The Chemical lnnovators-7 John F. Henahan, Senior Editor
John J. Singer, Jr. Chemical claws at a reasonable price
The Beechcraft Bonanza stands ready for business and duck-hunting jaunts
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C & E N SEPT. 14, 1970
Jack Singer likes to do things for himself, whether it be flying his own airplane, building his own house, or starting a spunky little chemical company, which is now in the enviable position of producing a product for which the demand far outstrips the supply. Dr. Singer is the burly, shirt-sleeved president of Hampshire Chemical division of W. R. Grace & Co. The product so greatly in demand is a chelate called NTA—nitrilotriacetic acid: N(CH.,COOH) 8 . Some people predict that its availability will help reverse an ecological trend that may already have sentenced many of the world's large lakes and rivers to a premature death. In a large way, Dr. Singer is responsible for the fact that NTA probably will gradually replace phosphates in household detergents—such phosphates being labeled in some quarters as a major environmental contaminant. What began the movement to NTA was an improved process for chelate production that Dr. Singer and an associate, Dr. Mark Weisberg, first devised in 1954. Dr. Singer's evolution toward Hampshire Chemical Co. and NTA began, typically enough, from the usual "boy with chemistry set" in Camden, N.J. It was a logical progression to the A.B. and M.A. degrees he later received at Clark University in Worcester, Mass. His quest for a Ph.D. in physical chemistry was delaved three vears while he served as a
heavy-bomber pilot in World War II. Shot down over Vienna, he bailed out and was welcomed to Austria with a punch in the face from a German. The German was then thrashed in turn by local Naziophobes who'd apparently had enough of such brutality. He languished for a year in Stalag Luft # 3 , which was also the home of the indomitable British tunnel builders who provided the dramatic plot for the movie "The Great Escape." Freed by General Patton's tank corps, Jack Singer returned to Clark where he got his Ph.D. in 1949. Molecular claws. Long before he and Dr. Weisberg invented the NTA process, Dr. Singer had been intrigued with chelates and the almost magical ability of their molecular claws to tie up heavy metal atoms when not wanted or free them when desired. Chelates, for example, are medically useful for removing lead from the blood stream in poisoning cases, or for releasing iron, zinc, or copper to nutritionally deficient soils. His initial taste of the chelate industry came when he was hired as the seventh employee by Bersworth Chemical Co., in Framingham, Mass., a firm then run by "four brothers-inlaw and three fellows who pushed the barrels around." The company was the first to manufacture ethylenediaminetetraacetic acid (EDTA) and other important chelates in the U.S., using a process invented by the company's founder, Frederick C. Bers-
worth. Dr. Singer functioned as chemist, production manager, sales man, author of technical literature, and pilot of the company plane. He often used the plane to swoop down on po tential customers to tell them how and why they should be using chelates. "The fascinating thing about che lates is that you could go to almost any industry with a problem and demon strate how chelates might solve it. They were great clarifying agents and antioxidants for liquid soaps and de tergents, removed deleterious metallic impurities in textile finishing and dye ing, were useful in synthetic rubber manufacture, in photographic solu tions, and pharmaceutical manufac ture. There's nothing better than sell ing something that works," Dr. Singer says. In the citrus groves of Florida, Dr. Singer found that chelate compounds containing iron, in a vermiculite for mulation, were a kind of miracle drug for a fruit tree nutrient deficiency that leads to chlorosis. In the iron-starved soil of Florida, leaves of affected trees turn yellow and drop off. Fruit loss follows, and the tree dies. Singer's sales techniques for iron chelate were direct and productive. "We'd get in a car and roam through the citrus fields and find a grove with yellow leaves. After finding out who owned the grove, we'd discuss the situation with the local agronomist be fore we ran our test. Then we'd sprinkle some iron chelate on the ground, come back a month later and the tree would be green. It was a very impressive test and the grower would invariably ask us to send him a 'batch of that stuff.' Treatment for a single tree costs only about 10 to 15 cents a year, so it was extremely worthwhile for a fruit grower who had nothing to look forward to but the loss of his sick trees," Dr. Singer recalls. See Singer. While he was still at Bersworth Chemical, Dr. Singer en countered Bradley Dewey, undoubt edly one of the world's most colorful chemical entrepeneurs. Over a period of years, Dr. Dewey, who, as a 30year-old full colonel in the U.S. Army, was in charge of gas defense in World War I, established Dewey and Almy Chemical Co. (now a division of W. R. Grace), operated on many impor tant technical fronts for the Govern ment during World War II, and gen erally kept his eyes open for interest ing looking chemists and chemical companies. (In 1946 he was Presi dent of ACS.)
ι Jack Singer and his wife built most of
In an unsuccessful bid to buy Bers worth Chemical, Dr. Dewey became very impressed with the young chem ist, especially when the answer to the older man's probes about sales, manu facturing, or technical problems at Bersworth was invariably "see Singer." Meanwhile, Dow got there first, bought the company, and left Dr. Singer with three options: work for Dow in Midland, work for Dr. Dewey at Dewey and Almy, or fend for him self in the greenery of New England. He chose the third, with the admoni tion from Bradley Dewey, "Well, if you ever come up with anything I might be interested in, give me a call wher ever I happen to be and I'll take a look at it."
ir colonial home themselves
On his own, Dr. Singer set up a chemical importing and consulting service in his home, specializing in chelates and related compounds. He then joined the late Dr. Mark Weisberg to establish United Chemical Corp. in Providence, R.I., which again continued the chelate orientation. "At the time, we didn't really have anything to sell," says Dr. Singer, "but we had a lot of ideas we wanted to work on together. One was a new process for EDTA and other chelates." What triggered Dr. Singer's original idea for the new process was Du Pont's announcement in 1956 that it could make liquid hydrogen cyanide (HCN) available in tank-car lots at 20 cents a pound or less. Before then, SEPT. 14, 1970 C&EN
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"We were lucky, I guess.
It was a case where everything we tried worked"
HCN was out of reach of smaller chemical companies that couldn't afford to make it. Dr. Singer knew that all other chelate processes then in use required sodium cyanide, formaldehyde, and an amine to give products of 80 to 85% purity. Purity aside, he reasoned that if he could get HCN at 20 cents a pound and make it work in a chelate process it would be much more economical on a weight-forweight basis than sodium cyanide at its then current 17 cents a pound. After hashing out his idea with Dr. Weisberg, Dr. Singer disappeared into the lab and within a few weeks had a continuous process for producing EDTA and related materials in 99.5% purity in nearly quantitative yield. "We were lucky, I guess. It was a case where everything we tried worked," he says. To produce EDTA, the SingerWeisberg process involved the addition of HCN and ethylenediamine to formaldehyde to give the amine nitrile. This was then saponified.to the salt with sodium hydroxide. If ammonia is used instead of ethylenediamine, NTA is produced,
NH3 + 3CHzO + 3HChi
HaSo4 -^~
N(CH Z CN) 3 + 3H z o N(CH X CN) 3
+ 3NaOH + SH^O-^·
N(cHz.COONa)3 + 3MH3 52 C&EN SEPT. 14, 1970
but at that time Dr. Singer had no inkling that NTA might someday be more important than EDTA. Realizing that he could now produce a better grade of chelate more economically than anybody else was then doing, Dr. Singer decided to contact Bradley Dewey for help in setting up a plant to make chelates. Dr. Dewey was in Europe at the time, but his secretary checked her employer's "little black book" of special names, found Dr. Singer's there, and sent a cable off to Dr. Dewey with sketchy details of the new process. Dr. Dewey immediately ricocheted back: "Don't do anything until I return. I'll see you Monday." When he returned, Dr. Dewey's first move was to alert W. R. Grace & Co., where he was a board member, but at that time Grace was not ready to underwrite this project from the bottom up. It was then left to Dr. Singer, Dr. Dewey, and Dr. Weisberg to raise enough money to build a tiny chelate plant on a grassy field in Nashua, N.H., which became Hampshire Chemical Co. Less than a year later, in August 1958, the company produced its first batch of EDTA. "It was a time when the United States needed another EDTA producer like it needed fleas. Dow and Geigy were in the business, along with a bunch of small companies in the South that supplied chelates to the textile industry," says Bob Pollard, now vice president in charge
of sales and marketing at Hampshire Chemical. He joined the Hampshire Chemical staff in the early "seat of the pants days" along with several other energetic young gamblers who were attracted from secure positions in larger established companies by the sky rocket gleam in Jack Singer's eye. Most of the early members of the cadre still remain at Hampshire Chemical, in various executive positions. "In those days, everybody did everything, and we spent a lot of time plotting marketing strategy at Bradley Dewey's house, either in Cambridge or at his summer home in Lake Sunapee, N.H.," Mr. Pollard adds. "Otherwise, we all pitched in at the plant, tracked down customers and distributors and whatever else we could do to break into the chelate market with what we knew was a vastly improved product." In the competitive arena, the Singer-Weisberg process gave the scrappy little company an immediate advantage over its big-time competitors, all of whom reliecl on the more expensive, less efficient sodium cyanide process. "They were locked into that process," Dr. Singer explains, "and unless they wanted to spend a lot of money to retrench or develop a better product than they were then making, about all they could do was ignore us and hope for the best. Meanwhile, we were getting a lot of their customers with a higher quality product, while
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concentrating on developing applications in areas where chelates were not yet being used." During the first year and a half of operations, Hampshire Chemical lost $400,000, the following year there was a "cash flow," and by 1961 a profit appeared and has built steadily since then. NTA emerges. Although EDTA and its relatives were used in minor concentrations to stabilize liquid soaps and detergents, Dr. Singer had a good deal of laboratory evidence to show that they might perform better than the inorganic phosphates, such as sodium tripolyphosphate (STP), that were then being used at the billion pound level as "builders" in the fastgrowing detergent industry. Builders have no detergent power themselves, but increase the effectiveness of surfactants and other detergent ingredients primarily by softening the water. When he went to the major producers of detergents with the idea, they turned him away with, "EDTA might be a good builder, but we won't even look at it unless you can sell it to us for 20 cents a pound!" Dr. Singer knew it was technologically impossible to make EDTA available at much below its then current selling price of about 40 cents a pound. On the other hand, NTA might be a good alternative because, pound for pound, it was a better water softener than EDTA or the phosphates. Even with that stretch of
Dr. Singer's imagination, it was too expensive. At that point, a string of unrelated circumstances, coaxed along by Dr. Singer's talent for being at the right place at the right time with the right idea, began to brighten the future for NTA. The first break was the discovery that Standard Oil ( O h i o ) ^ acrylonitrile plant in Lima, Ohio, was turning out large amounts of HCN as a by-product and Sohio was more than anxious to get rid of it. In short order, Dr. Singer made a deal with Sohio that allowed him to put up an HCN recovery system behind its plant to recover the unwanted HCN at a cost much less than Hampshire Chemical was then paying Du Pont for its carload quantities. "Previously we were wrestling with a real dilemma," Dr. Singer explains. "To make cheap NTA, you needed cheaper HCN, but you couldn't get cheaper HCN until you used extremely large quantities and you couldn't consume it in larger quantities unless you were making large amounts of NTA. It was a vicious circle, but the Sohio HCN finally allowed us to break that chain." After Hampshire Chemical made a sizable batch of NTA using the cheaper HCN, Dr. Singer hopped on a plane to Cincinnati, dropped in on Procter & Gamble and told them, "Here's NTA at a price you can afford." His timing was impeccable. The major detergent manufacturers, including P&G, were just emerging from an earlier ecology crisis in which the surfactants they were then using (alkylbenzene sulfonates) were billowing up in large foamy clouds in lakes, rivers, and sewage plants. They were nonbiodegradable; that is, not consumed by bacteria that normally destroy harmful materials in sewage treatment processes. In the course of changing over to linear alkyl sulfonates, which were biodegradable, P&G was game to take a closer look at NTA as a builder. "It was like removing one card from a house of cards," Dr. Singer says. "If they weren't in the middle of a process changeover, they probably would never have gotten around to incorporating NTA. But they did, and it worked, and we were in business." During the time that Dr. Singer was energetically making a case for NTA as a detergent builder, a number of companies became very interested in acquiring Hampshire Chemical and its high-flying president. Dr. Singer invariably answered "no," however, until W. R. Grace came along. "It became obvious that if we were really going to get into the NTA busi-
ness, we would need far more plantbuilding money than we could possibly raise with private stock offerings and still have a company we could call our own. We decided that the best way to do it was to pick a company that could do the most for us. Coincidentally, Grace decided that Hampshire Chemical looked like a good bet; they made an offer and our stockholders couldn't pass it up." NTA in. After the acquisition by Grace in 1965 allowed Hampshire Chemical to build an NTA plant, P&G became the first bulk customer and initiated a consumer testing program replacing 10 to 12% of the phosphates with NTA in various detergent formulations. Phosphates, which make up about 50% of typical detergents, are now consumed at the rate of more than 2.5 billion pounds a year in the U.S. alone. P&G's primary motive was to improve detergent performance with NTA; the growing furor over the possible detrimental effects of phosphates on lakes and rivers had not yet come to a boil. The objections of conservationists, fortified by two intensive Congressional hearings in recent months, however, are now producing loud calls for the abolition of phosphates in detergents because they allegedly contribute to excessive eutrophication, or aging, of the world's lakes and rivers. Eutrophication is a natural process, in which phosphorus, nitrogen, carbon dioxide, and other nutrients fertilize the growth of algae and other aquatic weeds to the extent that they monopolize the oxygen supply, smother fish life, decay, and eventually convert the lake to a slimy bog. At the hearings convened by Rep. Henry S. Reuss (D.-Wis.), Prof. P. H. Jones of the University of Toronto pointed out that although other factors are involved in eutrophication, phosphorus is the limiting factor; that is, if phosphorus were removed, the eutrophication process would be slowed down accordingly. Because phosphates come from many other sources, including human wastes and soil runoff, detergent industry spokesmen believe that improved sewage treatment might be a preferred approach to zeroing in on detergent phosphates. While these arguments wax and wane, it is generally accepted that, thanks to man, Lake Erie has experienced 50,000 years of eutrophication in the past 50 years, and that the Potomac River is also dying at an accelerated rate. In the course of the Reuss hearings, as well as àt later hearings of the International Joint Commission (formed by the U.S. and Canada to solve border water pollution problems), Dr. Singer was asked to comment on the possibility or desirability of using NTA SEPT. 14, 1970 C&EN 53
'If there's something to be done with the head or hands, Dr. Singer's the man
as a replacement for detergent phosphates. H e spoke with his usual enthusiasm on behalf of his favorite product, but admitted that formulation and other problems might necessitate the use of some inorganic phosphate along with NTA. Phosphates received another setback when the Administration's Council on Environmental Quality recently recommended that they be removed from detergents. To meet the demand, Hampshire Chemical is now operating at its full 60 million pound-a-year capacity, with a significant plant expansion in the offing. Lever Bros, followed suit with the announcement that it would begin to buy NTA from a new Monsanto plant, which licenses the Singer patents, while a new Grace plant in Teesside, England, another in Ontario, Canada, and its Rexolin Division in Sweden will also supply the detergent industry with Singer-Weisberg process NTA. Other detergent manufacturers withhold their enthusiasm for NTA, hinting that they have doubts about its long-range ecological effects and that they may have something better on the line. On the other hand, Dr. Singer notes that NTA is extremely biodegradable and that all of the toxicological studies done to date give NTA a very clean bill of health. "From those studies, we know of no information which would indicate that NTA is harmful in any way to fish, animals, people, or the ecology in general," Dr. Singer says. "Some critics suggest that when NTA gets into the system, it may be converted to carcinogenic or otherwise harmful substances, but there is absolutely no experimental documentation for that assumption. However, since NTA will 54 C&EN SEPT. 14, 1970
eventually be used at the billion pound level, Td be the first to admit that such questions should be asked," Dr. Singer adds. In the thick of it. With the pressure on for more NTA as soon as possible, Jack Singer keeps his hard hat and breathing apparatus at the ready for frequent trouble-shooting sorties into the plant. A recent production bottleneck, for example, involved a number of large NTA storage silos, each of about 90,000 pounds capacity, that clogged badly enough that the NTA wouldn't feed into waiting railway cars. In a matter of hours, Dr. Singer developed a simple rotating screw device that when inserted into the clogged end of the silo got the NTA moving again. "That's the way he is. He often bypasses the drawing board and leaps into the plant that way," says Ed Najjar, vice president of research and development at Hampshire Chemical. "It's hard for some people to believe he's for real. He's the kind of guy who might be digging clams on the beach with a shovel and get fed up enough that he'd just have to come up with some sort of creative gimmick to do the job better." Mr. Najjar, who came to Hampshire Chemical via MIT and Standard Oil of New Jersey's refinery at Everett, Mass., has set up a pilot plant that the company will ultimately expand into a larger multipurpose facility for new cyanide-derived specialty chemicals. He predicts, along with Dr. Singer, that these amino acids, cyanohydrins, nitriles, and thionamides, when added to Hampshire Chemical's present line of chelates and fatty acid sarcosinates, should fortify the company's future when and if the bloom ever goes off NTA. One such product, still classified, may have widespread use in the
textile industry to improve the properties of cotton in the permanent press field, Mr. Najjar predicts. Multilevel man. As the NTA plant pressures subside, Dr. Singer hopes to be able to concentrate most of his energies on research, but the bets around Hampshire Chemical are that he'll continue to operate at his usual several levels. "I never met anybody who could do so many things—and do them well —at one time," says Tom La Barre, another long-time Hampshire-ite. "We were out on a call once, and when I got back to the motel, there was Jack lying on the bed reading a science fiction paperback and watching a western on-TV. I asked him how he could read and watch TV at the same time and he said, 'it's easy,' and filled me in on what was going on in both cases." Mr. La Barre is vice president of administration and co-owner of the Beechcraft Bonanza that he and Dr. Singer fly around the country on business or occasional duck hunting jaunts. Mr. La Barre also looks forward, he thinks, to doing some acrobatic flying next year when Dr. Singer finishes building a biplane (a Starduster II) in the barn behind the house in Hollis, N.H. Known around the company as the Singer Hilton, Dr. Singer built most of the sprawling gambrel roofed colonial with his own hands, paneling it throughout with sturdy pumpkin pine lumber, adorning it with a magnificent staircase to the second floor, and an equally impressive Singermade front door. Riding along in the wake of his many interests are Dr. Singer's wife, Naomi Jane (Nome) and three daughters, Jane 22, Suzanne 18, and Carolyn 16. Jane recently presented the 49year-old Dr. Singer with his first grandchild, a boy named Jonathan Peter Dixon. The family has lived through Dr. Singer's three boat-building projects and watched him make a comfortable home from a sketch and laminated beams and cedar planking. To keep in closer touch with her husband's aerial exploits, Nome Singer is now taking a "pinch-hitter" flying course to back him up in emergency situations, and she looks forward warily to her first acrobatic experience in the biplane. Beyond that, she anticipates with philosophical calm whatever he next sets out to do. "Building an airplane is just another project for Jack. If it isn't that, or boats, or a house, it will certainly be something else." Or, as Dr. Singer's secretary puts it: "If there's something to be done with the head or hands, Dr. Singer's the man who can do it."
