reaction. Merck uses the stereochemistry of this alcohol feedstock

in a practical crystallization-induced asymmetric transformation to set

the remaining stereogenic centers of the molecule during two subsequent transformations. The new process nearly doubles the yield of

the first-generation synthesis. Much of the chemistry developed for the

new route is novel and has wider applications. In particular, the use of

a stereogenic center that is an integral part of the final target molecule

to set new stereocenters with high selectivity is applicable to the largescale synthesis of other chiral molecules, especially drug substances.

Implementing the new route has drastically improved the environmental impact of aprepitant production. Merck’s new route eliminates all of

the operational hazards associated with the first-generation synthesis,

including those of sodium cyanide, dimethyl titanocene, and gaseous

ammonia. The shorter synthesis and milder reaction conditions have

also reduced the energy requirements significantly. Most important,

the new synthesis requires only 20 percent of the raw materials and

water used by the original one. By adopting this new route, Merck has

eliminated approximately 41,000 gallons of waste per 1,000 pounds of

aprepitant that it produces.

The alternative synthetic pathway for the synthesis of aprepitant as

discovered and implemented by Merck is an excellent example of

minimizing environmental impact while greatly reducing production

costs by employing the principles of green chemistry. Merck implemented the new synthesis during its first year of production of

Emend®; as a result, Merck will realize the benefits of this route for

virtually the entire lifetime of this product. The choice to implement

the new route at the outset of production has led to a huge reduction

in the cost to produce aprepitant, demonstrating quite clearly that

green chemistry solutions can be aligned with cost-effective ones.
40 2005 Award

Greener Reaction Conditions Award

BASF Corporation

A UV-Curable, One-Component, Low-VOC Refinish Primer:

Driving Eco-Efficiency Improvements

Innovation and Benefits

BASF developed a new automobile paint primer that contains less than

half the amount of volatile organic compounds (VOCs) used in conventional primers. The new primer is also free of diisocyanates, a major source

of occupational asthma. Use in repair facilities has shown that only onethird as much of this primer is needed compared to conventional primer

and that waste is reduced from 20 percent to nearly zero.

The market for automotive refinish coatings in North America exceeds

$2 billion for both collision repairs and commercial vehicle applications.

Over 50,000 body shops in North America use these products. For

more than a decade, automotive refinishers and coating manufacturers have dealt with increasing regulation of emissions of volatile

organic compounds (VOCs). At first, coating manufacturers were able

to meet VOC maximums with high-performance products such as twocomponent reactive urethanes, which require solvents as carriers for

their high-molecular-weight resins. As thresholds for VOCs became

lower, however, manufacturers had to reformulate their reactive

coatings, and the resulting reformulations were slow to set a film.

Waterborne coatings are also available, but their utility has been

limited by the time it takes the water to evaporate. Continuing market

pressures demanded faster film setting without compromising either

quality or emissions.

Through intense research and development, BASF has invented a new

urethane acrylate oligomer primer system. The resin cross-links with

monomer (added to reduce viscosity) into a film when the acrylate

double bonds are broken by radical propagation. The oligomers and

monomers react into the film’s cross-linked structure, improving

adhesion, water resistance, solvent resistance, hardness, flexibility, and
2005 Greener Reaction Conditions Award 41

cure speed. The primer cures in minutes by visible or near-ultraviolet

(UV) light from inexpensive UV-A lamps or even sunlight. BASF’s UVcured primer eliminates the need for bake ovens that cure the current

primers, greatly reducing energy consumption. BASF’s primer performs

better than the current conventional urethane technologies: it cures

ten times faster, requires fewer preparation steps, has a lower

application rate, is more durable, controls corrosion better, and has an

unlimited shelf life. BASF is currently offering its UV-cured primers in its

R-M® line as Flash FillTM VP126 and in its Glasurit® line as 151-70.

BASF’s primer contains only 1.7 pounds of VOCs per gallon, in contrast

to 3.5–4.8 pounds of VOCs per gallon of conventional primers, a

reduction of over 50 percent. The primer meets even the stringent

requirements of South Coast California, whereas its superior properties

ensure its acceptance throughout the U.S. market. The onecomponent nature of the product reduces hazardous waste and

cleaning of equipment, which typically requires solvents. Applications

in repair facilities over the past year have shown that only one-third as

much primer is needed and that waste is reduced from 20 percent to

nearly zero. The BASF acrylate-based technology requires less complex,

less costly personal protective equipment (PPE) than the traditional

isocyanate-based coatings; this, in turn, increases the probability that

small body shops will purchase and use the PPE, increasing worker

safety.

This eco-efficient product is the first step in an automobile refinishing

coating system for which BASF plans to include the globally accepted

waterborne basecoat from BASF (sold under the Glasurit® brand as

line 90). In the near future, this system can be finished with the

application of a one-component, UV-A-curable clearcoat. The system

will deliver quality, energy efficiency, economy, and speed for the

small businessperson operating a local body shop, while respecting

the health and safety of the workers in this establishment and the

environment in which these products are manufactured and used. To

fully support these claims, BASF has conducted an eco-efficiency study

with an independent evaluation.
42 2005 Award

Designing Greener Chemicals Award

Archer Daniels Midland Company

Archer RCTM: A Nonvolatile, Reactive Coalescent for the Reduction of

VOCs in Latex Paints

Innovation and Benefits

Latex paints require coalescents to help the paint particles flow together

and cover surfaces well. Archer Daniels Midland developed Archer RCTM, a

new biobased coalescent to replace traditional coalescents that are

volatile organic compounds (VOCs). This new coalescent has other performance advantages as well, such as lower odor, increased scrub

resistance, and better opacity.

Since the 1980s, waterborne latex coatings have found increasingly

broad acceptance in architectural and industrial applications. Traditional

latex coatings are based on small-particle emulsions of a synthetic

resin, such as acrylate- and styrene-based polymers. They require

substantial quantities of a coalescent to facilitate the formation of a

coating film as water evaporates after the coating is applied. The

coalescent softens (plasticizes) the latex particles, allowing them to

flow together to form a continuous film with optimal performance

properties. After film formation, traditional coalescents slowly diffuse

out of the film into the atmosphere. The glass transition temperature

of the latex polymer increases as the coalescent molecules evaporate

and the film hardens. Alcohol esters and ether alcohols, such as

ethylene glycol monobutyl ether (EGBE) and Texanol® (2,2,4-trimethyl1,3-pentanediol monoisobutyrate), are commonly used as coalescents.

They are also volatile organic compounds (VOCs). Both environmental

concerns and economics continue to drive the trend to reduce the

VOCs in coating formulations. Inventing new latex polymers that do

not require a coalescent is another option, but these polymers often

produce soft films and are expensive to synthesize, test, and commercialize. Without a coalescent, the latex coating may crack and may not

adhere to the substrate surface when dry at ambient temperatures.
2005 Designing Greener Chemicals Award 43

Archer RCTM provides the same function as traditional coalescing

agents but eliminates the unwanted VOC emissions. Instead of

evaporating into the air, the unsaturated fatty acid component of

Archer RCTM oxidizes and even cross-links into the coating. Archer RCTM

is produced by interesterifying vegetable oil fatty acid esters with

propylene glycol to make the propylene glycol monoesters of the fatty

acids. Corn and sunflower oils are preferred feedstocks for Archer RCTM

because they have a high level of unsaturated fatty acids and tend to

resist the yellowing associated with linolenic acid, found at higher

levels in soybean and linseed oils. Because Archer RCTM remains in the

coating after film formation, it adds to the overall solids of a latex

paint, providing an economic advantage over volatile coalescents.

The largest commercial category for latex paint, the architectural

market, was 618 million gallons in the United States in 2001. Typically,

coalescing solvents constitute 2–3 percent of the finished paint by

volume; this corresponds to an estimated 120 million pounds of

coalescing solvents in the United States and perhaps three times that

amount globally. Currently, nearly all of these solvents are lost into the

atmosphere each year.

Archer Daniels Midland Company has developed and tested a number

of paint formulations using Archer RCTM in place of conventional

coalescing solvents. In these tests, Archer RCTM performed as well as

commercial coalescents such as Texanol®. Archer RCTM often had other

advantages as well, such as lower odor, increased scrub resistance,

and better opacity. Paint companies and other raw material suppliers

have demonstrated success formulating paints with Archer RCTM and

their existing commercial polymers. Archer RCTM has been in commercial use since March 2004.
44

2004 Winners

Academic Award

Professors Charles A. Eckert and Charles L. Liotta

Georgia Institute of Technology

Benign Tunable Solvents Coupling Reaction and Separation Processes

Innovation and Benefits

Professors Eckert and Liotta found ways to replace conventional organic

solvents with benign solvents, such as supercritical CO2 or water “tuned”

by carefully selecting both temperature and pressure. These methods

combine reactions and separations, improving efficiency and reducing

waste in a variety of industrial applications.

For any chemical process, there must be both a reaction and a separation. Generally, the same solvent is used for both but is optimized only

for the reaction. The separation typically involves 60–80 percent of the

cost, however, and almost always has a large environmental impact.

Conventional reactions and separations are often designed separately,

but Professors Charles A. Eckert and Charles L. Liotta have combined

them with a series of novel, benign, tunable solvents to create a

paradigm for sustainable development: benign solvents and improved

performance.

Supercritical CO2

, nearcritical water, and CO2-expanded liquids are

tunable benign solvents that offer exceptional opportunities as replacement solvents. They generally exhibit better solvent properties

than gases and better transport properties than liquids. They offer

substantial property changes with small variations in thermodynamic

conditions, such as temperature, pressure, and composition. They also

provide wide-ranging environmental advantages, from human health

to pollution prevention and waste minimization. Professors Eckert,

Liotta, and their team have combined reactions with separations in a

synergistic manner to use benign solvents, minimize waste, and

improve performance.
2004 Academic Award 45

These researchers have used supercritical CO2 to tune reaction equilibria and rates, improve selectivities, and eliminate waste. They were the

first to use supercritical CO2

 with phase transfer catalysts to separate

products cleanly and economically. Their method allows them to

recycle their catalysts effectively. They have demonstrated the feasibility of a variety of phase transfer catalysts on reactions of importance in

the chemical and pharmaceutical industries, including chiral syntheses.

They have carried out a wide variety of synthetic reactions in nearcritical

water, replacing conventional organic solvents. This includes acid- and

base-catalysis using the enhanced dissociation of nearcritical water,

negating the need for any added acid or base and eliminating subsequent neutralization and salt disposal. They have used CO2

 to expand

organic fluids to make it easier to recycle homogeneous catalysts,

including phase transfer catalysts, chiral catalysts, and enzymes. Finally,

they have used tunable benign solvents to design syntheses that

minimize waste by recycling and demonstrate commercial feasibility by

process economics.

The team of Eckert and Liotta has combined state-of-the-art chemistry

with engineering know-how, generating support from industrial

sponsors to facilitate technology transfer. They have worked with a

wide variety of government and industrial partners to identify the

environmental and commercial opportunities available with these

novel solvents; their interactions have facilitated the technology

transfer necessary to implement their advances.
46 2004 Award

Small Business Award

Jeneil Biosurfactant Company

Rhamnolipid Biosurfactant: A Natural, Low-Toxicity Alternative to

Synthetic Surfactants

Innovation and Benefits

Billions of pounds of surfactants are used each year to lubricate, clean, or

reduce undesired foaming in industrial applications. Jeneil Biosurfactant

Company developed biobased surfactants that are less toxic and more

biodegradable than conventional surfactants. Jeneil makes its biosurfactants using a simple fermentation.

Surfactants are chemicals that reduce the surface tension of water.

Surfactants are widely used in soaps, laundry detergents, dishwashing

liquids, and many personal care products, such as shampoos. Other

important uses are in lubricants, emulsion polymerization, textile

processing, mining flocculates, petroleum recovery, and wastewater

treatment. Most currently used surfactants are derived from petroleum

feedstocks. The total worldwide chemical surfactant consumption in

the year 2000 has been estimated to be approximately 36 billion

pounds. Many of these chemical surfactants pose significant environmental risks because they form harmful compounds from incomplete

biodegradation in water or soil.

Jeneil Biosurfactant Company has successfully produced a series of

rhamnolipid biosurfactant products, making them commercially available and economical for the first time. These biosurfactant products

provide good emulsification, wetting, detergency, and foaming

properties, along with very low toxicity. They are readily biodegradable

and leave no harmful or persistent degradation products. Their superior qualities make them suitable for many diverse applications.

Rhamnolipid biosurfactant is a naturally occurring extracellular glycolipid

that is found in the soil and on plants. Jeneil produces this biosurfactant commercially in controlled, aerobic fermentations using particular
2004 Small Business Award 47

strains of the soil bacterium, Pseudomonas aeruginosa. The

biosurfactant is recovered from the fermentation broth after sterilization and centrifugation, then purified to various levels to fit intended

applications.

Rhamnolipid biosurfactants are a much less toxic and more environmentally friendly alternative to traditional synthetic or petroleumderived surfactants. Rhamnolipid biosurfactants are also “greener”

throughout their life cycle. Biosurfactant production uses feedstocks

that are innocuous and renewable compared to those used for

synthetic or petroleum-derived surfactants. In addition, their production

requires less resources, employs processes that are less complex and

less capital- and energy-intensive, and does not require the use and

disposal of hazardous substances.

Some current uses of rhamnolipid biosurfactant are in consumer

cleaning products, in solutions to clean contact lenses, and in an

agricultural fungicide as the active ingredient. These biosurfactants are

also extremely effective in precluding harmful environmental impacts

and remediating environmental pollution. For example, rhamnolipid

biosurfactants can facilitate removal of hydrocarbons or heavy metals

from soil, clean crude oil tanks, and remediate sludge; often they can

facilitate recovery of a significant amount of the hydrocarbons. In many

applications, these biosurfactants can replace less environmentally

friendly synthetic or petroleum-derived surfactants. Further, these

biosurfactants have excellent synergistic activity with many synthetic

surfactants and, when formulated together in a cosurfactant system,

can allow a substantial reduction in the synthetic surfactant component.

Although rhamnolipid biosurfactants have been the subject of considerable research, they had previously been produced only on a small

scale in laboratories. Jeneil Biosurfactant Company, in conjunction with

its associated company, Jeneil Biotech, Inc., has commercialized the

rhamnolipid technology by developing efficient bacterial strains, as well

as cost-effective processes and equipment for commercial-scale

production. Jeneil’s facility in Saukville, WI produces the surfactants.
48 2004 Award

Greener Synthetic Pathways Award

Bristol-Myers Squibb Company

Development of a Green Synthesis for Taxol® Manufacture via Plant

Cell Fermentation and Extraction

Innovation and Benefits

Bristol-Myers Squibb manufactures paclitaxel, the active ingredient in the

anticancer drug, Taxol®, using plant cell fermentation (PCF) technology.

PCF replaces the conventional process that extracts a paclitaxel building

block from leaves and twigs of the European yew. During the first five

years of commercialization, PCF technology will eliminate an estimated

71,000 pounds of hazardous chemicals and materials, eliminate 10 solvents

and 6 drying steps, and save a significant amount of energy.

Paclitaxel, the active ingredient in the anticancer drug Taxol®, was first

isolated and identified from the bark of the Pacific yew tree, Taxus

brevifolia, in the late 1960s by Wall and Wani under the auspices of the

National Cancer Institute (NCI). The utility of paclitaxel to treat ovarian

cancer was demonstrated in clinical trials in the 1980s. The continuity of

supply was not guaranteed, however, because yew bark contains only

about 0.0004 percent paclitaxel. In addition, isolating paclitaxel required stripping the bark from the yew trees, killing them in the

process. Yews take 200 years to mature and are part of a sensitive

ecosystem.

The complexity of the paclitaxel molecule makes commercial production by chemical synthesis from simple compounds impractical. Published syntheses involve about 40 steps with an overall yield of approximately 2 percent. In 1991, NCI signed a Collaborative Research and

Development Agreement with Bristol-Myers Squibb (BMS) in which

BMS agreed to ensure supply of paclitaxel from yew bark while it

developed a semisynthetic route (semisynthesis) to paclitaxel from the

naturally occurring compound 10-deacetylbaccatin III (10-DAB).
2004 Greener Synthetic Pathways Award 49

10-DAB contains most of the structural complexity (8 chiral centers) of

the paclitaxel molecule. It is present in the leaves and twigs of the

European yew, Taxus baccata, at approximately 0.1 percent by dry

weight and can be isolated without harm to the trees. Taxus baccata is

cultivated throughout Europe, providing a renewable supply that does

not adversely impact any sensitive ecosystem. The semisynthetic

process is complex, however, requiring 11 chemical transformations

and 7 isolations. The semisynthetic process also presents environmental concerns, requiring 13 solvents along with 13 organic reagents and

other materials.

BMS developed a more sustainable process using the latest plant cell

fermentation (PCF) technology. In the cell fermentation stage of the

process, calluses of a specific taxus cell line are propagated in a wholly

aqueous medium in large fermentation tanks under controlled conditions at ambient temperature and pressure. The feedstock for the cell

growth consists of renewable nutrients: sugars, amino acids, vitamins,

and trace elements. BMS extracts paclitaxel directly from plant cell

cultures, then purifies it by chromatography and isolates it by crystallization. By replacing leaves and twigs with plant cell cultures, BMS

improves the sustainability of the paclitaxel supply, allows year-round

harvest, and eliminates solid biomass waste. Compared to the

semisynthesis from 10-DAB, the PCF process has no chemical transformations, thereby eliminating six intermediates. During its first five

years, the PCF process will eliminate an estimated 71,000 pounds of

hazardous chemicals and other materials. In addition, the PCF process

eliminates 10 solvents and 6 drying steps, saving a considerable

amount of energy. BMS is now manufacturing paclitaxel using only

plant cell cultures.
50 2004 Award

Greener Reaction Conditions Award

Buckman Laboratories International, Inc.

Optimyze®: A New Enzyme Technology to Improve Paper Recycling

Innovation and Benefits

Paper mills traditionally use hazardous solvents, such as mineral spirits, to

remove sticky contaminants (stickies) from machinery. Optimyze® technology uses a novel enzyme to remove stickies from paper products prior to

recycling, increasing the percentage of paper that can be recycled. Each

paper mill that switches to Optimyze® can reduce its hazardous solvent

use by 200 gallons daily, reduce its chemical use by approximately

600,000 pounds yearly, increase its production by more than 6 percent,

and save up to $1 million per year.

Recycling paper products is an important part of maintaining our

environment. Although produced from renewable resources, paper is

a major contributor to landfilled waste. Paper can be recycled numerous times, and much progress has been made: about one-half of the

paper and paperboard currently used in the United States is collected

and reused. Some papers, however, contain adhesives, coatings,

plastics, and other materials that form sticky contaminants, creating

serious problems during the paper recycling process. These contaminants, called “stickies” by the paper industry, can produce spots and

holes in paper goods made from recycled materials, ruining their

appearance and lowering their quality.

Stickies also waste significant manufacturing resources when production must stop to clean the equipment. One source estimates the cost

to the industry from production downtime alone to be more than

$500 million annually. Further, this cleaning is traditionally done with

chemical solvents, typically mineral spirits, which can have health and

safety problems, are obtained from nonrenewable, petroleum resources, and are not readily recycled. These solvents are volatile

organic compounds (VOCs) that contribute to air pollution. As a result,

some paper grades cannot be recycled into reusable products.
2004 Greener Reaction Conditions Award 51

Optimyze® technology from Buckman Laboratories is a completely

new way to control the problems associated with stickies. It uses a

novel enzyme to eliminate common problems in the manufacture of

paper from recycled papers. A major component of the sticky contaminants in paper is poly(vinyl acetate) and similar materials. Optimyze®

contains an esterase enzyme that catalyzes the hydrolysis of this type

of polymer to poly(vinyl alcohol), which is not sticky and is watersoluble. A bacterial species produces large amounts of the Optimyze®

enzyme by fermentation. As a protein, the enzyme is completely

biodegradable, much less toxic than alternatives, and much safer. Only

renewable resources are required to manufacture Optimyze®.

Optimyze® has been commercially available since May 2002. In that

short time, more than 40 paper mills have converted to Optimyze® for

manufacturing paper goods from recycled papers. In one U.S. mill,

conversion to Optimyze® reduced solvent use by 200 gallons per day

and chemical use by about 600,000 pounds per year. Production

increased by more than 6 percent, which amounted to a $1 million

benefit per year for this mill alone.

This new enzyme technology has improved production of a broad

range of paper products, including tissue, paper toweling, corrugated

cartons, and many other materials. It improves the quality and efficiency of papermaking, dramatically reducing downtime to clean

equipment. As a result, more paper is being recycled and grades of

paper that were not recyclable earlier are now being recycled. Paper

mills adopting Optimyze® have been able to greatly reduce the use of

hazardous solvents.

In summary, Optimyze® makes it possible to recycle more grades of

paper, allows more efficient processing of recycled papers, and

produces higher-quality paper goods from recycled materials. The

Optimyze® technology comes from renewable resources, is safe to

use, and is itself completely recyclable.
52 2004 Award

Designing Greener Chemicals Award

Engelhard Corporation (now BASF Corporation)

Engelhard RightfitTM Organic Pigments: Environmental Impact,

Performance, and Value

Innovation and Benefits

RightfitTM azo pigments contain calcium, strontium, or barium; they

replace conventional heavy-metal-based pigments containing lead, hexavalent chromium, or cadmium. Because of their low potential toxicity and

very low migration, most of the RightfitTM azo pigments have received U.S.

Food and Drug Administration (FDA) and Canadian Health Protection

Branch (HPB) approval for indirect food contact applications. By 2004,

Engelhard expects to have replaced all 6.5 million pounds of its heavymetal-based pigments with RightfitTM pigments.

Historically, pigments based on lead, chromium(VI), and cadmium

have served the red, orange, and yellow color market. When the U.S.

EPA began regulating heavy metals, however, color formulators typically turned to high-performance organic pigments to replace heavymetal-based pigments. Although high-performance pigments meet

performance requirements, they do so at the expense of the following: (1) their higher cost often acts as a deterrent to reformulation;

(2) their production uses large volumes of organic solvents; (3) some

require large quantities of polyphosphoric acid, resulting in phosphates in the effluent; and (4) some are based on dichlorobenzidine

or polychlorinated phenyls.

Engelhard has developed a wide range of environmentally friendly

RightfitTM azo pigments that contain calcium, strontium, or sometimes

barium instead of heavy metals. True to their name, the RightfitTM

pigments have the right environmental impact, right color space, right

performance characteristics, and right cost-to-performance value. Since

1995, when Engelhard produced 6.5 million pounds of pigments

containing heavy metals, it has been transitioning to RightfitTM azo

pigments. In 2002, Engelhard produced only 1.2 million pounds of
2004 Designing Greener Chemicals Award 53

heavy-metal pigments; they expect to phase them out completely in

2004.

RightfitTM pigments eliminate the risk to human health and the environment from exposure to heavy metals such as cadmium, chromium(VI), and lead used in the manufacture of cadmium and chrome

yellow pigments. They are expected to have very low potential toxicity

based on toxicity studies, physical properties, and structural similarities

to many widely used food colorants. Because they have low potential

toxicity and very low migration, most of the RightfitTM pigments have

been approved both by the U.S. Food and Drug Administration (FDA)

and the Canadian Health Protection Branch (HPB) for indirect food

contact applications. In addition, these pigments are manufactured in

aqueous medium, eliminating exposure to the polychlorinated intermediates and organic solvents associated with the manufacture of

traditional high-performance pigments.

RightfitTM pigments have additional benefits, such as good dispersibility, improved dimensional stability, improved heat stability, and

improved color strength. Their higher color strength achieves the same

color values using less pigment. RightfitTM pigments also cover a wide

color range from purple to green-shade yellow color. Being closely

related chemically, these pigments are mutually compatible, so two or

more can combine to achieve any desired intermediate color shade.

RightfitTM pigments meet the essential performance characteristics at

significantly lower cost than high-performance organic pigments. Thus,

formulators get the right performance properties at the right cost,

resulting in a steadily increasing market for these pigments. RightfitTM

pigments provide environmentally friendly, value-added color to

packaging used in the food, beverage, petroleum product, detergent,

and other household durable goods markets.
54

2003 Winners

Academic Award

Professor Richard A. Gross

Polytechnic University

New Options for Mild and Selective Polymerizations Using Lipases

Innovation and Benefits

Professor Gross developed a highly selective, more efficient way to make

polyesters using enzymes. This technique requires less energy and toxic

substances than conventional methods that typically use heavy metal

catalysts and hazardous solvents. This innovation also makes it possible to

manufacture new types of polyesters.

Isolated lipases, harvested from living organisms, have been used as

catalysts for polymer synthesis in vitro. Professor Richard A. Gross’s

developments on lipase-catalyzed polymer synthesis have relied on

the ability of enzymes to reduce the activation energy of polymerizations and, thus, to decrease process energy consumption. Further, the

regioselectivity of lipases has been used to polymerize polyols directly.

Alternative synthetic pathways for such polymerizations require protection-deprotection chemical steps. The mild reaction conditions allow

polymerization of chemically and thermally sensitive molecules.

Current alternative chemical routes require coupling agents (e.g.,

carbodiimides) that would be consumed in stoichiometric quantities

relative to the reactants. Fundamental studies of these polymerizations

have uncovered remarkable capabilities of lipases for polymerization

chemistry. Selected examples include: (1) lipases catalyze transesterification reactions between high-molecular-weight chains in melt

conditions; (2) lipases will use non-natural nucleophiles such as carbohydrates and monohydroxyl polybutadiene (Mn 19,000) in place of

water; (3) the catalysis of ring-opening polymerization occurs in a controlled manner without termination reactions and with predictable

molecular weights; and (4) the selectivity of lipase-catalyzed stepcondensation polymerizations leads to nonstatistical molecular weight

distributions (polydispersities well below 2.0). These accomplishments

are elaborated on the next page.
2003 Academic Award 55

A series of polyol-containing polyesters was synthesized via a one-pot

lipase-catalyzed condensation polymerization. By using various mixtures

of polyols (e.g., glycerol, sorbitol) with other diacid and diol building

blocks, the polyols are partially or completely solubilized, resulting in

highly reactive condensation polymerizations. By this method, organic

solvents and activated acids (e.g., divinyl esters) are not needed. The

polymerization reactions give high-molecular-weight products (Mw up

to 200,000) with narrow polydispersities (as low as 1.3). Further, the

condensation reactions with glycerol and sorbitol building blocks

proceed with high regioselectivity. Although the polyols used have

three or more hydroxyl groups, only two of these hydroxyl groups are

highly reactive in the polymerization. Thus, instead of obtaining highly

cross-linked products, the regioselectivity provided by the lipase leads

to lightly branched polymers where the degree of branching varies with

the reaction time and monomer stoichiometry. By using lipase as the

catalyst, highly versatile polymerizations result that can simultaneously

polymerize lactones, hydroxyacids, cyclic carbonates, cyclic anhydrides,

amino alcohols, and hydroxylthiols. The method developed offers

simplicity, mild reaction conditions, and the ability to incorporate carbohydrates, such as sugars, into polyesters without protectiondeprotection steps.

Professor Gross’s laboratory discovered that certain lipases catalyze

transesterification reactions between high-molecular-weight chains that

contain intrachain esters or have functional end-groups. Thus, lipases,

such as Lipase B from Candida antarctica, catalyze intrachain exchange

reactions between polymer chains as well as transesterification reactions between a monomer and a polymer. For polymers that have

melting points below 100 °C, the reactions can be conducted in bulk.

Transacylation reactions occur because the lipase has the ability to

accommodate large-molecular-weight substrates and to catalyze the

breaking of ester bonds within chains. Immobilized Candida antarctica

Lipase B (Novozyme-435) catalyzed transesterification reactions

between aliphatic polyesters that had Mn values in excess of

40,000 grams per mole. In addition to catalyzing metal-free transesterifications at remarkably low temperatures, lipases endow transesterification reactions with remarkable selectivity. This feature allows the

preparation of block copolymers that have selected block lengths.
56 2003 Award

Small Business Award

AgraQuest, Inc.

Serenade®: An Effective, Environmentally Friendly Biofungicide

Innovation and Benefits

Serenade® is a new biofungicide for fruits and vegetables based on a

naturally occurring strain of bacteria. Serenade® is nontoxic to beneficial

and other nontarget organisms, does not generate any hazardous chemical residues, and is safe for workers and groundwater. It is well-suited for

use in integrated pest management (IPM) programs and is listed with the

Organic Materials Review Institute (OMRI) for use in organic agriculture.

Serenade® Biofungicide is based on a naturally occurring strain of

Bacillus subtilis QST-713, discovered in a California orchard by

AgraQuest scientists. Serenade® has been registered for sale as a

microbial pesticide in the United States since July 2000. It is also

registered for use in Chile, Mexico, Costa Rica, and New Zealand.

Registration is pending in the Philippines, Europe, Japan, and several

other countries. The product is formulated as a wettable powder,

wettable granule, and liquid aqueous suspension. Serenade® has

been tested on 30 crops in 20 countries and is registered for use in

the United States on blueberries, cherries, cucurbits, grape vines,

greenhouse vegetables, green beans, hops, leafy vegetables, mint,

peanuts, peppers, pome fruit, potatoes, tomatoes, and walnuts. It is

also registered for home and garden use. AgraQuest has been issued

four U.S. patents; several international patents are pending on the

QST-713 strain, associated antifungal lipopeptides, formulations, and

combinations with other pesticides.

Serenade® works through a complex mode of action that is manifested both by the physiology of the bacteria and through the action

of secondary metabolites produced by the bacteria. Serenade® prevents plant diseases first by covering the leaf surface and physically

preventing attachment and penetration of the pathogens. In addition,

Serenade® produces three groups of lipopeptides (iturins, agrastatins/
2003 Small Business Award 57

plipastatins, and surfactins) that act in concert to destroy germ tubes

and mycelium. The iturins and plipastatins have been reported to have

antifungal properties. Strain QST-713 is the first strain reported to

produce iturins, plipastatins, and surfactins, as well as two new compounds with a novel cyclic peptide moiety, the agrastatins. The

surfactins have no activity on their own, but low levels (25 ppm or less)

in combination with the iturins or the agrastatin/plipastatin group

cause significant inhibition of spores and germ tubes. In addition, the

agrastatins and iturins have synergistic activities towards inhibition of

plant pathogen spores.

The Serenade® formulation is available as a wettable powder, wettable

granule, and aqueous suspension that is applied just like any other

foliar fungicide. It can be applied alone or tank mixed; it can also be

alternated with traditional chemical pesticides. Serenade® is not toxic

to beneficial and nontarget organisms, such as trout, quail, lady

beetles, lacewings, parasitic wasps, earthworms, and honey bees.

Serenade® is exempt from tolerance because there are no synthetic

chemical residues and it is safe to workers and ground water.

Serenade®’s wettable granule formulation is listed with the Organic

Materials Review Institute (OMRI) for use in organic agriculture and will

continue to be listed under the National Organic Standards, which

were enacted in the United States in October 2002.

Serenade®’s novel, complex mode of action, environmental friendliness, and broad spectrum control make it well-suited for use in

integrated pest management (IPM) programs that utilize many tools,

such as cultural practices, classical biological control, and other fungicides. Serenade® can be applied right up until harvest, providing

needed pre- and post-harvest protection when there is weather

conducive to disease development around harvest time.
58 2003 Award

Greener Synthetic Pathways Award

Süd-Chemie Inc.

A Wastewater-Free Process for Synthesis of Solid Oxide Catalysts

Innovation and Benefits

Süd-Chemie’s new process to synthesize solid oxide catalysts used in

producing hydrogen and clean fuel has virtually zero wastewater discharge, zero nitrate discharge, and no or little NOX

 emissions. Each

10 million pounds of oxide catalyst produced by the new pathway eliminates approximately 760 million pounds of wastewater discharges,

29 million pounds of nitrate discharges, and 7.6 million pounds of NOX

emissions. The process also saves water and energy.

Some major achievements in pollution reduction have been made

recently through advancement of catalytic technologies. One such

effort is in the area of hydrogen and clean fuel production. However,

the synthesis of catalysts for such reactions is often accompanied by

the discharge of large amounts of wastewater and other pollutants,

such as NOX

, SOX, and halogens.

As a result of their commitment to continuously develop and invest in

new and improved catalyst synthesis technologies, Süd-Chemie successfully developed and demonstrated a new synthetic pathway that is

able to achieve virtually zero wastewater discharge, zero nitrate discharge, and no or little NOX

 emissions. Meantime, it substantially

reduces the consumption of water and energy. For example, it is

estimated that about 760 million pounds of wastewater discharges,

about 29 million pounds of nitrate discharges, and about 7.6 million

pounds of NOX

 emissions can be eliminated for every 10 million

pounds of oxide catalyst produced.

The new synthetic pathway is based on very simple chemistry. Instead

of acid-base precipitation typically using metal nitrate as raw material,

the new process starts with a clean metal that is readily and economically available in commercial quantities. The synthesis proceeds by
2003 Greener Synthetic Pathways Award 59

reaction of the metal with a mild organic acid in the presence of an

oxidation agent. The function of the acid is to activate the metal and

extract electrons to form the oxide precursor. With assistance of the

oxidation agent (typically air), a porous solid oxide is synthesized in one

step at ambient temperature without any wastewater discharge. The

other active ingredients of the catalyst can be incorporated using the

concept of wet-agglomeration. In contrast, the precipitation process

requires intensive washing and filtration to remove nitrate and the

other salts. Further, the new process substantially reduces the consumption of water and energy for production of solid oxide catalysts

over conventional methods. The emission in the entire process is only

pure water vapor and a small amount of CO2

 that is generated during

spray-drying and afterburning of hydrogen.

This wastewater-free process for making solid oxide catalysts has been

demonstrated, and more than 300 kilograms of the metal oxide

catalysts have been produced. Patent protection is being sought for

the development. The catalysts made by the green process give

superior performance in the synthesis of clean fuels and chemicals.

The market for such solid oxide catalysts is estimated to be approximately $100 million. Süd-Chemie is the first in the industry to use the

green process for making a catalyst for the synthesis of “green” fuels

and chemicals.
60 2003 Award

Greener Reaction Conditions Award

DuPont

Microbial Production of 1,3-Propanediol

Innovation and Benefits

DuPont and Genencor International jointly developed a genetically

engineered microorganism to manufacture the key building block for

DuPont's Sorona® polyester. The process uses renewable cornstarch

instead of petroleum to make environmentally friendly, cost-competitive

textiles.

DuPont is integrating biology in the manufacture of its newest polymer platform, DuPont Sorona® polymer. Combining metabolic engineering with polymer science, researchers are introducing a microbial

process in a business that, historically, has relied solely on traditional

chemistry and petrochemical feedstocks. This achievement, comprising biocatalytic production of 1,3-propanediol from renewable resources, offers economic as well as environmental advantages. The

key to the novel biological process is an engineered microorganism

that incorporates several enzyme reactions, obtained from naturally

occurring bacteria and yeast, into an industrial host cell line. For the

first time, a highly engineered microorganism will be used to convert a

renewable resource into a chemical at high volume.

The catalytic efficiency of the engineered microorganism allows

replacement of a petroleum feedstock, reducing the amount of

energy needed in manufacturing steps and improving process safety.

The microbial process is environmentally green, less expensive,

and more productive than the chemical operations it replaces.

1,3-Propanediol, a key ingredient in the Sorona® polymers, provides

advantageous attributes for apparel, upholstery, resins, and nonwoven

applications.

Scientists and engineers from DuPont and Genencor International,

Inc. redesigned a living microbe to produce 1,3-propanediol. Inserting
2003 Greener Reaction Conditions Award 61

biosynthetic pathways from several microorganisms into an industrial

host cell line allows the direct conversion of glucose to 1,3-propanediol, a route not previously available in a single microorganism. Genes

from a yeast strain with the ability to convert glucose, derived from

cornstarch, to glycerol were inserted into the host. Genes from a

bacterium with the ability to transform glycerol to 1,3-propanediol were

also incorporated. Additionally, the reactions present naturally in the

host were altered to optimize product formation. The modifications

maximize the ability of the organism to convert glucose to 1,3-propanediol while minimizing its ability to produce biomass and unwanted byproducts. Coalescing enzyme reactions from multiple

organisms expands the range of materials that can be economically

produced by biological means.

For more than 50 years, scientists have recognized the performance

benefits of polyesters produced with 1,3-propanediol; however, the

high cost of manufacturing the ingredient using petroleum feedstock

and traditional chemistry kept it from the marketplace. The biological

process using glucose as starting material will enable cost-effective

manufacture of Sorona® polymer, which will offer consumer fabrics

with softness, stretch and recovery, easy care, stain resistance, and

colorfastness. A unique kink in the structure of the polymer containing

1,3-propanediol allows recovery at a high rate when it is stretched. As a

result, Sorona® improves fit and comfort because the fabric quickly

recovers its original shape when stretched, for example, in knees or

elbows. The resilience of Sorona® also adds beneficial features to

automotive upholstery and home textiles. In resin applications,

Sorona®‘s barrier characteristics protect moisture, taste, and odor.

Biology offers chemical manufacturers attractive options for the production of chemicals while adhering to the principles of green chemistry.

This microbial production of a key polymer ingredient from renewable

sources is one example. By integrating biology with chemistry, physics,

and engineering, DuPont develops new solutions that enhance the

environment and improve upon existing materials.
62 2003 Award

Designing Greener Chemicals Award

Shaw Industries, Inc.

EcoWorxTM Carpet Tile: A Cradle-to-Cradle Product

Innovation and Benefits

Conventional backings for carpet tiles contain bitumen, polyvinyl chloride

(PVC), or polyurethane. EcoWorxTM carpet tiles have a novel backing that

uses less toxic materials and has superior adhesion and dimensional stability. Because EcoWorxTM carpet tiles can be readily separated into carpet

fiber and backing, each component can be easily recycled.

Historically, carpet tile backings have been manufactured using

bitumen, polyvinyl chloride (PVC), or polyurethane (PU). While these

backing systems have performed satisfactorily, there are several inherently negative attributes due to their feedstocks or their ability to be

recycled. Although PVC has, to date, held the largest market share of

carpet tile backing systems, it was Shaw’s intent to design around PVC

due to the health and environmental concerns around vinyl chloride

monomer, chlorine-based products, plasticized PVC-containing phthalate esters, and toxic byproducts of combustion of PVC, such as dioxin

and hydrochloric acid. While some claims are accepted by the Agency

for Toxic Substances and Disease Registry (ATSDR) and the U.S. EPA,

those resulting from publicly debated consumer perceptions provide

ample justification for finding a PVC alternative.

Due to the thermoset cross-linking of polyurethanes, they are extremely difficult to recycle and are typically downcycled or landfilled at

the end of their useful life. Bitumen provides some advantages in

recycling, but the modified bitumen backings offered in Europe have

failed to gain market acceptance in the United States and are unlikely

to do so.

Shaw selected a combination of polyolefin resins from Dow Chemical

as the base polymer of choice for EcoWorxTM due to the low toxicity of

its feedstocks, superior adhesion properties, dimensional stability, and
2003 Designing Greener Chemicals Award 63

its ability to be recycled. The EcoWorxTM compound also had to be

designed to be compatible with nylon carpet fiber. Although EcoWorxTM

may be recovered from any fiber type, nylon-6 provides a significant

advantage. Polyolefins are compatible with known nylon-6 depolymerization methods. PVC interferes with those processes. Nylon-6 chemistry is well-known and not addressed in first-generation production.

From its inception, EcoWorxTM met all of the design criteria necessary to

satisfy the needs of the marketplace from a performance, health, and

environmental standpoint. Research indicated that separation of the

fiber and backing through elutriation, grinding, and air separation

proved to be the best way to recover the face and backing components, but an infrastructure for returning postconsumer EcoWorxTM to

the elutriation process was necessary. Research also indicated that the

postconsumer carpet tile had a positive economic value at the end of

its useful life. The cost of collection, transportation, elutriation, and

return to the respective nylon and EcoWorxTM manufacturing processes

is less than the cost of using virgin raw materials.

With introduction in 1999 and an anticipated lifetime of ten to fifteen

years on the floor, significant quantities of EcoWorxTM will not flow back

to Shaw until 2006 to 2007. An expandable elutriation unit is now

operating at Shaw, typically dealing with industrial EcoWorxTM waste.

Recovered EcoWorxTM is flowing back to the backing extrusion unit.

Caprolactam recovered from the elutriated nylon-6 is flowing back into

nylon compounding. EcoWorxTM will soon displace all PVC at Shaw.
64

2002 Winners

Academic Award

Professor Eric J. Beckman

University of Pittsburgh

Design of Non-Fluorous, Highly CO2-Soluble Materials

Innovation and Benefits

Carbon dioxide (CO2) is a nontoxic chemical that can be used as a solvent

in many industrial processes. Professor Beckman developed new detergents that allow a broad range of substances to dissolve in CO2

. Any

process that can now use CO2 may reduce or eliminate the use of hazardous solvents.

Carbon dioxide (CO2), an environmentally benign and nonflammable

solvent, has been investigated extensively in both academic and

industrial settings. Solubility studies performed during the 1980s had

suggested that CO2

’s solvent power was similar to that of n-alkanes,

leading to hopes that the chemical industry could use CO2

 as a “dropin” 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 CO2

 is actually a rather feeble solvent compared to alkanes. As the

1980s drew to a close, a number of research groups began to explore

the design of CO2

-philic materials, that is, compounds that dissolve in

CO2

 at significantly lower pressures than do their alkyl analogs. These

new CO2

-philes, primarily fluoropolymers, opened up a host of new

applications for CO2

 including heterogeneous polymerization, protein

extraction, and homogeneous catalysis.

Although fluorinated amphiphiles allow new applications for CO2

, their

cost (approximately $1 per gram) reduces the economic viability of CO2

processes, particularly given that the use of CO2 requires high-pressure

equipment. Furthermore, data have recently shown that fluoroalkyl

materials persist in the environment, leading to the withdrawal of

certain consumer products from the market. The drawbacks inherent
2002 Academic Award 65

to the use of fluorinated precursors, therefore, have inhibited the

commercialization of many new applications for CO2

, and the full

promise of CO2

-based technologies has yet to be realized. To address

this need, Professor Eric J. Beckman and his group at the University of

Pittsburgh have developed materials that work well, exhibiting miscibility pressures in CO2

 that are comparable or lower than fluorinated

analogs and yet contain no fluorine.

Drawing from recent studies of the thermodynamics of CO2

 mixtures,

Professor Beckman hypothesized that CO2

-philic materials should

contain three primary features: (1) a relatively low glass transition

temperature; (2) a relatively low cohesive energy density; and (3) a

number of Lewis base groups. Low glass transition temperature

correlates to high free volume and high molecular flexibility, which

imparts a high entropy of mixing with CO2

 (or any solvent). A low

cohesive energy density is primarily a result of weak solute–solute

interactions, a necessary feature given that CO2

 is a rather feeble

solvent. Finally, because CO2

 is a Lewis acid, the presence of Lewis

base groups should create sites for specific favorable interactions with

CO2

.

Professor Beckman’s simple heuristic model was demonstrated on

three sets of materials: functional silicones; poly(ether-carbonates); and

acetate-functional polyethers. Poly(ether-carbonates) were found to

exhibit lower miscibility pressures in CO2

 than perfluoropolyethers, yet

are biodegradable and 100 times less expensive to prepare. Other

families of non-fluorous CO2

-philes will inevitably be discovered using

this model, further broadening the applicability of CO2

 as a greener

process solvent.
66 2002 Award

Small Business Award

SC Fluids, Inc.

SCORR—Supercritical CO2 Resist Remover

Innovation and Benefits

SCORR (Supercritical CO2 Resist Remover) technology cleans residues from

semiconductor wafers during their manufacture. SCORR improves on

conventional techniques: it minimizes hazardous solvents and waste, is

safer for workers, costs less, and uses less water and energy. SCORR also

eliminates rinsing with ultrapure water and subsequent drying.

The semiconductor industry is the most successful growth industry in

history, with sales totaling over $170 billion in the year 2000. The

fabrication of integrated circuits (ICs) relies heavily on photolithography

to define the shape and pattern of individual components. Current

manufacturing practices use hazardous chemicals and enormous

amounts of purified water during this intermediate step, which may be

repeated up to 30 times for a single wafer. It is estimated that a typical

chip-fabrication plant generates 4 million gallons of wastewater and

consumes thousands of gallons of corrosive chemicals and hazardous

solvents each day.

SC Fluids, in partnership with Los Alamos National Laboratory, has

developed a new process, SCORR, that removes photoresist and postash, -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 corrosive chemicals. Neat CO2

 is also utilized for the rinse step, thereby eliminating the

need for a deionized water rinse and an isopropyl alcohol drying step.

In the closed-loop SCORR process, CO2

 returns to a gaseous phase

upon depressurization, leaving the silicon wafer dry and free of residue.
2002 Small Business Award 67

SCORR is cost-effective for five principal reasons. It minimizes the use

of hazardous solvents, thereby minimizing costs required for disposal

and discharge permits. It thoroughly strips photoresists from the wafer

surface in less than half the time required for wet-stripping and far

outperforms plasma, resulting in increased throughput. It eliminates

rinsing and drying steps during the fabrication process, thereby simplifying and streamlining the manufacturing process. It eliminates the

need for ultrapure deionized water, thus reducing time, energy, and

cost. Supercritical CO2

 costs less than traditional solvents and is recyclable.

SCORR will meet future, as well as current technology demands. To

continue its astounding growth, the semiconductor industry must

develop ICs that are smaller, faster, and cheaper. Due to their high

viscosity, traditional wet chemistries cannot clean small feature sizes.

Vapor cleaning technologies are available, but viable methods for

particle removal in the gas phase have not yet been developed. Using

SCORR, the smallest features present no barriers because supercritical

fluids have zero surface tension and a “gaslike” viscosity and, therefore, can clean features less than 100 nm. The low viscosity of supercritical fluids also allows particles less than 100 nm to be removed. The

end result is a technically enabling “green” process that has been

accepted by leading semiconductor manufacturers and equipment and

material suppliers.

SCORR technology is being driven by industry in pursuit of its own

accelerated technical and manufacturing goals. SCORR was initially

developed through a technical request from Hewlett Packard (now

Agilent). A joint Cooperative Research and Development Agreement

between Los Alamos National Laboratory and SC Fluids has led to the

development of commercial units (SC Fluids’s ArroyoTM System). Other

industry leaders, such as IBM, ATMI, and Shipley, are participating in

the development of this innovative technology.
68 2002 Award

Greener Synthetic Pathways Award

Pfizer, Inc.

Green Chemistry in the Redesign of the Sertraline Process

Innovation and Benefits

Pfizer dramatically improved its manufacturing process for sertraline, the

active ingredient in its popular drug, Zoloft ®. The new process doubles

overall product yield, reduces raw material use by 20–60 percent, eliminates the use or generation of approximately 1.8 million pounds of hazardous materials, reduces energy and water use, and increases worker safety.

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 United States, and that costs society $43.7 billion (1990 dollars). As

of February 2000, more than 115 million Zoloft® prescriptions had been

written in the United States.

Applying the principles of green chemistry, Pfizer has dramatically

improved the commercial manufacturing process of sertraline. After

meticulously investigating 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.
2002 Greener Synthetic Pathways Award 69

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, and hexane) from the original synthesis. Pfizer’s

innovative use of solubility differences to drive the equilibrium toward

imine formation in the first reaction of the combined steps eliminated

approximately 310,000 pounds per year of the problematic reagent

titanium tetrachloride. This process change eliminates

220,000 pounds of 50 percent sodium hydroxide, 330,000 pounds of

35 percent hydrochloric acid waste, and 970,000 pounds of solid

titanium dioxide waste per year.

By eliminating waste, reducing solvents, and maximizing the yield of

key intermediates, Pfizer has demonstrated significant green chemistry

innovation in the manufacture of an important pharmaceutical agent.
70 2002 Award

Greener Reaction Conditions Award

Cargill Dow LLC (now NatureWorks LLC)

NatureWorksTM PLA Process

Innovation and Benefits

The NatureWorksTM process makes biobased, compostable, and recyclable

polylactic acid (PLA) polymers using 20–50 percent less fossil fuel resources than comparable petroleum-based polymers. The synthesis of PLA

polymers eliminates organic solvents and other hazardous materials,

completely recycles product and byproduct streams, and efficiently uses

catalysts to reduce energy consumption and improve yield.

NatureWorksTM polylactic acid (PLA) is the first family of polymers

derived entirely from annually renewable resources that can compete

head-to-head with traditional fibers and plastic packaging materials on a

cost and performance basis. For fiber consumers, this will mean a new

option for apparel and carpeting applications: a material that bridges

the gap in performance between conventional synthetic fibers and

natural fibers such as silk, wool, and cotton. Clothing made with

NatureWorksTM fibers features a unique combination of desirable

attributes such as superior hand, touch, and drape, wrinkle resistance,

excellent moisture management, and resilience. In packaging applications, consumers will have the opportunity to use a material that is

natural, compostable, and recyclable without experiencing any

tradeoffs in product performance.

The NatureWorksTM PLA process offers significant environmental

benefits in addition to the outstanding performance attributes of the

polymer. NatureWorksTM 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
2002 Greener Reaction Conditions Award 71

only has exceptionally high yields (over 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 biodegradable applications and were not

commercially viable. Only now has Cargill Dow been able to perfect the

NatureWorksTM process and enhance the physical properties of PLA

resins to compete successfully with commodity petroleum-based

plastics. Cargill Dow is currently producing approximately 8.8 million

pounds of PLA per year to meet immediate market development

needs. Production in the first world-scale 310-million-pound-per-year

plant began November 1, 2001.

The NatureWorksTM 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,

NatureWorksTM PLA products can be either recycled or composted after

use.
72 2002 Award

Designing Greener Chemicals Award

Chemical Specialties, Inc. (now Viance)

ACQ Preserve®: The Environmentally Advanced Wood Preservative

Innovation and Benefits

ACQ Preserve® is an environmentally advanced wood preservative designed to replace chromated copper arsenate (CCA) wood preservatives,

which have been phased out because of their toxicity. ACQ Preserve® will

eliminate the use of 40 million pounds of arsenic and 64 million pounds of

hexavalent chromium each year. It also avoids the potential risks associated with producing, transporting, using, and disposing of CCA wood

preservatives and CCA-treated wood.

The pressure-treated wood industry is a $4 billion industry, producing

approximately 7 billion board feet of preserved wood per year. More

than 95 percent of the pressure-treated wood used in the United

States is currently preserved with chromated copper arsenate (CCA).

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 chromium(VI) were used to manufacture these

CCA wood preservatives.

Over the past few years, scientists, environmentalists, and regulators

have raised concerns regarding the risks posed by the arsenic that is

either dislodged or leached from CCA-treated wood. A principal concern is the risk to children from contact with CCA-treated wood in

playground equipment, picnic tables, and decks. This concern has led

to increased demand for and use of alternatives to CCA.

Chemical Specialties, Inc. (CSI) developed its alkaline copper quaternary (ACQ) wood preservative as an environmentally advanced formula

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
2002 Designing Safer Chemicals Award 73

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 United States each year is

used to make CCA, replacing CCA with ACQ will virtually eliminate the

use of arsenic in the United States. In addition, ACQ Preserve® will

eliminate the use of 64 million pounds of chromium(VI). Further, ACQ

avoids the potential risks associated with the production, transportation, use, and disposal of the arsenic and chromium(VI) contained in

CCA wood preservatives and CCA-treated wood. In fact, ACQ does not

generate any RCRA (i.e., Resource Conservation and Recovery Act)

hazardous waste from production and treating facilities. The disposal

issues associated with CCA-treated wood and ash residues associated

with the burning of treated wood will also be avoided.

In 1996, CSI commercialized ACQ Preserve® in the United States. More

than one million active pounds of ACQ wood preservatives were sold in

the United States in 2001 for use by 13 wood treaters to produce over

100 million board feet of ACQ-preserved wood. In 2002, CSI plans to

spend approximately $20 million to increase its production capacity for

ACQ to over 50 million active pounds. By investing in ACQ technology,

CSI has positioned itself and the wood preservation industry to transition away from arsenic-based wood preservatives to a new generation

of preservative systems.
74

2001 Winners

Academic Award

Professor Chao-Jun Li

Tulane University

Quasi-Nature Catalysis: Developing Transition Metal Catalysis in Air

and Water

Innovation and Benefits

Professor Li developed a novel method to carry out a variety of important

chemical reactions that had previously required both an oxygen-free

atmosphere and hazardous organic solvents. His reactions use metal

catalysts and run in open containers of water. His method is inherently

safer, requires fewer process steps, operates at lower temperatures, and

generates less waste.

The use of transition metals for catalyzing reactions is of growing

importance in modern organic chemistry. These catalyses are widely

used in the synthesis of pharmaceuticals, fine chemicals, petrochemicals, agricultural chemicals, polymers, and plastics. Of particular importance is the formation of C–C, C–O, C–N, and C–H bonds. Traditionally,

the use of an inert gas atmosphere and the exclusion of moisture

have been essential in both organometallic chemistry and transitionmetal catalysis. The catalytic actions of transition metals in ambient

atmosphere have played key roles in various enzymatic reactions

including biocatalysis, biodegradation, photosynthesis, nitrogen

fixation, and digestions, as well as the evolution of bioorganisms.

Unlike traditionally used transition-metal catalysts, these “natural”

catalytic reactions occur under aqueous conditions in an air atmosphere.

The research of Professor Chao-Jun Li has focused on the development

of numerous transition-metal-catalyzed reactions both in air and water.

Specifically, Professor Li has developed a novel [3+2] cycloaddition

reaction to generate 5-membered carbocycles in water; a synthesis of

β-hydroxyl esters in water; a chemoselective alkylation and pinacol
2001 Academic Award 75

coupling reaction mediated by manganese in water; and a novel

alkylation of 1,3-dicarbonyl-type compounds in water. His 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 polyhydroxylated natural products, medium-sized

rings, and macrocyclic compounds, yields shorter reaction sequences.

Transition-metal-catalyzed reactions in water and air offer many advantages. Water is readily available and inexpensive; it 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

temperature of reactions performed in aqueous media is also easier to

control since water has such a high heat capacity. The open-air feature

offers convenience in operations of chemical synthesis involving smallscale combinatorial synthesis, large-scale manufacturing, and catalyst

recycling. As such, Professor Li’s work in developing transition-metalmediated and -catalyzed reactions in air and water offers an attractive

alternative to the inert atmosphere and organic solvents traditionally

used in synthesis.
76 2001 Award

Small Business Award

EDEN Bioscience Corporation

Messenger®: A Green Chemistry Revolution in Plant Production and

Food Safety

Innovation and Benefits

EDEN Bioscience Corporation discovered and commercialized harpins, a

new class of nontoxic, naturally occurring, biodegradable proteins, as an

alternative to traditional pesticides. Harpins activate a plant's defense and

growth mechanisms, thereby increasing crop yield and quality, and minimizing crop losses. EDEN manufactures Messenger®, its commercially

available, harpin-containing, EPA-approved product, using a water-based

fermentation system.

In today’s competitive agricultural environment, growers must maximize crop productivity by enhancing yield and minimizing crop losses.

The Food and Agriculture Organization of the United Nations estimates that annual losses to growers from pests reach $300 billion

worldwide. In addition to basic agronomic practices, growers generally

have two 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 occurring proteins called harpins, which were first discovered by

Dr. Zhongmin Wei, EDEN’s Vice President of Research, and his colleagues during his tenure at Cornell University. Harpin proteins trigger

a plant’s natural defense systems to protect against disease and pests

and simultaneously activate certain plant growth systems without

altering the plant’s DNA. When applied to crops, harpins increase
2001 Small Business Award 77

plant biomass, photosynthesis, nutrient uptake, and root development, and, ultimately, lead to greater crop yield and quality.

Unlike most agricultural chemicals, harpin-based products are produced in a water-based fermentation system that uses no harsh

solvents or 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 a U.S. EPA-approved product called

Messenger® that has been demonstrated on more than 40 crops to

effectively stimulate plants to defend themselves against a broad

spectrum of viral, fungal, and bacterial diseases, including some for

which there currently is no effective treatment. In addition, Messenger® has been shown through an extensive safety evaluation to have

virtually no adverse effect on any of the organisms tested, including

mammals, birds, honey bees, plants, fish, aquatic invertebrates, and

algae. Only 0.004–0.14 pounds of harpin protein per acre per season is

necessary to protect crops and enhance yields. As with most proteins,

harpin is a fragile molecule that is degraded rapidly by 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 environment by reducing total agricultural inputs and partially

replacing many higher-risk products. Using environmentally benign

harpin protein technology, growers for the first time in the history of

modern agriculture will be able to harness the innate defense and

growth systems of crops to substantially enhance yields, improve crop

quality, and reduce reliance on conventional agricultural chemicals.
78 2001 Award

Greener Synthetic Pathways Award

Bayer Corporation

Bayer AG

BaypureTM CX (Sodium Iminodisuccinate): An Environmentally Friendly

and Readily Biodegradable Chelating Agent

Innovation and Benefits

Chelating agents are ingredients in a variety of products, such as detergents, fertilizers, and household and industrial cleaners. Most traditional

chelating agents do not break down readily in the environment. Bayer

Corporation and Bayer AG developed a waste-free, environmentally

friendly manufacturing process for a new, biodegradable, nontoxic

chelating agent. This new process eliminates the use of formaldehyde and

hydrogen cyanide.

Chelating agents are used in a variety of applications, including

detergents, agricultural nutrients, and household and industrial

cleaners. Most traditional chelating agents, however, are poorly

biodegradable. Some are actually quite persistent and do not adsorb

at the surface of soils in the environment or at activated sludge in

wastewater treatment plants. Because of this poor biodegradability

combined with high water solubility, traditional chelators are readily

released into the environment and have been detected in the surface

waters of rivers and lakes and in make-up water processed for drinking

water.

As part of its commitment to Responsible Care®, Bayer Corporation

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(III), copper(II), 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”
2001 Greener Synthetic Pathways Award 79

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 environmentally 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 produced from maleic anhydride (a raw

material also produced by Bayer), water, sodium hydroxide, and

ammonia. The only solvent used in the production process is water,

and the only side 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 nonpolluting alternative to other chelating agents, it can be used

in a variety of applications that employ chelating agents. For example,

it can be used as a builder and bleach stabilizer in laundry and

dishwashing detergents to extend and improve the cleaning properties of the eight billion pounds of these products that are used annually. Specifically, sodium iminodisuccinate chelates calcium to soften

water and improve the cleaning function of the surfactant. In photographic film processing, sodium iminodisuccinate complexes metal

ions and helps to eliminate precipitation onto the film surface. In

agriculture, chelated metal ions help to prevent, correct, and minimize

crop mineral deficiencies. Using sodium iminodisuccinate as the

chelating agent in agricultural 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, environmentally friendly chelating agent that is also manufactured in a waste-free

process.
80 2001 Award

Greener Reaction Conditions Award

Novozymes North America, Inc.

BioPreparationTM of Cotton Textiles: A Cost-Effective, Environmentally

Compatible Preparation Process

Innovation and Benefits

Novozymes North America developed BioPreparationTM, a technology to

separate natural waxes, oils, and contaminants from cotton before it is

made into fabric. This technology uses enzymes instead of corrosive

chemicals and could save 7–12 billion gallons of water each year.

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; it must be removed to prepare

the textile for dyeing and finishing. Conventional chemical preparation

processes involve treatment of the cotton substrate with hot solutions

of sodium hydroxide, chelating agents, and surface active agents,

often followed by a neutralization step with acetic acid. The scouring

process is designed to break down or release natural waxes, oils, and

contaminants and emulsify or suspend these impurities in the scouring

bath. Typically, scouring wastes contribute high biological oxygen

demand (BOD) loads during cotton textile preparation (as much as

50 percent).
2001 Greener Reaction Conditions Award 81

Novozymes’s BioPreparationTM technology is an alternative to sodium

hydroxide that offers many advantages for textile wet processing,

including reduced biological and chemical oxygen demand (BOD/

COD) and decreased water use. BioPreparationTM 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 performance properties of cotton fabrics.

The practical implications that BioPreparationTM 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 BioPreparationTM uses fewer rinsing

steps than required during a traditional caustic scour. Significant time

savings were also demonstrated by combining treatment steps. A

recent statistical survey determined that 162 knitting mills typically use

24 billion gallons per year of water in processing goods from scouring

to finishing; the BioPreparationTM approach would save from

7–12 billion gallons per year of water. In addition, field trials established that BOD and COD loads are decreased by 25 and 40 percent,

respectively, when compared to conventional sodium hydroxide

treatments. Furthermore, these conservation measures translate

directly into cost savings of 30 percent or more. As such, this patented

process provides an economical and environmentally friendly alternative to alkaline scour systems currently used in the textile industry.
82 2001 Award

Designing Greener Chemicals Award

PPG Industries

Yttrium as a Lead Substitute in Cationic Electrodeposition Coatings

Innovation and Benefits

PPG Industries developed a novel metal primer that uses yttrium instead of

lead to resist corrosion in automobiles. The metal yttrium is far less toxic to

human health and the environment than is lead and is more effective in

preventing corrosion. PPG's primer should eliminate one million pounds of

lead from automobile manufacture over the next few years. In addition,

this primer does not require chromium- or nickel-based pretreatments,

potentially eliminating the use of 25,000 pounds of chromium and

50,000 pounds of nickel each year.

PPG Industries introduced the first cationic electrodeposition primer to

the automotive industry in 1976. During the succeeding years, this

coating technology became very widely used in the industry such that

today essentially all automobiles are given a primer coat using the

chemistry and processing methods developed by PPG. The major

benefits of this technology are corrosion resistance, high transfer

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 (galvanized) steel could not

be tolerated. Lead is very effective for protecting cold-rolled steel,

which is still a common material of construction in automobiles.

For more than 20 years, PPG and other paint companies have sought a

substitute for lead in this application. This search led to PPG’s discovery

that yttrium can replace lead in cationic electrocoat without any sacri-
2001 Designing Greener Chemicals Award 83

fice 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 indicated by the LD50 of over 10 grams per kilogram in rats,

which is in stark contrast to lead. The ubiquitous nature of yttrium in

the environment and the insoluble ceramic-like nature of the oxide

combine to make it an unlikely cause of future environmental or

health problems.

An environmental side benefit of yttrium is its performance over lownickel and chrome-free metal pretreatments. In automotive production, a metal pretreatment is always applied to the body prior to

electrocoat, which is designed to assist in adhesion and corrosion

performance. This process generates significant quantities of chromium- and nickel-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 chromefree rinses and low-nickel or possibly nickel-free pretreatments, both of

which are commercially available today. This should be possible

without concern of compromising long-term vehicle corrosion performance. For PPG pretreatment customers, this should result in the

elimination of up to 25,000 pounds of chrome and 50,000 pounds of

nickel annually from PPG products. As PPG customers implement

yttrium over the next several years, approximately one million pounds

of lead (as lead metal) will be removed from the electrocoat applications of PPG automotive customers.
84

2000 Winners

Academic Award

Professor Chi-Huey Wong

The Scripps Research Institute

Enzymes in Large-Scale Organic Synthesis

Innovation and Benefits

Professor Wong developed methods to replace traditional reactions

requiring toxic metals and hazardous solvents. His methods use enzymes,

environmentally acceptable solvents, and mild reaction conditions. His

methods also enable novel reactions that were otherwise impossible or

impractical on an industrial scale. Professor Wong's methods hold promise

for applications in a wide variety of chemical industries.

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, however,

necessary to deal with the new classes of compounds that are becoming the key targets of molecular research and development.

Compounds with polyfunctional groups such as carbohydrates and

related structures pose particular challenges to nonbiological synthetic

methods but are natural targets for biological methods. In addition,

biological methods are necessary to deal with increasing environmental

concerns. Transition metals, heavy elements, and toxic organic solvents

are often used in nonbiological processes. When these materials are

used with great care and efficiency, they may still be environmentally

acceptable, but their handling and disposal pose problems. The ability

to use recombinant and engineered enzymes to carry out environmentally acceptable synthetic transformations that are otherwise impossible
2000 Academic Award 85

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

methodologies for use in large-scale chemistry. A recent study by the

Institute for Scientific Information ranked Professor Wong in the top 15

of the most-cited chemists in the world for the period 1994 to 1996.

According to this study, he is also the most-cited chemist worldwide

working in the area of enzymes.

Some of the strategies and methods developed by Professor Wong

are breakthrough achievements that laid the framework for much of

the current use of enzymes as catalysts in large-scale organic synthesis. The techniques and reagents developed in this body of pioneering

work are used widely today for research and development. The scope

of contributions ranges from relatively simple enzymatic processes

(e.g., chiral resolutions and stereoselective syntheses) to complex,

multistep enzymatic reactions (e.g., oligosaccharide synthesis). For

example, the irreversible enzymatic transesterification reaction using

enol esters in environmentally acceptable organic solvents invented by

Professor Wong represents the most widely used method for enantioselective transformation of alcohols in pharmaceutical development.

The multi-enzyme system based on genetically engineered glycosyltransferases coupled with in situ regeneration of sugar nucleotides

developed by Professor Wong has revolutionized the field of carbohydrate chemistry and enabled the large-scale synthesis of complex

oligosaccharides for clinical evaluation. All of these new enzymatic

reactions are carried out in environmentally acceptable solvents, under

mild reaction conditions, at ambient temperature, and with minimum

protection of functional groups. The work of Professor Wong represents a new field of green chemistry suitable for large-scale synthesis

that is impossible or impractical to achieve by nonenzymatic means.
86 2000 Award

Small Business Award

RevTech, Inc.

EnvirogluvTM: A Technology for Decorating Glass and Ceramicware with

Radiation-Curable, Environmentally Compliant Inks

Innovation and Benefits

RevTech developed the EnvirogluvTM process to print top-quality labels

directly on glass, replacing paper labels, decals, or applied ceramic

labeling. EnvirogluvTM inks do not contain heavy metals, contain little to no

volatile organic compounds (VOCs), and are biodegradable. This technology saves energy by replacing high-temperature ovens with ultraviolet

light, saves raw materials, wastes no ink, and produces decorated glass

that is completely recyclable.

Billions of products are sold in glass containers in the United States

every year. Most, if not all, of these glass containers are labeled in

some fashion. Typically, decorative indicia are applied to glass using

paper labels, decals, or a process known as applied ceramic labeling

(ACL). ACL involves first printing the glass with an ink composition that

contains various heavy metals such as lead, cadmium, and chromium,

then bonding the ink to the glass by baking in an oven known as a

lehr at temperatures of 1,000 °F or more for several hours.

All of these processes have disadvantages. Paper labels are inexpensive but can be easily removed if the container is exposed to water or

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 containers. More

important, decals are made from materials that are not biodegradable,

which causes serious problems in the recycling of glass containers that

are decorated by this method. The use and disposal of the heavy

metals required in ACL presents serious environmental concerns.

Moreover, the high-temperature lehr ovens required in ACL decorating

utilize substantial amounts of energy and raise safety issues with
2000 Small Business Award 87

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 energyefficient manner. EnvirogluvTM technology fills that need. EnvirogluvTM

is a glass decorating technology that directly silk-screens radiationcurable inks onto glass, then cures the ink almost instantly by exposure to UV light. The result is a crisp, clean label that is environmentally

sound, with a unit cost that is about half that of traditional labeling.

EnvirogluvTM technology offers many human health and environmental

benefits. The ink compositions used in the EnvirogluvTM process do not

contain any heavy metals and contain little to no VOCs. All EnvirogluvTM

pigments are biodegradable. The EnvirogluvTM inks are cured directly

on the glass by exposure to UV radiation, eliminating the high-temperature baking in a lehr oven that is associated with the ACL process.

This provides additional safety and environmental benefits, such as

reduced energy consumption and reduced chance of worker injury. In

addition, the process uses less raw materials and does not generate

any waste ink. Furthermore, EnvirogluvTM decorated glass containers

eliminate the need for extra packaging and are completely recyclable.

Applications suitable for the EnvirogluvTM process include tableware,

cosmetics containers, and plate glass.
88 2000 Award

Greener Synthetic Pathways Award

Roche Colorado Corporation

An Efficient Process for the Production of Cytovene®, a Potent Antiviral

Agent

Innovation and Benefits

Roche Colorado developed an environmentally friendly way to synthesize

Cytovene®, a potent antiviral drug. Their process eliminates nearly

2.5 million pounds of hazardous liquid waste and over 55,000 pounds of

hazardous solid waste each year. This process also increases the overall

yield more than 25 percent and doubles the production throughput.

The design, development, and implementation of environmentally

friendly processes for the large-scale production of pharmaceutical

products is one of the most technically challenging aspects of business

operations in the pharmaceutical industry. Roche Colorado Corporation

(RCC), in establishing management and operational systems for the

continuous improvement of environmental quality in its business

activities, has, in essence, adopted the Presidential Green Chemistry

Challenge Program’s basic principles of green chemistry: the development of environmentally friendly processes for the manufacture of

pharmaceutical products. In particular, RCC has successfully applied

these principles to the manufacture of ganciclovir, the active ingredient

in Cytovene®, a potent antiviral agent. Cytovene® is used in the

treatment of cytomegalovirus (CMV) retinitis infections in immunocompromised patients, including patients with AIDS, and also used for

the prevention of CMV disease in transplant recipients at risk for CMV.

In the early 1990s, Roche Colorado Corporation developed the first

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

110,000 pounds per year. Leveraging the basic principles of green

chemistry and molecular conservation into the design process, signifi-
2000 Greener Synthetic Pathways Award 89

cant improvements were demonstrated in the second-generation

Guanine Triester (GTE) Process. Compared to the first-generation

commercial manufacturing process, the GTE Process reduced the

number of chemical reagents and intermediates from 22 to 11, eliminated the (only) two hazardous solid waste streams, eliminated

11 different chemicals from the hazardous liquid waste streams, and

efficiently recycled and reused four of the five ingredients not incorporated into the final product. Inherent within the process improvements

demonstrated was the complete elimination of the need for operating

and monitoring three different potentially hazardous chemical reactions. Overall, the GTE Process provided an expedient method for the

production of Cytovene®, demonstrating a procedure that provided an

overall yield increase of more than 25 percent and a production

throughput increase of 100 percent.

In summary, the new GTE Process for the commercial production of

Cytovene® clearly demonstrates the successful implementation of the

general principles of green chemistry: the development of environmentally friendly syntheses, including the development of alternative

syntheses utilizing nonhazardous and nontoxic feedstocks, reagents,

and solvents; elimination of waste at the source (liquid waste:

2.5 million pounds per year and solid waste: 56,000 pounds per year);

and elimination of the production of toxic wastes and byproducts. The

process establishes new and innovative technology for a general and

efficient method for the preparation of Cytovene® and other potent

antiviral agents. It is registered with the U.S. Food and Drug Administration (FDA) as the current manufacturing process for the world’s

supply of Cytovene®.
90 2000 Award

Greener Reaction Conditions Awards

Bayer Corporation

Bayer AG

Two-Component Waterborne Polyurethane Coatings

Innovation and Benefits

Bayer developed a series of high-performance, water-based, twocomponent polyurethane coatings that eliminate most or all of the

organic solvents used in conventional polyurethane coatings. Bayer's

water-based polyurethane coatings reduce volatile organic compound

(VOC) and hazardous air pollutant (HAP) emissions by 50–90 percent.

Two-component (2K) waterborne polyurethane 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 compounds (VOCs) and hazardous air pollutants

(HAPs) used in conventional 2K solventborne polyurethane coatings

with water as the carrier, without significant reduction in performance

of the resulting coatings. This may seem an obvious substitution, but,

due to the particular chemistry of the reactive components of polyurethane, it is not that straightforward.

Two-component solventborne polyurethane coatings have long been

considered in many application areas to be the benchmark for highperformance coatings systems. The attributes that make these systems

so attractive are fast cure under ambient or bake conditions, high-gloss

and mirror-like finishes, hardness or flexibility as desired, chemical and

solvent resistance, and excellent weathering. The traditional carrier,

however, has been organic solvent that, upon cure, is freed to the

atmosphere as VOC and HAP material. High-solids systems and

aqueous polyurethane dispersions ameliorate this problem but do not

go far enough.

An obvious solution to the deficiencies of 2K solventborne polyurethanes and aqueous polyurethane dispersions is a reactive 2K polyure-
2000 Greener Reaction Conditions Award 91

thane system with water as the carrier. In order to bring 2K waterborne

polyurethane coatings to the U.S. market, new waterborne and waterreducible 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 cross-linker with water had to be addressed, as well as

problems with the chemical and film appearance resulting from this

side reaction. The work done on the 2K waterborne polyurethanes

over the past several years has resulted in a technology that will

provide several health and 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 applications will also

be reduced, and rugged interior coatings with no solvent smell will

now be available.

Today, 2K waterborne polyurethane is being applied on industrial lines

where good properties and fast cure rates are required for such varied

products as metal containers and shelving, sporting equipment, metaland fiberglass-reinforced utility poles, agricultural equipment, and

paper products. In flooring coatings applications where the marketdriving 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 pound organic solvent per gallon). In wood

applications, 2K waterborne polyurethane coatings meet the highperformance 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 United States,

the greatest market acceptance of 2K waterborne polyurethane is in

the area of special-effect coatings in automotive applications. These

coatings provide the soft, luxurious look and feel of leather to hard

plastic interior automobile surfaces, such as instrument panels and air

bag covers. Finally, in military applications, 2K waterborne polyurethane

coatings are being selected because they meet the demanding

military performance criteria that include flat coatings with camouflage

requirements, corrosion protection, chemical and chemical agent

protection, flexibility, and exterior durability, along with VOC reductions

of approximately 50 percent.
92 2000 Award

Designing Greener Chemicals Award

Dow AgroSciences LLC

SentriconTM Termite Colony Elimination System, A New Paradigm for

Termite Control

Innovation and Benefits

Dow's SentriconTM System eliminates termite colonies with highly specific

bait applied only where termites are active; it replaces widespread applications of pesticide in the soil around houses and other structures. The

U.S. EPA has registered SentriconTM as a reduced-risk pesticide. Dow's

system reduces the use of hazardous materials and reduces potential

impacts on human health and the environment. By late1999, SentriconTM

was used for over 300,000 structures in the United States.

The annual cost of termite treatments to the U.S. consumer is about

$1.5 billion, and each year as many as 1.5 million homeowners will

experience a termite problem and seek a control option. From the

1940s until 1995, the nearly universal treatment approach for subterranean termite control involved the placement of large volumes of

insecticide dilutions into the soil surrounding a structure to create a

chemical barrier through which termites could not penetrate. Problems

with this approach include difficulty in establishing an uninterrupted

barrier in the vast array of soil and structural conditions, use of large

volumes of insecticide dilution, and potential hazards associated with

accidental misapplications, spills, off-target applications, and worker

exposure. These inherent problems associated with the use of chemical barrier approaches for subterranean termite control created a need

for a better method. The search for a baiting alternative was the focus

of a research program established by Dr. Nan-Yao Su of the University

of Florida who, in the 1980s, had identified the characteristics needed

for a successful termite bait toxicant.

The unique properties of hexaflumuron made it an excellent choice for

use in controlling subterranean termite colonies. The SentriconTM

Termite Colony Elimination System, developed by Dow AgroSciences in
2000 Designing Greener Chemicals Award 93

collaboration with Dr. Su, was launched commercially in 1995 after

receiving U.S. EPA registration as a reduced-risk pesticide. SentriconTM

represents truly novel technology employing an Integrated Pest

Management approach using monitoring and targeted delivery of a

highly specific bait. Because it eliminates termite colonies threatening

structures using a targeted approach, SentriconTM delivers unmatched

technical performance, environmental compatibility, and reduced

human risk. The properties of hexaflumuron as a termite control agent

are attractive from an environmental and human risk perspective, but

more important, the potential for adverse effects is dramatically reduced because it is present only in very small quantities in stations with

termite activity. The comparisons to barrier methods show significant

reduction in the use of hazardous materials and substantial reduction

in potential impacts on human health and the environment.

The discovery of hexaflumuron’s activity with its unique fit and 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 SentriconTM 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 monitoring and baiting

typify the innovation that has been a hallmark of the project. More than

300,000 structures across the United States are now being safeguarded

through application of this revolutionary technology, and adoption is

growing rapidly.
94

1999 Winners

Academic Award

Professor Terry Collins

Carnegie Mellon University

TAMLTM Oxidant Activators: General Activation of Hydrogen Peroxide

for Green Oxidation Technologies

Innovation and Benefits

Professor Collins developed a series of activator chemicals that work with

hydrogen peroxide to replace chlorine bleaches. His TAMLTM activators

have many potential uses that include preparing wood pulp for papermaking and removing stains from laundry. This novel, environmentally

benign technology eliminates chlorinated byproducts from wastewater

streams and saves both energy and water.

In nature, selectivity is achieved through complex mechanisms using a

limited set of elements available in the environment. In the laboratory,

chemists prefer a simpler design that utilizes the full range of the

periodic table. The problem of persistent pollutants in the environment

can be minimized by employing reagents and processes that mimic

those found in nature. By developing a series of activators effective

with the natural oxidant, hydrogen peroxide, Professor Terry Collins has

devised an environmentally-benign oxidation technique with widespread applications. TAMLTM activators (tetraamido-macrocyclic ligand

activators) are iron-based and contain no toxic functional groups. These

activators offer significant technology breakthroughs in the pulp and

paper industry and the laundry field.

The key to quality papermaking is the selective removal of lignin from

the white fibrous polysaccharides, cellulose, and hemicellulose. Wood

pulp delignification has traditionally relied on chlorine-based processes

that produce chlorinated pollutants. Professor Collins has demonstrated that TAMLTM activators effectively catalyze hydrogen peroxide

in the selective delignification of wood pulp. This is the first lowtemperature peroxide oxidation technique for treating wood pulp,
1999 Academic Award 95

which translates to energy savings for the industry. Environmental

compliance costs may be expected to decrease with this new approach because chlorinated organics are not generated in this totally

chlorine-free process.

TAMLTM activators may also be applied to the laundry field, where most

bleaches are based on peroxide. When bound to fabric, most commercial dyes are unaffected by the TAMLTM-activated peroxide. However, random dye molecules that “escape” the fabric during laundering

are intercepted and destroyed by the activated peroxide before they

have a chance to transfer to other articles of clothing. This technology

prevents dye-transfer accidents while offering improved stain-removal

capabilities. Washing machines that require less water will be practical

when the possibility of dye-transfer is eliminated.

An active area of investigation is the use of TAMLTM peroxide activators

for water disinfection. Ideally, the activators would first kill pathogens in

the water sample, then destroy themselves in the presence of a small

excess of peroxide. This protocol could have global applications, from

developing nations to individual households.

The versatility of the TAMLTM activators in catalyzing peroxide has been

demonstrated in the pulp and paper and laundry industries. Environmental benefits include decreased energy requirements, elimination

of chlorinated organics from the waste stream, and decreased water

use. The development of new activators and new technologies will

provide environmental advantages in future applications.
96 1999 Award

Small Business Award

Biofine, Inc. (now BioMetics, Inc.)

Conversion of Low-Cost Biomass Wastes to Levulinic Acid and

Derivatives

Innovation and Benefits

Biofine developed a process to convert the waste cellulose in paper mill

sludge, municipal solid waste, unrecyclable waste paper, waste wood, and

agricultural residues into levulinic acid (LA). LA can be used as a building

block for many other useful chemicals. LA made from waste cellulose

reduces the use of fossil fuels and reduces the overall cost of LA from

$4–6 per pound to as little as $0.32 per pound.

Replacing petroleum-based feedstocks with renewable ones is a

crucial step toward achieving sustainability. When considering alternatives to traditional feedstocks, attention often focuses on plant-based

materials. Renewable biomass conserves our dwindling supplies of

fossil fuels and contributes no net CO2

 to the atmosphere. Biofine has

developed a high-temperature, dilute-acid hydrolysis process that

converts cellulosic biomass to levulinic acid (LA) and derivatives.

Cellulose is initially converted to soluble sugars, which are then

transformed to levulinic acid. Byproducts in the process include furfural, formic acid, and condensed tar, all of which have commercial

value as commodities or fuel. Feedstocks used include paper mill

sludge, municipal solid waste, unrecyclable waste paper, waste wood,

and agricultural residues.

Levulinic acid serves as a building block in the synthesis of useful

chemical products. Markets already exist for tetrahydrofuran, succinic

acid, and diphenolic acid, all of which are levulinic acid derivatives. The

use of diphenolic acid (DPA) as a monomer for polycarbonates and

epoxy resins is currently under investigation. An industry/government

consortium has conducted research on two additional derivatives with

commercial value: methyltetrahydrofuran (MTHF), a fuel additive, and

δ-amino levulinic acid (DALA), a pesticide.
1999 Small Business Award 97

The conversion of levulinic acid to MTHF is accomplished at elevated

temperature and pressure using a catalytic hydrogenation process.

MTHF is a fuel additive that is miscible with gasoline and hydrophobic,

allowing it to be blended at the refinery rather than later in the

distribution process. Using MTHF as a fuel additive increases the

oxygenate level in gasoline without adversely affecting engine

performance. MTHF also boasts a high octane rating (87) and a lower

vapor pressure, thereby reducing fuel evaporation and improving air

quality.

DALA can be obtained from levulinic acid in high yield using a threestep process. DALA is a broad-spectrum pesticide that is nontoxic and

biodegradable. Its activity is triggered by light, selectively killing weeds

while leaving most major crops unaffected. DALA also shows potential

as an insecticide.

Diphenolic acid is synthesized by reacting levulinic acid with phenol.

DPA has the potential to displace bisphenol-A, a possible endocrine

disruptor, in polymer applications. Brominated DPA shows promise as

an environmentally-acceptable marine coating, while dibrominated

DPA may find use as a fire retardant.

Currently, levulinic acid has a worldwide market of about one million

pounds per year at a price of $4–6 per pound. Large-scale commercialization of the Biofine process could produce levulinic acid for as

little as $0.32 per pound, spurring increased demand for LA and its

derivatives. Using the Biofine process, waste biomass can be

transformed into valuable chemical products. The ability to produce

levulinic acid economically from waste biomass and renewable

feedstocks is the key to increased commercialization of LA and its

derivatives.
98 1999 Award

Greener Synthetic Pathways Award

Lilly Research Laboratories

Practical Application of a Biocatalyst in Pharmaceutical Manufacturing

Innovation and Benefits

Lilly Research Laboratories developed a novel, low-waste process for drug

synthesis. One key aspect uses yeast to replace a chemical reaction.

Applying its process, Lilly eliminates approximately 41 gallons of solvent

and 3 pounds of chromium waste for every pound of a drug candidate that

it manufactures. Lilly's process also improves worker safety and increases

product yield from 16 to 55 percent.

The synthesis of a pharmaceutical agent is frequently accompanied by

the generation of a large amount of waste. This should not be surprising, as numerous steps are commonly necessary, each of which may

require feedstocks, reagents, solvents, and separation agents. Lilly

Research Laboratories has redesigned its synthesis of an anticonvulsant drug candidate, LY300164. This pharmaceutical agent is being

developed for the treatment of epilepsy and neurodegenerative

disorders.

The synthesis used to support clinical development of the drug

candidate proved to be an economically viable process, although

several steps proved problematic. A large amount of chromium waste

was generated, an additional activation step was required, and the

overall process required a large volume of solvent. Significant environmental improvements were realized upon implementing the new

synthetic strategy. Roughly 9,000 gallons of solvent and 660 pounds of

chromium waste were eliminated for every 220 pounds of LY300164

produced. Only three of the six intermediates generated were isolated, limiting worker exposure and decreasing processing costs. The

synthetic scheme proved more efficient as well, with percent yield

climbing from 16 to 55 percent.
1999 Greener Synthetic Pathways Award 99

The new synthesis begins with the biocatalytic reduction of a ketone to

an optically pure alcohol. The yeast Zygosaccharomyces rouxii demonstrated good reductase activity but was sensitive to high product

concentrations. To circumvent this problem, a novel three-phase

reaction design was employed. The starting ketone was charged to an

aqueous slurry containing a polymeric resin, buffer, and glucose, with

most of the ketone adsorbed on the surface of the resin. The yeast

reacted with the equilibrium concentration of ketone remaining in the

aqueous phase. The resulting product was adsorbed onto the surface

of the resin, simplifying product recovery. All of the organic reaction

components were removed from the aqueous waste stream, permitting the use of conventional wastewater treatments.

A second key step in the synthesis was selective oxidation to eliminate

the unproductive redox cycle present in the original route. The reaction

was carried out using dimethylsulfoxide, sodium hydroxide, and

compressed air, eliminating the use of chromium oxide, a possible

carcinogen, and preventing the generation of chromium waste. The

new protocol was developed by combining innovations from chemistry,

microbiology, and engineering. Minimizing the number of changes to

the oxidation state improved the efficiency of the process while

reducing the amount of waste generated. The alternative synthesis

presents a novel strategy for producing 5H-2,3-benzodiazepines. The

approach is general and has been applied to the production of other

anticonvulsant drug candidates. The technology is low-cost and easily

implemented; it should have broad applications within the manufacturing sector.
100 1999 Award

Greener Reaction Conditions Award

Nalco Chemical Company

The Development and Commercialization of ULTIMER®: The First of a

New Family of Water-Soluble Polymer Dispersions

Innovation and Benefits

The Nalco Chemical Company developed a novel way to synthesize the

polymers used to treat water in a variety of industrial and municipal operations. Nalco now manufactures these polymers in water, replacing the

traditional water-in-oil mixtures and preventing the release of organic

solvents and other chemicals into the environment.

High-molecular-weight polyacrylamides are commonly used as process

aids and water treatment agents in various industrial and municipal

operations. Annually, at least 200 million pounds of water-soluble,

acrylamide-based polymers are used to condition and purify water.

These water-soluble polymers assist in removing suspended solids and

contaminants and effecting separations. Traditionally, these polymers

are produced as water-in-oil emulsions. Emulsions are prepared by

combining the monomer, water, and a hydrocarbon oil–surfactant

mixture in approximately equal parts. Although the oil and surfactant

are required for processing, they do not contribute to the performance

of the polymer. Consequently, approximately 90 million pounds of oil

and surfactant are released to the environment each year. Nalco has

developed a new technology that permits production of the polymers

as stable colloids in water, eliminating the introduction of oil and

surfactants into the environment.

The Nalco process uses a homogeneous dispersion polymerization

technique. The water-soluble monomers are dissolved in an aqueous

salt solution of ammonium sulfate then polymerized using a watersoluble, free-radical initiator. A low-molecular-weight dispersant polymer

is added to prevent aggregation of the growing polymer chains. For

end-use applications, the dispersion is simply added to water, thereby

diluting the salt and allowing the polymer to dissolve into a clear,
1999 Greener Reaction Conditions Award 101

homogeneous, polymer solution. This technology has been successfully demonstrated with cationic copolymers of acrylamide, anionic

copolymers of acrylamide, and non-ionic polymers.

Development of water-based dispersion polymers provides three

important environmental benefits. First, the new process eliminates the

use of hydrocarbon solvents and surfactants required in the manufacture of emulsion polymers. Dispersion polymers produce no VOCs and

exhibit lower biological oxygen demand (BOD) and chemical oxygen

demand (COD) than do emulsion polymers. Second, the salt used,

ammonium sulfate, is a waste byproduct from another industrial

process, the production of caprolactam. Caprolactam is the precursor in

the manufacture of nylon; 2.5–4.5 million pounds of ammonium

sulfate are produced for every million pounds of caprolactam, providing

a ready supply of feedstock. Finally, dispersion polymers eliminate the

need for costly equipment and inverter surfactants needed for mixing

emulsion polymers. This technological advantage will make wastewater

treatment more affordable for small- and medium-sized operations.

Nalco’s dispersion polymers contain the same active polymer component as traditional emulsion polymers without employing oil and

surfactant carrier systems. The polymers are produced as stable colloids

in water, retaining ease and safety of handling while eliminating the

release of oil and surfactants into the environment. By adopting this

new technology, Nalco has conserved over one million pounds of

hydrocarbon solvent and surfactants since 1997 on two polymers alone.

In 1998, the water-based dispersions used 3.2 million pounds of

ammonium sulfate, a byproduct from caprolactam synthesis that would

otherwise be treated as waste. Additional environmental benefits will

be realized as the dispersion polymerization process is extended to

the manufacture of other polymers.
102 1999 Award

Designing Greener Chemicals Award

Dow AgroSciences LLC

Spinosad: A New Natural Product for Insect Control

Innovation and Benefits

Dow developed spinosad, a highly selective, environmentally friendly

insecticide made by a soil microorganism. It controls many chewing insect

pests in cotton, trees, fruits, vegetables, turf, and ornamentals. Unlike

traditional pesticides, it does not persist in the environment; it also has

low toxicity to mammals and birds.

Controlling insect pests is essential to maintaining high agricultural

productivity and minimizing monetary losses. Synthetic organic pesticides, from a relatively small number of chemical classes, play a

leading role in pest control. The development of new and improved

pesticides is necessitated by increased pest resistance to existing

products, along with stricter environmental and toxicological regulations. To meet this need, Dow AgroSciences has designed spinosad, a

highly selective, environmentally friendly insecticide.

High-volume testing of fermentation isolates in agricultural screens

produced numerous leads, including the extracts of a Caribbean soil

sample found to be active on mosquito larvae. The microorganism,

Saccharopolyspora spinosa, was isolated from the soil sample, and the

insecticidal activity of the spinosyns was identified. Spinosyns are

unique macrocyclic lactones, containing a tetracyclic core to which two

sugars are attached. Most of the insecticidal activity is due to a mixture

of spinosyns A and D, commonly referred to as spinosad. Products

such as Tracer® Naturalyte® Insect Control and Precise® contain

spinosad as the active ingredient.

Insects exposed to spinosad exhibit classical symptoms of neurotoxicity: lack of coordination, prostration, tremors, and other involuntary

muscle contractions leading to paralysis and death. Although the mode

of action of spinosad is not fully understood, it appears to affect
1999 Designing Greener Chemicals Award 103

nicotinic and γ-aminobutyric acid receptor function through a novel

mechanism.

Spinosad presents a favorable environmental profile. It does not leach,

bioaccumulate, volatilize, or persist in the environment. Spinosad will

degrade photochemically when exposed to light after application.

Because spinosad strongly adsorbs to most soils, it does not leach

through soil to groundwater. Spinosad demonstrates low mammalian

and avian toxicity. No long-term health problems were noted in

mammals, and a low potential for acute toxicity exists due to low oral,

dermal, and inhalation toxicity. This is advantageous, because low

mammalian toxicity imparts reduced risk to those who handle, mix,

and apply the product. Although spinosad is moderately toxic to fish,

this toxicity represents a reduced risk to fish when compared with

many synthetic insecticides currently in use.

Spinosad has proven effective in controlling many chewing insect

pests in cotton, trees, fruits, vegetables, turf, and ornamentals. High

selectivity is also observed: 70–90 percent of beneficial insects and

predatory wasps are left unharmed. Spinosad features a novel molecular structure and mode of action that provide the excellent crop

protection associated with synthetic products coupled with the low

human and environmental risk found in biological products. The

selectivity and low toxicity of spinosad make it a promising tool for

integrated pest management.
104

1998 Winners

Academic Award

Professor Barry M. Trost

Stanford University

The Development of the Concept of Atom Economy

Innovation and Benefits

Professor Trost developed the concept of atom economy: chemical

reactions that do not waste atoms. Professor Trost's concept of atom

economy includes reducing the use of nonrenewable resources, minimizing the amount of waste, and reducing the number of steps used to

synthesize chemicals. Atom economy is one of the fundamental cornerstones of green chemistry. This concept is widely used by those who are

working to improve the efficiency of chemical reactions.

The general area of chemical synthesis covers virtually all segments of

the chemical industry—oil refining, bulk or commodity chemicals, and

fine chemicals, including agrochemicals, flavors, fragrances, pharmaceuticals, etc. Economics generally dictates the feasibility of processes

that are “practical”. A criterion that traditionally has not been explicitly

recognized relates to the total quantity of raw materials required for

the process compared to the quantity of product produced or, simply

put, “how much of what you put into your pot ends up in your product.” In considering the question of what constitutes synthetic efficiency, Professor Barry M. Trost has explicitly enunciated a new set of

criteria by which chemical processes should be evaluated. They fall

under two categories—selectivity and atom economy.

Selectivity and atom economy evolve from two basic considerations.

First, the vast majority of the synthetic organic chemicals in production

derive from nonrenewable resources. It is self-evident that such

resources should be used as sparingly as possible. Second, all waste

streams should be minimized. This requires employment of reactions

that produce minimal byproducts, either through the intrinsic stoichi-
1998 Academic Award 105

ometry of a reaction or as a result of minimizing competing undesirable reactions (i.e., making reactions more selective).

The issues of selectivity can be categorized under four headings—

chemoselectivity (differentiation among various functional groups in a

molecule), regioselectivity (locational), diastereoselectivity (relative

stereochemistry), and enantioselectivity (absolute stereochemistry).

The chemical community at large has readily accepted these considerations. In too many cases, however, efforts to achieve the goal of

selectivity led to reactions requiring multiple components in stoichiometric quantities that are not incorporated into the product, thus

creating significant amounts of waste. How much of the reactants end

up in the product (i.e., atom economy) traditionally has been ignored.

When Professor Trost’s first paper on atom economy appeared in the

literature, the idea generally was not adopted by either academia or

industry. Many in 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 application 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.
106 1998 Award

Academic Award

Dr. Karen M. Draths and Professor John W. Frost

Michigan State University

Use of Microbes as Environmentally Benign Synthetic Catalysts

Innovation and Benefits

Adipic acid, a building block for nylon, and catechol, a building block for

pharmaceuticals and pesticides, are two chemicals of major industrial

importance. Using environmentally benign, genetically engineered

microbes, Dr. Draths and Professor Frost synthesized adipic acid and

catechol from sugars. These two chemicals are traditionally made from

benzene, a petroleum product; they can now be made with less risk to

human health and the environment.

Fundamental change in chemical synthesis can be achieved by

elaboration of new, environmentally benign routes to existing chemicals. Alternatively, fundamental change can follow from characterization and environmentally benign synthesis of chemicals that can

replace those chemicals currently manufactured by environmentally

problematic routes. Examples of these design principles are illustrated

by the syntheses of adipic acid and catechol developed by Dr. Karen

M. Draths and Professor John W. Frost. The Draths-Frost syntheses of

adipic acid and catechol use biocatalysis and renewable feedstocks to

create alternative synthetic routes to chemicals of major industrial

importance. These syntheses rely on the use of genetically manipulated microbes as synthetic catalysts. Nontoxic glucose is employed as

a starting material, which, in turn, is derived from renewable carbohydrate feedstocks, such as starch, hemicellulose, and cellulose. In

addition, water is the primary reaction solvent, and the generation of

toxic intermediates and environment-damaging byproducts is avoided.

In excess of 4.2 billion pounds of adipic acid are produced annually

and used in the manufacture of nylon 6,6. Most commercial syntheses

of 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 manufacture of adipic acid em-
1998 Academic Award 107

ploys 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 cis,cis-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 Klebsiella pneumoniae, Acinetobacter calcoaceticus, and Escherichia coli. The cis,cis-muconic acid, which accumulates

extracellularly, is hydrogenated to afford adipic acid.

Yet another example of the Draths-Frost strategy for synthesizing

industrial chemicals using biocatalysis and renewable feedstocks is

their synthesis of catechol. Approximately 46 million pounds of catechol are 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-t-butylcatechol, veratrol).

Although some catechol is distilled from coal tar, petroleum-derived

benzene is the starting material for most catechol production. The

Draths-Frost synthesis of catechol uses a single, genetically engineered

microbe to catalyze the conversion of glucose into catechol, which

accumulates extracellularly. As mentioned previously, plant-derived

starch, hemicellulose, and cellulose can serve as the renewable

feedstocks from which the glucose starting material is derived.

In contrast to the traditional syntheses of adipic acid and catechol, the

Draths-Frost syntheses are based on renewable feedstocks, carbohydrate starting materials, and microbial biocatalysis. As the world moves

to national limits on carbon dioxide (CO2

) emissions, each molecule of

a chemical made from a carbohydrate may well be counted as a credit

due to the CO2

 that is fixed by plants to form the carbohydrate.

Biocatalysis using intact microbes also allows the Draths-Frost syntheses to use water as a reaction solvent, near-ambient pressures, and

temperatures that typically do not exceed human body temperature.
108 1998 Award

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

Innovation and Benefits

PYROCOOL Technologies developed PYROCOOL F.E.F., a fire extinguishing

foam that is nontoxic and highly biodegradable. PYROCOOL F.E.F. replaces

ozone-depleting gases and aqueous foams that release toxic and persistent chemicals to the environment during use. PYROCOOL F.E.F. is

effective at approximately one-tenth the concentration of conventional

fire extinguishing chemicals.

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 10–16 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
1998 Small Business Award 109

to microbial degradation, often leading to contamination of groundwater supplies and failure of wastewater treatment systems.

In 1993, PYROCOOL Technologies initiated a project to create a fire

extinguishment and cooling agent that would be effective in extinguishing fires and that would greatly reduce the potential long-term

environmental and health problems associated with traditional products. To achieve this objective, PYROCOOL Technologies first determined that the product (when finally developed) would contain no

glycol ethers or fluorosurfactants. In addition, it decided that the

ultimate formulation must be an effective fire extinguishment and

cooling agent at very low mixing ratios. PYROCOOL F.E.F. is a formulation of highly biodegradable nonionic surfactants, anionic surfactants,

and amphoteric surfactants with a mixing ratio (with water) of

0.4 percent. In initial fire tests at the world’s largest fire-testing facility

in 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 160 million pounds 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 traditional fire extinguishment agents.

Because PYROCOOL F.E.F. is mixed with water at only 0.4 percent, an

87–93 percent reduction in product use 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.
110 1998 Award

Greener 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

Innovation and Benefits

Flexsys developed a new method to eliminate waste from a critically important reaction used to manufacture a wide range of chemical products. They

are using this method to manufacture 4-ADPA, a key, high-volume building

block for a rubber preservative. Converting just 30 percent of the world's

production capacity of this key building block to the Flexsys process would

reduce chemical waste by 74 million pounds per year and wastewater by

1.4 billion pounds per year.

The 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 chlorinated aromatics, has funded

research over the years to explore alternative synthetic reactions for

manufacturing processes that do not require the use of chlorine. It was

clear that replacing chlorine in a process would require the discovery of

new atom-efficient chemical 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
1998 Greener Synthetic Pathways Award 111

300 million pounds per year, of which Flexsys is the world’s largest

producer. (Flexsys is a joint venture of the rubber chemicals operations

of Monsanto and Akzo Nobel.)

Flexsys’s current process to 4-ADPA is based on the chlorination of

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 are highly

unfavorable. A significant portion of the waste is in the form of an

aqueous stream that contains high levels of inorganic salts contaminated with organics that are difficult and expensive to treat. Furthermore, the process also requires the storage and handling of large

quantities of chlorine gas. Flexsys found a solution to this problem in a

class of reactions known as nucleophilic 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 pounds less chemical waste

would be generated per year and 1.4 billion pounds less wastewater

would be generated per year. 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 throughout the scientific

community as a breakthrough in the area of nucleophilic aromatic

substitution chemistry.

This new process for the production of 4-ADPA has achieved the goal for

which all green chemistry endeavors strive: the elimination of waste at

the source via the discovery of new chemical reactions that can be implemented into innovative and environmentally safe chemical processes.
112 1998 Award

Greener Reaction Conditions Award

Argonne National Laboratory

Novel Membrane-Based Process for Producing Lactate Esters—

Nontoxic Replacements for Halogenated and Toxic Solvents

Innovation and Benefits

Argonne developed a novel process to synthesize organic solvents from

sugars. These solvents can replace a wide variety of more hazardous solvents, such as methylene chloride. Argonne's process requires little

energy, is highly efficient, eliminates large volumes of salt waste, and

reduces pollution and emissions. These solvents can potentially replace

7.6 billion pounds of toxic solvents used annually by industry, commerce,

and households.

Argonne National Laboratory (ANL) 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 retaining the alcohol,

acid, and ester. The ammonia is recovered and reused in the fermentation to make ammonium lactate, eliminating the formation of waste

salt. The innovation overcomes major technical hurdles that had made

current production processes for lactate esters technically and economically noncompetitive. The innovation will enable the replacement

of toxic solvents widely used by industry and consumers, expand the

use of renewable carbohydrate feedstocks, and reduce pollution and

emissions.

Ethyl lactate has a good temperature performance range (boiling

point: 309 °F, melting point: 104 °F), is compatible with both aqueous
1998 Greener Reaction Conditions Award 113

and organic systems, is easily biodegradable, and has been approved

for food by the U.S. Food and Drug Administration (FDA). Lactate

esters (primarily ethyl lactate) can replace most halogenated solvents

(including ozone-depleting chlorofluorocarbons (CFCs), carcinogenic

methylene chloride, toxic ethylene glycol ethers, perchloroethylene,

and chloroform) on a 1:1 basis. At 1998 prices ($1.60–2.00 per pound),

the market for ethyl lactate is about 20 million pounds per year for a

wide variety of specialty applications. The novel and efficient ANL

membrane process will reduce the selling price of ethyl lactate to

$0.85–1.00 per pound and enable ethyl lactate to compete directly with

the petroleum-derived toxic solvents currently in use. The favorable

economics of the ANL membrane process, therefore, can lead to the

widespread substitution of petroleum-derived toxic solvents by ethyl

lactate in electronics manufacturing, paints and coatings, textiles,

cleaners and degreasers, adhesives, printing, de-inking, and many

other industrial, commercial, and household applications. More than

80 percent of the applications requiring the use of more than

7.6 billion pounds of solvents in the United States each year are

suitable for reformulation with environmentally friendly lactate esters.

The ANL process has been patented for producing esters from all

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-pound-per-year

demonstration plant is being planned for early 1999, followed by a

100-million-pound-per-year, full-scale plant.
114 1998 Award

Designing Greener Chemicals Award

Rohm and Haas Company

Invention and Commercialization of a New Chemical Family of

Insecticides Exemplified by CONFIRMTM Selective Caterpillar Control

Agent and the Related Selective Insect Control Agents MACH 2TM and

INTREPIDTM

Innovation and Benefits

Rohm and Haas developed CONFIRMTM, a novel insecticide for controlling caterpillar pests in turf and a variety of crops. CONFIRMTM is less toxic

than other insecticides to a wide range of nontarget organisms, poses

no significant hazard to farm workers or the food chain, and does not

present a significant spill hazard. U.S. EPA has classified CONFIRMTM as a

reduced-risk pesticide.

The value of crops destroyed worldwide by insects exceeds tens of

billions of dollars. Over the past fifty years, only a handful of classes

of insecticides have been discovered to combat this destruction.

Rohm and Haas Company has discovered a new class of chemistry,

the diacylhydrazines, that offers farmers, consumers, and society a

safer, effective technology for insect control in turf and a variety of

agronomic crops. One member of this family, CONFIRMTM, is a

breakthrough in caterpillar control. It is chemically, biologically, and

mechanistically novel. It effectively and selectively controls important

caterpillar pests in agriculture without posing significant risk to the

applicator, the 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.

CONFIRMTM 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, CONFIRMTM powerfully
1998 Designing Greener Chemicals Award 115

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, CONFIRMTM is inherently safer than

other insecticides to a wide range of nontarget organisms such as

mammals, birds, earthworms, plants, and various aquatic organisms.

CONFIRMTM is also remarkably safe to a wide range of key beneficial,

predatory, and parasitic insects such as honeybees, lady beetles,

parasitic wasps, predatory bugs, beetles, flies, and lacewings, as well

as other predatory arthropods such as spiders and predatory mites.

Because of this unusual level of safety, the use of these products will

not create an outbreak of target or secondary pests due to destruction

of key natural predators or parasites in the local ecosystem. This

should reduce the need for repeat applications of additional insecticides and reduce the overall chemical load on both the target crop

and the local environment.

CONFIRMTM has low toxicity to mammals by ingestion, inhalation, and

topical application and has been shown to be completely non-oncogenic, nonmutagenic, and without adverse reproductive effects.

Because of its high apparent safety and relatively low use rates,

CONFIRMTM poses no significant hazard to the applicator or the food

chain and does not present a significant spill hazard. CONFIRMTM 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 CONFIRMTM among the safest,

most selective, and most useful insect control agents ever discovered.
116

1997 Winners

Academic Award

Professor Joseph M. DeSimone

University of North Carolina at Chapel Hill (UNC)

and North Carolina State University (NCSU)

Design and Application of Surfactants for Carbon Dioxide

Innovation and Benefits

Professor DeSimone developed new detergents that allow carbon dioxide

(CO2

), a nontoxic gas, to be used as a solvent in many industrial applications. Using CO2

 as a solvent allows manufacturers to replace traditional,

often hazardous chemical solvents and processes, conserve energy, and

reduce worker exposure to hazardous substances.

It has been a dilemma of modern industrial technology that the

solvents required to dissolve the environment’s worst contaminants

themselves have a contaminating effect. Now, new technologies for

the design and application of surfactants for carbon dioxide (CO2

),

developed at UNC, promise to resolve this dilemma.

Over 30 billion pounds of organic and halogenated solvents are used

worldwide each year as solvents, processing aids, cleaning agents,

and dispersants. Solvent-intensive industries are considering alternatives that can reduce or eliminate the negative impact that solvent

emissions can have in the workplace and in the environment. CO2

 in a

solution state has long been recognized as an ideal solvent, extractant, and separation aid. CO2

 solutions are nontoxic, nonflammable,

energy-efficient, cost-effective, waste-minimizing, reusable, and safe

to work with. Historically, the prime factor inhibiting the use of this

solvent replacement has been the low solubility of most materials in

CO2

, in both its liquid and supercritical states. With the discovery of CO2

surfactant systems, Professor Joseph M. DeSimone and his students

have dramatically advanced the solubility performance characteristics of

CO2

 systems for several industries.
1997 Academic Award 117

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< 212 °F and P< 4,350 psi). As an offshoot

of Professor DeSimone’s research program on polymer synthesis in

CO2

, he and his researchers exploited the high solubility of a select

few CO2

-philic polymeric segments to develop nonionic surfactants

capable of dispersing high-solids polymer latexes in both liquid and

supercritical CO2

 phases. The design criteria they developed for

surfactants, which were capable of stabilizing heterogeneous polymerizations in CO2

, have been expanded to include CO2-insoluble compounds in general.

This development lays the foundation by which surfactant-modified

CO2

 can be used to replace conventional (halogenated) organic

solvent 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.
118 1997 Award

Small Business Award

Legacy Systems, Inc.

ColdstripTM, A Revolutionary Organic Removal and Wet Cleaning

Technology

Innovation and Benefits

During manufacture, silicon-based semiconductors and flat-panel displays

require cleaning to remove manufacturing residues, usually with corrosive

acid solutions. Legacy Systems developed the ColdstripTM process, which

uses only water and oxygen to clean silicon semiconductors. ColdstripTM

has the potential to cut the use of corrosive solutions by hundreds of

thousands of gallons and also save millions of gallons of water each year.

For over 30 years, the removal of photoresists with Piranha solutions

(sulfuric acid, hydrogen peroxide, or ashers) has been the standard in

the semiconductor, flat panel display, and micromachining industries.

Use of Piranha solutions has been associated with atmospheric,

ground, and water pollution. Legacy Systems, Inc. (LSI) has developed

a revolutionary wet processing technology, ColdstripTM, which removes

photoresist and organic contaminants for the semiconductor, flat panel

display, and micromachining industries.

LSI’s ColdstripTM process is a chilled-ozone process that uses only

oxygen and water as raw materials. The active product is ozone, which

safely decomposes to oxygen in the presence of photoresist. Carbon

dioxide, carbon monoxide, oxygen, and water are formed. There are

no high 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.
1997 Small Business Award 119

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.

In 1995, the U.S. Patent Office granted LSI Patent 5,464,480 covering

this technology. The system has the lowest environmental impact of

any wet-resist-strip process, eliminating the need for thousands of

gallons of Piranha chemicals and millions of gallons of water a year.
120 1997 Award

Greener Synthetic Pathways Award

BHC Company (now BASF Corporation)

BHC Company Ibuprofen Process

Innovation and Benefits

BHC Company developed an efficient method to make ibuprofen, a

commonly used painkiller, using only three steps instead of six. BHC

recovers and recycles the waste byproduct from the manufacturing

process and has virtually eliminated large volumes of aqueous salt wastes.

BASF Corporation, one of the BHC partners, uses this process in one of the

largest ibuprofen production plants in the world.

BHC Company has developed a new synthetic process to manufacture ibuprofen, a well-known nonsteroidal anti-inflammatory painkiller

marketed under brand names such as AdvilTM and MotrinTM. Commercialized since 1992 in BHC’s 7.7-million-pound-per-year facility in

Bishop, TX, the new process has been cited as an industry model of

environmental excellence in chemical processing technology. For its

innovation, BHC was the recipient of the Kirkpatrick Achievement

Award for “outstanding advances in chemical engineering technology”

in 1993.

The new technology involves only three catalytic steps with 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 hierarchy.

Virtually all starting materials are either converted to product or reclaimed byproduct or are completely recovered and recycled in the

process. The generation of waste is practically eliminated.
1997 Greener Synthetic Pathways Award 121

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 associated with the traditional stoichiometric

use of auxiliary chemicals for chemical conversions). Large volumes of

aqueous wastes (salts) normally associated with such manufacturing

are virtually eliminated. The anhydrous hydrogen fluoride catalyst/

solvent is recovered and recycled with greater than 99.9 percent

efficiency. No other solvent is needed in the process, simplifying

product recovery and minimizing fugitive emissions. The nearly complete atom utilization of this streamlined process truly makes it a

waste-minimizing, environmentally friendly technology.
122 1997 Award

Greener Reaction Conditions Award

Imation

DryViewTM Imaging Systems

Innovation and Benefits

Imation's DryViewTM Imaging Systems use a new type of photographic film

for medical imaging that uses heat instead of hazardous developer

chemicals. During 1996, Imation delivered more than 1,500 DryViewTM

Imaging Systems worldwide. These units alone eliminate the annual

disposal of over half a million gallons of developer chemicals and

54.5 million gallons of contaminated water and reduce workers' exposure

to chemicals.

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 DryViewTM Imaging Systems

use no wet chemistry, create no effluent, and require no additional

postprocess steps such as drying.

In contrast, silver halide photographic films are processed by being

bathed in a chemical developer, soaked in a fix solution, washed with

clean water, and finally dried. The developer and fix solutions contain

toxic chemicals such as hydroquinone, silver, and acetic acid. In the

wash cycle, these chemicals, along with silver compounds, are flushed

from the film and become part of the waste stream. The resulting

effluent amounts to billions of gallons of liquid waste each year.

Significant developments in photothermographic image quality have

been achieved that allow it to compete successfully with silver halide

technology. During 1996, Imation placed more than 1,500 DryViewTM
1997 Greener Reaction Conditions Award 123

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.

DryViewTM 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. DryViewTM is valued by these industries because it supports

pollution prevention through source reduction.
124 1997 Award

Designing Greener Chemicals Award

Albright & Wilson Americas (now Rhodia)

THPS Biocides: A New Class of Antimicrobial Chemistry

Innovation and Benefits

Albright & Wilson discovered the antimicrobial properties of THPS and

developed it into a safer biocide that can be used to control the growth of

bacteria and algae in industrial water systems. THPS, or tetrakis(hydroxymethyl)phosphonium sulfate, offers many advantages over other,

traditional biocides because, for example, it is significantly less toxic to

nontarget organisms, is effective at much lower concentrations, and is

more biodegradable than other biocides.

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 discovered by

Albright & Wilson Americas. THPS biocides represent a completely new

class of antimicrobial chemistry that combines superior antimicrobial

activity with a relatively benign toxicology profile. THPS’s benefits

include low toxicity, low recommended treatment level, rapid breakdown in the environment, and no 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 treatment 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 substantially broken down before the treated

water enters the environment. The degradation products have been

shown to possess a relatively benign toxicology profile. Furthermore,
1997 Designing Greener Chemicals Award 125

THPS does not bioaccumulate and, therefore, offers a much-reduced

risk to higher life forms.

THPS biocides are aqueous solutions and do not contain volatile

organic compounds (VOCs). Because THPS is halogen-free, it does not

contribute to the formation of dioxin or absorbable organic halides

(AOX). Because of its low overall toxicity and easier handling compared

to alternative products, THPS provides an opportunity to reduce the risk

of health and safety incidents.

THPS has been applied to a range of industrial water systems for the

successful control of microorganisms. The U.S. industrial water treatment market for nonoxidizing biocides alone is 42 million pounds

per year and growing at 6–8 percent annually. There are over

500,000 individual user sites in this industry category. Because of its

excellent environmental profile, THPS has already been approved for

use in environmentally sensitive areas around the world and is being

used as a replacement for higher risk alternatives.
126

1996 Winners

Academic Award

Professor Mark Holtzapple

Texas A&M University

Conversion of Waste Biomass to Animal Feed, Chemicals, and Fuels

Innovation and Benefits

Professor Holtzapple developed a family of technologies that convert

waste biomass, such as sewage sludge and agricultural wastes, into animal

feed products, industrial chemicals, or fuels, depending on the technology used. Because these technologies convert waste biomass into useful

products, other types of basic resources, such as petroleum, can be

conserved. Also, the technologies can reduce the amount of biomass

waste going to landfills or incinerators.

A family of technologies has been developed by Professor Mark

Holzapple 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, and

bagasse) may be used as ruminant animal feeds. Alternatively, the

lime-treated biomass can be fed into a large anaerobic fermentor in

which rumen microorganisms convert the biomass into volatile fatty

acid (VFA) salts, such as calcium acetate, propionate, and butyrate. The

VFA salts are concentrated and may be converted into chemicals or

fuels via three routes. In one route, the VFA salts are acidified, releasing acetic, propionic, and butyric acids. In a second route, the VFA salts

are thermally converted to ketones, such as acetone, methyl ethyl

ketone, and diethyl ketone. In a third route, the ketones are hydrogenated to their corresponding alcohols such as isopropanol, isobutanol, and isopentanol.

The technologies above offer many benefits for human health and the

environment. Lime-treated animal feed can replace feed corn, which is
1996 Academic Award 127

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.

Fuels (e.g., alcohols) produced from waste biomass have the benefits

cited above (i.e., reduced environmental impact from waste disposal

and reduced trade deficit). In addition, oxygenated fuels derived from

biomass are cleaner-burning and do not add net carbon dioxide to the

environment, thereby reducing factors that contribute to global warming.
128 1996 Award

Small Business Award

Donlar Corporation (now NanoChem Solutions, Inc.)

Production and Use of Thermal Polyaspartic Acid

Innovation and Benefits

Donlar developed TPA, a nontoxic, environmentally safe, biodegradable

polymer for use in agriculture, water treatment, and other industries.

Donlar manufactures TPA using a highly efficient process that eliminates

use of organic solvents, cuts waste, and uses less energy. TPA has been

used successfully in a variety of applications, such as improving fertilizer

uptake in plants, and improving the efficiency of oil and gas production.

Millions of pounds of anionic polymers are used each year in many

industrial applications. Polyacrylic acid (PAC) is one important class of

such polymers, but the disposal of PAC is problematic because it is not

biodegradable. An economically viable, effective, and biodegradable

alternative to PAC is thermal polyaspartate (TPA).

Donlar Corporation invented two highly efficient processes to 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 wastefree.

The second TPA production process involves using a catalyst during the

polymerization, which allows a lower heating temperature to be used.

The resulting product has improvements in performance characteristics, lower color, and biodegradability. The catalyst can be recovered

from the process, thus minimizing waste.
1996 Small Business Award 129

Independent toxicity studies of commercially produced TPA have been

conducted using mammalian and environmental models. Results

indicate that TPA is nontoxic and environmentally safe. TPA 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 biodegradable

when tested under these same conditions.

Many end-uses of TPA have been discovered, such as in agriculture to

improve fertilizer or nutrient management. TPA increases the efficiency

of plant nutrient uptake, thereby increasing crop yields while protecting the ecology of agricultural lands. TPA can also be used for water

treatment, as well as in the detergent, oil, and gas industries.
130 1996 Award

Greener Synthetic Pathways Award

Monsanto Company

Catalytic Dehydrogenation of Diethanolamine

Innovation and Benefits

DSIDA is a key building block for the herbicide RoundUp®. Monsanto's

novel synthesis of DSIDA eliminates most of the manufacturing hazards

associated with the previous synthesis; it uses no ammonia, cyanide, or

formaldehyde. This synthesis is safer to operate, has a higher overall yield,

and has fewer process steps.

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 possibility of a runaway reaction. The overall process also generates up to

1 pound of waste for every 7 pounds of product, and this waste must

be treated prior to safe disposal.

Monsanto has developed and implemented an alternative DSIDA

process that relies on the copper-catalyzed dehydrogenation of

diethanolamine. The raw materials have low volatility and are less toxic.

Process operation is inherently safer, because the dehydrogenation

reaction is 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
1996 Greener Synthetic Pathways Award 131

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 amino-alcohols to amino acid salts

has been known since 1945. Commercial application, however, was

not known until Monsanto developed a series of proprietary catalysts

that made the chemistry commercially feasible. Monsanto’s patented

improvements on metallic copper catalysts afford an active, easily

recoverable, highly selective, and physically durable catalyst that has

proven itself in large-scale use.

This catalysis technology also can be used in the production of other

amino acids, such as glycine. Moreover, it is a general method for

conversion of primary alcohols to carboxylic acid salts; it is potentially

applicable to the preparation of many other agricultural, commodity,

specialty, and pharmaceutical chemicals.
132 1996 Award

Greener Reaction Conditions Award

The Dow Chemical Company

100 Percent Carbon Dioxide as a Blowing Agent for the Polystyrene

Foam Sheet Packaging Market

Innovation and Benefits

Dow developed a process for manufacturing polystyrene foam sheets that

uses carbon dioxide (CO2) as a blowing agent, eliminating 3.5 million

pounds per year of traditional blowing agents. Traditional blowing agents

deplete the ozone layer or contribute to ground-level smog. In addition,

Dow will obtain CO2 only from existing commercial and natural sources

that generate it as a byproduct, so this process will not contribute to

global CO2 levels.

In recent years the chlorofluorocarbon (CFC) blowing agents used to

manufacture 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 applications for polystyrene foam include

thermoformed meat, poultry, and produce trays; fast food containers;

egg cartons; and serviceware.

The use of 100 percent CO2

 offers optimal environmental performance

because CO2

 does not deplete the ozone layer, does not contribute to

ground-level smog, and will not contribute to global warming because

CO2

 will be used from existing byproduct commercial and natural

sources. The use of CO2

 byproduct from existing commercial and

natural sources, such as ammonia plants and natural gas wells, will

ensure that no net increase in global CO2

 results from the use of this
1996 Greener Reaction Conditions Award 133

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 Dow 100 percent CO2

 technology eliminates the use of

3.5 million pounds per year of hard CFC-12 and soft HCFC-22. This

technology has been scaled from pilot-line to full-scale commercial

facilities. Dow has made the technology available through a commercial license covering both patented and know-how technology. The

U.S. Patent Office granted Dow two patents for this technology

(5,250,577 and 5,266,605).
134 1996 Award

Designing Greener Chemicals Award

Rohm and Haas Company

Designing an Environmentally Safe Marine Antifoulant

Innovation and Benefits

Rohm and Haas developed Sea-NineTM, a novel antifoulant to control the

growth of plants and animals on the hulls of ships. In 1995, fouling cost the

shipping industry approximately $3 billion a year in increased fuel consumption. Sea-NineTM replaces environmentally persistent and toxic tincontaining antifoulants.

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-isothiazolone 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-NineTM antifoulant) was chosen as the candidate for commercial development.
1996 Designing Greener Chemicals Award 135

Extensive environmental testing compared Sea-NineTM antifoulant to

TBTO, the current industry standard. Sea-NineTM antifoulant degraded

extremely rapidly with a half-life of one day in seawater and one hour

in sediment. Tin had bioaccumulation factors as high as 10,000-fold,

whereas Sea-NineTM antifoulant’s bioaccumulation was essentially

zero. Both TBTO and Sea-NineTM were acutely toxic to marine organisms, but TBTO had widespread chronic toxicity, whereas Sea-NineTM

antifoulant showed no chronic toxicity. Thus, the maximum allowable

environmental concentration (MAEC) for Sea-NineTM antifoulant was

0.63 parts per billion (ppb) whereas the MAEC for TBTO was 0.002 ppb.

Hundreds of ships have been painted with coatings containing SeaNineTM worldwide. Rohm and Haas Company obtained U.S. EPA

registration for the use of Sea-NineTM antifoulant, the first new

antifoulant registration in over a decade.
136

Program Information

Additional information on the Presidential Green Chemistry Challenge

program is available from:

• The Green Chemistry Program Web site at

http://www.epa.gov/greenchemistry

• The Industrial Chemistry Branch of EPA by e-mail at

greenchemistry@epa.gov or by telephone at 202-564-8740 and

• EPA’s Pollution Prevention Information Clearinghouse by e-mail at

ppic@epa.gov or by telephone at 202-566-0799.

Disclaimer

Note: The summaries provided in this document were obtained from

the entries received for the 1996–2008 Presidential Green Chemistry

Challenge Awards. They were edited for space, stylistic consistency,

and clarity, but they were neither written nor officially endorsed by the

U.S. 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.