Rubber Program

Butadiene. Although butadiene was produced in the United States in the eady 1920s, it was not until the start of Wodd War 11 that significant quantities were produced to meet the war effort. A number of processes were investigated as part of the American Synthetic Rubber Program. Catalytic dehydrogenation of / -butenes and / -butanes (Houdry process) and thermal cracking of petroleum hydrocarbons were chosen (12). 

The original recipe adopted by the U.S. Government Synthetic Rubber Program was known as the "Mutual Recipe" and is shown iu Table 4. As can be seen, the reaction temperature was set at 50°C, which resulted iu 75% conversion to polymer iu about 12 h. The reaction was then stopped by addition of a "shortstop," such as 0.1 parts hydroquinone, which destroyed any residual catalyst (persulfate), and generated quiuone, which helped inhibit any further polymerisation. 

The revolutionary development of stereospecific polymerization by the Ziegler-Natta catalysts also resulted ia the accomplishment ia the 1950s of a 100-year-old goal, the synthesis of i7j -l,4-polyisoprene (natural mbber). This actually led to the immediate termination of the U.S. Government Synthetic Rubber Program ia 1956 because the technical problem of dupHcating the molecular stmcture of natural mbber was thereby solved, and also because the mbber plantations of the Far East were again available. 

With minor modifications that rubber is still used for passenger cars. It is not suitable for large trucks and bomber tires because of the excess of heat build-up in operation. Before the end of the rubber program, two of the companies, Firestone and Goodrich, had developed processes that produced rubber essentially like natural rubber. Firestone used a lithium catalyst for the polymerization, and Goodrich used a modified Ziegler catalyst. These materials were manufactured for a while until the oil prices became too prohibitive and the natural rubber was again used for heavy-duty tires. 

I, too, was caught up in the wave of enthusiasm for this new science which had the lofty goal of relating the properties of materials to their molecular structure, and, in the end, to "tailor-making molecules for specific properties. Since one of the big developments at that time was the newly-started synthetic rubber programs of the American and Canadian governments, I chose the topic of the emulsion copolymerization of butadiene-styrene as the subject of my doctoral dissertation. 

When Japan attacked Hawaii in December 1941, the most critical chemical problem was the solution to the rubber shortage because the far Eastern suppliers were cut off. Since Speed had become a polymer chemist during 1930-1940, he became part of this rubber program. The major rubber companies, many universities, and other chemical companies put aside their competition and pooled their research efforts and in about a year s time developed a usable SR that was manufactured and used in smaller types of tires. 

Speed helped organize, prior to the war years, a rubber program on the synthesis of rubber for the National Defense Research Committee under Adams, which was eventually responsible for the production of rubber during the war. He was also drafted and helped on a research program for the Committee on Medical Research dealing with malaria research. 

POLYMER MILESTONES—THE AMERICAN SYNTHETIC RUBBER PROGRAM... 

The theory of Harkins (57), which was developed during discussions with many other workers during the expansion of the synthetic rubber program, suggests that the principal locus for the initiation of the reaction was in the extremely small amount of solubilized monomer oil inside the soap micelles. This monomer is surrounded on all sides by a monomolecu-lar film of soap molecules, oriented as in Fig. 8 with their hydrocarbon groups towards the oil and their polar groups (e.g., —COO) towards the water outside. By this process small nuclei of polymer particles are formed. 

This investigation was carried out under the sponsorship of the Office of Rubber Reserve, Reconstruction Finance Corporation, in connection with the Government Synthetic Rubber Program. 

Magnusson, F.S. (1978) Petrochemical Feedstocks, Chemicals and Rubber Program, Office of Basic Industrial Materials Division, Industry and Trade Administration, US Department of Commerce, Washington, DC, November. 

Rubber Reserve Company, Report on the Rubber Program 1940-1945. Covers activities of Rubber Reserve Company from June 1940 to February 1945. Data on government-owned plants in the synthetic rubber program. 

These acquisitions and the expansion of its rubber chemicals operation in Akron served as a base for the company s participation in the synthetic rubber programs during World War 11, for which it became a major provider of styrene and polystyrene and thus a major player in the polymer/petrochem-ical revolution. By the time the industry returned to peacetime production, Monsanto had become the nation s fifth-largest diversified multisectored chemical company. 

For the impact of World War II, see Whitehead, The Dow Story, ch. 12. Brandt, Growth Company, pp. 177-185, provides essential details, including Dow s participation in the synthetic rubber program, a move that led to the creation of the Canadian subsidiary. Ibid., pp. 192, 194, and 198. 

At the beginning of 1942 it became necessary to produce butadiene for the synthetic rubber program. Butadiene was then obtained commercially by catalysis from alcohol or butenes, both materials of strategic importance. 

United States Synthetic Rubber Program, 1939 1945. National Historic Chemical Landmarks, American Chemical Society. http //acswebcontent.acs.org/landmarks/landmarks/rbb/ rbb begin.html (accessed on December 29, 2005). 

It was my privilege to know Paul when he was at Cincinnati and I was at Akron. I envied his university association and was surprised when he left Cincinnati to join Standard Oil at Linden, NJ in 1940. Our paths crossed again when I served as a consultant for Rubber Reserve Corp. on the butyl rubber program. However, to my knowledge, Paul did not attempt to correct tlie difficulties experienced by Standard Oil when its attempts to produce this elastomer at Baton Rouge, LA were unsuccessful. Of course, it is a pleasure for me to report that Dr. John Durland and I were able to solve the production problem and make possible the commercial products of this important elastomer. 

He considered three possible loci for the initiation of pol5nner particle nuclei (79), based on his studies during 1942-1943 in connection with the Rubber Reserve Company (Synthetic Rubber Program of the United States Government) (1) the soap micelles, if present, (2) the aqueous phase, excluding soap micelles and polymer-monomer particles, and (3) the monomer droplets. He considered the monomer droplets as... 

In 1939 the US. government started a crash program to develop a manufactured elastomer, called the Synthetic Rubber Program (23). The new material was called GR-S (government rubber-styrene). GR-S was made by emulsion polymerization. While the Bunas was catalyzed by sodium, the latter was catalyzed by potassium persulfate. Incidentally, the emulsifier in those... 

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