United States
v>EPA    Presidential
          Green Chemistry Challenge
          Awards Program:
          Summary of 2012 Award
          Entries and Recipients
         A U.S. EPA Program
        An electronic version of this document is available at:
            http: //www. epa.gov/greenchemistry



Introduction [[[ 1

Awards [[[ 3

      Academic Awards............................................ 3

      Small Business Award.	 5

      Greener Synthetic Pathways Award	6

       Greener Reaction Conditions Award	7

      Designing Greener Chemicals Award	8

Entries from Academia ............................................ 9

Entries from Small Businesses ...................................... 15


     Each year chemists, engineers, and other scientists from across  the United States nominate
  their technologies for a Presidential Green Chemistry Challenge Award. This prestigious award
  highlights and honors innovative green chemistry technologies, including cleaner processes; safer
  raw materials; and safer, better products. These awards recognize and promote the environmental
  and economic benefits of developing and using novel green chemistry.
     The  U.S.  Environmental  Protection Agency  (EPA)  celebrates  this  year's  innovative,
  award-winning technologies selected from among  scores of high-quality nominations. Each
  nomination must represent one or more recently developed chemistry technologies that prevent
  pollution through source reduction. Nominated technologies are also meant to succeed in the
  marketplace: each is expected to illustrate the technical feasibility, marketability, and profitability
  of green chemistry.
     Throughout the 17 years of the awards program, EPA has received  1,492 nominations and
  presented awards to 88 winners. By recognizing groundbreaking scientific solutions to real-world
  environmental problems, the Presidential  Green Chemistry Challenge has significantly reduced
  the hazards associated with designing, manufacturing, and using chemicals.
     Each year our 88 winning technologies are together responsible for:
     •     Reducing the use or generation of 825 million pounds of hazardous chemicals
     •     Saving 21 billion gallons of water
     •     Eliminating 7-9  billion pounds of carbon dioxide releases to air
     And adding the benefits from the nominated technologies would greatly increase the program's
  total benefits.
     This booklet summarizes entries submitted for the 2012 awards that fell within the scope of
  the program. An independent panel of technical experts  convened by the American Chemical
  Society Green Chemistry Institute'*' judged the entries for the 2012 awards. Judging criteria
  included health  and environmental benefits, scientific innovation, and industrial applicability.
  Six of the nominated technologies were selected as winners and were nationally recognized on
  June 18, 2012, at an awards ceremony in Washington, D.C.
     Further information about  the Presidential Green Chemistry Challenge Awards and  EPA's
  Green Chemistry Program is available at www.epa.gov/greenchemistry.
 Note: The summaries provided in this document were obtained from the entries received for the 2012 Presidential Green Chemistry
 Challenge Awards. EPA edited the descriptions for space, stylistic consistency, and clarity, but they were not written or officially-
 endorsed by the Agency. The summaries are intended only to highlight a fraction of the information contained in the nominations.
 These summaries were not used in the judging process; judging was based on all information contained in the entries received.
 Claims made in these summaries have not been verified by EPA.



Synthesizing Biodegradable Polymers from
Carbon Dioxide        Carbon Monoxide
Cornell University
  Innovation and Benefits
  Carbon monoxide and carbon dioxide derived from biomass or other carbon sources are ideal
  feedstocks for chemicals, but there had been no efficient way to make them into valuable
  polymers. Professor Coates developed a family of catalysts that convert carbon dioxide and
  carbon monoxide into polymers. Novomer, Inc. is using his discoveries to develop a range of
  innovative, high-performance products, including can and coil coatings, adhesives,  foams,
  and plastics.
   Plastics improve  our lives  in countless  ways,  but  they  also pose a serious threat to our
environment. Virtually all plastics are  derived from  scarce fossil fuels  that pose their  own
danger, including oil well leaks and global warming induced by carbon dioxide (CO?). Of the
150 million tons of plastics made each year worldwide,  only a small fraction is recycled. The rest
end up in landfills or worse as litter.
   CO2 and carbon monoxide (CO)  are ideal feedstocks for polymer synthesis. They can be
derived from many low-cost sources including biorenewable agricultural waste, abundant coal, or
even from industrial waste gas. The challenge with using them, however, lies in converting them
into useful products efficiently. Professor Geoffrey Coates has developed innovative processes to
synthesize plastics from inexpensive, biorenewable substances including carbon dioxide, carbon
monoxide, plant oils, and lactic acid.
   Professor Coates has developed a new family of catalysts over the last decade that can effectively
and economically turn CC>2 and CO into valuable polymers. These catalysts have high turnover
frequencies, turnover numbers, and sclcctivitics. As a result, only a small amount of catalyst is
required leading to cost-effective commercial production for the first time. These catalysts can
also be used in highly efficient continuous flow processes.
   Professor Coates has invented active and selective catalysts to copolymerize CO2 and epoxides
into high-performance polycarbonates. Professor Coates also invented a  class of catalysts that
can insert one or two molecules of CO into an cpoxidc ring to produce (3-lactones and succinic
anhydrides. Both of these products  have  many uses in synthesizing pharmaceuticals, fine
chemicals, and plastics. Polymers made from CO2 and CO contain ester and carbonate linkages.
These polymers exhibit unique performance in current commodity plastic applications and in
some cases are ultimately biodegradable.
   Professor Coates's work forms the scientific foundation of Novomer Inc., a start-up company
backed by venture capital. In 2010, Novomer and DSM  announced an agreement to develop
coatings using the new polycarbonates  made with Coates's catalysts. Prototype high-performance
industrial coil coatings are moving from development toward commercialization. There is potential
to develop a coating system to  replace the bisphenol A (BPA) epoxy coatings that line most food
and drink cans worldwide. This discovery is important, as BPA is a suspected endocrine disrupter
that can migrate out of coatings over time. The novel polymer is currently sold to companies that
manufacture electronics  because the thermally degradable nature of the  polymer allows  more
efficient production of electronic components. The new polycarbonate coating is expected to
require 50 percent less petroleum to produce and will sequester up to 50 weight percent COi-
Lifecycle analysis shows that at full market penetration, Novomer's materials have the potential to
sequester and avoid approximately  180 million metric tons of annual CO2 emissions.


Dr. James L.
Organic Catalysis: A  Broadly Useful Strategy for Green
Polymer Chemistry
  Innovation and Benefits

  Traditional metal catalysts required  to synthesize polyesters and other common plastics
  end up trapped in the plastic, raising human health and environmental concerns. Professor
  Waymouth and Dr. Hedrick  discovered an array of alternatives—metal-free  catalysts—
  that are highly active and able to make a wide variety of plastics. Their  discoveries include
  catalysts that can depolymerize plastic and enable cradle-to-cradle recycling.
                                   Catalysis is a foundation for sustainable chemical processes, and the discovery of highly active,
                                environmentally benign, catalytic processes is a central goal of green chemistry. Conventional
                                routes to polyesters rely on metal catalysts such as those derived from tin complexes, even though
                                the residual  metal catalysts used for high-volumes plastics can  have negative environmental
                                impacts in solid waste. For this reason, the European Union recently phased out many organotin
                                compounds. As a result, research on organic catalysts to replace the tin-based workhorse catalysts
                                has gained significant prominence in industrial settings related to important commodity polymers
                                such as siloxanes, urethanes, nylons, and polyesters.
                                   Dr. James L.  Hedrick and Professor  Robert M. Waymouth have developed a broad  class
                                of highly active, environmentally benign organic catalysts for synthesizing  biodegradable and
                                biocompatible plastics. Their technology applies  metal-tree organic catalysts to the synthesis
                                and  recycling of polyesters. They discovered new organic  catalysts for polyester synthesis
                                whose activity and selectivity rival or exceed those of metal-based alternatives. Their approach
                                provides an environmentally attractive, atom-economical, low-energy alternative to traditional
                                metal-catalyzed  processes.   Their  technology   includes  organocatalytic  approaches   to
                                ring-opening,  anionic,   zwitterionic,  group  transfer,  and condensation  polymerization
                                techniques. Monomer feedstocks include  those from renewable resources, such as lactides, as well
                                as  petrochemical feedstocks. In addition to polyesters, Dr.  Hedrick and Professor Waymouth
                                have discovered organocatalytic  strategies (1)  to synthesize polycarbonates,  polysiloxanes, and
                                polyacrylates, (2) to chemically recycle polyesters, (3) to use metal-free polymers as templates
                                for inorganic nanostructures for microelectronic applications, and (4) to develop new syntheses
                                for high-molecular-weight cyclic polyesters. This  team has shown  that the  novel mechanisms
                                ot  enchainment  brought about by organic catalysts can create polymer architectures that are
                                difficult to synthesize by conventional approaches.
                                   The team also developed  organic catalysts to depolymerize poly(ethylene terephthalate)(PET)
                                quantitatively, allowing recycling for PET from bottles into new bottles as a way to mitigate the
                                millions of pounds of PET that plague our landfills. Dr.  Hedrick  and Professor Waymouth also
                                demonstrated that their organic catalysts tolerate a wide variety ot functional  groups, enabling
                                the synthesis of well-defined biocompatible polymers for biomedical applications. Because these
                                catalysts do not remain bound to the polymer chains, they are effective at low concentrations.
                                These results, coupled with cytotoxicity measurements in  biomedical applications, highlight
                                the environmental and human health benefits of this approach. Professor Waymouth and Dr.
                                Hedrick have produced over 80 manuscripts and eight patents on  the design  of organic catalysts
                                for polymer chemistry with applications in sustainable plastics, biomedical materials, and plastics
                                for recycling.


 Using Metathesis Catalysis to Produce High-Performing,
 Green Specialty Chemicals at Advantageous Costs
  Innovation and Benefits

  Elevance employs Nobel-prize-winning catalyst technology to break down natural oils and
  recombine  the fragments into  novel, high-performance green chemicals. These chemicals
  combine the benefits of both petrochemicals and  biobased  chemicals. The  technology
  consumes significantly less energy and reduces greenhouse gas  emissions by  50 percent
  compared to petrochemical technologies. Elevance is producing specialty chemicals for many
  uses, such as highly concentrated cold-water detergents that  provide better cleaning with
  reduced energy costs.
   Elevance produces high-performance, cost-advantaged green chemicals from renewable oils. Its
processes use Nobel Prize-winning innovations in metathesis catalysis, consume significantly less
energy, and reduce greenhouse gas (GHG) emissions by 50 percent compared to petrochemical
technologies. The processes use a highly efficient, selective catalyst to break down natural oils and
recombine fragments. The core technology is based on the work of Nobel Laureate Dr. Robert H.
Grubbs. In 2011, Elevance expanded its proprietary technology with a licensing agreement with
XiMo AG to use proprietary molybdenum and tungsten metathesis catalysts based on the work of
Nobel Laureate Dr. Richard Schrock.
   The resulting products  are high-value, difunctional  chemicals  with  superior  functional
attributes previously unavailable commercially. These molecules combine the functional attributes
of an olefin, typical of petrochemicals, and a monofunctional ester or acid, typical of biobased
oleochemicals, into a single molecule. Conventional producers have to blend petrochemicals and
biobased oleochemicals in attempts to  achieve these functional attributes simultaneously, which
when possible, increase their production costs. Elevance's difunctional building blocks  change
this paradigm by creating specialty chemical molecules which  simultaneously include  desired
attributes enabled by both chemical families, such as lubricant  oils with improved stability or
surfactants with improved solvency.
   Elevance's  low-pressure, low-temperature processes  use a diversity of renewable feedstocks
that yield products and byproducts with low toxicity. Elevance's  processes result in lower source
pollution, production costs, and capital expenditures than petrochemical refineries. Currently,
Elevance is the only company that can produce these difunctional chemicals. The  company's
ability to manufacture biochemicals for multiple products reduces reliance on petrochemicals and
provides more effective, sustainable products to consumers.
   The company makes difunctional molecules as part of its specialty chemical business. Elevance's
products enable novel surfactants, lubricants, additives, polymers, and engineered thermoplastics.
For instance, Elevance is producing specialty chemicals to enable cold water detergents that
have more  concentrated formulations  and improved  solvency for  better cleaning,  to improve
sustainability metrics, and to reduce energy costs for customers and consumers. Other examples
include biobased anti-frizz and shine additives for leave-in hair care products to replace petroleum-
based petrolatum, alternatives to paraffin for high performance waxes, novel plastic additives for
poly(vinyl chloride) (PVC) and unique  monomers for biobased polymers and engineered plastics.
   Elevance has completed validation in toll manufacturing. It  is building  world-scale facilities
in Grcsik,  Indonesia, and Natchez, Mississippi,  with combined annual production capacity
over  1 billion pounds and exploring sites in South America. Elevance has also secured strategic
partnerships with value chain global leaders to accelerate rapid deployment and commercialization
for these products.


Professor Yi Tang,
Uniwersity of
An Efficient Biocatalytic Process  to Manufacture Simvastatin
  Innovation and Benefits
  Simvastatin, a leading drug tor treating high cholesterol, is manufactured from a natural
  product. The  traditional  multistep  synthesis was wasteful  and used  large amounts of
  hazardous reagents. Professor Tang conceived a synthesis using an engineered enzyme and a
  practical low-cost feedstock. Codexis optimized both the enzyme and the chemical process.
  The resulting process greatly reduces hazard and waste, is cost-effective and meets the needs
  of customers. Some manufacturers in Europe and India use this process to make simvastatin.
                                  Simvastatin, a leading cholesterol lowering drug, was originally developed by Merck under
                               the brand name Zocor®. In 2005, Zocor*' was Merck's best selling drug and the second-largest
                               selling statin in  the world with about $5 billion in sales.  After when Zocor'*1 went off patent
                               in 2006, simvastatin became the most-prescribed statin, with 94 million prescriptions filled in
                               2010, according to IMS Health.
                                  Simvastatin is a semisynthetic derivative of lovastatin, a fungal natural product. Simvastatin
                               contains an additional methyl group at the C2' position of the lovastatin side chain. Introduction
                               of this  methyl group in lovastatin  using traditional methods requires  a multistep chemical
                               synthesis. In one route, lovastatin is hydrolyzed to the triol, monacolin J, which is protected
                               by selective silylation, esterified with dimethylbutyryl chloride, and deprotected. Another route
                               involves protecting the carboxylic acid and alcohol, methylating the C2' with methyl iodide, and
                               deprotecting. Despite considerable optimization, these processes have overall yields of less than
                               70 percent, are mass-intensive due to protection/deprotection, and require copious amounts of
                               toxic and hazardous reagents.
                                  Professor Yi Tang and his group at UCLA conceived a new simvastatin manufacturing process
                               and identified both a biocatalyst for regioselective acylation and a practical, low-cost acyl donor.
                               The biocatalyst is LovD, an acyltransferase that selectively transfers the 2-methylbutyryl side chain
                               to the C8 alcohol of monacolin J sodium or ammonium salt. The acyl donor, dimethylbutyryl-
                               S-methylmercaptopropionate (DMB-SMMP), is very efficient for the LovD-catalyzed reaction,
                               is safer than traditional alternatives, and is prepared in a single step from inexpensive precursors.
                               Codexis licensed this process from  UCLA  and subsequently optimized  the  enzyme and  the
                               chemical process for commercial manufacture. Codexis carried out nine iterations of in vitro
                               evolution, creating 216 libraries and screening 61,779 variants to develop a LovD variant with
                               improved activity, in-process stability, and tolerance to product inhibition. The approximately
                               1,000-fold improved enzyme and the new process pushed  the reaction to completion  at high
                               substrate loading and minimized the amounts of acyl donor and of solvents for extraction and
                               product separation.
                                  In the  new route, lovastatin  is hydrolyzed and converted  to the water-soluble ammonium
                               salt of monacolin J. Then a genetically evolved variant of LovD acyltransferase from E. coli uses
                               DMB-SMMP as the acyl donor to make the water-insoluble ammonium salt of simvastatin. The
                               only coproduct of simvastatin synthesis is methyl 3-mercaptopropionic acid, which is recycled.
                               The final yield of simvastatin ammonium salt is over 97 percent  at a loading of 75 grams per
                               liter of monacolin J. The nominated technology  is practical and cost-effective. It avoids  the
                               use of several hazardous chemicals including tert-butyl dimethyl silane chloride, methyl iodide,
                               and  w-butyl lithium. Customers have evaluated the simvastatin produced biocatalytically and
                               confirmed that it meets their needs. Over 10 metric tons of simvastatin have been manufactured
                               using this new process.

MAXHT^' Bayer Sodalite Scale Inhibitor
  Innovation and Benefits
  The "Bayer process" converts bauxite to alumina, the raw material for making aluminum,
  Mineral scale deposited on the heat exchangers and pipes in Bayer process plants increases
  energy use. Removing the scale requires stopping production and cleaning with sulfuric
  acid. Cytec's product hinders scale growth. Eighteen plants worldwide are using MAX HT®
  inhibitor, saving trillions of Btu (British thermal units) annually. Fewer cleaning cycles also
  reduce hazardous acid waste by millions of pounds annually.
   The Bayer process converts bauxite ore to alumina, the primary raw material for aluminum.
The process involves extracting alumina trihydrate from bauxite ore using hot caustic solution.
After separating out the insoluble solids, the alumina trihydrate is precipitated and the spent liquor
is recycled. Heat exchangers re-concentrate the liquor to the optimum concentration of caustic
and then heat it to the proper temperature for digestion. Silica present as silicates, primarily clay
materials, dissolves quickly in typical Bayer liquor used to digest alumina, resulting in the liquor
being supersaturated in silica, particularly after precipitation of the alumina trihydrate. The  silica
in the liquor reacts with the caustic and  alumina on the hot surfaces of the heat  exchangers;
as a result, sodalite  scale (i.e., crystalline aluminosilicate) builds up on the heat exchangers and
interstage piping in the process. This reduces the efficiency of the heat exchangers. Periodically,
Bayer process plant operators must take the equipment offline for cleaning that involves removing
the scale with sulfuric acid. The used acid  is  a waste stream that requires disposal. In addition to
the acid cleaning, much of the interstage piping requires cleaning with mechanical means such as
jackhammers to remove the scale.
   Cytec developed  its MAX HT'S' Bayer Sodalite Scale Inhibitor products for the Bayer process.
There are no  other scale inhibitors  on the market for  this application. The active polymeric
ingredient contains silane functional groups that inhibit crystal growth by incorporation into
the crystal or adsorption onto its surface. The polymers have molecular weights in the range
10,000 and 30,000. Their synthesis  involves polymerizing a monomer containing a silane group
or reacting polymer backbone with  a reagent containing the  silane group. Dosages range  from
20 to 40 ppm. Assessments of these polymers under EPA's Sustainable Futures Program indicate
low overall concern  for human health and the aquatic environment.
   Eliminating sodalite  scale  from heater  surfaces has many benefits. Heat recovery from the
steam produced in  various unit operations  is more efficient.  Increased  evaporation makes the
countercurrent washing circuit more efficient and  reduces caustic losses. Reducing the use of steam
reduces emissions from burning carbon-based fuels.  Finally, reducing the sulfuric acid used to
clean heaters reduces both worker exposure and  waste. Typically, MAX HT*'1 inhibitor increases
the on-stream time for a heater from 8—10  days to 45—60 days for digestion and from 20—30 days
to over 150 days for evaporators.
   There are about 73 operating  Bayer  process plants worldwide with  annual capacities  of
0.2—6 million tons of alumina per plant; most plants are in the 1.5—3 million ton range. Eighteen
Bayer process plants worldwide have adopted  this technology; seven  more plants are testing it.
Each plant using MAX HT* saves $2 million to $20 million annually. The realized annual energy
savings for all plants together are 9.5 trillion to 47-5 trillion Btu, which is the equivalent of about
1.1 billion to 7-7 billion pounds of carbon dioxide (CC>2) not released to the atmosphere. Fewer
cleaning cycles and  less acid per cycle result in a realized annual  hazardous waste reduction of
76 million to 230 million pounds for all plants together.
Cytec Industries Inc.

International, Inc.
Enzymes Reduce the Energy and Wood Fiber Required
to Manufacture High-Quality Paper and Paper board
                                Innovation and Benefits
                                Traditionally, making strong paper required costly wood pulp, energy-intensive treatment,
                                or chemical additives. But that may change. Buckman's Maximyze'8' enzymes modify the
                                cellulose in wood to increase the number of "fibrils" that bind the wood fibers to each other,
                                thus making paper with improved strength and quality—without additional chemicals
                                or energy. Buckman's process  also allows papermaking with less wood fiber and higher
                                percentages of recycled paper, enabling a single plant to save $1 million per year.
                                The paper and packaging industry is an important part of the U.S. economy with product
                              sales of $115 billion per year and employment of about 400,000 people. Previously, papermakers
                              who needed to improve paper strength were limited to adding costly pulps, increasing mechanical
                              treatment that expends significant energy, or using various chemical additives such as glyoxalated
                              polyacrylamides and polyacrylamide copolymers.
                                Enzymes are extremely efficient tools for  replacing conventional chemicals in papermaking
                              applications. Buckman's Maximyze®  technology consists  of new  cellulase  enzymes  and
                              combinations of enzymes derived from natural sources  and produced by fermentation. These
                              enzymes were not  previously available commercially. Wood  fibers treated with  Maximyze®
                              enzymes prior to refining (a mechanical treatment unique to papermaking) have substantially
                              more fibrils that bind the wood fibers to each other. Maximyze® enzymes modify the cellulose
                              polymers in the wood fiber so that the same level of refining produces much more  surface area
                              for hydrogen bonding, which is the basic source of strength in paper. As a result,  Maximyze*
                              treatment produces  paper and paperboard with improved strength and quality.
                                Maximyze'8' improves strength so the weight of the paper product can be reduced or some
                              of the wood fiber can be replaced with a mineral  filler such as calcium carbonate.  Maximyze®
                              treatment makes it  possible to use higher percentages of recycled paper. Maximyze*' treatment
                              uses less steam because  the paper drains faster (increasing the production rate) and uses less
                              electricity for refining. Maximyze'8' treatment is less toxic than current alternatives  and is safer
                              to handle, manufacture, transport, and use than current chemical  treatments. These and other
                              benefits are produced by Maximyze® treatment, a biotechnology that comes from renewable
                              resources, is safe to use, and is itself completely recyclable.
                                 The first commercial application began with the production of fine paper within the past
                              two years. In 2011, a pulp and paper manufacturer in the Northwest began to add  Maximyze*
                              enzymes to  the bleached pulp  used to produce paperboard for food containers. This change
                              increased machine speed by 20 feet per minute for a 2  percent increase in production. It also
                              reduced the level of mechanical refining by 40 percent for a substantial savings in  energy. Finally,
                              it reduced the basis weight (density) of the paper by 3  pounds per 1,000 square feet without
                              changing the specifications for quality. Overall, Maximyze'8' treatment reduced  the amount  of
                              wood pulp required by at least 1 percent, which reduced the annual amount of wood needed to
                              produce the food containers  by at least 2,500 tons. Buckman estimates that using  Maximyze*
                              technology for this one machine can save wood pulp equivalent to 25,000 trees per year. Another
                              large mill producing fine paper has used Buckman's technology since January 2010 and saved
                              over $1 million per year. Since introducing this new technology, Buckman has expanded it and is
                              now applying it successfully in over 50 paper mills in the United States and beyond.

Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of

Diary I Aldimines

   Imines are essential intermediates in many pharmaceutical syntheses. For example,  diaryl
aldimines are feedstocks for blockbuster drugs such as Taxol'*1 (used for chemotherapy) and
Zetia®  (used to  reduce cholesterol).  Diaryl  aldimines added  to polyethylene increase  its
photodegradation in the environment. Unfortunately, traditional syntheses of diaryl aldimines
often require hazardous solvents and include energy-intensive, multihour reflux steps. Although
some imine syntheses use more benign solvents or conditions, they still require long reaction
times, recrystallization, or other environmentally unfriendly procedures.
   Recently, Professor Bennett  found that ethyl L-lactate, an FDA-approved food additive, can
replace the hazardous solvents  commonly used to synthesize imines.  Her method is extremely
efficient under ambient  conditions  and requires less solvent than published  methods.  It has
a median yield of over 92 percent and a median reaction time of less than  10 minutes. The
resulting imines are  usually pure enough without recrystallization, avoiding additional waste.
Professor Bennett's method "tunes" the polarity of ethyl L-lactate by adding water. The starting
materials remain dissolved, but the imine crystallizes out of solution as it forms. Although
traditional methods often drive  reactions forward by  removing water, Professor  Bennett's
method drives the reaction forward by removing the product through crystallization. To date,
she and her undergraduate research students  have  synthesized nearly 200 imines  using this
method; her students in teaching labs have made more than half of these in a green chemistry
project. In summary, the ethyl L-lactatc method is faster, usually results in higher purity and
yield, uses less energy, uses less solvent, generates less waste, and uses a  more benign solvent than
published methods.
   A patent application for this method was published in 2011. Professor Bennett is now studying
these imines in biological and other applications. All are fluorescent and some are photochromic.
Several show promise as fluorescent cell markers and antibacterial agents.

Sustainable Molecular Design  through Biorefineries:

Biomass as an Enabling Platform for Safe

Oil- Thickening Agents  (Amphiphiles)

   Non-polymeric amphiphiles can form  molecular gels  or viscoelastic materials when they
self-assemble by noncovalcnt interactions such as surface tension and capillary action. Amphiphiles
can immobilize a large pool of organic or aqueous solvent into a gel. A wide variety of amphiphiles
are currently derived, at least in part, from nonrenewable resources. In addition, their synthesis
frequently requires  multiple  steps, energy-intensive purifications,  and complex,  expensive
catalysts. Structuring an amphiphile such as vegetable oil into a gel alters its physical properties
with or without altering its chemical properties. Current structuring agents and methods used for
food tend to increase the content of saturated fatty acids and tram-fatty acids in oils, which may
increase the risk of vascular and heart disease.
   Professor John and his group have developed potent amphiphiles from biobased resources using
enzyme-mediated transesterification of sugar alcohols with fatty acid donors. Upon self-assembly,
these amphiphiles produce soft materials in aqueous and organic solvents. These amphiphiles
exhibit superior ability to structure vegetable oils without increasing their saturated fatty acids.
They are also nontoxic and biodegradable. The ease of synthesis and cheap raw materials translate

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into low-cost  production  of efficient sugar-based amphiphilic gelators.  In addition, these
self-assembled  gels have a  remarkable ability to trap  highly volatile pheromones, and release
them slowly, so they remain effective longer. Another application is environmentally benign oil
spill recovery: when added  to an oil-water mixture, Professor John's amphiphiles can selectively
partition into the oil phase and convert it to a gel. This technology offers the potential to replace
current oil structuring agents with safe, biobased amphiphiles resulting in enhanced performance
at lower cost.
   Currently,  Professor John   is   developing  next-generation,  biobased  amphiphiles  to
structure hydrophobic  liquids such  as vegetable oils  and related compounds  for food and
cosmetic applications. Several food  and personal care companies have  expressed  interest  in
licensing this technology.

 Chemical Conversion ofBiomass into New Generations

 of Renewable Fuels, Polymers,        Value-Added


   The  gradual  decline of  the prevailing,  worldwide  petroleum economy is creating an
extraordinary need for  alternative technologies and, hence, bioenergy  research. Consequently,
researchers are  developing schemes to exploit lignocellulose, the most abundant organic material
on the planet.  These schemes vary considerably, but each aims to cleave  lignocellulose into its
monosaccharide components, then derive useful products from the  monosaccharides efficiently
and inexpensively. The most successful schemes will be those that (1) produce the highest yields,
(2) minimize capital and operating expenses, and (3) allow feedstocks from the most sources.
   In 2008,  Professor Mascal and his group described a process  that meets  all three objectives.
Their method  involves digestion  of cellulose in a biphasic aqueous acid—organic solvent reactor
to give remarkably high yields of the novel organic platform chemical, 5-(chloromethyl) furfural
(CMF). The method  works equally well on raw biomass, producing not only CMF from the
cellulose of the feedstock, but also furfural itself from the C5 sugar fraction (i.e., hemicellulose).
It uses all of the carbohydrate in the biomass without requiring that lignin  first be stripped from
the lignocellulose.
   Recently,  Professor Mascal has  upgraded his technology:  it  now  produces an  overall
89  percent  yield  from  cellulose  consisting of CMF (84  percent)   and levulinic  acid
(LA, the well-known carbohydrate breakdown product) (5 percent). The new process requires 20-
fold less solvent and recycles solvent after use. The same method processes sucrose into CMF and
LA in a  remarkable 95 percent overall yield. The method also works well on oil seed feedstocks
and leads to a 25 percent increase in biodiesel production from safflower  seeds. No other
method  produces  simple organic products directly from cellulosic  materials with comparable
yields. Important  CMF derivatives include biofuels, renewable  polymers, agrochemicals,  and
pharmaceuticals. The  green tech  companies Micromidas and Incitor technology have adopted
the technology with backing from major chemical and energy company partners.

 Highly Efficient,  Practical Mono hydro lysis of

 Symmetric  Diesters to Half-Esters
   Half-esters have considerable commercial value: they are highly versatile building blocks for
polymers, dendrimers, and hyperbranched polymers that have applications in many industrial
products. Because the two ester  groups in the symmetric diesters are equivalent,  however, the
statistically expected  yield of half-esters is  only 50 percent. Classical saponification usually
produces complex mixtures of dicarboxylic acids, half-esters, and the  starting diesters, which

are difficult to separate and therefore, generate a large amount of undesirable waste. Alternate
ring-opening reactions of cyclic acid anhydrides to halt-esters are also undesirable because they
require hazardous organic solvents.
   Among various synthetic conversions, the desymmetrization of symmetric compounds is one
of the most atom-economical, cost-effective reactions. The symmetric starting compounds are
typically available commercially at low cost or easily made from inexpensive precursors. Water
is among the most environmentally friendly solvents and is the least expensive of all solvents.
Water-mediated desymmetrization of symmetric organic compounds is, therefore, of tremendous
synthetic value and can make a significant contribution to creating greener reaction conditions.
   Professor  Niwayama  pioneered  an environmentally  safe,  highly  efficient,  practical  ester
monohydrolysis of symmetric diesters to half-esters. In this reaction, aqueous sodium hydroxide
(NaOH) or potassium hydroxide (KOH)  is added to a  symmetric diester suspended in water
at  0 °C  that may also contain a small amount of an aprotic cosolvent such as tetrahydrofuran
(THF).  Monohydrolysis occurs at  the interface between the  aqueous phase and the organic
phase containing the diester. The reaction produces pure  half-esters in high to near-quantitative
yields without hazardous organic  solvents  or dirty waste products. Wako Chemicals USA and
Kishida  Chemical Company have licensed the technology and  10 resulting half-esters are now
 available commercially.

Improved Resource Use in Carbon Nanotube  Synthesis

via Mechanistic Understanding

   Carbon nanotube (CNT)  production by  catalytic chemical vapor deposition  (CVD)
 currently exceeds 300 tons per year and is growing. The current CVD process has very low yields
 (3 percent or  less) and high energy requirements. Emissions from ethene- and H?-fed CVD
 reactors contain over 45 distinct chemicals including:  the potent greenhouse gas, methane;
 toxic and  smog-forming compounds, such as benzene and 1,3-butadiene; and trace quantities
 of polycyclic aromatic hydrocarbons. Eliminating thermal treatment of the feedstock gases may
 prevent the formation of unwanted byproducts, reduce  energy demands, and improve  overall
 control of the synthesis, but heating the  feedstock gas is necessary  to  generate the critical,
 previously unidentified, CNT precursor molecules required for  rapid CNT growth.
   Using  in  situ  CNT  height  measurements  and  gas  analysis, Professor  Plata  and her
 group   identified  the heat-generated  compounds correlated  with  rapid  CNT formation
 (e.g., propyne and but-l-en-3-yne). She then mixed each of these chemicals with typical feedstock
 gases (C2H4 and H2) without preheating and tested them  with a heated  metal catalyst. She found
 that several alkynes (e.g., ethyne, propyne, and but-l-en-3-yne) accelerate CNT formation.  This
 new mechanism for CNT formation features C—C bond  formation  between intact chemical
 precursors, similar to polymerizations. It challenges the accepted hypothesis that precursors must
 completely dissociate into C or C-2 units before '"precipitating" from the metal.
   Using these mechanistic insights, Professor Plata can form  high-purity CNTs rapidly. Her
 technology improves yields  by 15  fold, reduces energy  costs by  50 percent, and reduces the
 ethene  and H? starting materials by 20 and 40  percent,  respectively. It also reduces unwanted
 byproducts by over 10-fold (translating to ton-sized reductions in toxic and smog-forming
 chemicals and greenhouse gases). The reduced starting materials and energy requirements also
 lower the  cost of CNTs  without sacrificing product quality. A commercial CNT manufacturer
 has licensed this  patent-pending work.
Plata,  Department
of Civil and

Professor T. ¥.
(Baby) RajanBaby,
Department of
Chemistry, The Ohio
of Chemical
University of
Ethylene: A Feedstock for Fine Chemical Synthesis
   New carbon—carbon bond-forming processes have been responsible for significant advances in
organic synthesis. Practical methods using feedstock carbon sources as starting materials to form
enantioselective carbon—carbon bonds are rare, however. Ideally, any new reaction must: (1) use
abundantly available, carbon-neutral sources; (2) produce  a functional intermediate for other
common organic functional groups; (3) be highly catalytic, generating little or no waste including
toxic metals; (4) provide  high, reagent-dependent selectivity to produce all isomers including
enantiomers; and (5) include easy product recovery. A broadly applicable reaction using ethylene
to install highly versatile  vinyl groups enantiomerically could thus have significant impact in
organic synthesis.
   Professor RajanBabu and his group have developed highly catalytic (substrate—catalyst ratio
up to 7,412:1)  protocols  for nearly quantitative (isolated yields can be over  99 percent) and
highly  selective  (approximately 100 percent  regioselectivity; enantiomeric ratios  of over 99:1)
co-dimerization of ethylene and  various functionalized vinylarenes, 1,3-dienes, and  strained
alkenes. These reactions proceed under mild conditions (-52 °C to 25 °C; 1 atmosphere of ethylene)
to produce intermediates such as 3-arylbutcnes, which can be  transformed  to  nonsteroidal
anti-inflammatory drugs (NSAIDs) in two steps. These reactions consume both starting materials,
leaving no side products. Successes include highly  enantioselective syntheses  of common
NSAIDs, such as ibuprofen,  naproxen, flurbiprofen, and  fenoprofen, from the corresponding
styrenes and ethylene.
   Cyclic and acyclic  1,3-diencs also undergo efficient enantioselective addition of ethylene.
Syntheses of several 1-vinylcycloalkenes  and l-substituted-l,3-butadienes achieve yields up to
99 percent. Professor RajanBabu has found expeditious routes to biologically relevant classes of
compounds including bisabolanes, herbindoles, trikentrins, steroid D-ring 205- or 20J?-derivatives,
(-)-desoxyeseroline, pseudopterosin A—F, G—J, and K—L  aglycones, and  helioporins. These
syntheses require fewer steps than traditional methods and produce uncommon configuradonal
isomers. In 2010 and 2011, Professor RajanBabu published five papers on this work.

 A Truly  Green Process for Converting Ethylene to

Ethylene Oxide

   The LeFort process, the only industrial process currently used to make ethylene oxide (EO),
emits huge amounts of carbon dioxide  (CC>2, about 3.6 million tons/year). This venerable
gas-phase technology also presents safety hazards due to  the explosive potential of heated ethylene
and oxygen gases.
   At the Center for Environmentally Beneficial Catalysis (CEBC), Professor Subramaniam and
his colleagues are developing an alternative green technology for EO manufacture. In the CEBC
process, a highly reactive oxidation catalyst, methyltrioxorhenium (MTO), transfers an oxygen
atom from hydrogen peroxide (HbC^) to ethylene with total selectivity, high conversion, no
substrate or solvent burning (to cause CO2 emissions),  and no explosion hazard.
   Despite requiring an H?O2 oxidant and rhenium-based catalyst that cost more than the LeFort
system's CH oxidant and silver catalyst, the CEBC process can potentially compete economically
if it has reliable  in-service  lifetimes of 2—3 months. Experiments indicate that the CEBC system
should be capable of this critical in-service lifetime. Mechanistic studies with isotopic tracers
identified only one detectable mechanism tor catalyst  destruction and conditions necessary to
avoid it. CEBC will soon attempt long-term, continuous process operations.
   The  CEBC process  has   relatively  high  productivity  (40—50 percent versus LeFort
10—15  percent) because it exploits  the critical properties of ethylene  to  greatly increase its
solubility. For similar  production capacities, the carbon footprint  of the CEBC process is net

23  percent  lower  than the LeFort  process;  thus,  the  additional carbon  emissions  from
manufacturing H2O2 are  considerably less than the emissions  eliminated by  not  burning
substrate or product. The CEBC process is the first economically competitive alternative to the
LeFort Process. The new EO process excels in conversion, selectivity, safety and sustainability,
and the two processes appear to be comparable in manufacturing costs and productivity. A U.S.
patent for this process was allowed in 2011.

A Novel Bacteriophage-based Test  to Identify MRSAI

MSSA Acquired Infections
   At the Colorado School of Mines (CSM), Professor Voorhees and his colleagues have developed
a bacteriophage (phage)  amplification platform that rapidly identifies Staphylococcus aureus and
determines whether it is methicillin resistant (MRSA) or methicillin susceptible (MSSA) without
extensive bacterial culturing. CSM licensed the technology to Micro Phage, which was founded in
2002 by Professor Voorhees and Mr. Jack Wheeler to provide medical devices. These point-of-care
devices fulfill needs such as determining S. aureus susceptibility while reducing the nonrenewable
materials used in manufacturing and the generation of medical waste.
   Phages are viruses that infect bacteria in a species-specific fashion and then multiply rapidly.
The amplification process can  generate up to a  105  increase in phage  and reduce incubation
times to 1—5 hours down from 24—48 hours for traditional microbiological  culture assays. The
MicroPhage and CSM KeyPath™ test is conducted with modern chemical detection methods on
a millilitcr scale. The test resembles a typical immunoassay whereby a blood culture containing  a
suspected pathogen is added to two  reaction tubes: one containing phage and a nutrient media;
and the second  containing phage, media, and methicillin. The test samples  are mixed with the
tube contents and incubated, followed by analysis on a dual-track lateral flow  immunoassay strip.
A positive result on the first track shows the presence of S. aureus, A positive result on the second
track shows  that the S. aureus  is  also  methicillin-resistant. The manufacturing and use of the
KeyPath™ kit address several of the 12 principles of green chemistry.
   This phage amplification platform is the first and only rapid in vitro diagnostic test approved
by the U.S. Food and Drug Administration (FDA) to identify bacteria directly and determine
their antibiotic resistance or susceptibility. During 2011, the FDA gave  501 (k) approval for the
sale of these human diagnostic devices and sales began in the United States.
Biobased Polymers and Composites
   Professor Richard Wool's research has shown that recent advances in green chemistry, genetic
engineering, composite science, and natural fiber development offer significant opportunities
for new, improved materials from renewable resources that are recyclable, biocompatible, and
biodegradable, thereby enhancing global sustainability. He typically makes composite resins from
highly saturated  plant oils such as soy or linseed oils and makes pressure-sensitive adhesives,
coatings, and  elastomers  from high oleic oils. When he combines  his  biobased resins with
natural plant and poultry fibers, starch, and lignin, he can produce new low-cost composites,
pressure-sensitive adhesives, elastomers, and foams that are economical in many high-volume
applications. These high-performance composites are designed for use in energy-efficient solar
integrated roofs, wind foil blades, hurricane-resistant housing, sub-aqua hydro turbines, and
hydrogen storage, in addition to agricultural equipment, automotive sheet molding compounds,
civil and rail infrastructures, marine applications, electronic materials, and sports equipment.
   Professor Wool makes foams, usually from various mixtures of oils depending on the required
rigidity, using carbon dioxide (CC>2) as the blowing agent.  Recently, he  developed a biobased
foam  to replace polyurethane and its toxic precursors, methylene diphenyl diisocyanate (MDI)
and toluene diisocyanate (TDI). Professor Wool developed it in collaboration with Crey Bioresins;
currently, several packaging and automotive suppliers are exploring this foam.
Professor Kent
Department of

MicroPhage, Inc.
for Composite
University of

       In  collaboration with Crey Bioresins and  Dixie Chemical TX,  Professor Wool developed
    biobased composite resins  that  have been  in worldwide distribution  since  2011. Also  in
    2011, Professor Wool invented eco-leather, made from natural fibers  including chicken feathers,
    flax, and plant oils. This breathable leather substitute can potentially replace 50 billion pounds
    of toxic waste currently  generated by the leather  industry. Nike and  Puma are exploring this

 Geothermal Heat Pumps: A Greener and More

 Energy-Efficient Renewable Energy Resource

   Because buildings account for nearly 40 percent of U.S. energy consumption and greenhouse
gas emissions, they are a  prime  target  for energy conservation. Although  geothermal heat
pumps (GHPs) save energy in  the range of 30—60 percent compared to  typical heating and
air conditioning units, their high initial cost and long payback period hamper their adoption.
Today's GHPs use propylene glycol—water or ethylene glycol—water mixtures as  circulating fluids
in their ground source loops. Ethylene glycol is a toxic chemical that presents environmental risks
and disposal problems.
   ACTA Technology  has  developed fluids containing nanoparticles  (i.e.,  nanofluids)  with
improved heat-transfer efficiency  that can reduce  the lifecycle cost of GHPs by  17 percent.
Adding  nanoparticles  to  propylene  glycol—water  mixtures  improves  their  heat  transfer  by
48 percent. ACTA also improves the heat transfer of Paratherm*' LR (a food-grade, heat-transfer
oil) by adding alumina nanoparticles at  2  percent  by weight and a surfactant. The nanofluid
Paratherm'K LR is a better heat-transfer fluid than either ethylene or propylene glycol mixtures.
Because ACTA's nanofluids increase the  heat transfer rate of the ground loop in a GHP, the
ground loop can be smaller and the GHP can pump less fluid. This technology reduces both the
initial and lifecycle costs.
   ACTA manufactures nanoparticles by a pyrogenic  (flame) process. The  resulting fumed
nanoparticles  have  large surface-area-to-volume ratios  that increase the heat-transfer  rate and
decrease the thermal response time. They arc hydrophilic, with hydroxyl groups over approximately
40 percent of their surfaces. They are easily removed from nanofluids for recycling.
   ACTA's technology offers circulating fluids for GHPs without the harmful effects of ethylene
glycol. These  greener nanofluids could also improve the  fuel  economy of automobiles because
radiators could be smaller with less fluid to pump. ACTA applied for a U.S. patent  for their
technology in 2011.

 Producing Chemicals and Carbon from Waste Tires,

 Plastics,  Carpet,  and Biomass
   Vast amounts of waste  tires,  plastics,  and biomass have been discarded in  landfills because
there  was  no  practical way to  dcpolymcrizc them for reuse.  BCD Group-II has developed
catalytic transfer hydrogenation (CTH), a modified base-catalyzed decomposition (BCD) process
that depolymerizes  plastics, tires, rubber, other polymers, and biomass into chemicals or solid
products with carbon contents of at least 84 percent. The CTH process is non-oxidative. Unlike
pyrolysis and liquefaction processes that require temperatures of 450—700 °C, the CTH process
converts polymers into reusable chemicals and carbon at 130—300 °C within 30—90 minutes. The
proprietary reaction medium is composed of an alkali metal carbonate or hydroxide, a hydrocarbon
donor/solvent (usually a high-boiling aliphatic hydrocarbon), and a proprietary catalyst/water
absorption agent. Reactive hydrogen from  the hydrogen donor breaks bonds between hctcroatoms
to produce monomers, oligomers, polymers from copolymers, and sodium salts  of anions.
Products are also easily converted into syngas. Depolymerization of polyester, polyurethane,
polycarbonates, or carpets by existing technologies requires much higher temperatures, higher
pressures, and more expensive reagents.
   CTH technology can replace coke, a traditional  fuel in solid oxide fuel cells (SOFCs).  Coke
production from coal requires processing for 16—24 hours at temperatures of around 2,000 °C.
The CTH technology produces carbon from tires and biomass that is useful as SOFC fuel.
ACTA Technology,
      Group-II, Inc.

Blue Marble
Biomaterials LLC
Colonial Chemical,
   A U.S. patent application describing this technology was submitted (Provisional Application
# 61/571,383) on July 7, 2011. In  2011, BCD Group-11  and C-4 Polymer Inc., of Chagrin
Falls, OH, completed laboratory-scale studies to depolymerize and recover polypropylene from
copolymer waste generated by the food packaging and auto industries. BCD Group-II expects
to complete pilot-scale tests and initiate commercial development during 2012. Licensees of the
original BCD process and an India chemical firm have expressed interest  in CTH technology;
the Environmental Business Cluster in Silicon Valley, California, will present this technology to
venture capitalists.

Greening the Design  of Chemical Production with Microbes
   Currently,  chemical synthesis using energy-intensive processes  and  fossil-based  materials
produces the  majority of fine chemicals.  In contrast, the biosynthesis of fine  chemicals from
biobased feedstocks has demonstrated feasibility and promise, however, over the past few years.
Blue Marble Biomaterials is developing  microbial systems to lower the  carbon intensity and
improve the lifecycle sustainability of fine chemical production.
   Blue Marble has developed a proprietary combination of microbes that produce a wide variety
of fine chemicals and chemical intermediates including carboxylic acids, esters, thiols, and other
organosulfur compounds  in a  single  batch. Blue Marble's unique polyculture fermentation
uses no genetically modified organisms and resists environmental stress. This fermentation can
process low-cost,  nonsterile lignin, cellulose, and protein-based waste byproducts from food,
forestry, and algae companies without chemical or thermal preprocessing. Using  these feedstocks
for fermentation prevents landfilling or burning them and  abates approximately 15.28 tons of
carbon dioxide equivalents (CC>2eq) per ton of feedstock. Compared to microbial systems that use
carbon- and energy-intensive virgin or preprocessed plant materials, Blue Marble's system recycles
waste biomass, capturing the carbon it contains.
   In 2010, the company scaled up production to a commercial facility in Missoula, MT. This
facility is currently undergoing food-grade and kosher certification. It will operate at 100 percent
capacity in the first quarter of 2012.  Each year,  it will  use 860 wet tons of feedstock to produce
414,900 kg of carboxylic  acids, esters, thiols,  and other organosulfur compounds. An on-site
water recycling system will reuse 75 percent of the  water required for  fermentation, saving
574,000 gallons of water per month. Finally, all biogas from the fermentation  system will run
through an algae remediation system to reduce facility emissions by scrubbing CCH and methane.
Blue Marble is working with several major manufacturers in the flavoring, food, and personal care
industries and with Sigma-Aldrich Fine Chemicals toward global distribution of seven compounds.

Sugd^Nate: A Safer,  Milder,  Greener Surfactant

   Although lauryl sulfate and  its ethoxylated  version, lauryl ether sulfate, are  the two most
common anionic surfactants used in formulating shampoo,  body wash, and  other personal
care products, these ingredients are highly irritating to eyes and  skin.  Products formulated
with ethoxylated  lauryl  ether  sulfate also  contain  various levels  of 1,4-dioxin,  a probable
human carcinogen. Finally, a large percentage  of these surfactants  are made from ethylene, a
nonrenewable petroleum feedstock.
   Colonial Chemical has developed sulfonated alkyl polyglucosides as safer surfactants: they
replace lauryl alcohol with alkyl polyglucosides as the hydrophobic  component. These unique,
patented surfactants represent a breakthrough in mild surfactant technology. They are naturally
derived, biodegradable raw materials  that are  nearly 90 percent renewable and could reach
100 percent renewable as development progresses. These new surfactants do not irritate eyes or
skin, allowing formulators of personal care products to use totally irritation-free ingredients.

  Unlike ethoxylated  lauryl ether sulfates, Colonial Chemical's surfactants  are completely free
  of dioxin.  An unexpected property is their ability to  withstand  microbial contamination.
  Outside testing showed that Suga®Nate 160 has reasonably good antimicrobial activity at the
  16 percent active level, which is a normal concentration for a primary surfactant in higher-end
  shampoos. As a result, Suga®Nate can reduce or even eliminate the antimicrobial additives used
  in formulations.
    The Suga®Nate synthesis has  added benefits: it is atom-economical;  sodium chloride  is
  the only byproduct; and water is the only solvent. The relatively mild reaction conditions are
  closer to ambient than those of  competing surfactants, and there is no need for separation
  or purification. The toxicity of these new surfactants is much lower than that of competing
  products,  and the new surfactants are even less toxic than their starting  materials. In 2011,
  Suga'*'Nate was certified as a biobascd product by the U.S. Department of Agriculture (USDA).

 Glycerol ten-Butyl Ether (GTBE): A Bio fuel Additive
for  Today
   Current  petroleum-based  additives   for  boosting  octane  in   gasoline  improve  the
miles-per-gallon (mpg) of  vehicles,  but not  significantly. The traditional  fuel additive,
methyl fert-butyl ether (MTBE), has been phased out in many states due to its toxicity and has
no obvious replacement.
   Glycerol tert-butyl  ether (GTBE) is a high-value, biobased fuel additive that improves the
combustion and efficiency of petroleum and biobased fuels. CPS Biofuels has developed a process
to make GTBE from waste glycerol, a low-value, high-volume byproduct of biodiesel production.
CPS makes GTBE by acid  catalysis of glycerol and isobutylene  or other appropriate olefins
followed by fractional distillation. Sulfuric add is the preferred acid catalyst. Although GTBE can
have up to three ether  linkages, it is preferable to have at least one or two free hydroxyl groups to
hydrogen-bond with ethanol and help lower its vapor pressure.
   GTBE is a biobased, nontoxic, biodegradable alternative fuel oxygenate and octane booster that
helps fuel combust more completely and improves fuel efficiency with cleaner resulting emissions.
It both improves gas mileage and reduces greenhouse gas (GHG) emissions; with petroleum diesel
fuels, it reduces up to 35 percent of particulates. It is useful as a fuel system icing inhibitor (FSII)
in military (JP-8) and  commercial  (Jet A) kerosene-type jet fuel. GTBE can replace PRIST*', the
existing jet fuel FSII, which is severely detrimental to human health.
   CPS is focusing on improving the efficiency of the  ElO and El 5 blends of biofuels for
the existing energy infrastructure. GTBE fuel additives  are compatible with  the U.S. energy
infrastructure, providing tremendous advantages over alternatives that require  new production
facilities or new engines for vehicles. CPS recently completed manufacturing trials, and testing of
GTBE showed extremely efficient,  essentially emission-free combustion and an octane rating over
120. GTBE has been commercially available as CPS PowerShot™ since January 2011.

Formaldehyde-Free,  High-Strength Biocomposites fiom

Sustainable  Resources
   The formaldehyde  and volatile organic  compounds  (VOCs)  used  to make conventional
coatings, binders, and laminates for the wood composites in  furniture contribute significantly
to indoor air pollution. e2e Materials is commercializing biocomposite products that  contain no
formaldehyde or VOCs and arc made without hydrocarbons or toxic feedstocks.
   e2e's biocomposites are made  from  lignocellulosic  bast fibers,  soy protein,  and  plant
polysaccharides; they are biodegradable at the end of their  useful lives. The long bast fibers,  from
sources including kenaf, jute, flax,  and  hemp, are lightweight and contribute to higher strengths
in ways that the short wood fibers  used in particleboard and medium-density fiberboard (MDF)
CPS            Inc.

cannot. The soy protein and plant polysaccharidcs are feedstocks for a natural resin system that
binds the fibers together into biocomposites.
   e2e's biocomposite  material is 3—4  times stronger than  today's wooden  particleboard and
MDE  e2e can mold its biocomposites into three-dimensional parts  (i.e., net-shape them into
whole, structural components) that replace traditional 4 x 8-foot sheets. Net-shaping can create
stronger components by molding them as one part rather than assembling them from pieces.
The e2e biocomposites also retain screws better than wood composites. These features combine
to create stronger  furniture while reducing the total amount  of material  and weight. e2e's
biocomposites are inherently fire-resistant because they contain a modified soy protein instead
of petrochemical resins. They  use only 19 percent of the embodied energy of today's  products
because the manufacturing process requires less energy and regionally integrated manufacturing
minimizes transportation costs.
   Products made from todays wood composites have a $100 billion market. e2e is  replacing
those  products  with  higher  performing,  safer,  more efficient,  and more  cost-effective
biocomposite-based products.  These products complement its proprietary  biocomposite core
with green, cost-effective coatings. Following successful pilot production in 2011 and responding
to strong  demand for its commercial office furniture  products, e2e recently  announced  a
100,000 square foot manufacturing expansion.

Generally Recognized as Safe (GRAS)  Coatings

   Using materials  that are generally  regarded as safe (GRAS) for human consumption, Ecology
Coatings has developed coatings that can be applied to food or used  in food packaging. These
GRAS coatings protect food from outside elements, are safe for human consumption, and use
natural ingredients, not plastics or other chemicals derived from fossil fuels. GRAS coatings have
barrier properties to air, water, and solvents that will allow them to replace coatings originating
from fossil fuels, especially plastic  coatings made  using acrylates and  mcthacrylatcs. GRAS
coatings have the potential to make food packaging greener and more sustainable by eliminating
toxic plastics. Their environmental friendliness could allow increased recycling of food packaging.
   The coating includes  a polypeptide such as albumin,  a denaturing agent, and  water  as
the solvent.  It can also include a natural gum, a flavoring agent, a  dye, a  de-foaming agent,
maltodcxtrin, and  an  oil. When  the mixture is exposed to  UV light, it cures and cross-links,
but does not coagulate. Used on food,  the nominated coating will inhibit oxygen exposure and
increase shelf life. GRAS coatings on food packages will also resist grease and can substitute for
polyethylene or other  petroleum-based coatings. Ecology Coatings' GRAS coating can also be
used as a  photoinitiator with  conventional UV-curable materials that are approved  for direct
contact with food.
   GRAS coating components in powdered form not only promote UV curing but can extend
the coverage of pigments. In this use, the nominated technology could replace silica fillers. Finally,
the GRAS coating can  be used  as a matting agent, which cures into the finished film and enhances
the UV-curing process. Combined with other biobased additives, the GRAS coating can produce
a rough surface that resists water and grease migration. In 2010, Ecology Coatings filed a patent
application for this technology.

Zero-Emission Production of the Green Lithium  Ion

SuperPolymei® Battery
   The lithium ion cell and battery industry is a multibillion-dollar business that also pollutes
the environment. The manufacturing  process for lithium ion electrodes includes coating the
electrodes  with the toxic solvent N-methyl pyrrolidone (NMP), then removing NMP by slow

evaporation in a furnace up to 100 meters long. Although manufacturers attempt to recover
NMP, some escapes. NMP is listed as potentially causing birth defects by environmental agencies
in California, Japan, the European Union (EU), and elsewhere. The large quantities of toxic
solvents in cell and battery manufacturing also lead to high costs for capital equipment and plant
operations as well as uncertain future liabilities.
   Electrovaya's SuperPolymer® batteries are based on a nanostructured lithiated manganese oxide
material that allows more energy to be stored in  a smaller space,  making applications smaller,
lighter, and more powerful. They also produce approximately 25 percent less carbon dioxide
(CC>2) over their lifecycle than do NMP batteries. Electrovaya developed a  unique, nontoxic
process to manufacture its fuel cells that eliminates all solvents including NMP. Electrovaya has
also eliminated some energy intensive drying and solvent-recovery processes.
   Electrovaya's SuperPolymer® batteries address the problem of energy generation and storage.
Advanced energy storage for plug-in hybrid electric vehicles and e-bikes can provide an alternative
to nonrenewable resources and reduce greenhouse  gas emissions. Currently, Electrovaya is testing
its battery technology nationwide in a fleet of plug-in hybrid electric versions of Chrysler's RAM
pickup trucks and Minivans.
   High-capacity  energy-storage systems  are essential if renewable sources  are to supply a
significant portion of a grid's energy. Electrovaya's technology is useful for grid energy storage
systems to  solve the power stability and energy storage problems  associated with  electricity
generated by renewable resources. Electrovaya recently delivered a 1.5 MW energy-storage system
to an electric utility in the Southwest United States for use with its photovoltaic operations.

Polymeric,  Nonbalogenated Flame Retardants  with Broad

Applicability in Multiple Industries

   Traditional, halogenated, small-molecule flame retardant  (FR)  additives  readily migrate
to the surface of plastic formulations, exposing  humans to these  often toxic chemicals and
diminishing their FR protection. Today, over 60  percent of FR plastic formulations are based
on halogen-containing  additives like brominated  and chlorinated  hydrocarbons.  Electronic
device manufacturers have instituted voluntary bans on halogen-containing FR additives; other
industries are also replacing them. Consequently, the plastics industry needs alternatives.
   FRX POLYMERS®  Inc. (FRXP)  is the first company to  develop polymeric forms  of
phosphorus for use as nonmigrating, halogen-free  FR additives that are also cost-effective. FRXP
converts diphenyl methylphosphonate (DPMP) into polymers with over 10 percent phosphorus.
These polymers have a limited oxygen index (LOI) of 65 percent, the highest  LOI measured for
thermoplastic materials,  indicating strong FR capability. They can be used alone or can  deliver
FR performance  and additional benefits  to polycarbonate blends, polyesters,  thermoplastic
polyurethane, unsaturated polyesters, epoxies, and polyureas. FRXP polymers can be used in
melt-processed fibers and blow-molded articles where previous FR  additives could not.  Being
polymeric,  the FRXP materials allow the  physical  properties of plastics to  remain  essentially
unchanged.  FR additives with phosphorus replacing bromine also should allow greater plastic
   The DPMP monomer synthesis has essentially quantitative yields. The polymer synthesis is
a solvent-free, melt-based process which only major byproduct, phenol, can be recycled into
starting monomers. FRXP expects less than 5 percent waste from its polymer and copolymer
   FRXP is scaling up its additives for use in electronic housings, industrial carpeting, textiles,
electrical connectors and switches, wires and cables, printed  circuit boards, and transparent
laminates. Following Premanufacture Review under the Toxic Substances Control Act (TSCA),
the FRXP materials are proceeding toward global registration. FRXP plans to  expand  its current
polymer pilot plant from 50 to  100 metric tons per year (TPA)  in early 2012 and is  building a
2,500 TPA commercial plant for start-up in October 2013-                                  19
FRX                Inc.

Technology, Inc.
InfiChem Polymers,
 Conserving Water and Eliminating Chemical Treatment

 in  Cooling Towers
   Commercial HVAC and industrial cooling towers evaporate water to  transfer heat to the
atmosphere. These systems use roughly 5 trillion  gallons of water  annually in the United
States,  The aqueous  environment  in  cooling  towers  presents  four  significant challenges
to sustained  efficient operation:  mineral  scaling,  corrosion,  biological  activity,  and  water
conservation. Traditional control measures require chemicals specific to each problem, many of
which are hazardous.
   H-O-H  Water Technology's  ''Green Machine" is  generating significant resource  savings,
eliminating traditional chemical additives, and reducing chemical hazards and  pollution.  In
the Green  Machine, carefully engineered  electrolytic extraction of calcium carbonate from
recirculating cooling water controls deposit formation on heat exchangers and other surfaces.
Electrolysis of ion-rich water produces exploitable chemicals in situ so the system requires no
external reagents other than electricity.
   The Green Machine contains steel tubes that constitute the cathodes of an electrolytic cell,
where water is  reduced to  form molecular hydrogen and hydroxide ion and where  calcium
carbonate  subsequently accumulates. Centered  in  each  tube typically is the anode of the
electrolytic cell: a titanium rod coated with ruthenium and iridium oxides called a dimensionally
stable anode (DSA). The coating of the anode drives the oxidation of water to produce molecular
oxygen, hydrogen ions, and higher oxygen species such as hydroxyl free radicals and ozone. DSA
technology allows the efficient splitting  of water at a low practical voltage potential. Recently,
H-O-H supplemented DSAs with anodes  coated  with boron-doped,  ultrananocrystallinc
diamond (BD-UNCD), which controls  troublesome calcium carbonate deposition,  forms
chlorine in  situ, and degrades  organic components more efficiently. Microbiological control in
cooling water is significantly more efficient as well.
   During 2011, Green Machines  installed in 127 cooling water systems totaling 86,660 tons
of cooling capacity saved a total of 248 million gallons of make-up water including 44.7 million
gallons due to the new BD-UNCD technology.
InfiGreen Polyols
                                 Polyurethane manufacturers are seeking to pursue sustainability by reducing their carbon
                               footprint, improving their green image, and cutting costs. The growing market for the polyols
                               used to make polyurethane is currently about 11  billion pounds, but has few green options.
                               Biobased polyols (primarily soy-based polyols) reduce polyurethane's carbon footprint, but have
                               significant consequences  including higher prices for food and agricultural  land. In addition,
                               polyurethane  manufacturing  generates significant amounts  of  scrap,  and virtually all post
                               consumer polyurethane scrap goes into landfills.

                                 With InfiGreen™ polyols and  recycling technology,  InfiChem Polymers  is  providing
                               sustainable, green, economical raw materials that are not biobased and do not divert land from
                               food production. This technology transforms polyurethane foams  into InfiGreen1 M polyols with
                               over 60 percent recycled content for reuse in polyurethanes. The process liquefies scrap foam in
                               a reaction with glycol, and then transposes it into various InfiGreenIM polyols by propoxylation
                               or patent-pending chemical steps; it typically generates less than  one percent waste.  InfiChem
                               Polymers  demonstrated  its process on  a  pilot scale with both flexible and rigid foam scrap.
                               Substituting  one pound  of conventional petroleum-based polyols with InfiGrccn"™  polyols
                               reduces the carbon footprint by approximately two pounds of carbon dioxide (CC*2).
                                 Polyurethane manufacturers can  benefit  from closed-loop recycling  of their polyurethane
                               production scrap,  which can significantly reduce  their landfill costs and provide them with

InfiGreen™ polyols at prices typically below  those  for conventional petroleum-based and
biobased polyols.
   InfiGreen™ polyols are currently used in automotive seat cushions and in the construction
industry. InfiChem Polymers  expects to reach its  current  capacity of one million pounds
of InfiGreen1 M polyols in late 2011; within 5 years, it expects sales of 50 million pounds in
NAFTA countries. With projected worldwide production of 180 million pounds of InfiGreen™
polyols, the company will consume approximately 106 million pounds of polyurethane scrap or
approximately 0.03 percent of all polyurethane produced.

Development       Commercialization of Okie Estolide  Esters
   Each year, 2.4 billion gallons of lubricants are used in the United States, according to industry
and EPA estimates. Lubricants comprised of sustainable carbon that perform well in demanding
applications are in  high demand. Naturally occurring vegetable oils  (triglycerides) provide
excellent lubricity and  have high viscosity indexes; they are  also biodegradable, nontoxic, and
economically attractive. Their oxidative and hydrolytic  instability and their poor performance
at low temperatures, however, exclude their  use in passenger-car motor oils (PCMOs) and low
temperature environments.
   LubriGreen has overcome the inherent disadvantages of vegetable oils and preserved their
favorable properties by derivatizing  fatty acids from  triglycerides into estolides, which  are
oligomers of fatty acids. Patented oleic estolide esters are central to LubriGreeris technology.
Their synthesis proceeds by an acid-catalyzed  Sx,-1 addition of the carboxyl of one fatty acid to the
site of unsaturation on another to form an estolide. (The catalyst is a recoverable, reusable organic
superacid.) The free acid estolides are then cstcrificd with a branched alcohol. The novel structure
of oleic estolides gives them excellent lubricity high viscosity indexes, and good cold temperature
properties. Like triglycerides, oleic estolides  are beneficial in environmentally sensitive settings
because they are biodegradable and nontoxic. Because the estolides  are fully saturated  and their
secondary esters create a steric barrier to  hydrolysis, they have good oxidative and hydrolytic
stability. Estolides are viable for the most severe lubricant and industrial applications, including
PCMOs, hydraulic fluids, greases, gear oils, metal working fluids, and  dielectric fluids.
   Estolides  have the  potential to  displace a  significant  portion of  the lubricant market,
reducing emissions and the release of hazardous chemicals into  the  environment. Test results
show that oleic estolide esters may also have  advantages  in performance and fuel efficiency over
petroleum-based PCMOs. LubriGreen is currently working with the world's largest formulators,
lubricant distributors, and others to commercialize its products during 2013.

 Biobased Chemicals from Low-Cost Lignocellulosic Sugars
   Most fermentation routes  that produce industrial  chemicals require glucose as  the main
 carbon source. These fermentations have significant disadvantages, however, due to the high cost
 of glucose, the volatility of the sugar markets, and competition with the food and feed industries.
 The substitution of inexpensive, abundant lignocellulose feedstocks for glucose can create a great
 advantage for producing organic chemicals.
   Lignocellulosic hydrolysates contain a variety of 5- and  6-carbon sugars as  well as toxins
 such as  acetic acid, furfural, and 5-hydroxymethylfurfural  (HMF). Because these toxins can
 inhibit bacteria from metabolizing sugars to  products, companies usually must remove them
 by "detoxification"  of the hydrolysates in a process  that adds unit operations and cost to the
 fermentation. Efficient fermentation of lignocellulosic hydrolysates requires microorganisms that
 can metabolize both 5- and 6- carbon sugars as well as tolerate the toxins  present in hydrolysates.
My riant Corporation

                    Myriant has successfully developed a proprietary process including evolved E. coli strains that
                 are able to metabolize multiple sugars simultaneously and can ferment lignocellulosic hydrolysate
                 without any detoxification. These proprietary biocatalysts are capable of fermenting low-cost,
                 non-food, lignocellulosic hydrolysate sugars as well as clean sugars to produce  organic acids
                 including lactic acid and succinic acid.
                    Lifecycle  studies  comparing Myriant's biosuccinic  acid  technology to  petroleum-derived
                 succinic acid showed a potential reduction in greenhouse gases (GHGs) of more than 50 percent,
                 Myriant's biosuccinic acid and biolactic acid will be used as drop-in and replacement chemicals
                 in current petroleum-based markets, Myriant is developing processes to manufacture biobased
                 butanediol, pyrrolidone, and acrylic acid.
                    In 2009, Myriant was awarded  $50  million from U.S.  Department of Energy (DOE),
                 which is supporting the company's commercialization of its lignocellulosic biosuccinic acid and
                 construction of a 30 million pound capacity  biosuccinic acid facility in Lake Providence, LA.
                 This facility will use primarily £ coli strain KJ122 to produce succinic acid from sorghum flour.
inc.          i   High-Performance Polyohfrom  CO2 at Low Cost
                    The vast majority of polyols currently used in coatings, foams, adhesives, elastomers, and
                  thermoplastic polyurethanes are derived exclusively from petrochemicals. Novomer has developed
                  a proprietary technology platform that transforms waste carbon dioxide (CCb) into very precise,
                  high-performance polyols at lower cost than polyols from either petroleum or natural oils.
                    Novomer's polyol technology platform combines several innovations. Novomer has developed
                  a breakthrough cobalt-based CO2~-epoxidc catalyst that is over 500-fold more active and far more
                  precise than past zinc-based catalysts. In 2011, Novomer modified its catalyst system with resin
                  bed technology to recover and recycle the catalyst without losing activity or selectivity, Novomer
                  wras also the first to develop lowr-molecular-wreight CC>2-based polyols using chain-transfer agents,
                  The manufacturing  process for Novomer's CC^-based polyols is a proven, low-cost, synthetic
                  technology based on chemistry. It can be completed in existing chemical industry infrastructure
                  under mild reaction  conditions with conversions of over 90 percent in short  timeframes. Using
                  CO? cuts raw material costs nearly in half, yielding a significant cost advantage.
                    The environmental and human health benefits  of Novomer's CO2-based  polyol technology
                  platform  are  considerable.  Because these polyols contain 40—50 percent CO2 by weight,
                  they can potentially sequester 10 billion pounds of CO2 per year in targeted polyol  markets.
                  More important, they enable the chemical industry to  eliminate 10 billion pounds per year of
                  petroleum-based raw materials, a source  reduction that impacts the entire petrochemical  value
                  chain. In addition, because Novomer polycarbonate polyols  contain no bisphenol A (BPA), they
                  can potentially eliminate the use of BPA-containing resins in food-contact coatings.
                    Novomer is commercializing its polyols in several markets. Jointly with the Dutch company,
                  DSM, Novomer will introduce its first large-scale commercial polyol product for coil coating
                  applications in 2012. In partnership with industry-leading polyol producers, formulators, and
                  end users, Novomer is developing additional polyol products for footwear foams, rigid insulating
                  foams, and polyurethane adhesives.

Electrodialysis       Chromatographic Separation

 Technology for Chlorine-Free Production of Potassium

Hydroxide and Hydrochloric Acid

  The United States consumes approximately 2 billion pounds of potassium hydroxide (KOH)
per year. The traditional chloralkali process for KOH uses electrolysis of potassium chloride in
water and produces chlorine gas (C13), hydrogen gas (H2), and KOH. C13 is a hazardous air
pollutant (HAP) that faces declining demand due to the phase-out of chlorinated chemicals.
  NSR has commercialized the first environmentally friendly, cost-effective alternative to the
chloralkali process in decades. NSR's new process manufactures  45—50 percent KOH  and
7 percent hydrochloric acid (HC1). The process uses NSR's novel electrodialysis lonSel™ stacks,
which include bipolar membranes of specialty polystyrenes modified with ion exchange groups.
The novel design of lonSel™ stacks allows the cells to operate at high efficiency consume
40 percent less energy, and generate high-purity products. The process rearranges ions in solution
and is particularly suited  to recycling  salts generated in other applications including those
from the  pulp and paper  industries  and  from the environmental control systems  in  coal-fired
power plants.
  NSR's  process yields high-purity, food-grade products without mercury (a health hazard to
children)  or oxidizing species like chlorate and hypochlorite. The lower energy consumption per
unit of KOH made by NSR's process allows smaller plants  to produce equivalent amounts of
HC1 and  KOH profitably. Smaller plants cost less, can be built close to end-users, and reduce
transportation hazards. NSR supplies food grade 7 percent HC1 to Archer Daniels Midland by
pipeline.  This efficient  transfer eliminates the  unnecessary transport and  accidental  release of
fuming 35 percent HC1.
  NSR's  single plant eliminated the production of 2 million pounds of C17 during 2011; at
full  capacity, it would eliminate the production of 10 million pounds per year of C12. NSR's
technology could potentially eliminate the production of billions of pounds of unnecessary C12.
each year.

Producing Industrial Chemicals by Fermenting Renewable

Feedstocks at a  Lower Cost
  Chemical producers are searching to meet growing worldwide demands for many  of today's
industrial chemicals with  renewable feedstocks and environmentally sustainable methods. The
transition to renewable feedstocks has been slow, however, because environmentally sustainable
processes must be cost-competitive with traditional petroleum-based chemicals.
  OPX Biotechnologies  (OPXBIO) has developed a proprietary platform technology called
Efficiency Directed Genome Engineering  (EDGE™). This technology allows OPXBIO to
develop and engineer microorganisms and bioprocesses faster and less expensively than traditional
methods. OPXBIO can now develop multiple chemicals cost-effectively from multiple renewable
  In 2011, OPXBIO developed a bioprocess for biobased acrylic acid (bioacrylic acid). OPXBIO
used its EDGE1M process to engineer both a microorganism to produce  3-hydroxypropionic
add  (3-HP) and  a process to manufacture  bioacrylic acid  renewably. A key focus was
developing a microbial strain with increased cellular pools of malonyl-CoA, the first committed
intermediate in the 3-HP production pathway. Many commercial products may be derived from
malonyl-CoA, including fatty acids (and  hence long chain alkanes), polyketides, and 3-HP.

  An initial lifecycle analysis (LCA) indicates that OPXBIO's process for bioacrylic add would
reduce greenhouse gas emissions by more than 77 percent and crude oil use by 82  percent
compared to traditional acrylic acid synthesis from propylene. If the entire global market for
acrylic acid (4.5 million tons annually) were replaced with OPXBIO's bioacrylic acid, greenhouse
gas emissions would be reduced by more than 5 million tons annually, and industry's use of crude
oil would decrease by approximately 2.5  million tons.
  In 2011, OPXBIO scaled up  its process  and  demonstrated the fermentation and primary
purification of 3-HP at 3,000 liters. If dextrose feedstock costs $0.14  per pound,  metrics
predict a commercial cost of bioacrylic acid at approximately $0.75 per  pound. This cost  is
competitive with the average cost ot petroleum-based acrylic acid in 2011, making the process
both environmentally and economically sustainable.

BURN-OUT™ Durable,  Green, Nontoxic Flame Retardant
  Each year, an estimated 4 billion pounds of polybrominated diphenyl ethers (PBDEs) are
used in flame retardant (FR) applications. There is growing evidence, however, that PBDEs
are toxic.
  Performance  Chemical has developed Burn-Out™ FR, a totally green, nontoxic, durable
replacement for PBDEs and other persistent, bioaccumulative, toxic  FRs. The Burn-Out™
compound is made of materials that comply with U.S. Food and Drug Administration (FDA)
regulations  for indirect food contact and safe for disposal. Phosphorus  and nitrogen arc  its
active ingredients; it is  formaldehyde-free. In  a  fire, Bum-Out™ FR  forms an intumescent,
thermal-insulating carbonaceous  char that acts as a barrier between the burning and unburned
material. Inert gases, mostly carbon dioxide (CC>2) and water, dilute the combustion gases and
cool the surface. Phosphorous-containing compounds react to form phosphoric acid and cause
charring. The Burn-Out™ compound releases nitrogen gas and dilutes the flammable gases in
synergy with the phosphorus.
  Burn-OutIM  FR resists water, alcohol,  oil, and grease, yet cleans up with soap and water.
Burn-Out™ FR contains ingredients that resist the growth of bacteria and fungi. In insulation
materials, Burn-Out™  FR resists the formation of airborne Legionella  bacteria, which can
multiply in water systems and are a source of Legionnaires' disease.
  In  customer  formulations,  Burn-Out™ FR compounds offer potential cost savings  of
20— 50 percent compared to current FRs containing halogen and PBDE—antimony. Performance
is equal to or exceeds that of other products.  Burn-Out™ FR reduces landfill  disposal  costs
associated with hazardous materials.
  Burn-Out1 M FR may be used in virtually all aqueous systems and  many polymer  systems.
Applications include paper, corrugated  packaging, woven  and  nonwoven textiles, insulation,
ceiling tiles, construction materials (e.g., wood, urethane insulation, and steel intumescent
coatings), adhesives, paints, and other FR coatings, especially in the automotive,  military,
and  marine markets.  Performance  Chemicals  is  planning  to  test Burn-Out™ FR  in
bedding  and mattresses. Performance Chemicals commercialized Burn-Out™ FR in 2011.
RPS Environmental
Solytions, LP
Zero-VOC Cleaning and Remediation Technology
  The pollutants in indoor environments can actually reach higher levels than those found
outdoors. Although several factors contribute to indoor air quality, fumes and residues from
the  cleaning chemicals currently used in our  homes, offices, and schools have a significant
negative effect  on  the quality of  the  air we breathe.  Many common cleaners  contain
dangerous  and harmful chemicals that are carcinogens, neurotoxins, hormone disrupters, and
reproductive toxins.

  RPS Environmental Solutions has developed products without volatile organic compounds
(VOCs) or harsh chemicals that it is currently using in a wide range of cleaning products from
degreasers and odor eliminators to adhesive removers and pet  care products. These products
are hypoallergenic, rapidly biodegradable, and have undergone rigorous testing to ensure the
greatest possible safety and efficacy. RPS carefully manages the entire lifecycle of its products from
manufacturing in a zero-discharge facility to using minimal-impact packaging.  Independent
laboratory testing with the American Society for Testing and Materials International (ASTM)
D 4488 protocol for cleaning efficacy shows RPS's products to be 3.5 times more effective than
those of the leading ''green" competitor, over twice as effective as those of the most-recognizable
name-brand  competitors, and over 30 percent more effective than those of the most powerful
competitor. Although  many competitive products compromise safety for effectiveness, RPS
cleaning products are both safer and more effective than those of their competitors.
   RPS technology has  leveraged hydration—dehydration,  metal  ion reaction, surface charge
modification, and the mechanics of conversion  to provide  cleaning and remediation products
that are safer for use near people, pets, and plants. RPS technology not only eliminates the need
to produce many dangerous chemicals, but can actually remediate environmental damage caused
by many harmful substances and improve human health by improving indoor air quality. RPS
expanded and launched several product lines during 2011; RPS products have been recognized
by EPA's Design for the Environment partnership program.

Sodium  Silicide: A New Alkali Metal Derivative for Safe,

Sustainable, and On-Demand Generation of Hydrogen

   Sodium silicide (NaSi) is  a stabilized, alkali metal silicide powder  that reacts with any
water solution to generate hydrogen instantly. SiGNa's patented NaSi powder is modified to
delocalize the electrons across the clathrate, forming an air-stable, free-flowing powder.
   In a fuel cell, NaSi produces pure hydrogen  gas as needed at pressures lower than those in
soda cans. NaSi overcomes the most-significant challenges that have prevented lowr-temperature
proton exchange membrane (PEM)  fuel cells from commercialization: storing high-pressure
hydrogen and building costly infrastructure. NaSi is clean, sustainable,  inexpensive, easily
transportable, and safe for indoor use. Fuel cells powered by  NaSi produce only hydrogen
and wrater vapor; they create no greenhouse gases, toxic byproducts, or harmful emissions.
Recyclable fuel cartridges deliver  NaSi to any PEM fuel  cell; once the NaSi is spent,  the
nontoxic, environmentally benign residue can be recycled as an industrial feedstock.
   SiGNa's NaSi technology offers significant environmental benefits throughout its lifecycle.
NaSi is  manufactured from  renewable, sustainable  materials that are  independent of oil
prices. The manufacturing process requires little energy and has a very small carbon footprint.
Replacing lithium batteries and internal combustion (1C) engines with NaSi fuel cells can
reduce the release of greenhouse gases (GHG)  by nearly 14  percent and significantly reduce
the amount  of toxic materials entering the waste stream.
   SiGNa's novel hydrogen-storage approach can enable cost-effective back-up and portable
fuel cells  for the medical, military, transportation, disaster  relief, and consumer electronics
industries. SiGNa's technology is proving that hydrogen fuel cells are not only commercially
viable, but even more high-performing and cost-effective than batteries or small 1C engines. For
example, NaSi can replace the combustion engine/gas back-up in battery-hybrid cars to extend
their range by 50 miles. Also, e-bikes powered by NaSi can go 3—4-times farther than bicycles
powered by lithium batteries. During 2011, licensee myFC commercialized  PowcrTrekk,  a
portable hydrogen charger, in Europe.

Verdezyne, Inc.
Biobased Adipic Acid for Renewable Nylon
Polyurethane Resins
¥H Biotechnology,
   Adipic acid (CgHioCX}) is an important industrial dicarboxylic acid with an estimated global
market of $6,5 billion. It is a feedstock for nylon 6,6 and polyurethane resins. It is currently
produced from petrochemicals by the nitric acid catalyzed oxidation of cyclohexane. This process
generates a waste gas stream including nitrous oxide, non-methane volatile organic compounds
(VOCs), carbon monoxide, and nitrogen oxides. The production of adipic acid from renewable
resources would result in substantial reductions of environmental pollutants.
   Verdezyne has engineered  an industrial strain of the yeast  Candida to produce adipic acid
from natural  plant-based oils. This yeast normally grows on fatty acids as  its  sole carbon
source by  cyclic  degradation  through its [3-oxidation  pathway.  A  Candida strain  in  which
this  pathway is  completely  blocked can  convert  these  substrates to the  corresponding
dicarboxylic acids  by selective oxidation  of terminal methyl  groups through  its co-oxidation
pathway to produce diacids with  a chain-length distribution  that precisely mimics that of its
plant-based oil feedstock. By engineering  both  the (3-oxidation and w-oxidation pathways of
yeast, Verdezyne has enabled the highly selective production of adipic acid from any plant-based
oil. This engineered strain tolerates saturating concentrations of adipic acid in the fermentation
broth, growing at the same rate and to  the same density as in its absence.
   In addition, Verdezyne has developed  fermentation and downstream  purification processes
to recover polymer-grade bioadipic acid from the fermentation broth  and  has synthesized nylon
6,6 fibers and pellets from bioadipic acid. The advantages of Verdezyne's biobased technology over
petroleum-based manufacturing include lower cost, sustainable feedstock supply, and a smaller
environmental footprint. Verdezyne estimates that its production costs will be  30—35 percent
lower than the petrochemical process. Verdezyne recently opened a pilot plant in Carlsbad, CA
to demonstrate the scalability of its process, validate its cost projections,  and generate enough
biobased adipic acid for commercial market development.

Bacteriocins: A Green, Antimicrobial Pesticide

   Pesticides  are used worldwide  to protect crops  and structures, manage pests,  and  prevent
the  spread of disease. Pesticides are intended to be toxic,  but only to their target organisms.
Their intrinsic properties, however, lead these pesticides to pose risks for human health and the
environment. There is a continuing need for safer pesticides to replace those that are toxic to
nontargct species.
   Through evolution, bacteria have acquired the ability to produce molecules such as bacteriocins
that  inhibit  other microorganisms. Bacteriocins  are  gene-encoded, ribosomally  synthesized,
antimicrobial peptides that are often  small in size (20—60 ami no acid residues).  Bacteriocins
combine with negatively charged surface constituents of target  bacteria, creating transmembrane
pores that make the target bacterial membrane permeable and thus kill the bacteria. Bacteriocins
are not toxic to eukaryotic organisms. They are generally recognized as safe  (GRAS)  by the
U.S. Food and Drug Administration. Moreover, they are currently  considered for therapeutic
applications  such  as the development of new vaccines against pathogenic, multidrug-resistant
bacteria and  as cytotoxic agents against human cancer cells.
   VH  Biotechnology has  developed a  novel,  green bacteriocin  composition  for use as a
microbicide in commercial applications including pulp and paper mills, fuels, biofuels, cooling
water systems, and poultry farms.  The bacteriocins are obtained by standard fermentation using
lactic acid bacteria. Two paper mills using these bacteriocins showed much  lower bacterial counts.
In diesel fuel, bacteriocins reduced microbial  levels by 99.95 percent over controls; in gasoline,
the  reduction was 89 percent. When  used to sanitize water on poultry  farms, bacteriocins at

100 grams per cubic meter of water were able to match the performance of chlorine at 12 grams
per cubic meter. VH Biotechnology developed this technology in 2008 and filed a U.S. patent
application for it in March 2010.


Concrete-Friendly™  Powdered Active Carbon  (C-PACM)

to Remove Mercury from Flue Gas Safely

   Coal-fired  power plants emit 45  tons  of gaseous  mercury into the air and  produce
65-5 million metric (MM) tons of fly ash annually in the United States, Fly ash has a composition
similar to that of volcanic ash, and is an excellent replacement for cement in concrete. Currently,
about half the concrete produced in the United States contains fly ash. Of the 65.5 MM tons
of fly ash generated in 2008, more than 11.5 MM tons were used in concrete and 16.0 MM
tons were used in structure fills, soil modification, and other applications. According  to EPA's
2008 report to Congress, federal concrete projects used  5-3 MM tons  of fly ash  in 2004 and
2005 to replace cement, saving about 25 billion megajoules of energy, saving 2.1 billion liters of
water, and reducing carbon dioxide (CCn) emissions by about 3.8 MM tons.
   Powdered activated carbon injection (ACI) is a conventional technology that injects  mercury
sorbents into  flue gas  in power plants and captures the mercury-laden sorbents in fly ash.
Although this reduces mercury emissions, the resulting  fly  ash is unsuitable for concrete and
requires disposal  in landfills. It mercury contamination  made all fly ash  unsuitable tor  use in
concrete, the 11.5 MM tons now used in concrete each year would require  more than 33 million
cubic feet of new landfill space at a cost of about $196 million.
   Albemarle designed, synthesized, developed, and commercialized its novel Concrete  Friendly
mercury sorbcnt, Concrete-Friendly™ Powdered Active Carbon (C-PAC™) .  C-PAC™ is
activated carbon  with tailored pore structures and surface properties. Albemarle manufactures
C-PAC 1Mfrom renewable carbon sources using a greener synthesis that includes gas-phase catalytic
bromination. C-PAC1M removes large amounts of mercury from air, preserves the quality of fly
ash for concrete use, safely sequesters  the mercury in  the concrete, and eliminates the  need for
new landfill space. Several power plants across the United States currently use C-PAC1M.

Upcycling Waste Plastic Bags into  Valuable Carbon

Nanotubes       Carbon Spheres
   Carbon spheres (CSs) and carbon nanotubes (CNTs) find uses in water purification, as additives
for lubrication,  in energy storage devices such as common  lithium-ion batteries, and in other
applications. At Argonne National Laboratory, Dr. Vilas Pol has discovered, implemented, and
patented an environmentally friendly process to remediate or upcycle waste plastic bags (WPBs)
into CSs and CNTs. Argonne's solvent-tree, solid-state-controlled pyrolytic process heats WPB of
single or mixed types to 700 °C in a sealed chamber  to produce pure CSs or CNTs. Systematic
characterization of the atomic structure, composition, and morphology ot the  CSs and CNTs with
advanced, structural, spectroscopic, and imaging techniques has elucidated, the mechanism of CS
and CNT formation.
   With no catalyst,  the process yields smooth CSs of 2—10 microns in diameter that are
conductive and paramagnetic. They can be used in toners and printers, as additives for lubricants,
and in the tire industry. Industrial collaborators, Superior Graphite and ConocoPhillips, have
heat-treated CSs at higher  temperatures; this improves their  electrochemical performance as
anodes for lithium-ion batteries.
   With a ferrocene catalyst, the  process yields  CNTs that Argonne has successfully tested as
anodes for energy storage devices and additives for lubrication. This process is the cheapest, most
straightforward way to fabricate CNTs in mass quantities. It also avoids the air and water pollution
caused by landfilling or incinerating "WPBs.

Armstrong World
Industries, Inc.
Armstrong World
Industries, Inc.
   The process uses less energy to manufacture these materials than  existing methods; it also
replaces a petrochemical feedstock with WPBs. By diverting plastic bags from landfills or toxic
incineration factories, this process reduces air and water pollution, ultimately reducing the hazards
to public health and environment.
   Argonne has designed  and  built a prototype  reactor  with  80 cubic centimeter  capacity
and  optimized the  reaction  conditions. Argonne is working  with Grupo  Simplex and
G2 NanoTcchnologies, LLC to commercialize this technology.

BioBased Tile®: A Non-PVC Flooring Made  with

Rapidly Renewable Resources
   Historically, resilient vinyl composition tile (VCT)  flooring has  been  manufactured  with
binders derived from fossil fuel. Poly(vinyl chloride) (PVC) is the primary binder used to combine
plasticizers, processing aids, stabilizers, limestone,  and  pigments into resilient flooring. Other
binders include polyolefins, ethylene acrylic resins, and synthetic rubbers.
   In 2008, Armstrong commercialized BioBased Tile'*' flooring, a revolutionary flooring product
that  uses natural limestone and a proprietary  polyester binder made from rapidly renewable
materials. Armstrong developed BioBased Tile® specifically to provide a PVC- and phthalate-
free alternative to VCT tor K-12 education applications. Armstrong is the first manufacturer in
over  100 years to develop a biobased polymer as  a binder for a hard-surface flooring product.
The  new binder created a new category of floor tile that couples improved indoor air quality and
environmental benefits with improved performance and affordability.
   The polymer binder contains 13 percent biobased content from rapidly renewable corn, which
reduces reliance on fossil fuels and lowers the  carbon footprint. It was built on technologies that
previously won Presidential Green Chemistry Challenge Awards (i.e., biobased polylactic acid
and  1,3-propanediol) to replace phthalate-plasticized PVC. The consumer product also  contains
10 percent preconsumer recycled limestone. Each year, replacing VCT with BioBased Tile® flooring
could save 140 million pounds of virgin limestone,  eliminate 336,000 pounds of volatile organic
compounds (VOCs) from manufacturing, capture  44 million pounds of carbon dioxide (CC>2)
from the atmosphere in biobased components, and  reduce energy consumption equivalent to
475  billion Btu (or 56 million pounds of CC>2).
   BioBased Tile® flooring is certified by Floor Score with no detectable VOCs. It  contains
no materials listed in the  table  of Chronic Reference Exposure Levels (CRELs) established  by
California's Office of Environmental Health Hazard Assessment (OEHHA). For green building
initiatives, BioBased Tile® contributes up to four points toward LEED certification and will  be
NSF 332 certified in January 2012.

Breakthrough Formaldehyde-Free Coating for Ceiling  Tiles
   Ceiling tiles  can sag if  they are not engineered to resist  humidity. Armstrong  and other
ceiling  tile  manufacturers  have historically  applied rnelamine—urea—formaldehyde or  other
formaldehyde-based  resins as  back  coats to prevent ceiling tiles from  sagging.  Although
formaldehyde is key ingredient in many building products, there is now great concern for its use.
Formaldehyde is a colorless, flammable, odorous gas that is a classified as a "known carcinogen"
by the International Agency for Research on Cancer (IARC) and as "reasonably anticipated to be
a human carcinogen" by the National Toxicology Program (NTP).
   Armstrong World Industries has developed a formaldehyde-free, waterborne coating that can
be applied to the surface of any fibrous panel such as a ceiling tile to  prevent  sagging. Armstrong
did extensive research to develop a new coating that expands hydroscopicly at high humidity to
resist sag, maintains a high modulus even at high humidity, and is compatible with other coatings

and fillers. The new coating system includes a binder based on a combination of dextrose and
ammonia-neutralized polyacrylic acid.
   Armstrong will use its newly invented coating technology to replace all formaldehyde resin
ceiling tile applications. By implementing this new technology globally, Armstrong will eliminate
8.3 million pounds of formaldehyde resins, 416,000  pounds  of formaldehyde  air  emissions,
and 134,000  pounds of triethylamine air emissions annually. Eliminating formaldehyde resin
(1) avoids employee formaldehyde exposure at four Armstrong manufacturing facilities in  the
United States and five international facilities; (2) eliminates formaldehyde and triethylamine stack
emissions associated with the cross-linking process  for the  traditional melamine—formaldehyde
ceiling tile back coat; (3) eliminates potential formaldehyde emissions from finished products after
installation; and  (4) reduces lifecycle  assessment impacts associated  with  upstream production
of formaldehyde. Armstrong has already successfully converted several key products to the new
technology and is converting its remaining products.

Envirez* Technology: Incorporating Renewable

Recycled Feedstocks into  Unsaturated Polyester Resins

   Unsaturated  polyester resins are key  components  of  fiber-reinforced  plastic  thermoset
composites. The annual production of these resins in North America is approximately 1 billion
pounds. Historically, these resins have been made almost exclusively from virgin petrochemicals.
Expanding on the pioneering work of Professor Richard Wool  at the University of Delaware,
Ashland developed Envire"/™ resins, a novel, versatile family of unsaturated polyester resins made
from either renewable or recycled raw materials or both. Ashland uses biobased building blocks
including soybean oil, ethanol, 1,3-propanediol, and  other proprietary monomers from  soybeans,
corn,  and  other renewable raw materials. Additional building blocks for Envirez1M  resins are
recycled monomers and polymers including postconsumer poly(ethylene tcrcphthalatc) (PET).
   Ashland recently developed the first EnvirezIM resins that employ recycled raw materials and
use combinations of both recycled and renewable rawr materials. Envirez™ resins now contain
more  types and higher percentages (up to 40 percent) of renewable raw materials. Ashland has
developed formulations for a wide variety of composite fabrication methods including infusion,
pultrusion, casting, and  gelcoats. These formulations expand the reach  of Envirez1M into  an
assortment of products and markets including green buildings and wind energy devices. They
enable composite fabricators to use sustainable components.
   EnvirezIM technology leads to reduced  dependence  on petroleum, lower emissions, energy
savings, and a smaller carbon footprint. In the last three years, Envirez™ resins have incorporated
over 12 million pounds of recycled PET. Using a novel, biobased reactive intermediate, Ashland
has developed EnvirezIM lowstyrcne resins that lower the traditional styrene content by  one-third
and reduce both hazardous air pollutants (HAPs) and volatile organic compounds (VOCs). The
Envirez™ product line has experienced double-digit growth in the past several years. Envirez™
low styrene resins have completed review under the  Toxic Substances  Control Act (TSCA) and
are undergoing field trials at numerous composite fabricators.

Compostable Multilayer Food Packaging
   Most conventional  food  packaging consists of  a multilayer film structure  comprised  of
polyolefin  or polyamide resins  and adhesives. The  layers include barriers, colorful print, and
adhesives to bond all the layers together. Because conventional packaging is neither recyclable nor
compostable, landfills are the only disposal option.  When organic material goes into  a landfill
it degrades over  time, releasing landfill  gas (LFG), which  is  a  mixture of the environmental
Ashland Performance
BASF Corporation

     Bayer AG
                               pollutants methane gas and carbon dioxide (CC>2). Because less than 30 percent of the landfills
                               in the United States collect LFG, the majority of organic material placed into landfills eventually
                               releases LFG,
                                 In 2011, BASF's Biodegradable Polymers Group successfully made a completely compostable
                               multilayer food packaging structure with high barrier properties. The structure consists of six
                               layers: an Ecoflex'8' and Ecovio'8' outer layer, Joncryl SLX (printing ink layer), Epotal P 100 ECO
                               (adhesive coating), a metallization layer, Versamid'8'  (pre-met primer), and an Ecoflex® and
                               Ecovio*1 inner layer. Ecoflex'8'is a bioplastic copolyester and Ecovio® is a compound of Ecoflex'*
                               with polylactic acid (PLA). This packaging structure meets the barrier requirements for a large
                               number of packaged consumer goods.
                                 For the first time, food packaging wastes can be diverted to industrial composting facilities
                               that create end-of-life value far beyond putting the packaging in landfills. Composting and the
                               subsequent use of the finished compost produce beneficial factors for the  environment and
                               resource management. BASF compostable multilayer packaging will allow landfill  diversion
                               for programs throughout the United States that are working  toward Zero Waste.  One of the
                               benefits of diverting organic waste from landfills is increasing landfill lifespans. This reduces the
                               need to build new landfills or expand existing ones, which will save energy, reduce  emissions to
                               water, and reduce air pollutants from building new landfills. BASF is partnering with the Seattle
                               Mariners in their zero waste initiative through the Green Sports Alliance to replace trash cans
                               with recycle and compost bins.
One-Component,  UV-Curable, Waterborne
Polyuretbane  Coatings
                                 In the 198()'s, Bayer MaterialScience (BMS) developed water-based unsaturatcd polyesters
                               that were  UV-  or peroxide-curable and reduced volatile organic compounds  (VOCs) and
                               very hazardous air pollutants (VHAPs). Unfortunately, this technology did  not displace the
                               acid-catalyzed nitrocellulose lacquer systems. In 1992, Bayer's two-component (2K) water-based
                               polyurethane coatings entered the wood coatings market. This technology displaced high-VOC
                               and high-VHAP coating systems and won the 2000 Presidential Green Chemistry Award, but
                               it was limited in its  user-friendliness and slow drying speeds,  especially on automated wood
                               coating lines.
                                 In 1999, BMS developed a one-component (IK), UV-curable, waterborne  polyurethane
                               with reduced VOCs  and VHAPs for wood coatings. In this nominated process,  BMS reacts a
                               polyisocyanate and a polyol in a BMS production facility to create a polyisocyanate prepolymer.
                               They then react this with a UV-curable polyol through an  isocyanate—alcohol reaction to
                               form IK, UV-curable waterborne polyurethanes. The process develops high-molecular-weight
                               polymers (over 200,000 g/mol) in water without residual isocyanate monomer or polyisocyanate
                               prepolymer. The product contains ultra-low VOCs because BMS's proprietary process removes
                               the acetone carrier after manufacturing.
                                 Renowned manufacturers of office furniture now advertise  products made with  BMS
                               coating systems as having low emissions and being environmentally compatible. Large furniture
                               companies are increasingly specifying coating systems with low or no solvent. BMS coatings cure
                               in just seconds under UV light and meet low- or no-solvent specifications very cost-effectively.
                                 Between 2007 and  2011, commercial use of this coating system to replace acid-catalyzed
                               varnishes or  nitrocellulose lacquers resulted  in reductions of  50—90 percent for VOCs and
                               50—99 percent for VHAPs, which is equivalent to removing  2.6 million pounds of organic
                               solvents  and 49,000  pounds of formaldehyde from the U.S. environment. Emerging markets
                               for BMS's IK UV-curable waterborne polyurethane include aerospace and  defense, site-applied
                               UV-cured  flooring, sunshine-cured  wood decking, special effects coatings, and wet-strength

FIREBLOCfC™ Intumescent Resin
   Composites used  to  manufacture interior and  exterior parts for  applications  in  trains,
tramways, subways and other rolling stock must meet fire retardant specifications. Traditional
chemicals used in fire retardant composites are decabromodiphenyl ethers and antimony trioxide,
which  are carcinogens, mutagens, and reproductive toxins. The manufacturing of these fire
retardant composites requires handling highly toxic substances. In case of accidental combustion,
polybrominated aromatic compounds release free radicals that act in synergy with  antimony
trioxide to produce bromide radicals and toxic fumes.
   Intumescent coatings  swell with heat, offering passive fire protection. Intumescent coatings
have been known for years, but these products were very difficult to formulate and apply. In 2008,
CCP Composites developed a breakthrough product, FIREBLOCK™ intumescent unsaturated
polyester resins (LJPRs), which can be molded with glass fiber to manufacture fire retardant parts.
In the intumescence mechanism, high temperatures cause  ammonium polyphosphate to  release
an acid  that simultaneously reacts with melamine in the resin to liberate a gas. The gas diffuses
into small bubbles and carbonizes the carbon-rich polyalcohol. These actions form foam  that
solidifies into a char and shields the underlying material to  stop the combustion cycle.
   FIREBLOCK™ resin is a commercially viable alternative to bromine-containing fire retardant
LJPRs used in a wide variety of composites. It is completely free of halogens, mutagens, carcinogens,
and reproductive toxins. In addition to meeting the same standards on materials fire behavior as
do  traditional fire retardants, FIREBLOCK™  intumescent resin also has a lower density than
standard unsaturated polyester resins. It is environmentally friendly, with a 13 percent reduction
in carbon dioxide  (CO2) emissions compared to standard fire retardants in the railway industry.
A significant portion of today's estimated  10 million pounds annual use of brominated  LJPRs
could be converted into FIREBLOCK™ technology in the next five years in the United States.

Vegetable Oil Insulating Fluid for Improved High Voltage

Transformer Capability
   Fob/chlorinated biphenyls (PCBs) form  the basis for traditional dielectric coolant fluids,  but
they present environmental problems and liabilities for the electric power industry. Cooper  Power
Systems has developed a replacement insulating fluid, Envirotemp™ FR3™ fluid, to provide the
electric power industry with a sustainable dielectric coolant  that has an innocuous environmental
and health profile. Envirotemp™ FR3™  fluid contains approximately 97 percent food-grade
soy oil blended with small amounts of additives for long-term performance.
  The National Institute of Standards and Technology (NIST) directly compared FR3™ fluid
to mineral oil in its total lifecycle assessment called BEES®  4.0, Building for Environmental and
Economic Sustainability.  Using the carbon  dioxide equivalent (CO2 eq.) amount of greenhouse
gas  (GHG) generated from raw materials through end of life, FR3™ fluid has reduced  GHG
emissions by over 98 percent (or over 102,000 tons of CC>2 eq.) to date compared to mineral oil.
This essentially carbon-neutral result assumes that FR3™' fluid or mineral oil would be placed in
equivalent transformers. Roughly 450,000  transformers now contain over 25 million gallons of
Envirotemp™ FR3™ fluid instead of petroleum-based mineral oil.
   In  2011, Cooper  combined  the  chemistries of FR3™ fluid and  solid insulating  paper
with advanced high voltage transformer design  to produce a new generation  of even greener
biotransformers. The chemical interactions between FR3 ™ fluid and the solid insulating structure
create greater thermal capacity that allows an optimized biotransformcr design. With this increased
capacity, Cooper removed 3—15 percent of the fluid volume and  3 percent of the construction
Cooper Power

Cytec              Inc.
materials from the biotransformers. Using the BEES analysis on 25 million gallons of FR3™ fluid,
the new generation of biotransformers could save an additional 2,000 tons of GHG emissions.
Other advantages include improved fire safety, remediation of accidental spills, and sustainable
supply benefitting U.S. farmers. New transformer designs with FR3™  fluid will be available
in 2012.

Saturated Polyester—Phenolic Resin Systems for Bisphenol

A-Free Interior Can Coatings for Food Packaging
   Bisphenol A (BPA) is a key raw  material for the binders in interior coatings of food cans,
but recent animal studies  have found that BPA exhibits potential endocrine-disrupting effects.
Because these coatings are a significant source of consumer exposure to BPA, the food industry
is demanding coatings without BPA. Although  U.S. regulatory agencies have not promulgated
regulations, the elimination of BPA from interior can coating systems is a matter of public and
scientific  interest.
   Cytec  has developed  a  new generation of BPA-free, saturated polyester resins  for the main
binder. These polyester resins, together with phenolic resins, can be used in interior can coatings.
Coating  systems based on these  resins exhibit performance comparable to conventional,
high-molecular-weight epoxy systems with the additional advantage of being completely free of
residual epoxy resin monomers and their byproducts (e.g., BPA, bisphenol A diglycidyl ether, and
its derivatives).
   Cytec's saturated polyester resin, DUROFTAL PE 6607/60BGMP, has a predominantly linear
structure  and a molecular weight of approximately 10,000 daltons. All  the monomers in its
synthesis  comply with food contact laws. It does not contain any significant levels of free solvent
if properly cured, and it complies fully with the U.S. Food and Drug Administration's (FDA's)
regulation 21 CFR §175.300  for polyesters. Computer modeling indicates that DUROFTAL
PE 6607/60BGMP docs  not have the cstrogenic properties of BPA. It is more flexible than
conventional systems based on high-molecular-weight epoxy resins.
   Although DUROFTAL PE 6607/60BGMP is compatible with most  existing cross-linkers
(predominantly phenolic resins and  amino resins), Cytec designed a new,  tailor-made phenolic
resin  for  interior can coatings so  the system  can eliminate  BPA  completely and perform
comparably to existing systems. Commercial sales began in 2008. In 2010, Cytec began its  first
full-scale production of the phenolic part of the system. In 2011, Cytec's first commercial sales of
DUROFTAL PE 6607/60BGMP eliminated about 10 tons of BPA.
The Dowr Chemical
EVOQUE™Pre-Composite Polymers
   Titanium dioxide  (TiO?)  is the primary white  pigment in  paint; it provides opacity by
scattering visible light. The process that derives TiOi from titanium ore requires large quantities
of energy, complete digestion with excess chlorine or sulfuric acid, and a multistcp purification.
   Dow has developed EVOQUE™  Pre-Composite  Polymer Technology for making paint
with 10—20 percent less TiO2. Dow controls the interaction between individual pre-composite
polymers and TiO2 pigment particles to achieve a TiO?-centered structure  surrounded by
polymer molecules. As the pigment-polymer composites in paint dry to a film, the prc-compositc
polymers keep the individual TiC>2 particles separated so they are evenly distributed. Performance
benefits resulting from improved film formation and reduced photodegradation (due to reduced
TiO2,  which promotes  photodegradation)  are expected to  improve exterior durability by
20 percent.

   Third-party validated, lifecycle assessment (LCA) shows that TiC>2 reductions facilitated by
EVOQUE™ Pre-Composite Polymer Technology in exterior house paint reduce the associated
carbon footprint by 22.5 percent, water consumption by 30 percent, NOx and SOx emissions
by 24 percent, potential water eutrophication (algal bloom) by 27 percent, potential chemical
oxygen demand (COD) by 30 percent, and non-methane volatile compounds (NMVOC) by 35
percent. These last two factors impede water quality and air quality, respectively.
   EYOQUE1M Pre-Composite  Polymer  Technology is currently compatible with wrhite and
pastel acrylics, which account for approximately 165  million  gallons of U.S. paint produced
annually. Based onTiC>2 removal alone, using EVOQUEIM Pre-Composite Polymer Technology
in half of this paint could reduce associated greenhouse gas (GHG) emissions by approximately
54,000 metric tons of carbon  dioxide equivalents (CO? eq.). The enhanced performance and
durability expected from paints  with EVOQUE™ Pre-Composite Polymer Technology could
increase this reduction to 123,000 metric tons of CO2 eq., which is comparable to the annual
CO2 emissions generated from the gasoline used by approximately 14,000 cars.
         SED Olefin Block Copolymers
   INFUSE™ Olefin Block Copolymers (OBCs) are produced with a patent-pending shuttling
process  that represents an innovation  in catalyst  technology and that delivers breakthrough
performance using new combinations of properties. These block copolymers have  alternating
blocks of "hard" (highly rigid) and "soft" (highly elastomeric) segments as the result of reversible
chain transfers between two  different catalysts. Dow's catalytic shuttling technology generates
a variable, yet controllable, distribution of block lengths that can generate tailor-made olefins
for specific uses. OBCs have  highly differentiated material properties that break the traditional
relationship between flexibility and heat resistance. They also  provide significantly improved
compression set and elastic recovery properties compared to other  polyolefin plastomers and
elastomers. OBCs possess the ease of formulation and processing that are typical of polyolefins.
   The unique block architecture of OBCs enables Dow's  customers to expand into a wide
range of innovative market applications currently  served by high-performance thermoplastic
elastomers, thereby adding value  to fabricators and end-users alike. The sustainable chemistry
benefits of OBCs include (1) atom  efficiency due  to improved  selectivity; (2) reduced toxicity
and risk compared to other polymers; (3) minimized auxiliary substances  because the  complex
chain-shuttling, dual-catalyst  system is highly efficient; (4) reduced energy requirements for both
polymer synthesis and fabrication; and (5) better recycling and end-of-life management because
OBCs are compatible with disparate plastic waste streams and can even enhance the quality of
waste streams. The OBC manufacturing process fits into existing facilities with only limited
changes to equipment, leading to  significant resource savings. OBCs are suitable for a very large
number of applications; their economic benefits are great, thereby enhancing market  selection.
   Dow created  INFUSE™ OBCs using its 1NSITE™ Technology. From 2008 to 2011, Dow
OBCs replaced a number of existing  polymers including styrene— ethylene— butylene— styrene
(SEBS),  thermoplastic vulcanizatcs (TPV),  and   flexible  poly(vinyl chlorine)  (f-PVC) for
85 customers  worldwide.

Chlorantraniliprole: Increased Food Production,  Reduced

Risks,  More Sustainable Agriculture

   The caterpillar larvae of many lepidopteran species are major agricultural pests,  defoliating
plants and attacking  fruit and root systems. Lepidopteran pests  are likely responsible for
30—40 percent of insect damage to crops; they consume 50 percent of all crops in many developing
countries. Although insecticides arc available to control these pests, many present significant risks
to humans or the environment.
The Dow Chemical
 DyPont Company

       DuPont redesigned its discovery  process for new pesticides  by integrating chemistry and
    biology with lexicological, environmental,  and site-of-action studies  to  optimize  safety and
    product performance simultaneously. The resulting product, chlorantraniliprole,  has  excellent
    safety and environmental profiles yet is one of the most potent, efficacious  chemical insecticides
    ever discovered.
       Chlorantraniliprole selectively interferes with muscle contraction in insects by activating a site
    in ryanodine receptor channels that is highly divergent between insects and mammals. Because
    it selectively targets insects, chlorantraniliprole is inherently safer to people and other nontarget
    organisms. EPA  classifies chlorantraniliprole as  a reduced risk pesticide. It  may be the safest  of
    all lepidopteran  insecticides, including those derived from  natural sources. Chlorantraniliprole
    is usually one to two orders of magnitude more potent against target pests  than are pyrethroids,
    carbamates, and organophosphates. Its lower use rates mean less pesticide gets  into the environment
    with a corresponding reduction in the exposure of workers and the public.  ChlorantraniHprole's
    proven safety to bees and other beneficial arthropods allows its use in integrated pest management
    (IPM) programs. In  addition, its mode of action provides an important new tool for managing
    insecticide resistance.
       DuPont manufactures chlorantraniliprole  in a convergent commercial process that minimizes
    organic solvents, recovers and  recycles  the  solvents  it does use, minimizes  waste, eliminates
    regulated waste products, and establishes inherently safer reaction conditions. Chlorantraniliprole
    is rapidly  displacing less desirable products from many key markets. In 2011  alone, more than
    20 million farmers and 400 crops benefitted from insect control by chlorantraniliprole.

 I  Development of a Commercially Viable, Integrated,

    Cellulosic Ethanol Production Process
      Traditional production of ethanol from starches, such as corn grain, diverts resources from
    food production. DuPont has developed a biochemical technology that  produces ethanol from
    non-food lignocellulosic bio mass such as corn stover. DuPont's process is an integrated pathway
    with sufficiently  high yields and liters of ethanol to be commercially viable.
       It integrates three components: First, dilute ammonia pretreatment decouples the carbohydrate
    polymers from the lignin matrix with minimal formation of compounds that inhibit subsequent
    fermentation. This pretreatment runs at up  to  70 percent biomass with less than 10  percent
    ammonia  by weight. Second, genetically engineered cellulase and hemicellulase enzymes from
    Hypocrea jecorina (a filamentous fungus) produce high yields and liters of fermentable 6-carbon
    and 5-carbon sugars. Third, the optimized metabolic pathways of a recombinant ethanologen
    (Zymomonas mobilis)  produce  ethanol efficiently  by simultaneously  metabolizing  both the
    6-carbon and 5-carbon sugars. Integrating and optimizing these three components enables a very
    efficient process, a green footprint, and lower costs, including less capital investment than other
    known cellulosic ethanol processes. If corncob feedstocks cost $50 per dry ton, the ethanol from
    DuPont's process could cost less than  $2 per gallon.
      Removing the yield, titer, and cost barriers to commercializing cellulosic ethanol is a significant
    step  toward large-scale  production  of cleaner,  more  sustainable liquid transportation  fuels.
    Comprehensive well-to-wheel lifecycle assessments  (WTW  LCA) show that  DuPont's  process
    could potentially reduce greenhouse  gas (GHG) emissions  by over 100 percent compared to
    gasoline, which  is substantially larger than GHG reductions from other grain-based  ethanol
      A flexible-feedstock, 250,000 gallon-per-year demonstration facility in Vonore, TN is currently
    yielding over 70 gallons per U.S. ton of biomass and ethanol titers in excess of 70 grams per liter.
    In 2014, the first commercial-size facility to convert corn stover  to over 25 million gallons of
    ethanol annually is expected to start up in Nevada, IA.


Production  of Isobutanol from the Synergy between

Metabolic and Process Engineering

   Isobutanol, an  advanced biofuel, offers significant technical and commercial advantages over
fossil fuels and ethanol.  Isobutanol has a high octane number, good distillation qualities, low
vapor pressure, high compliance value in fuels, materials compatibility, low toxidty, and the
ability to reach targeted production economics,
   DuPont was the first to create and develop integrated biological and process technologies
that use microbes to produce isobutanol from renewable resources. DuPont's strategy for low-
cost commercialization includes retrofitting existing ethanol  plants to produce isobutanol from
current ethanol-industry feedstocks (i.e., corn grain and sugarcane), lignocellulosic biomass, and
macroalgae (seaweed). A proprietary yeast strain engineered  with a novel biosynthetic pathway
ferments sugars from these feedstocks to isobutanol. DuPont selected key enzymes based on their
isobutanol specificity and cofactor requirements, then maintained flux through to isobutanol by
eliminating byproduct reactions that could compete with the chosen pathway. This yeast-based
isobutanologen is  a drop-in biocatalyst suitable for  retrofitted ethanol plants.
   A major challenge in commercial isobutanol production by microbes is the intolerance of the
microbes to commercially relevant aqueous liters of isobutanol. DuPont met this challenge by
reducing the aqueous concentration of isobutanol in fermentations, thereby avoiding enzyme
inhibition by its product while minimizing production cost and environmental footprint.
   The  fermentation rate, titer,  and yield  are significantly superior to  those of traditional
acetone—butanol—ethanol (ABE)  fermentations. This performance  demonstrates cost-effective
biological production of isobutanol for chemicals  and fuels. DuPont's technology can displace
petroleum-based syntheses for  isobutanol and directly replace refined gasoline from crude oil
with a greener, biobased product. Further, its advantages over incumbent technologies include
reducing greenhouse gas (GHG) emissions by 40—70 percent, local and  national  economic
benefits, and increased national security through domestic fuel supplies. During 2011, DuPont
began operating a large-scale demonstration plant for isobutanol in the United Kingdom in  a
joint venture with Butamax™ Advanced BioFuels.

Grignard Reactions  Go Greener with Continuous

   The synthetic pathways of numerous intermediates tor food additives, industrial chemicals, and
pharmaccuticals have included  the Grignard reaction since the start of the 20th century. Despite
these successes, the acute hazards of the Grignard reaction make it one of the more challenging
reactions to bring to commercial scale. These hazards include: (1) strongly exothermic activation
and reaction steps; (2) heterogeneous reactions with potential problems suspending and mixing
the  reaction mixture; and (3)  extreme operational hazards posed by ethereal solvents such as
diethyl ether.
   Eli Lilly and Company has developed inherently safer Grignard chemistry using a continuous
stirred tank  reactor (CSTR)  that allows continuous  formation  of Grignard reagents  with
continuous coupling and quenching operations. This strategy minimizes hazards by operating
at a small reaction volume, performing metal activation only once for each  campaign and using
2-methyltetrahydrofuran  (2-MeTHF), as a Grignard  reagent and reaction  solvent that may be
derived from renewable resources. Grignard reactions using 2-MeTHF also result in products with
enhanced chemo- and stereoselectivity. Relative to batch processing, the continuous approach
allows rapid, steady-state control and  overall reductions up to 43  percent in magnesium, 10
percent in Grignard reagent stoichiometry, and 30 percent in process mass intensity (PMI). The
DuPont Company

Eli Lilly and

continuous approach reduces reaction impurities substantially. In addition, small-scale operation
at end-of-reaction dilution allows all ambient processing conditions.
  Lilly is using its CSTR Grignard approach to produce three pharmaceutical intermediates. One
of these is the penultimate intermediate of LY2216684. HC1, a norepinephrine reuptake inhibitor
that is under phase 3 clinical investigation for treatment of depression. Lilly uses a similar approach
to synthesize an intermediate for LY500307, an investigational new drug candidate under clinical
evaluation  to  treat  benign prostatic hyperplasia. Lilly anticipates commercial production  on
22 liter scales that will replace the 2,000 liter reactors used in batch processes.

Catalytic Treatment of Hydrogen Peroxide  in IBM

Semiconductor Wastewater

  Semiconductor manufacturing produces a large ammonia and hydrogen peroxide wastewater
stream that requires treatment. Through 2009, the industry standard for treating this wastewater
stream was to reduce the hydrogen peroxide with sodium bisulfate then  to neutralize it with
sodium hydroxide. The next step was separating ammonia by distilling the wastewater to remove
ammonium hydroxide. The added sodium bisulfite and sodium  hydroxide contributed high
levels of total dissolved solids (TDS) to IBM's wastewaters and final effluent discharge, and both
were also becoming increasingly expensive.
   In 2003,  IBM's East Fishkill plant (EFK)  began an initiative with  the New York State
Department of Environmental Conservation to reduce the TDS in the site's effluent discharge to a
small receiving stream. Over the next six years, IBM EFK investigated alternative technologies to
remove sources of TDS from its manufacturing wastewaters and wastewater treatment processes.
In early 2009, IBM qualified a catalytic enzyme process to replace  the existing sodium bisulfate
process for removing hydrogen peroxide from the ammonia wastewater. This process uses a small
quantity of a  catalase derived from Aspergillus niger fermentation  to decompose peroxide into
water and oxygen. It does not contribute TDS to the site's effluent discharge and costs a fraction
of the previous treatment. The new process incorporates existing building equipment as much as
possible and integrates flawlessly into the existing treatment system.
  IBM started and completed design and construction  of the full-scale peroxide treatment
system  in 2009,  with startup continuing through March 2010. Annually, this  new process
eliminates the use of 510,000 gallons of 38 percent sodium bisulfite and 135,000 gallons of
50 percent sodium hydroxide for acid neutralization. It reduces chemical costs by $675,000 per
year. The catalytic reduction of hydrogen peroxide process has been online continuously since
the beginning of 2010 and is currently patent-pending.

Elimination ofPFOSandPFOA in IBM  Semiconductor

Manufacturing Processes       Development ofPhotoacid

Generators Free of Perfluoroalkyl Sulfonates

   In 2002, EPA restricted new applications of perfluorooctane sulfonate (PFOS) compounds
because scientific evidence showed that PFOS persists and bioaccumulatcs in the environment.
Because semiconductor manufacturers demonstrated limited release and exposure for PFOS,
however, EPA allowed PFOS compounds "as a component of a photoresist substance, including
a photoacid generator or surfactant,  or as a component of anti-reflective  coating, used in a
photolithography process to produce semiconductors or similar components of electronic or
other miniaturized devices."

   Voluntarily, IBM began searching for alternatives to PFOS and perfluorooctanoate (PFOA).  In
2006, IBM issued a Corporate Directive to eliminate PFOS  and PFOA from all manufacturing
processes by 2010. IBM worked  with  chemical suppliers to  identify and qualify a non-PFOS
replacement tor the  PFOS surfactant in buffered oxide etch (BOE)  chemicals. In 2008, after a
multiyear investigation and extensive qualifications, both IBM fabrication plants finished replacing
the PFOS surfactant in all BOE chemicals with perfluorobutane sulfonate (PFBS), for which EPA
has fewer environmental concerns.
   IBM also sought replacements for specific photoresists  and  antireflective coatings (ARCs) that
contained PFOS or PFOA as a surfactant or photoadd generator (PAG). In January 2010, after
significant investment and qualification of replacement chemistries  across many wet etch and
photolithography processes, IBM completed its conversion to non-PFOS, non-PFOA lithographic
chemicals. This change eliminates  approximately 140 kilograms of PFOS and PFOA annually.
Total annual PFOS consumption by the semiconductor industry worldwide is estimated at 8,000
kilograms. IBM believes it is the only company in the world to eliminate PFOS and PFOA compounds
completely from semiconductor manufacturing. IBM has also developed PAGs free of perfluoroalkyl
sulfonates (PFAS) for both dry and immersion 193-nm semiconductor photolithography processes,
with equivalent performance  in 45-nm and 32-nm semiconductor technology. IBM is pursuing
technology transfer  opportunities  to  commercialize its PFAS-free PAGs  for a wider range  of
NATRASURFIM PS-Ill Polymeric Surfactant: Achieving

Next Generation Mildness in Personal Care Products with

a Reduced Environmental Footprint
   The production of personal  cleansing  products,  such  as shampoos, body washes, and facial
cleansers, consumes sizable, ever-increasing volumes of surfactants. Traditionally,  the  industry
used largely nonrenewable, petroleum-derived synthetic detergents to achieve mildness in personal
cleansers. Although these well-established surfactants are safe and cost-effective, they could be
improved in their mildness, renewability, manufacturing processes, and biodegradability.
   Johnson  &  Johnson  and  AkzoNobel  have  collaborated  to   develop  NATRASURF™
PS-Ill, an innovative, starch-based polymeric  surfactant (PS) for  formulating mild  personal
care products.  PS-Ill is based on  the patented discovery that  PSs  overcome the problem of
surfactant-induced  irritation  because they  cannot penetrate  living tissue.  NATRASURF1M
PS-111, the first personal care ingredient of its kind, delivers the cleaning and foaming performance
of traditional surfactants and. has virtually no irritation potential.
   NATRASURF1M   PS-Ill   minimizes  environmental  impacts   throughout   its   lifecycle.
PS-Ill  is sodium hydrolyzed potato starch dodecenylsucdnate, a 90 percent renewable material
derived  by reacting  hydrolyzed potato  starch  with an  alkenylsucdnic  anhydride.  This  low-
temperature, aqueous  esterification offers many advantages over traditional esterifications, including
energy efficiency and  atom economy. The starch ester used for PS-111  is nonirritating to skin and
eyes, nonallergenic, nontoxic to  humans and aquatic organisms, nonbioaccumulative, and readily
biodegradable.  PS-Ill  is  supplied  to manufacturers  as  a  self-preserving, spray-dried  powder;
this eliminates  the need for chemical preservatives and reduces the energy  used to store  and ship
conventional aqueous surfactant  solutions.
   PS-Ill  has  the potential to replace  millions of pounds per year of  nonrenewable, poorly
biodegradable surfactants and emulsifiers. Further, this technology can  be readily leveraged for use
Johnson Consumer
Companies, Inc.
AkzoNobel Surface
Chemistry LLC

Kop-Coat, Inc.

in agricultural, household, and industrial applications. NATRASURF™ PS-111 exemplifies how
green chemistry can enable cost-effective, sustainable materials that benefit both consumers and
the environment without sacrificing performance or efficacy. In December 2011, Johnson &C
Johnson launched the AVEENO® Pure Renewal line of shampoos, the first products containing

 Tru-Core® Protection System for Wood
   Wood  is the most  widely  used residential  building material  in the  United States.  Its
environmentally positive characteristics include excellence as a carbon sink, low embodied energy,
and high sustainability. Among its few shortcomings, however, is its relative lack of durability due
to its susceptibility to decay and insect attack. Preservatives and insecticides can improve the
durability of wood significantly, but methods to deliver  these protectants into wood are largely
based on old, environmentally damaging technologies.
   Kop-Coat developed Tru-Core® Protection System  to treat  wood in an  environmentally
positive manner. The Tru-Core* system incorporates the principles of green chemistry in several
ways. For example, most conventional treatments for wooden window frames and doors use
petroleum-based solvent carriers, such as mineral spirits, that emit volatile organic compounds
(VOCs). The Tru-Core® process uses water as the carrier, resulting in a significant reduction in
organic solvent use. Because the Tru-Core® process uses only a small amount of water to carry
the preservatives, it also eliminates the energy-intensive step of re-drying wood after treatment.
   The Tru-Core® system employs a unique chemical infusion process that includes nonvolatile,
highly polar bonding carriers (amine oxides in water) that  penetrate the cellular structure of
wood to deposit and bind wood protection chemicals  (preservatives  and insecticides) within
the substrate. Buffers such  as borates maintain a basic pH that inhibits the natural acids present
in wood, allowing the amine oxides and preservatives to penetrate rapidly. Tru-Core* extends
the service life of wood at  a cost that is less than one quarter the cost of the closest competing
treatment technology.
   In 2010, EPA registered the patented Tru-Core'*1 technology as a wood preservative. In 2011,
Tru-Core® technology was used in the dual treatment  process for approximately two million
railroad ties. Tru-Core® Type 1 is currently undergoing evaluation by ICC-ES  (International
Code Council Evaluation Service) for acceptance  into the 2012 International Building Code.

 Oil-Based Performance in a Water-Based Formula with Less

Environmental Impact
    Solvent- and shellac-based stain-blocking primers typically include resins that require petroleum-
based solvents such as mineral  spirits  or ethanol. These solvents  are not only combustible (and
in  some cases flammable); they also release significant amounts  of volatile organic compounds
(VOCs) during application and drying. Water-based primers made with a variety of acrylic and
styrene—acrylic resins are available,  but they have extended dry times and cannot approach the
stain-blocking properties of solvent-based primers.
    Masterchem  Brands  has  developed  KILZ MAX™  primer,  using  specialized  epoxy-
based resin  technology to provide   heavy  stain-blocking  and odor  blocking in a  more
eco-friendly,  water-based formula.  This product has the benefits  of solvent- or shellac-based

primers including the ability to block severe stains and odors, resist tannin stains, and  more. It
does not have  the  associated drawbacks of high  odor, high VOCs, or clean up that requires
mineral spirits.  Independent testing confirms that KILZ MAX™ performs as well or better than
oil- and shellac-based primers on virtually all problem stains, odors, and other surface imperfections.
It also meets or  exceeds the performance of many products marketed as having similar technology.
   KILZ MAXIM primer has a VOC level  near 75 grams per liter; this is over seven-fold lower
than competitive shellac-based primers and six-fold lower than typical competitive specialty primers.
Replacing the solvent with  water in  KILZ MAX™ primer eliminates approximately 3 pounds
of VOCs per gallon compared to KILZ'8'  Original solvent-based primer.  In 2007, Masterchem
Brands  sold  over 3-3  million  gallons of KILZ®  Original primer.  Replacing the higher-VOC
version with KILZ MAX™  primer would reduce airborne VOCs by as much as 9 million pounds
annually. Another benefit is the ability to sell high-performance stain-blockers in areas regulated
by the South Coast Air Quality Management District (SCAQMD), the California  Air Resources
Board  (CARB), and others. KILZ MAX™ primer was first produced  and launched  in  retail
markets in 2011.

Revolutionizing Insect Control: Bt Technology

   Crop insect pests have limited food  production tor centuries. Although chemical insecticides
were the most advanced tools for insect control until the 1990s, they had undesirable environmental
effects, were toxic to some nontarget organisms, and required repeated applications to crops.
   Unlike traditional pesticides, Monsanto's  recently patented technology uses insect control present
in  nature.  Bacillus  thuringiensis (Bt,  a ubiquitous soil  microbe) produces  Cry (crystal) proteins,
which are  insectiddal  toxins. Using  biotechnology,  Monsanto combined its knowledge of Cry
proteins with pioneering plant molecular genetics to create crop plants that express synthetic Bt
Cry proteins engineered to  be  highly specific toxins against insect  pests. In addition  to reducing
the use of pesticides, the specificity of Cry proteins ensures only target organisms are affected and
not humans, animals,  or nontarget, beneficial  insects. Monsanto's application of biotechnology
to  controlling pests makes both pesticide manufacturing and chemical pesticide applications less
   Farmers planting insect-resistant crops experience improved safety and health because of reduced
handling and use of pesticides. They spend less time applying insecticides. Reduced applications
mean fewer containers, less fuel, and less aerial spraying: all factors that benefit the environment
while increasing yields and enhancing farmers' lives.
   Bt  technology continues to be applied across  many plant  varieties, increasing yields  and
reducing the need for chemical pesticides. All Bt traits  in commercial use have been created with
Monsanto's patented synthetic  Bt gene technology; traits Monsanto developed have been licensed
to  and sold by numerous seed companies, as well as by Monsanto itself.  Some  companies have
developed  their own insect resistance traits, but all of these traits have used Monsanto's synthetic
gene technology covered by a recently issued patent (U.S. patent 7,741,118 Bl).  In  2010,
65 percent of all corn grown in the United States and 75 percent of all cotton grown in the United
States included one or more Bt traits.
Monsanto Company

Pacific Northwest

     Archer Daniels
NALCO s APEX™ Program: Sustainable Technology for

Paint Detackification

   For decades, manufacturers have used hazardous melamine—formaldehyde—acid colloids to
detackify paint overspray in spray booths. Melamine is an irritant, however, and chronic exposure
may cause cancer or reproductive damage. Formaldehyde is a known carcinogen  according to
the Occupational Safety and Health Administration (OSHA). Further,  the colloid is derived
from feedstocks based on nonrenewable petroleum or natural gas. In searching for an alternative,
U.S.-based manufacturing companies established an initiative to create a green method for paint
detackification using innovative chemistry.
   NALCO developed the APEX™ program to support this initiative. The APEX™ program
consists of an etherified, cationically modified corn starch mixed with a small amount of
a proprietary amphoteric polymer and a polybasic aluminum salt. It is  formulated from over
99 percent sustainable resources. When added to  a  paint system at a pH above 7-0, APEX™
generates a highly cross-linked "sweep floe" that rapidly coagulates and  completely detackifies
paint solids, creating an easily dcwaterable sludge. The APEX™ program completely eliminates
formaldehyde and other harmful, nonrenewable raw materials in these applications.
   The APEX™ program benefits every manufacturing company that adopts it by:  (1) reducing
total costs of operation (typically over 30 percent); (2) reducing chemical use (typically over
80 percent); (3) reducing the generation and transportation of wastes (typically over 50 percent);
(4) reducing water use; and (5) reducing emissions of volatile organic compounds (VOCs).
   A large automotive plant in  Alabama first  implemented APEX™, where  it reduced solid
waste generation by 267,000 pounds and saved $90,000 in disposal costs.  It reduced VOC
generation by over  3,000 pounds (an 80%  reduction). It also reduced the frequency of booth
cleaning from weekly to once per quarter, saving an additional $160,000  in operating costs and
significantly reducing use of cleaning chemicals. NALCO's APEX™'program is currently used in
85 assembly plants.

Propylene  Glycolfrom Renewable  Sources

   Propylene glycol (PG) is a commodity chemical used in everyday consumer products such as
liquid detergents, hand sanitizers, pharmaceuticals, and cosmetics, as well as in industrial products
such as plastics, paint, antifreeze, and aircraft deicer. The largest use of PG is as a  monomer in
plastics, especially fiberglass resins. Until recently, PG has been produced almost entirely from
petroleum resources.  Each year,  worldwide PG production consumes more than two  billion
pounds of petroleum.
   To eliminate this  use of petroleum and to replace the toxic feedstocks involved, Battelle
scientists at Pacific Northwest National Laboratory  (PNNL) developed  a catalytic process for
producing PG from renewable sources. The propylene glycol from renewable  sources (PGRS)
process relies on a carbon-supported  bifunctional metal  catalyst in combination with a soluble
base co-catalyst. The multistep process proceeds  in a single reactor to  produce  PG in high
selectivity and at high conversion. This safe,  sustainable, cost-competitive,  and commercially
viable alternative converts plant-based, seed-oil-derived glycerol or plant sugar alcohols into PG,
which can then be purified to meet a variety of market specifications. The glycerol can come from
a variety of sources, including the crude glycerol byproduct of biodiesel production. The PGRS
process currently produces propylene glycol for the first time on a commercial scale entirely from
renewable resources. A lifecyde analysis shows that the PGRS process eliminates up to 61 percent
of the greenhouse gas (GHG) produced by the traditional propylene oxide route to PG.

   Archer Daniels Midland (ADM) commissioned and is now operating a new 100,000 metric ton
per year PG facility using Battelle's technology. This  represents the first of its kind in the world:
an operational, commercial-scale facility producing  PG  that meets  U.S.  Pharmacopeia (LISP)
specifications entirely from renewable resources. Other competing technologies have been unable to
produce PG from renewable materials of this high-quality material at full scale.

New Green  Commercial Biocatalytic  Route to

Atorvastatin Calcium,  the Lipitor API
   Atorvastatin is the active pharmaceutical ingredient (API) in Lipitor. Since its launch in 1997,
Lipitor has been the most-prescribed branded cholesterol-lowering medication in the world. This
success, together  with Pfizer's  commitment  to continuous improvement,  made the production
of atorvastatin an obvious  target for  improvement. Pfizer challenged itself to make  dramatic
improvements in  both the efficiency and environmental performance of the manufacturing route
to atorvastatin.
   The original manufacturing process  required a chiral starting material. Because optimizing this
process would not achieve the transformational changes that Pfizer sought, the company developed
a completely new, more efficient, commercial route to atorvastatin calcium using a biocatalytic
   The new  green  process  incorporates  a water-based 2-deoxyribose-5-phosphate aldolase
(DERA) enzyme at the beginning of the  route to make a lactol  from an  amino  aldehyde
(i.e., 3-phthalimidopropionaldehyde; PPA) and acetaldehyde. The synthesis  eliminates the use of
cyanide or azide moieties to introduce nitrogen because it is already present in the lactol. In contrast
to the original synthesis, the DERA enzyme sets both stereocenters with high  selectivity in water
at room temperature. Converting the resulting lactol into isopropyl acetonide atorvastatin (IAA) is
extremely efficient: it involves four high-yield chemical steps (oxidation, esterification, deprotection,
Paal Knorr) with only the  IAA  product being  isolated as a solid. Finally,  IAA is converted to
atorvastatin calcium, the API product.
   Pfizer's green process substantially reduces the environmental impact by eliminating hazardous
steps and reducing or eliminating required chemicals. For example, the new synthesis eliminates the
previous high-pressure hydrogenation step with its associated metal catalysts. It also avoids pyrophoric
K-butyl lithium and its associated butane waste  gas.  The need for  significant  other reagents and
solvents has either been eliminated or dramatically reduced. The U.S. Food and Drug Administration
(FDA) approved the new manufacturing process in April 2010. Pfizer manufactured commercial
scale validation batches in 2011 and is currently transitioning to full-scale commercial manufacture.
Ethos™ Modular Commercial Floor  Coverings
   Polymeric poly(vinyl butyral) (PVB) is a thermoplastic terpolymer of vinyl acetate, vinyl alcohol,
and vinyl butyral that provides shatterproof properties to windshields and other safety glass. Although
rccyclcrs have recovered the glass from safety glass and sold it into other markets for years, most of
the PVB film has been sent to landfills or burned for energy.
   Tandus Flooring is the first manufacturer to use the abundant PVB waste stream and recycle it into
high-performance carpet backing. Ethos™ secondary backing, made from PVB film reclaimed from
windshields  and other safety glass, can replace other structured carpet backings such as poly(vinyl
chloride) (PVC), ethylene—vinyl acetate (EVA), polyurcthane, polyolcfin, and bitumen. Producing
ethos1M backing from  recycled material reduces the  energy and environmental impacts  associated
with extracting, harvesting, and transporting virgin raw materials.
Tandus Flooring

   Tandus evaluated PVB against 10 other polymer-based materials using stringent performance
and  environmental criteria. In  these  tests, PVB  was  superior to  the  other polymers  in
material  availability, recyclabiliry,  reduction  of virgin  resources,  avoidance  of  hazardous
emissions  (e.g., dioxin), and elimination of chemicals  of concern  such as  chlorine,  fly ash,
and  phthalate plasticizers.  In  addition,  ethosIM backing has extremely  low  environmental
lifecycle impacts compared  to other products. Tandus's  patented, closed-loop process can also
recycle postconsumer carpet with ethos1M backing  and other manufacturing waste into new
floor coverings.
   Initially, Tandus successfully introduced a six-foot-wide ethos™ cushion backing, Powerbond,
to meet the  needs  of Kaiser Permanente for high-performance, PVC-free, soft-surface flooring.
In November 2009, the  company introduced ethos™ modular. Its production has increased
18-fold  in the last two years.  Every square yard of ethos1M modular replaces  approximately
5.25 pounds of PVC in  carpet backing. To date, Tandus has recycled more than 10 million
pounds  of PVB into flooring products, keeping PVB from landfills, and potentially replacing
52 million pounds of PVC.

 Pyrolase® Cellulase Enzyme Breaker as a Biodegradable

 Replacement for Corrosive Adds        Oxidizers in

 Hydraulic Fracturing Operations

   Hydraulic fracturing (fracking) is an advanced drilling technique used to unlock vast stores of
 oil and shale gas across  the country. It involves pumping pressurized water, sand,  and chemicals
 underground to open fissures in oil- and gas-containing formations such as shale and improve
 the flow to  the surface. Fracturing uses a host of corrosive acids  and oxidizers to degrade and
 remove  fracturing fluid residues from formation pores. The fracturing process has drawn harsh
 criticism from environmentalists claiming that potential contamination of underground water by
 fracturing poses a significant environmental risk. In December 2011, EPA first stated publicly
 that fracturing might be to blame for groundwater pollution in Wyoming.
   Verenium has  developed Pyrolase'5' cellulase to replace the corrosive acids and hazardous
 oxidizers used in fracturing. Verenium discovered and isolated the gene  for Pyrolase* cellulase, a
 thermostable enzyme from the eubacterium Thermotoga maritime, found in geothermally heated
 sediment on the ocean floor. Pyrolasc® cellulase is a broad-spectrum p-glycosidase with both
 endo- and exo-glucanase activities that provides a complete viscosity break on fracturing fluids
 across a broader range of temperatures, wider pH ranges, and higher salinity than other commercial
 enzymes. Pyrolase'*1 cellulase is also useful in a wider variety of down-hole conditions. It excels in
 hydrolyzing  linear and cross-linked fluids, such as guar gum, derivati/ed guar, and carboxymethyl
 cellulose, at speeds easily controlled by varying the enzyme loading. It offers superior performance
 with zero environmental impact.
   Pyrolase'8'cellulase is an easy-to-use liquid. One pound of biodegradable Pyrolase* cellulase can
 replace more than 20 pounds of hazardous chemicals, some of which are implicated in soil and
 water contamination. Pyrolase*' cellulase is a significant step toward addressing the environmental
 and health concerns over hydraulic fracturing both for workers and for those living near fracturing
 operations. Verenium launched a campaign in 2011 to commercialize Pyrolase® cellulase to the
 oil and gas services industry.


ACTA               Inc.
Geo'thermal Heat Pumps: A Greener and More Energy-Efficient Renewable
Energy Resource [[[ 15

                       Chemistry LLC                &
NATRASURF™ PS-Ill Polymeric Surfactant: Achieving Next Generation Mildness in
Personal Care Products with a Reduced Environmental Footprint ................ .39

Concrete-Friendly™ Powdered Active Carbon (C-PAC™) to Remove Mercury from Flue
Gas Safely	29

Propylene Gly col from Renewable Sources.................................. .42

Upcycling Waste Plastic Bags into Valuable Carbon Nanotubes and Carbon Spheres . ... 29

BioBased Tile9: A Non-PVC Flooring Made with Rapidly Renewable Resources....... 30
Breakthrough Formaldehyde-Free Coating for Ceiling Tiles	30

Envirez^Technology: Incorporating Renewable and Recycled Feedstocks into Unsaturated
Polyester Resins	31

Compostable Multilayer Food Packaging ................................... 31

One-Component, UV-Curable, Waterborne Polyurethane Coatings	32

One-Component, UV-Curable, Waterborne Polyurethane Coatings ............... .32

Producing Chemicals and Carbon fi'om Waste Tires, Plastics, Carpet, and Biomass	15

                                       of             &
       University of      York                 SUMY

Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis ofDiarylAldimines	9

   Greening the Design of Chemical Production with Microbes ..................... 16

   Elimination ofPFOSandPFOA in IBM Semiconductor Manufacturing Processes and
   Development ofPhotoacid Generators Free ofPerfluoroalkyl Sulfonates	39

   Enzymes Reduce the Energy and Wood Fiber Required to Manufacture High-Quality Paper
   Production ofIsobutanolfrom the Synergy between Metabolic and Process Engineering. . 37
   FIREBLOCK^* Intumescent Resin	33
   The City          of     City             of       York,
   of Chemistry,
   Sustainable Molecular Design through Biorefineries: Biomass as an Enabling Platform for
   Safe Oil-Thickening Agents (Amphiphiles)	9
   Synthesizing Biodegradable Polymers from Carbon Dioxide and Carbon Monoxide . .... 3
   *Codexis, Inc.       Yi Tang,              of California, Los
   An Efficient Biocatalytic Process to Manufacture Simvastatin	6
   Colonial Chemical, Inc.
   Sugd*Nate: A Safer, Milder, Greener Surfactant. ............................. 16
                      of                        of Chemistry,
   EA Novel Bacteriophage-based Test to Identify MRSA/MSSA Acquired Infections . .... 13

   Vegetable OH Insulating Fluid for Improved High Voltage Transformer Capability	33
   * Cornel I Uniwersity,            W.
   Synthesizing Biodegradable Polymers from Carbon Dioxide and Carbon Monoxide	3
   Glycerol tert-Butyl Ether (GTBE): A Biofitel Additive for Today	17
   *Cytec             Inc.
   *MAXHT* Bayer Sodalite Scale Inhibitor .................................. 7
   Saturated Polyester-Phenolic Resin Systems for Bisphenol A-Free Interior Can Coatings for
   Food Packaging.	34

EVOQUE™ Pre-Composite Polymers	34
INFUSE^Olefin Block Copolymers ..................................... .55

                                   of Civil
Improved Resource Use in Carbon Nanotube Synthesis via
Mechanistic Understanding. ............................................ 11

Chlorantraniliprole: Increased Food Production, Reduced Risks, More
Sustainable Agriculture	35
Development of a Commercially Viable, Integrated, Cellulosic
Ethanol Production Process ............................................. 36

DuPont                  Bulamax™                        LLC
Production of Isobutanolfrom the Synergy between Metabolic and Process Engineering. . 37

Formaldehyde-Free, High-Strength Biocomposites from Sustainable Resources	17

Generally Recognized as Safe (GRAS) Coatings	18

Zero-Emission Production of the Green Lithium Ion SuperPolymef3 Battery	15

*EIevance                          Inc.
Using Metathesis Catalysis to Produce High-Performing, Green Specialty Chemicals at
Advantageous Costs	5

Eli Lilly
Grignard Reactions Go Greener with Continuous Processing	37

FRX               Inc.
Polymeric, Nonhalogenated Flame Retardants with Broad Applicability in
Multiple Industries	19

*Hedrick,         L.f                                                   M.
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry	4

H-O-H        Technology, Inc.
Conserving Water and Eliminating Chemical Treatment in Cooling Towers	20
         o                   o                          o

*IBM                                        L.                        M.
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry	4

  Catalytic Treatment of Hydrogen Peroxide in IBM Semiconductor Wastewater	38
  Elimination ofPFOSandPFOA in IBM Semiconductor Manufacturing Processes and
  Development ofPhotoacid Generators Free ofPerfluoroalkyl Sulfonates	38

              Polymers, LLC
  InfiGreen Polyols	20

                                  of              The City           of
  City              of
  Sustainable Molecular Design through Biorefineries: Biomass as an Enabling Platform for
  Safe Oil-Thickening Agents (Amphiphiles)	9

            &                                      Inc.
  NATRASURF'[M PS-111 Polymeric Surfactant: Achieving Next Generation Mildness in
  Personal Care Products with a Reduced Environmental Footprint ................. 39

  Kop-Coat, Inc.
  Tm-Core* Protection System for Wood	40

  Development and Commercialization of Okie Estolide Esters .................... 21

                                  of                           of
  Chemical Conversion of Biomass into New Generations of Renewable Fuels, Polymers, and
  Value-Added Products	10

       MAX™PRIMER-SEALER-STAINBLOCKER: Oil-Based Performance in a
  Water-Based Formula with Less Environmental Impact.	40

                 Inc.                                       of
  A Novel Bacteriophage-based Test to Identify MRSA/MSSA Acquired Infections	13

  Revolutionizing Insect Control: Bt Technology	41

  Bio based Chemicals from Low-Cost Lignocellulosic Sugars. ..................... .21

  NALCO's APEX™ Program: Sustainable Technology for Paint Detackification	42


  Highly Efficient, Practical Monohydrolysis of Symmetric Diesters to Half-Esters ....... 10

High-Performance Polyols from CO'2 at Low Cost	22

ElectJ'odialysis and Chromatographic Separation Technology for Chlorine-Free Production
of Potassium Hydroxide and Hydrochloric Acid,	23

The              Uniwersity,                of Chemistry,
Ethylene: A. Feedstock for Fine Chemical Synthesis	12

Producing Industrial Chemicals by Fermenting Renewable Feedstocks at a Lower Cost .  ,23

Propylene Glycolfrom Renewable Sources	42

                Chemicals,  LLC
BURN-OUT™ Durable, Green, Nontoxic Flame Retardant	24

New Green  Commercial Biocatalytic Route to Atorvastatin Calcium, the Lipitor API . .43

                 L.,                of Civil

Improved Resource Use in Carbon Nanotube Synthesis via Mechanistic Understanding. .11

              T.V.                        of              The

Ethylene: A  Feedstock for Fine Chemical Synthesis. ...........................  .12

Zero-VOC Cleaning and Remediation Technology	24


Highly Efficient, Practical Monohydrolysis of Symmetric Diesters.................. 10

Sodium Silicide: A. New Alkali Metal Derivative for Safe, Sustainable, and On-Demand
Generation  of Hydrogen ............................................... 25

* Stanford University,                of                       M.
Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry	4
                    of       York                 SUMY
                              of              &

Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of Diary I Aldimines	9

                 University of
  y4 Trw/y Green Process for Converting Ethylene to Ethylene Oxide	12

  SUNY                                                   of
                            of              &

  Ethyl L-Lactate as a Tunable Solvent for Greener Synthesis of DiarylAMimines	9

  Ethos™-Modular Commercial Floor Coverings	43

  *Tang, Yi,             of California,                               Inc.
  ylw Efficient Biocatalytic Process to Manufacture Simvastatin	6

               Uniwersity,                of

  Highly Efficient, Practical Monohydrolysis of Symmetric Diesters	10

              of California,                       of

  Chemical Conversion ofBiomass into New Generations of Renewable Fuels, Polymers, and
  Value-Added Products. ................................................ 10

  *Uni¥ersity of California,                Yi Tang                Inc.
  An Efficient Biocatalytic Process to Manufacture Simvastatin	6

               (ACRES)         for
  Biobased Polymers and Composites. ......................................  13

               of                          of

  /I 7n//y Green Process for Converting Ethylene to Ethylene Oxide. ................. 12

  Biobased Adipic Acid for Renewable Nylon and Polyurethane Resins .............. .26

  Pyrolase® Cellulose Enzyme Breaker as a Biodegradable Replacement for Corrosive Acids
  and Oxidizers in Hydraulic Fracturing Operations...........................  44

  VH                   Inc.
  Bacteriocins: A Green, Antimicrobial Pesticide	26

                     of Mines,      MicroPhage, Inc.
  A Novel Bacteriophage-based Test to Identify MRSA/MSSA Acquired Infections	13

*¥tfay mouth,          M.f                                    L.

Organic Catalysis: A Broadly Useful Strategy for Green Polymer Chemistry	4
Wool,           P.,
            (ACRES)         for
Biobased Polymers and Composites	13

Office of Pollution                            744K12001
Prevention and                               June 2012
Toxics (7406M)                               www.epa.gov