DuPont Central Research
Encyclopedia
In 1957, the research organization of the Chemicals Department of E. I. du Pont de Nemours and Company was renamed Central Research Department, beginning the history of the premier scientific organization within DuPont and one of the foremost industrial laboratories devoted to basic science. Located primarily at the DuPont Experimental Station
DuPont Experimental Station
The DuPont Experimental Station is the largest research and development facility of E. I. du Pont de Nemours and Company. Located on the banks of the Brandywine Creek in Wilmington, Delaware, it is home to some of the most important discoveries of the modern chemical industry...

 and Chestnut Run, in Wilmington, Delaware
Wilmington, Delaware
Wilmington is the largest city in the state of Delaware, United States, and is located at the confluence of the Christina River and Brandywine Creek, near where the Christina flows into the Delaware River. It is the county seat of New Castle County and one of the major cities in the Delaware Valley...

, it has expanded to include laboratories in Geneva, Switzerland, Seoul, South Korea, Shanghai, China, and Hyderabad, India.
The company established a tradition of basic scientific research starting with hiring of Wallace Carothers
Wallace Carothers
Wallace Hume Carothers was an American chemist, inventor and the leader of organic chemistry at DuPont, credited with the invention of nylon....

 in 1928 and his systemization of polymer science that led to the development of polyamides such as nylon-6,6 and polychloroprene (neoprene) in the early 1930s. This tradition waned during World War II
World War II
World War II, or the Second World War , was a global conflict lasting from 1939 to 1945, involving most of the world's nations—including all of the great powers—eventually forming two opposing military alliances: the Allies and the Axis...

 then underwent a renaissance in the 1950s. The establishment of Central Research in 1957 formalized a corporate commitment to basic research. The execution and publication of high quality research assisted recruiting and promoted the image of DuPont while raising morale among the CRD staff. The purpose of the research was to discover "the next nylon
Nylon
Nylon is a generic designation for a family of synthetic polymers known generically as polyamides, first produced on February 28, 1935, by Wallace Carothers at DuPont's research facility at the DuPont Experimental Station...

", because Carothers' success and the resulting commercialization of nylon had driven the Company's profits through the 1950s. (This research objective that was never met.) Nonetheless, another important stated goal for CRD was “diversification through research,” and CRD produced a stream of scientific innovations that contributed to many different businesses throughout the corporation.
CRD Research Directors and
Vice Presidents
Years
Paul L.Salzberg 1957–1967
David M. McQueen 1968–1971
Theodore L. Cairns 1972–1975
Howard Ensign Simmons, Jr.
Howard Ensign Simmons, Jr.
Howard Ensign Simmons, Jr. was an American chemist who discovered the Simmons-Smith reaction.In 1976, Dr. Simmons served as Chair of the Organic division of the American Chemical Society.-References:...

1975–1979
C. Edward Lorenz 1980
Robert Naylor 1981
Charles Bottomley 1982–1983
Richard Quisenberry 1984–1992
Joseph Miller 1993–1995
James M. Meyer 1997–2000
Thomas M. Connelly 2001–2005
Uma Chowdhry
Uma Chowdhry
Uma Chowdhry was born in Mumbai, India in 1947. She received a Bachelors Degree in physics from Indian Institute of Science, Mumbai University in 1968 before coming to the United States. She received a Masters Degree in Science from Caltech in engineering science in 1970. After two years with...

2006–2010
Douglas W. Muzyka 2010–present

CRD combined industrial and fundamental research, and the mix of the two features was often determined by the head of CR&D. The title expanded from Director of Research to Vice President of Technology to Chief Technology Officer with varying degrees of impact on research throughout the corporation as well as in CRD. The name of CRD also changed to reflect the times, starting with Chemicals Department and moving through Central Research Department (CRD), Central Research and Development Department (CR&DD), to the present Central Research and Development (CR&D).

CRD conducted research in a number of topical areas, often requiring an interdisciplinary approach. DuPont’s explored chemical reactions in supercritical water in the 1950s to support its production of CrO2 for magnetic recording tapes. Hyperbaric recrystallization of ultra-high molecular weight polyethylene
Polyethylene
Polyethylene or polythene is the most widely used plastic, with an annual production of approximately 80 million metric tons...

 led to DuPont’s business in Hylamer polyethylene for bearing surfaces in hip and knee replacement arthroplasty
Arthroplasty
Arthroplasty is an operative procedure of orthopedic surgery performed, in which the arthritic or dysfunctional joint surface is replaced with something better or by remodeling or realigning the joint by osteotomy or some other procedure.-Background:Previously, a popular form of arthroplasty was...

. Urea
Urea
Urea or carbamide is an organic compound with the chemical formula CO2. The molecule has two —NH2 groups joined by a carbonyl functional group....

 and uracil
Uracil
Uracil is one of the four nucleobases in the nucleic acid of RNA that are represented by the letters A, G, C and U. The others are adenine, cytosine, and guanine. In RNA, uracil binds to adenine via two hydrogen bonds. In DNA, the uracil nucleobase is replaced by thymine.Uracil is a common and...

 compounds discovered in CRD were potent and selective herbicides, propelling DuPont into the agricultural chemicals business and culminating in sulfonylurea herbicides. Potassium titanyl phosphate
Potassium titanyl phosphate
Potassium titanyl phosphate or KTP is a nonlinear optical material which is commonly used for frequency doubling diode pumped solid-state lasers such as Nd:YAG and other neodymium-doped lasers. The material has a relatively high optical damage threshold , a great optical nonlinearity and excellent...

 or KTP is a versatile nonlinear optical material, originally designed to frequency doubling red laser
Laser
A laser is a device that emits light through a process of optical amplification based on the stimulated emission of photons. The term "laser" originated as an acronym for Light Amplification by Stimulated Emission of Radiation...

s to green for bloodless laser eye surgery; it now find additional application in urological surgery and hand-held green laser
Laser
A laser is a device that emits light through a process of optical amplification based on the stimulated emission of photons. The term "laser" originated as an acronym for Light Amplification by Stimulated Emission of Radiation...

 pointers.

In the 1950s, the CRD housed a broad-based research program aimed largely at the synthesis and study of new classes of compounds. Synthesis of new organic and inorganic compounds accounted for about half of the total research. When the National Institute of Health invited DuPont to submit compounds to its screening efforts, they rated DuPont as submitting by far the most diverse range of compounds – pharmaceutical companies were submitting things that looked like pharmaceuticals, but DuPont submitted compounds that would be classed internally as catalysts, optical materials, monomers, oligomers, ligands, inorganics, and other unusual materials.

In addition to chemical synthesis, CRD maintained efforts centered on new physical and analytical techniques, chemical structure and reaction mechanism, and solid-state physics. DuPont continued in polymer research. Biological research has increased significantly.

Until recent years, a substantial portion of research was of an academic nature. This academic research was reflected in the general atmosphere of the organization. In the late 1960s, CRD established a program for recruiting postdoctoral fellows. These fellowships were generally for two years and had the expectation that the fellow would leave to an academic institution. Every year one or two DuPont scientists would take one year leaves of absence for university study and teaching. It was also accepted that every year a number of scientists would leave DuPont for academic positions and that several professors would join the staff permanently. A notable example was Richard Schrock, who left CRD for MIT and won the Nobel Prize for Chemistry. CRD was supported by numerous high profile consultants who have made significant contributions to DuPont. Jack Roberts
John D. Roberts
John Dombrowski Roberts is an American chemist. He has made contributions to the integration of physical chemistry, spectroscopy and organic chemistry for the understanding of chemical reaction rates....

 of Caltech and Speed Marvel
Carl Shipp Marvel
Carl Shipp "Speed" Marvel was an American polymer chemist who worked at developing polybenzimidazoles, which are temperature-resistant polymers that are used in the aerospace industry and as a replacement for asbestos.He obtained the nickname "Speed" early on in his career as a chemist from his...

 each consulted for well over 50 years and provided a steady supply of well-trained chemists.) Robert Grubbs, who shared the Nobel Prize
Nobel Prize
The Nobel Prizes are annual international awards bestowed by Scandinavian committees in recognition of cultural and scientific advances. The will of the Swedish chemist Alfred Nobel, the inventor of dynamite, established the prizes in 1895...

 with Schrock, consulted for many years. These academic connections were sources of new generations of CRD researchers.

The scientific accomplishments of Theodore L. Cairns, William D. Phillips
William Dale Phillips
William Dale Phillips was a chemist, nuclear magnetic resonance spectroscopist, federal science policy advisor and member of the National Academy of Sciences. He was born October 10, 1925, in Kansas City, Missouri and died in St. Louis, Missouri, on December 15, 1993.-Training:Phillips graduated...

, Earl Muetterties
Earl Muetterties
Earl Muetterties , was an American inorganic chemist born in Illinois, who is known for his experimental work with boranes, homogeneous catalysis, heterogeneous catalysis, and fluxional processes in organometallic complexes.- Training :...

, Howard E. Simmons, Jr., and George Parshall
George Parshall
George W. Parshall is a distinguished member of the organometallic chemistry and homogeneous catalysis communities and has played a key role in advising the U.S...

 were recognized by their election to the National Academy of Sciences
United States National Academy of Sciences
The National Academy of Sciences is a corporation in the United States whose members serve pro bono as "advisers to the nation on science, engineering, and medicine." As a national academy, new members of the organization are elected annually by current members, based on their distinguished and...

.

CRD management fostered an open and collaborative style. At its founding, the division of labor in CRD was “management,” “bench chemists,” and “technicians,” with the management and bench chemists having separate but overlapped promotional tracks. Under the Hay Grade system of pay levels that was employed then and now, there were eight professional or promotional levels for the “bench chemists,” yet there was a single undistinguished title. This approach promoted interaction.

The Hay Grades for those in management started higher and ended considerably higher, but there was significant overlap with the bench chemist levels. Thus it was not unusual for a supervisor or manager to have one or more scientists reporting to him (there were no females in management at this time) who were at higher pay levels than he was. There was one reported instance where the supervisor never got to pass pay raises to the “bench chemist” because management didn’t want to make him feel bad; the next level Manager who did pass on the pay notification said, “They didn’t care how I felt.” Titles explicitly tied to salary level were instituted in May, 1993, but the openness remains today as does the situation of Managers managing higher level scientists.

At the beginning of CRD, “technicians” in CRD were usually high-school educated and often had military service. They were clearly just extra hands for the bench chemists who were all PhDs and the bench chemists were expected to spend most of their time at the bench. It was virtually impossible for a technician to progress in CRD, but they could at plant sites and would sometimes move for the opportunity. Starting in the early 1990s, mostly as a result of the growth of the pharmaceutical and life science efforts, technicians with Bachelors degrees and later, Master's degree
Master's degree
A master's is an academic degree granted to individuals who have undergone study demonstrating a mastery or high-order overview of a specific field of study or area of professional practice...

s became the norm. There are even some technicians holding PhDs from foreign universities. Nonetheless, it remains difficult for a technician to break into the bench chemist ranks and they usually transfer to business units in search of more opportunity.

Many of the PhDs who came to CRD transferred to business units. From the 1980s to early 90s, management tried to move all PhDs to a business unit within their first five years. The PhDs had spent their entire lives in an academic environment, so they knew nothing else, but it was realized that at some point they would grow up and realize that working at the bench was not what some of them would want to do their entire career. The issue was that they were too senior and naive to move into entry level positions in businesses and their competition were similarly aged BS engineers who would have had about five years of experience keeping a plant running. Of those who took the opportunity, about half returned to CR&D. Of those who returned, about half left again. The relatively high turnover provided more opportunity for CRD to hire outstanding new PhDs. Transfers to business units became less common in the 1990s and the average age of CRD personnel rose considerably as a result. With baby-boomers starting to retire, there is more recruiting and there is a noticeable rejuvenation of the staff.

Responsibility for the technical direction of research has shifted to the chemist as they carry out short-term projects in support of the business units. PhD
PHD
PHD may refer to:*Ph.D., a doctorate of philosophy*Ph.D. , a 1980s British group*PHD finger, a protein sequence*PHD Mountain Software, an outdoor clothing and equipment company*PhD Docbook renderer, an XML renderer...

s who get MBAs are now more common. Unlike the early years, all management has had business unit experience and many were hired into business units, coming into CRD later in their careers. These managers are often far more administrative in their approach, not having the strong technical backgrounds required to keep up with their technical employees. Some managers have come to rely upon their senior technical staff, but there is no clear guideline on the role that these senior scientists can or should play in managing the programs and careers of the younger scientists.

Organofluorine chemistry

A fluorocarbon backbone
The structural unit of Teflon
and other fluorocarbon molecules

On April 6, 1938, Roy Plunkett at DuPont’s Jackson Laboratory in New Jersey was working with gases related to DuPont’s Freon refrigerants when he and his associates discovered that a sample of gaseous tetrafluoroethylene
Tetrafluoroethylene
Tetrafluoroethylene is a chemical compound with the formula C2F4. It is the simplest alkene fluorocarbon. This gaseous species is used primarily in the industrial preparation of polymers.-Properties:...

 had polymerized spontaneously into a white, waxy solid. The polymer was polytetrafluoroethylene
Polytetrafluoroethylene
Polytetrafluoroethylene is a synthetic fluoropolymer of tetrafluoroethylene that finds numerous applications. PTFE is most well known by the DuPont brand name Teflon....

 (PTFE) commercialized by DuPont as Teflon in 1945. Because DuPont was basic in a variety of fluorinated materials, it was logical that organofluorine chemistry became important to DuPont. The discovery that tetrafluorethylene would cyclize with a wide variety of compounds to give fluorinated compounds opened up routes to a range of organofluorine compounds.

The hazards and difficulties of handling highly reactive and corrosive fluorinating reagents could be accommodated by DuPont’s emphasis on safety and DuPont’s association with the Manhattan Project
Manhattan Project
The Manhattan Project was a research and development program, led by the United States with participation from the United Kingdom and Canada, that produced the first atomic bomb during World War II. From 1942 to 1946, the project was under the direction of Major General Leslie Groves of the US Army...

 provided many chemists and engineers with the background necessary to carry out the work. Availability of the Pressure Research Lab on the Experimental Station
DuPont Experimental Station
The DuPont Experimental Station is the largest research and development facility of E. I. du Pont de Nemours and Company. Located on the banks of the Brandywine Creek in Wilmington, Delaware, it is home to some of the most important discoveries of the modern chemical industry...

 provided the necessary protection for most but not all of those reactions that went awry. Notable scientists included William Middleton, David England, Carl Krespan, William Sheppard, Owen Webster
Owen Webster
Owen W. Webster is a distinguished member of the organic and polymer chemistry communities. His polymerization technique for making block copolymer dispersing agents is used by DuPont to make ink-jet printer inks....

, Bruce Smart, Malli Rao, Robert Wheland, and Andrew Feiring, all of whom filed many patents for DuPont. Sheppard wrote one of the important early books on the subject. Smart's book followed. Smart’s comments in Chemical Reviews
Chemical Reviews
Chemical Reviews , is a peer-reviewed scientific journal, published since 1924 by the American Chemical Society. As the name indicates, it publishes comprehensive, critical reviews of an area rather than original research...

 in 1996, “Scientific and commercial interests in fluorine chemistry burgeoned after 1980, largely fueled by the need to replace industrial chlorofluorocarbons and the rapidly growing practical opportunities for organofluorine compounds in crop protection, medicine and diverse materials applications. Although fluorine is much less abstruse now than when I entered the field a generation ago, it remains a specialized topic and most chemists are unfamiliar, or at least uncomfortable, with the synthesis and behavior of organofluorine compounds,” remain true today.

CRD undertook a program on alternatives for chlorofluorocarbons in refrigerant
Refrigerant
A refrigerant is a substance used in a heat cycle usually including, for enhanced efficiency, a reversible phase change from a liquid to a gas. Traditionally, fluorocarbons, especially chlorofluorocarbons, were used as refrigerants, but they are being phased out because of their ozone depletion...

s in the late 1970s after the first warnings of damage to stratospheric
Stratospheric
Stratospheric is an instrumental guitar album , released by French guitarist Jean-Pierre Danel in 2000.Several songs from the album hit the web downloading charts, including three #1's....

 ozone
Ozone
Ozone , or trioxygen, is a triatomic molecule, consisting of three oxygen atoms. It is an allotrope of oxygen that is much less stable than the diatomic allotrope...

 were published. The Catalysis Center of CRD, under the leadership of Leo Manzer, was quick to respond with new technology to produce alternative hydrochlorofluorocarbons (HCFCs) that were commercialized as DuPont's Suva
Suva
Suva features a tropical rainforest climate under the Koppen climate classification. The city sees a copious amount of precipitation during the course of the year. Suva averages 3,000 mm of precipitation annually with its driest month, July averaging 125 mm of rain per year. In fact,...

 refrigerants.

Cyanocarbon chemistry

Cyanocarbon Backbone
Structural unit of
cyanocarbon molecules.

During the 1960s and 1970s, CRD developed a program under the direction of Theodore Cairns to synthesize long-chain cyanocarbons analogous to long-chain fluorocarbons like Teflon. The work culminated in a series of twelve papers in the Journal of the American Chemical Society
Journal of the American Chemical Society
The Journal of the American Chemical Society is a weekly peer-reviewed scientific journal that was established in 1879 by the American Chemical Society. The journal has absorbed two other publications in its history, the Journal of Analytical and Applied Chemistry and the American Chemical Journal...

 in 1958. Several authors of those papers grew to prominent positions at DuPont including Richard E. Benson (Associate Director, CRD), Theodore L. Cairns (Research Director, CRD), Richard E. Heckert (CEO of DuPont), William D. Phillips (Associate Director, CRD), Howard E. Simmons (Research Director and VP, CRD), and Susan A. Vladuchick (Plant Manager). This trend indicates the importance of technical qualification for promotion in the company at that time. The publication stimulated other researchers to investigate these compounds.
DISN
Diiminosuccinonitrile
DAMN
Diaminomaleonitrile

Prospective applications included dyes, pharmaceuticals, pesticides, organic magnets, and incorporation in new types of polymers. No commercial applications resulted from this extensive research effort. Partly for this work, Cairns was awarded medals for Creative Work in Synthetic Organic Chemistry by the American Chemical Society
American Chemical Society
The American Chemical Society is a scientific society based in the United States that supports scientific inquiry in the field of chemistry. Founded in 1876 at New York University, the ACS currently has more than 161,000 members at all degree-levels and in all fields of chemistry, chemical...

 and the Synthetic Organic Award of the Chemicals Manufacturers Association. Another line of chemistry developed around Owen Webster
Owen Webster
Owen W. Webster is a distinguished member of the organic and polymer chemistry communities. His polymerization technique for making block copolymer dispersing agents is used by DuPont to make ink-jet printer inks....

’s synthesis of diiminosuccinonitrile (DISN) that could be converted to diaminomaleonitrile (DAMN) leading to another series of patent and papers. Simmons used disodium dimercaptomaleonitrile for the preparation many novel substances of including tetracyanothiophene, tetracyanopyrrole, and pentacyanocyclopentadiene.

Metal oxides

Arthur Sleight led a team focused on perovskite
Perovskite
A perovskite structure is any material with the same type of crystal structure as calcium titanium oxide , known as the perovskite structure, or XIIA2+VIB4+X2−3 with the oxygen in the face centers. Perovskites take their name from this compound, which was first discovered in the Ural mountains of...

s, such as the K-Bi-Pb-O system, that laid the groundwork for subsequent breakthroughs in high-temperature superconductors. In solution phase chemistry of oxides, the work of Walter Knoth on organic soluble polyoxoanions led to the development of the now large area with numerous applications in oxidation catalysis.

Dynamic NMR spectroscopy

Indicative of interplay between applications and fundamental science were many studies on stereodynamics conducted at CRD by Jesson, Meakin, and Muetterties. One of the early studies focused on the non-rigidity of SF4, a reagent relevant to the preparation of fluorocarbons. Subsequent studies led to the discovery of the first stereochemically non-rigid octahedal complexes of the type FeH2(PR3)4.

Polymer science

Owen Webster
Owen Webster
Owen W. Webster is a distinguished member of the organic and polymer chemistry communities. His polymerization technique for making block copolymer dispersing agents is used by DuPont to make ink-jet printer inks....

 discovered group-transfer polymerization (GTP), the first new polymerization process developed since living anionic polymerization. The major aspects of the mechanism of the reaction were determined and the process was quickly converted to commercial application for automotive finishes and ink jet inks. The basic process of group transfer also has application to general organic synthesis
Organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the construction of organic compounds via organic reactions. Organic molecules can often contain a higher level of complexity compared to purely inorganic compounds, so the synthesis of organic compounds has...

, including natural products.

At about the same time, Andrew Janowicz developed a useful version of cobalt catalyzed chain transfer for controlling the molecular weight of free radicalpolymerization
Polymerization
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains...

s. The technology has been further developed by Alexei Gridnev and Steven Ittel
Steven Ittel
Steven Dale Ittel was born 1946 in Hamilton, Ohio. His father was a superintendent of a rural school district and a YMCA camp director, so he spent the first 19 summers of his life at Camp Campbell Gard. He is an American chemist specializing in organometallic chemistry and homogeneous catalysis...

. It, too, was quickly commercialized and a fundamental understanding of the process developed over a longer period of time.

Rudolph Pariser
Rudolph Pariser
Rudolph Pariser is a physical and polymer chemist. He was born in Harbin, China to merchant parents. He attended the Von Hindenburg Schule in Harbin, an American Missionary School in Beijing and American School in Tokyo...

 was the director of the Advanced Materials Science and Engineering at the time of these advances.

In 1995, Maurice Brookhart
Maurice Brookhart
Maurice S. Brookhart is the William R. Kenan, Jr. Professor of Chemistry in the Department of Chemistry at the University of North Carolina....

, professor at the University of North Carolina
University of North Carolina at Chapel Hill
The University of North Carolina at Chapel Hill is a public research university located in Chapel Hill, North Carolina, United States...

 and a DuPont CRD consultant, invented a new generation of post-metallocene catalyst
Post-metallocene catalyst
A post-metallocene catalyst is a kind of catalyst for olefin polymerization. "Post-metallocene" refers to the generation of catalysts following Kaminsky catalysts, which are metallocene catalysts discovered in 1980 by Walter Kaminsky, and have been highly publicized in the olefin polymerization...

s for olefin coordination polymerization
Coordination polymerization
Coordination polymerization is a form of addition polymerization in which monomer adds to a growing macromolecule through an organometallic active center...

 based upon late transition metals with his postdoctoral student, Lynda Johnson who later joined CRD. The technology, DuPont’s Versipol olefin polymerization technology, was developed by a substantial team of CRD scientists over the next ten years.

Organometallic chemistry

Cramer’s Dimer
Tebbe Reagent

CRD developed a major interest in inorganic and organometallic chemistry. Earl Muetterties established a program aimed at fundamental borane chemistry. Walter Knoth discovered the first polyhedral borane anion, B10H10=, and also discovered that the borane anions displayed a substitution chemistry similar to that of aromatic hydrocarbons. Norman Miller discovered the B12H12= anion in an effort to find a new route to B10H10=. George Parshall
George Parshall
George W. Parshall is a distinguished member of the organometallic chemistry and homogeneous catalysis communities and has played a key role in advising the U.S...

 joined CRD in 1954. His industrial sabbatical at Imperial College London
Imperial College London
Imperial College London is a public research university located in London, United Kingdom, specialising in science, engineering, business and medicine...

 with Geoffrey Wilkinson
Geoffrey Wilkinson
Sir Geoffrey Wilkinson FRS was a Nobel laureate English chemist who pioneered inorganic chemistry and homogeneous transition metal catalysis.-Biography:...

 in 1960-61 introduced him to organometallic chemistry
Organometallic chemistry
Organometallic chemistry is the study of chemical compounds containing bonds between carbon and a metal. Since many compounds without such bonds are chemically similar, an alternative may be compounds containing metal-element bonds of a largely covalent character...

. Muetterties left DuPont to join the faculty of Cornell in 1973. After Muetterties and Parshall, the organometallic chemistry group was led by Steven Ittel
Steven Ittel
Steven Dale Ittel was born 1946 in Hamilton, Ohio. His father was a superintendent of a rural school district and a YMCA camp director, so he spent the first 19 summers of his life at Camp Campbell Gard. He is an American chemist specializing in organometallic chemistry and homogeneous catalysis...

 and then Henry Bryndza before it was dispersed throughout a number of groups in CRD. Parshall and Ittel coauthored a book on “Homogeneous Catalysis” that has become the standard reference on the subject.

The seminal contributions of Richard Cramer and Frederick Tebbe are acknowledged by their named compounds, “Cramer’s dimer,” Rh2Cl2(C2H4)4, and the “Tebbe reagent.” Tebbe had an influence on his lab partner, Richard Schrock who initiated a program on M=C chemistry at DuPont and continued it when he moved to MIT. The chemistry forms the basis for olefin metathesis
Olefin metathesis
Olefin metathesis or transalkylidenation is an organic reaction that entails redistribution of alkylene fragments by the scission of carbon - carbon double bonds in olefins . Its advantages include the creation of fewer sideproducts and hazardous wastes. Yves Chauvin, Robert H. Grubbs, and Richard R...

, and Schrock ultimately shared the Nobel Prize
Nobel Prize
The Nobel Prizes are annual international awards bestowed by Scandinavian committees in recognition of cultural and scientific advances. The will of the Swedish chemist Alfred Nobel, the inventor of dynamite, established the prizes in 1895...

 with Robert Grubbs, a CRD consultant, for the metathesis work. Anthony Arduengo
Anthony Joseph Arduengo III
Anthony Joseph Arduengo, III is the Saxon Professor of Chemistry at the University of Alabama and an adjunct professor at the Institute for Inorganic Chemistry of Braunschweig University of Technology in Germany...

’s persistent carbene
Persistent carbene
A persistent carbene is a type of carbene demonstrating particular stability. The best-known examples are diaminocarbenes with the general formula 2C:, where the 'R's are various functional groups...

s opened up a new area of chemistry and they have proven to be important ligands in the metathesis process.

There was a vigorous effort on the activation of C-H bonds with contributions by Parshall, Thomas Herskovitz, Ittel, and David Thorn. Chad Tolman developed his “ligand cone angle
Ligand cone angle
The ligand cone angle is a measure of the size of a ligand. It is defined as the solid angle formed with the metal at the vertex and the hydrogen atoms at the perimeter of the cone . Tertiary phosphine ligands are commonly classified using this parameter, but the method can be applied to any...

” theory that developed into the widely accepted electronic and steric effects of ligand
Ligand
In coordination chemistry, a ligand is an ion or molecule that binds to a central metal atom to form a coordination complex. The bonding between metal and ligand generally involves formal donation of one or more of the ligand's electron pairs. The nature of metal-ligand bonding can range from...

s on inorganic and organometallic complexes.

Organometallic chemistry in CRD has further included R. Thomas Baker's heterobinuclear complexes, Patricia L. Watson's organolanthanides, William A. Nugent's metal-ligand multiple bonds, Jeffery Thompson's and Mani Subramanyam's development of technetium
Technetium
Technetium is the chemical element with atomic number 43 and symbol Tc. It is the lowest atomic number element without any stable isotopes; every form of it is radioactive. Nearly all technetium is produced synthetically and only minute amounts are found in nature...

 complexes for radiopharmaceuticals, and Bob Burch's and Karin Karel's fluoro-organometallic chemistry. The major outlet for organometallic chemistry is homogeneous catalysis. DuPont developed a major technology based upon the nickel catalyzed addition of two molecules of hydrogen cyanide to butadiene, giving adiponitrile
Adiponitrile
Adiponitrile is the organic compound with the formula 42. This dinitrile, a viscous, colourless liquid, is an important precursor to the polymer nylon 66. In 2005, about one billion kilograms were produced annually.-Early routes:...

, a nylon
Nylon
Nylon is a generic designation for a family of synthetic polymers known generically as polyamides, first produced on February 28, 1935, by Wallace Carothers at DuPont's research facility at the DuPont Experimental Station...

 intermediate. The mechanistic work to provide an understanding of the technology was done in CRD and led to a large program on next-generation technology before the business was sold to Koch Industries. Other applications of homogeneous catalysis studied in CRD include ethylene
Ethylene
Ethylene is a gaseous organic compound with the formula . It is the simplest alkene . Because it contains a carbon-carbon double bond, ethylene is classified as an unsaturated hydrocarbon. Ethylene is widely used in industry and is also a plant hormone...

 polymerization
Polymerization
In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form three-dimensional networks or polymer chains...

, cyclohexane
Cyclohexane
Cyclohexane is a cycloalkane with the molecular formula C6H12. Cyclohexane is used as a nonpolar solvent for the chemical industry, and also as a raw material for the industrial production of adipic acid and caprolactam, both of which being intermediates used in the production of nylon...

 oxidation to adipic acid
Adipic acid
Adipic acid is the organic compound with the formula 42. From the industrial perspective, it is the most important dicarboxylic acid: About 2.5 billion kilograms of this white crystalline powder are produced annually, mainly as a precursor for the production of nylon...

, and butadiene carbonylation
Carbonylation
Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry.-Organic chemistry:...

 to nylon
Nylon
Nylon is a generic designation for a family of synthetic polymers known generically as polyamides, first produced on February 28, 1935, by Wallace Carothers at DuPont's research facility at the DuPont Experimental Station...

 intermediates. Approaches to catalyst systems have included homogeneous organometallic catalysts, heterobinuclear catalysts, polyoxometalate
Polyoxometalate
In chemistry, a polyoxometalate is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form a large, closed 3-dimensional framework....

s, enzymes, catalytic membrane reactor
Membrane reactor
A membrane reactor is a piece of chemical equipment that combines a catalyst-filled reaction chamber with a membrane to add reactants or remove products of the reaction.Chemical reactors making use of membranes are usually referred to as membrane reactors...

s and supported organometallics.

Photochemistry and physics

David M. McQueen, one of the early Directors of CRD was a physical chemist from the University of Wisconsin–Madison
University of Wisconsin–Madison
The University of Wisconsin–Madison is a public research university located in Madison, Wisconsin, United States. Founded in 1848, UW–Madison is the flagship campus of the University of Wisconsin System. It became a land-grant institution in 1866...

. His research on photochemistry
Photochemistry
Photochemistry, a sub-discipline of chemistry, is the study of chemical reactions that proceed with the absorption of light by atoms or molecules.. Everyday examples include photosynthesis, the degradation of plastics and the formation of vitamin D with sunlight.-Principles:Light is a type of...

 and photography
Photography
Photography is the art, science and practice of creating durable images by recording light or other electromagnetic radiation, either electronically by means of an image sensor or chemically by means of a light-sensitive material such as photographic film...

 resulted in thirty-five patents. It was his background that got CRD started in photochemistry and photophysics. David Eaton later headed a strong team involved in photopolymerization color proofing for the printing industry.

There was a strong program in inorganic non-linear optical materials that resulted in optical frequency doubling for the “green lasers” mentioned above. This program was extended into organic materials with NLO properties.

There was also a strong effort on materials for the display industry and methods for preparing devices for displays. These included printable electronics, thermal transfer methods for color filters, carbon nanotubes for field emission displays, and OLED materials and devices. A substantial effort was made on next generation photoresist
Photoresist
A photoresist is a light-sensitive material used in several industrial processes, such as photolithography and photoengraving to form a patterned coating on a surface.-Tone:Photoresists are classified into two groups: positive resists and negative resists....

s for the semiconductor
Semiconductor
A semiconductor is a material with electrical conductivity due to electron flow intermediate in magnitude between that of a conductor and an insulator. This means a conductivity roughly in the range of 103 to 10−8 siemens per centimeter...

 industry containing hydrocarbon
Hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons from which one hydrogen atom has been removed are functional groups, called hydrocarbyls....

 and fluorocarbon
Fluorocarbon
Fluorocarbons, sometimes referred to as perfluorocarbons or PFCs, are organofluorine compounds that contain only carbon and fluorine bonded together in strong carbon–fluorine bonds. Fluoroalkanes that contain only single bonds are more chemically and thermally stable than alkanes...

 monomers to replace wavelengths of 193 nm with 157 nm wavelengths for better resolution. Though most of the requirements were achieved, the need for that shorter wavelength node was eliminated by the introduction of immersion lithography
Immersion lithography
Immersion lithography is a photolithography resolution enhancement technique for manufacturing integrated circuits that replaces the usual air gap between the final lens and the wafer surface with a liquid medium that has a refractive index greater than one. The resolution is increased by a factor...

 and new fluids for immersion lithography
Immersion lithography
Immersion lithography is a photolithography resolution enhancement technique for manufacturing integrated circuits that replaces the usual air gap between the final lens and the wafer surface with a liquid medium that has a refractive index greater than one. The resolution is increased by a factor...

 continue to be of substantial interest. Development of phase-shift mask
Phase-shift mask
Phase-shift masks are photomasks that take advantage of the interference generated by phase differences to improve image resolution in photolithography...

s was commercialized.

Biological sciences

One area always deemed important for diversification of CRD's programs was related to the biological sciences. Charles Stine had promoted biochemistry as a field of research for Du Pont and Stine Laboratories are named in his honor as a result. In the early 1950s, CRD began a program to investigate chemicals for biological applications. Charles Todd prepared substituted ureas as potential antibacterial agents, which when screened, proved to be effective herbicides. These led to DuPont’s very successful and very selective sulfonylurea herbicides. CRD's program included agricultural and veterinary chemicals and bacteriological and microbiological studies. The culmination of this work was DuPont’s purchase of Pioneer Hi-Bred
Pioneer Hi-Bred
Pioneer Hi-Bred is the largest U.S. producer of hybrid seeds for agriculture.- History :In 1926, farm journal editor and future U.S. Vice President Henry A. Wallace, along with a group of Des Moines, Iowa businessmen, founded the "Hi-Bred Corn Company". At the time, most corn farmers saved part of...

 Seeds
SEEDS
SEEDS is a voluntary organisation registered under the Societies Act of India....

 and its integration into DuPont’s agrichemical enterprise.

In the mid- 1950s, CRD began work on the chemistry of nitrogen fixation
Nitrogen fixation
Nitrogen fixation is the natural process, either biological or abiotic, by which nitrogen in the atmosphere is converted into ammonia . This process is essential for life because fixed nitrogen is required to biosynthesize the basic building blocks of life, e.g., nucleotides for DNA and RNA and...

 in plants, a study that would develop into a major effort over the next decade. In 1963, Ralph Hardy joined the CRD and brought Du Pont's nitrogen fixation research to international prominence with more than a hundred papers on the subject. Chemical Week called him, "one of the nation's top achievers in the dual role of scientist and scientific manager," though such managers remained common in CRD through the 1960s and 70s.

Fermentation
Industrial fermentation
Industrial fermentation is the intentional use of fermentation by microorganisms such as bacteria and fungi to make products useful to humans. Fermented products have applications as food as well as in general industry.- Food fermentation :...

 microbiology
Microbiology
Microbiology is the study of microorganisms, which are defined as any microscopic organism that comprises either a single cell , cell clusters or no cell at all . This includes eukaryotes, such as fungi and protists, and prokaryotes...

 and selective genetic modification became important to the CRD development of a biological route to 1,3-propylene glycol a new monomer for making polyester. The availability of this new monomer led to the development and commercialization of Sorona, a premium polyester
Polyester
Polyester is a category of polymers which contain the ester functional group in their main chain. Although there are many polyesters, the term "polyester" as a specific material most commonly refers to polyethylene terephthalate...

. Substantial success was also achieved in the synthesis of unnatural peptides and proteins to accomplish specific functions and prediction of their tertiary structures.

Advances in DNA sequencing
DNA sequencing
DNA sequencing includes several methods and technologies that are used for determining the order of the nucleotide bases—adenine, guanine, cytosine, and thymine—in a molecule of DNA....

 technology based on synthesis of novel fluorescent labels led to Qualicon, a DuPont venture that identifies bacteria
Bacteria
Bacteria are a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria have a wide range of shapes, ranging from spheres to rods and spirals...

 by examination of their DNA
DNA
Deoxyribonucleic acid is a nucleic acid that contains the genetic instructions used in the development and functioning of all known living organisms . The DNA segments that carry this genetic information are called genes, but other DNA sequences have structural purposes, or are involved in...

 using PCR. This technology has led to significant improvements in the safety of the food supply chain in the United States and around the world.

General references

  • David A. Hounshell
    David A. Hounshell
    David Allen Hounshell is the David M. Roderick Professor of Technology and Social Change in the Department of Social and Decision Sciences, Department of History, and the Department of Engineering and Public Policy at Carnegie Mellon University....

    and John Kenley Smith. Science and Corporate Strategy. DuPont R&D, 1902–1980. New York: Cambridge University Press, 1988.
  • J. J. Bohning. Howard E. Simmons, Jr., Oral History. Philadelphia: Chemical Heritage Foundation, 1993.
  • R. C. Ferguson. William D. Phillips and nuclear magnetic resonance at DuPont. In Encyclopedia of Nuclear Magnetic Resonance, Vol. 1, Eds. D. M. Grant and R. K. Harris, pp. 309–13, John Wiley & Sons, 1996.
  • R. G. Bergman, G. W. Parshall, and K. N. Raymond. Earl L. Muetterties, 1927–1984. In Biographical Memoirs, vol. 63, pp. 383–93. Washington, D.C.: National Academy Press, 1994.
  • B. C. McKusick and Theodore L. Cairns, Cyanocarbons in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, 6, 625-33 (1965)
The source of this article is wikipedia, the free encyclopedia.  The text of this article is licensed under the GFDL.
 
x
OK