RESEARCH

Polymers from Propylene Oxide Research at Penn shows isotactic form promising for films or plastics, atactic form for foam rubbers

ISOTACTIC POLYPROPYLENE, its pro­ducers believe, is a coming commercial plastic material. Indeed the whole field of isotactic olefins offers tremen­dous possibilities. But Charles C. Price of the University of Pennsylvania feels that an entirely new family of elas­tomers, headed by polypropylene oxide, may be no less important.

Price told 1400 chemists at Univer­sity of Rochester for the 15th National Organic Chemistry Symposium that work at Penn on the structure of poly­mer chains points to substituted pro­pylene oxides as good prospects for better resins. Beginning in 1950 at Notre Dame, Price's work on polymer conformation led him to investigate this epoxy compound. He first made iso­tactic polymers from propylene oxide in 1953. These seem promising as fibers and plastics (good crystalline structure and molecular weight as high as a half million), while softer atactic polymers look hopeful for improved foam rubbers.

• Catalyst Action. Catalysts can be chosen to produce polymer chains of any desired configuration. Consider a simple trans zig-zag chain:

H2

Where there is no regularity as to which side of the chain X and Y lie, the poly­mer is called "atactic." If all the X groups are on the same side, the poly­mer is "isotactic" and crystallizes best. If X and Y alternate regularly, the poly­mer is "syndiotactic."

Dow Chemical Co. has developed a catalyst for isotactic polypropylene oxide, described in U. S. Patents 2,706,-181, 2,706,182, and 2,706,189. The catalyst appears to be an iron-alcoholate complex in the form of "a viscous red oil of indeterminate composition," ac­cording to Price. At Penn, however, alkoxides of Lewis-acid metals poly­merize propylene oxide, too. Alu­minum isopropoxide (AIP) is most effective, particularly combined with zinc chloride.

Homogeneous liquid catalysis—either in the straight monomer or diluted in

diethyl e ther-a t SO" C. gives the best yields of the isotactic polymer, Price reports. Lower temperatures result in slower polymerization, higher tempera­tures in less isotactic material.

Optically active monomer produces an optically active polypropylene oxide; this has helped Price determine how the polymer is formed. He views the process as a coordination mechanism similar to that giving isotactic poly-olefins by Ziegler-Natta catalysis, in which Lewis-acid metals—under similar conditions—form a carbon-to-metal bond:

XN OR

M^ ~ x''

X^

x'

X OR

M " ,

X 0 — C H — C H 3

CH 2

OR

^ O C H 2 CH 3

• Further Prospects. Price plans further work with both the isotactic and atactic polypropylene oxide. He says the latter form should make better synthetic rubber than the olefins them­selves, and rubber-industry interest in this bears him out.

Other members of this new family will be polypropylene sulfide and poly­propylene imines. With propylene oxide now costing 12 to 15 cents per pound, polypropylene products seem attractive economically.

Atom Invades Gl Chow The Army soon will start limited

tests to see if radiation causes un­wanted off-taste and flavor in foods. The test is part of a research program on preservation of food with radiation.

Irradiated food research will go into high gear when the Army's Ionizing Radiation Center at Lathrop, Calif., begins operations in 1958—59, says the Interdepartmental Committee on Radi­ation Preservation of Food in its first report. The committee is made up of representatives from AEC and the De­partments of State, Agriculture, De­fense. Commerce, Interior, and Health. Education and Welfare.

While the center is being built, con­

centrated, testing of 20 selected foods is scheduled. Packaging and post-radiation handling will be tackled. The key problem of setting radiation close standards for foods will get top attention. For this purpose, the Na­tional Research Council has appointed a Dosimetry Subcommittee. Dosime­try programs will continue through 1960 at an accelerating pace, says the committee.

Production of irradiated food on a pilot plant basis is due during fiscal 1959, according to the committee's cal­endar. By this time, the process should he pretty well worked out and industry should b e getting in position to "move rapidly." Fiscal 1960, says the com­mittee, should see industry playing a big part in this field.

So far, though, only limited human feeding studies have been done. In a two-year test just completed, over 40 irradiated foods were fed volunteers at "Fitzsirnmons Army Hospital in Den­ver, Colo. No toxic effects have been seen. The food was frozen to hold down possible toxic products forma­tion from other sources. In another test, says the committee, more volun­teers will be fed a diet of 100% irra­diated food for six to 12 months, but this time the food will be kept at room temperature for 90 days before serv­ing.

By 1960, provided pilot tests and feeding experiments show favorable re­sults, the Army will start buying trial lots of irradiated foods. Industry, says the committee, should then be in a position to start "exploratory produc­tion" of irradiated foods.

New Jobs for Ions

"Solion," the Navy's electro­chemical device, looms as competition for vacuum tubes, transistors

ELECTOCHEMISTRY could give elec­tronics some tough competition soon. Last week the U. S. Naval Ordnance Laboratory introduced "solion," an electrochemical device that "may re­place vacuum tubes and transistors over a wide range of electronic applica­tions," Solions were developed by the Navy in cooperation with the Defense Research Laboratory at the University of Texas.

In vacuum tubes and transistors, ions now through gas, vacuum, or a solid. Solions depend on ions moving through a solution. (Solion is short for ions in solution.)

The device consists of a small cyl­inder divided into sections and contain­ing a chemical solution. Electrodes

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RESEARCH

"Solion" (second from left, bo t tom) may compete with transistor ( t h i r d ) , vacuum tube (fourth) . Display board shows all par ts . Solion uses as little as one thousandth t h e power of a transistor, is powered by bat tery (left bo t tom)

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are immersed in the solution. Internal make-up depends on the use the solion is pu t to . Porous ceramic filters and platinum gauze are typical of materials used to separate the chambers. Any reversible redox system can b e used for the solution.

One acoustical "type solion uses platinum electrodes and potassium iodide solution to which iodine is added. Here's what happens at the electrodes:

At the cathode: I3" At the anode: 3 I "

2e --> 3I-I3" 4- 2e

A low voltage battery starts the cur­rent flow. Agitation of solution be­tween electrodes causes a n increase in current, the current between electrodes being a function of the fluid flow be­tween them. Changes in conditions such as sound, temperature, pressure, and acceleration, ac t the same as agi­tation, increasing t h e flow of iodide ions and therefore current . This change in current can b e used to set off control devices. Apparently, t he number of I3~ ions controls the current in t h e system.

Other solions, using electro-osmotic pressure developed by restricting t he flow of ions with porous ceramic filters, can amplify electric current.

Here are some advantages the Navy sees for solions:

• L o w power needs. Solions use a hundred th to a thousandth as much

power as transistors. Operating on such low battery current, solions need no heavy electrical generating equip­ment .

• Fast, sensitive, and accurate. The heat of a match, a living body, or a light source can be detected from many feet away. Solions can detect rate or speed of change in conditions, rather than sensing that a change has already taken place. Thus they can actuate controls while a change occurs.

• Simple, small, easy to maintain. The average solion is about the size of a demitasse, but much smaller ones are possible. Maintenance is no prob­lem, since there are no complex mov­ing parts and nothing to wear out or replenish.

• Providing the Spark. Supplying the starting power for solions is a "practically indestructible" midget dry battery. About the size of a man's wrist watch, it has a lead-lead oxide anode and a silver cathode, with so­dium hydroxide as the electrolyte. A single cell puts out 0.9 volt, has a capacity of 1.5 ampere-hours. The bat tery apparently can be recharged for "years on end," says the Navy.

T h e Navy sees many uses for solions. Color changes in a solion could detect when a man has been exposed to ex­cessive harmful low frequency sound from jet engines. It could replace the slow thermostat now used for home furnaces. Solions could help keep

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guided missiles on course. Military uses for solions, says t h e Navy, a re classified, but the wide range of peace­ful applications makes them "increas­ingly attractive to industrialists."

Old Drug, New Use For two years, Bristol Labs has been

selling phenyltoloxamine over-the-counter as an antihistamine, "the only antihistamine allowed to be so sold without a prescription," says Bristol. Like many antihistamines, it affected the central nervous system, as well as relieving allergies.

Bristol decided to study these side effects for their own value. The re­sult: at another dosage level, phenyl­toloxamine can reach some chronic mental patients.

I n clinical trials at Marcy State Hos­pi tal , Marcy, Ν . Υ., 72 patients, 45 to 78 years old, were studied; all had been institutionalized at least 10 years. In 5 5 cases, "good" or "fairly good" results were obtained, based on im­proved behavior and ability to adapt to society. Bristol says the new drug acts somewhat like reserpine but is re­markably free from side effects.

Bristol thinks the drug may b e par­ticularly valuable in senile psychoses and wants to do a two-to-three year evaluation program in institutions. Phenyltoloxamine has been withdrawn as an antihistamine and will be avail­able as PRN only on prescription. At present it will be distributed primarily to institutions.

• High antituberculosis activity is shown by a series of phenazines being studied at the Laboratories of the Medical Research Council of Ireland, Trinity College, Dublin. In May 18, Nature, Vincent C. Barry and associates say that one of the compounds has re­markable biological properties:

CI H Ν—C—CH,

ιΛ'νΥ \ A N ^ \ A H

Ν

It is more active against tuberculosis in mice than isoniazid on a weight-for-weight basis and very much more ac­tive on a molar basis. I t is effective in mice in which tuberculosis is just de­veloping or is already established, as well as against isoniazid-resistant tu­berculosis.

• G a m m a globulin increases t h e ef­fectiveness of Chloromycetin, accord­ing to studies on 46 patients at Mil-

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RESEARCH

waukee County General Hospital. Thirty one patients, most of whom had infections which did not respond to other therapy, responded favorably, Burton A. Waisbren says in June Anti­biotics and Chemotherapy. GG ap­pears to strengthen the body defenses and so helps the antibiotic in its fight against the infection. The studies were started after animal tests at Parke-Davis showed the curative action of the antibiotic was increased as much as 50 times when GO was added.

• Allergic reactions of penicillin can be relieved with penicillinase, accord­ing to clinical studies by G. M. Davis of Great Lakes Naval Training Station and R M. Becker of Madison, Wis. Relief comes within a few hours to 24 hours, they told the New York meeting of the American Medical Association. Schenley Laboratories plans to intro­duce penicillinase under the name Neutrapen by the end of the year. It is a highly refined enzyme produced by a process on which Schenley now has a patent pending. • Human perspiration can b e inhibited by salts of malonic acid, especially the sodium salt, according to Elsa L. Gon­zalez and Adoph Rostenberg, Jr., of University of Illinois College of Medi­cine. The reason, they say, is that the compounds specifically inhibit succinic acid dehydrogenase, which is respon­sible for human perspiration. • Stanford Research Institute will build a $50,000 plastics laboratory for 32 scientists and technicians in its plas­tics research program; SRI is doing about $250,000 worth of such research in 1957. The new facility will include machines to make metal-adhesive-metal laminates, facilities to irradiate materials, testing devices, weathering and aging equipment, and vacuum and injection molding machines.

• Mellon Institute sets up a trust fund the income of which will support its new fundamental research program (C&EN, April 1, page 24 ) . So far grants have been made by the A. W. Mellon Educational and Charitable Trust, the Sarah Mellon Scaife Founda­tion, and the Richard King Mellon Foundation. The institute believes it can also get support from industry and government.

• Factors influencing properties of reinforced plastics will be studied by Owens-Corning Fiberglas under an 18-month technical program for the USAF's Air Materiel Command, Day­ton, Ohio. The research, which ties in with the company's own efforts, will go into the properties of component materials and the effects of molding processes.

NOMENCLATURE by LEONARD T. CAPELL

Pest Control Chemicals Interest in the development of

suitable short names for pesticidal chemicals is world-wide. The In­terdepartmental Committee on Pest Control of the U. S. Department of Agriculture, under the chairman­ship of the late S. A. Rohwer, initiated a cooperative undertaking with several interested national or­ganizations, including the ACS. for the approval of common names.

-. ., Leonard: T. Capell of Chemi­cal Abstracts, with the coopera­tion of CA staff associates, has resumed the column of the late Austin M. Patterson.

This work was continued for several years under the leadership of H. L. Haller. In order to cooperate more fully with international organiza­tions, the American Standards As­sociation was asked to organize a national project for the approval of such names. This has resulted in the organization of the American Standards Association Sectional Committee on Common Names for Pest Control Chemicals, K 62. This committee, of which Haller is chair­man, has approved an "American Standard Procedure for the Accept­ance of an American Standard Common Name for a Pest Control Chemical." Copies of this proce­dure may be obtained from the American Standards Association, 70 East 45th St., New York 17, N. Y.

This committee does not propose names. It considers only names submitted for those products which have reached a stage of develop­ment which is considered likely to result in commercial distribution. Selection of common names is based on the following principles. "A common name shall be prefer­ably short and need have no chemi­cal significance in itself, nor have any relationship to the chemical name or nature of the product. Commonly accepted chemical pre­fixes or suffixes shall be avoided as far as possible, but if used, such use shall in no way conflict with the standards of nomenclature of the AMERICAN CHEMICAL SOCIETY. The name should not be similar

phonetically or in spelling to sys­tematically formed names or to trade or common names of other commercial chemicals even though such chemicals may not be used in pest control. Proposed common names consisting of initials or num­bers or a combination of initials and numbers will not be consid­ered."

Multivalent Radicals There is a need for more liberal

rules for the formation of radical names. Official rules provide for univalent and bivalent radicals from acyclic compounds and cyclic hydrocarbons and univalent radi­cals from heterocycles. Friederich Richter of Beilstein Institute has suggested multivalent radicals such as butanediylidene ( = C H C H , -CH..CH ) and propan-l-vl-3-vfi-dene ( - C H 2 C H 2 C H = ) . Multiva­lent radicals from heterocycles, such as 2,7-acridinediyl and 2,4,6-s-triazinetriyl, would be very useful in systematic nomenclature.

Catechin, Catechol, et al. When there are two names for

one compound or one name for two different compounds the result is confusion in the literature. Orig­inally there were only two names, catechin for the pentahydroxyflavan and brenzcatechin for the o-dihydroxybenzene first obtained from catechin by distillation. In order to use the functional ending "ol," these names were changed to catechol and pyrocatechol. Fre­quent use of catechol to mean pyro­catechol has led to confusion. There can be no ambiguity if one always uses pyrocatechol for o-di-hydroxybenzene.

In Far-Off Fields • In Indonesia: A small guide to

the nomenclature of inorganic and organic chemistry with a vocabulary of chemical terms, has been published.

• In Japan: A revision (1957) of the Japanese "Nomenclature of Chemical Compounds."

2 8 C & E N J U L Y 8, 1 9 5 7