The Chemical World This Week RESEARCH & TECHNOLOGY
JANUARY
2 9, 1 9 6 2
CONCENTRATES
• Production of chemicals using fission fragments from a nuclear reactor is the subject of a research project to be launched by AerojetGeneral Nucleonics, San Ramon, Calif. The study, under a $4 million contract from the Air Force, will concentrate first on converting ammonia to hydrazine. AGN has already demonstrated the feasibility of this reaction on a laboratory scale. The company (a subsidiary of Aerojet-General) is building a large scale fissiochemistry loop designed to operate continuously inside a reactor. The loop is scheduled for completion in about 18 months. Proposed use of fission fragments from a nuclear reactor in a chemical process is a major departure from more conventional proposals of nuclear reactor applications—using heat or radiation generated by the reactor, for example. In 1959, AGN made public a "paper" process for nitrogen fixation by fission recoil energy. And later that year, Hercules suggested that ethylene glycol might be made by dimerizing methanol the same way. • Newly developed mercury lamps are behind the economic feasibility of the photochemical process for caprolactam, which is being commercialized by Toyo Rayon, Japan, in a 30 ton-perday plant due for completion this year. The lamps provide energy for the reaction of cyclohexanone oxime. The oxime, in turn, forms caprolactam via a Beckmann rearrangement. The 10-kw. lamps bring electrical requirements for the reaction down to less than 3 kwh. per pound of oxime, Toyo says. The company expects manufacturing cost of caprolactam in Japan to be about 20 cents per pound. • Advances in nitration of toluene, synthesis of new boron heterocyclics, and rhodium catalysts were among the highlights at last week's ACS Metropolitan Regional Meeting, held in New York. The ratio of o- to p-nitrotoluene can be lowered if the nitration is done in the presence of P2O5 or polyphosphoric acid, according to Dr. S. M. Tsang and co-workers at American Cyanamid, Bound Brook, N.J. Using alkyl nitrates and phosphoric acid also results in a lower ortho-topara ratio. Heterocyclic compounds in which boron is part of the ring system have been synthesized by Dr. Harry L. Yale and co-workers at the Squibb In-
stitute for Medical Research, New Brunswick, N.J. They make the compounds by cyclizing the appropriate intermediate with an arylene- or aralkane-boronic acid, or with trimethyl borate followed by controlled hydrolysis. Several of the boron heterocyclics show significant diuretic activity, according to preliminary tests on laboratory animals, Squibb says. Rhodium catalysts can be used to make stereoregular, crystalline trans- 1,4-polybutadiene by emulsion polymerization. The material is hard and brittle compared to the rubbery, noncrystalline form made by conventional catalysts, according to U.S. Rubber's Dr. Robert E. Rinehart and co-workers. Emulsion polymerization with the usual catalysts can't be used to make stereoregular £rans-l,4-polybutadiene because the catalysts are destroyed by water. Rhodium salts, though, hold up in water, Dr. Rinehart says. • A ruby optical maser has gone continuous at Bell Telephone Laboratories* The maser was developed by Bell's Dr. Willard S. Boyle and Dr. Donald F. Nelson. The device starts emitting a coherent beam of visible light at an input power of 850 watts, and produces a beam of a few milliwatts. Bell's original pulsed ruby maser needed over 1000-kw. The secret is in the pumping scheme which raises intensity of the exciting light from a mercury arc lamp to a level five times greater than that of other systems. Bell uses a crystal that's trumpet-shaped at one end. This acts as a radiation condenser and intensifies the incoming light. This is Bell's second continuous solid maser; the first was trivalent neodymium in calcium tungstate (C&EN, Jan. 8, page 46). ^ Self-sustaining nuclear fission without a coolant was achieved last week in a reactor at the Hallam Nuclear Power Facility, near Lincoln, Neb. Termed "dry critical," the chain reaction produced no heat. The test was made to verify calculations on the reactor core. Eventually, the reactor will be cooled by liquid sodium. The fuel is slightly enriched uranium alloyed with molybdenum. Atomics International designed the reactor, and Bechtel Corp., San Francisco, is architect-engineer. When the reactor reaches full power (75,000 kw.) this fall, it will be operated by Consumers Public Power District of Nebraska. Consumers' personnel helped Atomics International in the test. JAN.
29,
1962
PART
1 C&EN
35
