DuPont Central Research

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 and Chestnut Run, in Wilmington, Delaware, it expanded to include laboratories in Geneva, Switzerland, Seoul, South Korea, Shanghai, China, and India (Hyderabad). In January, 2016 a major layoff marked the end of the organization.[1]

History

The company established a tradition of basic scientific research starting with hiring of Wallace Carothers 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.[2] This tradition waned during World War II 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", because Carothers' success and the resulting commercialization of nylon had driven the Company's profits through the 1950s. (This research objective 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 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

Organofluorine chemistry

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 had polymerized spontaneously into a white, waxy solid. The polymer was polytetrafluoroethylene (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 tetrafluoroethylene 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 provided many chemists and engineers with the background necessary to carry out the work. Availability of the Pressure Research Lab on the Experimental Station 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, 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.[5] Smart's book followed.[6]

Cyanocarbon chemistry

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 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.

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 and the Synthetic Organic Award of the Chemical Manufacturers Association. Another line of chemistry developed around Owen Webster's synthesis of diiminosuccinonitrile (DISN), which could be converted to diaminomaleonitrile (DAMN), leading to another series of patent and papers. Simmons used sodium maleonitriledithiolate for the preparation many novel substances of including tetracyanothiophene, tetracyanopyrrole, and pentacyanocyclopentadiene.

Metal oxides

Arthur Sleight led a team focused on perovskites, such as the K-Bi-Pb-O system, that laid the groundwork for subsequent breakthroughs in high-temperature superconductors.[7] 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.[8]

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 octahedral complexes of the type FeH2(PR3)4.[9]

Polymer science

Owen Webster 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, including natural products.[10]

At about the same time, Andrew Janowicz developed a useful version of cobalt catalyzed chain transfer for controlling the molecular weight of free radicalpolymerizations. The technology has been further developed by Alexei Gridnev and Steven Ittel. It, too, was quickly commercialized and a fundamental understanding of the process developed over a longer period of time.[11]

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

In 1995, Maurice Brookhart, professor at the University of North Carolina and a DuPont CRD consultant, invented a new generation of post-metallocene catalysts for olefin coordination polymerization based upon late transition metals with his postdoctoral student, Lynda Johnson who later joined CRD.

Organometallic chemistry

CRD developed a major interest in inorganic and organometallic chemistry. Earl Muetterties established a program aimed at fundamental borane chemistry.[13] 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.[14] Norman Miller discovered the B12H12= anion in an effort to find a new route to B10H10=.[15] George Parshall joined CRD in 1954. His industrial sabbatical at Imperial College London with Geoffrey Wilkinson in 1960-61 introduced him to organometallic chemistry. Muetterties left DuPont to join the faculty of Cornell in 1973. After Muetterties and Parshall, the organometallic chemistry group was led by Steven Ittel and then Henry Bryndza before it was dispersed throughout a number of groups in CRD. Parshall and Ittel coauthored a book on “Homogeneous Catalysis”[16] that has become the standard reference on the subject.

Photochemistry and physics

David M. McQueen, one of the early Directors of CRD was a physical chemist from the University of Wisconsin–Madison. His research on photochemistry and photography 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 photoresists for the semiconductor industry containing hydrocarbon and fluorocarbon 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 and new fluids for immersion lithography continue to be of substantial interest. Development of phase-shift masks 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 Seeds and its integration into DuPont's agrichemical enterprise.

In the mid- 1950s, CRD began work on the chemistry of nitrogen fixation 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 microbiology 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. 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 technology based on synthesis of novel

General references

• David A. Hounshell 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)