"A Short History of Synthetics"

from the 2004 issue of the Petroleum History Institute's journal, OIL-INDUSTRY HISTORY

October, 2004

From the earliest impulses of western science to create something from something else, the malleability of hydrocarbon raw materials such as petroleum, natural gas and coal has been the focus of experiment. The process has been one of accidental discovery. Early efforts to develop synthetic pharmaceuticals inadvertently led to the artificial dye industry. The pursuit of the ideal artificial billiard ball led to a greater understanding of petrochemicals and thereby to celluloid for the emerging photographic industry. Moldable manufactured goods of all kinds found markets and motivated chemists to improve their methods.

The marketplace often drove the process: As electricity lit up civilization, its wiring needed affordable insulation. In peacetime expansions, and even during the Great Depression, the marketplace was the showcase of the new and remarkable, from consumer goods to industrial components. The world wars heightened demand for military products and shortages of natural commodities, especially in World War II, also drove industry.

After the extraordinary expansion following World War II, a backlash developed. Begun by concerns over human ability to cohabit healthfully and safely with the synthetic, eventually questions arose about the natural environment’s ability to tolerate the synthetic. In the last two decades, industry has begun to develop materials people can live with and methods to help the environment digest them.

Seeking to derive a synthetic quinine from what was called “coal tar” in the late 1840s, August Wilhelm von Hofmann, Director of London’s Royal College of Chemistry, set his eighteen-year-old assistant, William Henry Perkin, to work on the project. Oxidizing coal tar-derived aniline with potassium dichromate and then dissolving it in alcohol, Perkin got nothing. But when he spilled it and went to wipe it up, the rag turned a lovely lavender. Experimenting further, Perkin found he had an artificial purple dye superior to the only contemporary natural dye, an extract of mallow blossom. Perkin began a successful career in the dye business and, in England, the 1850s became known as “the Mauve Decade.”

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Following the American Civil War, billiards became very popular. The firm of Phelan & Collender, the most successful supplier of billiards equipment, offered a $10,000 reward to the inventor of an artificial replacement for the expensive and difficult-to-manufacture elephant ivory billiard ball. In pursuit of the reward, brothers John Wesley and Isaiah Smith Hyatt, upstate New York printers, sons of a blacksmith and home inventors, began molding pulps, binders, fillers and glues. But it wasn’t until John noticed that an accidentally spilled bottle of a mixture he called “collodion” congealed in a hard, transparent slab that the billiard balls began to take shape. Still, the artificial substance did not satisfactorily replace ivory. For one thing, the collodion, derived from nitrate and chemically related to TNT, retained a volatile quality and tended to ignite or explode when the balls collided, spoiling the billiard game. Then Isaiah mentioned to John that Parkes had used camphor as a solvent. However, Parkes had used liquid camphor diluted with alcohol. John used a more concentrated version to turn hot, pressurized nitrocellulose into a malleable mass. By titrating the camphor, it could be as hard as bone or as soft as rubber.

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In an early 1870s experiment he considered a failure, German chemist Adolf von Bayaer made a tar-like solid from a coal tar distillate turpentine-substitute called phenol and a wood-alcohol distillate embalming-fluid called formaldehyde. He called it a mere “schmiere” (German for goo or mess). Later, German manufacturer Ernst Krische marketed to schools a hardened white “Galalith” chalkboard-like writing board, made from Bavarian chemist Adolf Spitteler’s concoction of the milk protein casein stabilized by formaldehyde.

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Austrian chemist Adolf Luft was intrigued by Kleeberg’s black, amorphous, sticky stuff. Experimenting further with phenol and formaldehyde, he produced a brittle, amber-colored, heat-resistant solid similar but inferior to celluloid. His work was taken up in 1904 by English electrical engineer James Swinburne in his pursuit of a synthetic wiring insulation. In 1907, Swinburne finally found the solvent and the process by which Luft’s substance could be transformed into the perfect electrical insulator, but he got to the patent office one day late.

Leo Baekland, a Belgian immigrant, lived in comfort in the New York City suburb of Yonkers as the result of having sold a formula for photographic paper to George Eastman for $750,000 (approximately $25 million today). Since 1902, he had sought a way to perfect the phenol-formaldehyde work of von Bayaer and Kleeberg. In his “bakelizer,” a device developed to precisely control the pressure and temperature of the reaction, Baekland created the first completely synthetic “thermoset” plastic, a substance that once molded stayed molded. It would neither dissolve nor melt. This meant, as the “day-late” James Swinburne knew only too well, that Bakelite was an excellent substance to insulate the endless miles of electrical wiring just beginning to encircle the world, as the 19th century became the 20th.

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Perhaps the most enduring reaction by the world of design to the new materials is Art Deco, but the 1920s architectural theories of Le Corbusier and the Bauhaus also owed much to the increasing availability of synthetic materials. New plastics (from “plassein,” Greek, “to mold”) led to molded furniture, designed by the likes of Paul T. Frankl and Donald Deskey. In fact, designers, inventors and entrepreneurs molded synthetics into new niches throughout the marketplace, from the auto industry to medicine to building materials. In 1921, coal-tar resin production was 1.5 million pounds; in 1939, it was 141 million pounds. That year, Bakelite Corporation merged with Union Carbide and Carbon Corporation, a pioneer in extending the uses of petrochemical-derived synthetics. At the same time, synthetics were being aggressively developed by IG Farben (InteressenGemeinschaft Farbenwerke) in Germany and I.C.I. (Imperial Chemical Industries) in Britain.

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DuPont again took up pre-existing science, this time developing cellulose-based rayon, which revolutionized the fashion industry. Building on the rayon chemistry and doing groundbreaking work in polymer structure at DuPont’s research facility, Purity Hall, lead chemist Wallace Carothers’ unique team created in 1931 the first rubber-substitute from a petroleum derivative rather than coal tar. It was called neoprene. This led to a deeper understanding of how to make a polymer and to many more petroleum-derived polymer synthetics.

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World War II military uses for rubber and nylon turned these now largely petroleum-derived products, as well as many more synthetics developed in the 1920s and 1930s, into rationed commodities. Scientists at Germany’s IG Farben conspired for a while, in response to Hitler’s grotesque anti-Semitism, to prevent the development of their extraordinary synthetic, Buna rubber. Eventually, though, the company was thoroughly Nazified and Germany’s September, 1939, blitzkrieg of Poland rolled on Buna tires. Meanwhile, Buna’s developer, Jewish chemist Herman F. Mark, fled the murderous intolerance of Germany for the U.S., where he eventually became a leading polymer chemist.

Following the U.S. entry into the war, Standard Oil used its petroleum-based synthetic, butyl rubber, to leverage itself out of scandal and disgrace. A pre-war conspiracy between Standard and Farben to market Buna and suppress butyl, in exchange for marketing opportunities in Europe, had been revealed. A little-known Missouri senator named Harry Truman was using his senate committee to rake Standard over the coals of public opinion and threaten them with punitive action. Standard’s subsequent guilt- and fine-induced manufacturing frenzy raised 1944 U.S. production of synthetic rubber to levels above prewar crude rubber processing.

IG Farben responded, at Hitler’s urging, with a new division. At a new plant located where it could take advantage of a unique supply of very cheap labor, Farben’s board of directors was extremely optimistic about the profit potential of the new division, IG Auschwitz. With brutal irony, the new plant failed. Its cheap labor force was demoralized, inefficient and, eventually, mostly exterminated.

A hydrocarbon-derived polymer was accidentally developed by I.C.I. scientists in Britain in the mid-1930s as the result of an explosive pressurization of ethylene. They found little need for it until 1940, when polyethylene turned out to be the miraculously lightweight insulator necessary to make radar portable. Thus, British aircraft were able to take radar airborne, where the outnumbered Royal Air Force defeated the German onslaught. And the Royal Navy took radar to sea, where it defeated German sea-going technology. Germany had radar, but it did not have the miracle insulator, polyethylene, that made radar compact and mobile.

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The postwar rush on nylon hosiery from August, 1945, through Valentine’s Day, 1946, was like a mass hysteria. There were nylon riots at major department stores. It was war on the home front. American newspapers ran headlines like “Nylon Sale and No Casualties” and “Lady Raiders Take Nylon Beachhead” and “News is All Bad on the Nylon Front.” (h) A black market developed. Chicago police judged a murder not to be motivated by robbery because several pairs of nylon hose were left behind. But the petrochemical and synthetics industries retooled to meet peacetime needs and supply usually, after the mid-forties, met the demand created by the postwar dream of better living through chemistry.

In the postwar expansion, fractional distillation of naphthas (especially through a sophisticated process called platforming) from coal tar, petroleum, natural gas, wood and other sources provided an abundant supply of the raw materials. New resins, or superpolymers, with new qualities were born. Designers and inventors, real and fictional, became postwar heroes. In 1946, Frank Capra’s George Bailey (the Jimmy Stewart character) stayed home and learned “It’s a Wonderful Life” when he was bailed out at his time of crucial need by the boyhood pal who had become a plastics tycoon. In 1946-47, Earl S. Tupper became a real tycoon when he introduced Tupperware. Originally conceived to be disposable, Tupperware was so successful with consumers they collected and reused their burp-sealed containers. In 1948, DuPont brought out Dacron and introduced wash and wear. In 1949, Buckminster Fuller invented the geodesic dome, made with acrylics and light metals, and architecture was never the same. In 1950, we got the polyethylene squeeze bottle.

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Before WWII, toys were made from few materials. Expensive dolls with lifelike detailing were glass or porcelain while cheap ones were made from a paper mache-like pasteboard. Beginning in the late 1940s, the new hard plastics industry introduced a wide array of small, Ginny-type dolls that were charming, detailed and affordable. Perhaps the pinnacle of this progress was Barbie, introduced in 1959 and still with us today. The whiffle ball was invented in 1953 by a suburban Connecticut man so his sons could throw curveballs. A bright, white, hard plastic ball with holes in it to allow air currents to affect it, boys are still throwing curves past the hard plastic whiffle bat today. In the same time period, Silly Putty became a toy craze and Fred MacMurray’s “The Absent-Minded Professor” made flubber a movie craze a few years later. Wham-O set the world spinning with the Hula-Hoop and bought an invention it later renamed and marketed as the Frisbee.

Eventually, the innovations began to seem repetitive and synthetic products seemed more redundant than futuristic. In the 1960s, Buckminster Fuller’s domes got bigger and lighter but they were not leading to a better life. They morphed into Thomas Herzog’s giant inflated sculptures of breasts and condom-ensheathed phalluses, as pop artists began satirizing the proliferation of artificial materials. Andy Warhol reigned at a St. Marks Place multimedia happening he named “The Exploding Plastic Inevitable” where The Velvet Underground gave premature birth to the Punk movement.

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“Not long ago, cancer and plastic were associated with each other only in the writings of Norman Mailer…” wrote journalist Paul H. Weaver in 1974. Mailer was one of the earliest and most vigorous chroniclers of the failures and dangers of synthetic materials. (j) 1970 fires in an Ohio nursing home, a New York City high-rise, and the British Airways terminal at John F. Kennedy Airport were all started by plastic materials’ extreme ignitability and were made disastrous by burning plastic’s intense heat, smoke and toxic fumes. This fanned the flames of Mailer’s criticism and spurred attacks on the industry. In 1973, B.F. Goodrich’s PVC was shown to cause cancer and other serious health problems in its factories’ workers. In 1977, a Monsanto-developed plastic Coke bottle was revealed to release carcinogens into the beverage. Then Pepsi came up with a better bottle, to the frustration of environmentalists like Barry Commoner, who also expressed outrage at the proliferation of potentially carcinogenic AND non-degrading Styrofoam products. Fears of suffocation in plastic cleaners’ bags and of Teflon’s toxicity had arisen in the 1950s and then were squelched by effective public relations campaigns by the manufacturers. Such fears resurfaced in the 1970s with a vengeance when several plane crash incidents raised questions about flammability and toxic fumes from the synthetics in passenger compartments.

However, this was also the era when plastic manufacturing reached new heights of proficiency. Manipulations like platforming produced new petrochemical resin blends from coal tars, petroleum and liquefied natural gas. Biodegradable and flame retardant variations emerged. Modern life has come to include a love-hate relationship with synthetics. Despite fear of harm to our selves and our environment, we cannot seem to do without synthetic products like artificial hearts, Polartec winter wear and Kevlar bulletproof vests. Artificial environments like Disney World/Epcot, Universal City, the Six Flags theme parks, and fast food restaurants take intellectual criticism even as they reap enormous profits. And the intellectual criticism pours forth from and in synthetic, electronic technology.

Plastics are grouped in two broad categories, thermoset and thermoplastic. Although the boundaries are vague, most contemporary plastic is from thermoplastic resins and lends itself more easily to recycling. Thermoset resin materials of previous eras still challenge twenty-first century technology to find ways to replace them or recycle them before the landfills fill up. Both economics and popular sentiment make it certain the synthetics industries will seek with all their irrepressible capacity to rise to this challenge. If petroleum-based fuels are unacceptable for political and/or ecological reasons, fuels will be derived from other sources. If petroleum-based products are unacceptable for political and/or ecological reasons, crop-based plastics with polymers derived from corn or potatoes may soon make the question “Paper or plastic?” irrelevant. If plastic bottles will not degrade, they can be reprocessed into the fibers for bike shorts. If the proliferation of paper is destroying the forests, recyclable plastic paper that feels like expensive vellum can be created. If the landfills are filling up, thermal depolymerization may soon make garbage too valuable a source of hydrocarbon raw material for fuels and petrochemical feedstocks to just throw away. And, to bring it all back to the billiard ball, if demand for ivory has decimated populations of rare species and played havoc with third world economies, ever better synthetic forms of ivory might alleviate these pressures. Like gold, a material most malleable is most valuable.

(a) From an explanatory leaflet distributed at the 1862 Great International Exhibition in London. Quoted in Fenichell, p. 17-18.
(b) From a Meadows Company advertisement for the Bakelite washing machine impeller. Quoted in Fenichell, p. 96.
(c) Time 4, September 22, 1924. Quoted in Fenichell, p. 97-98.
(d) E-mail interview with Tommy Southall, Director, Industry Information Services, The Society of the Plastics Industry, August 1, 2003.
(e) Porter, Cole, “You’re the Top” from “Anything Goes,” copyright Warner-Chappell Music, New York.
(f) Advertising slogan originated by BBD&O Agency, popularized especially on DuPont sponsored radio show The Cavalcade of America. Quoted in Meikle, p.134.
(g) American Plastics Council website
(h) “Nylon Sale…”: Cortland (New York) Standard, September 24, 1945; “Lady Raiders…”: Los Angeles Daily News, January 19, 1946; “News Is All…”: Hattiesburg (Mississippi) American, April, 1946. As quoted in Meikle. p. 150-51.
(i) Plastics: Everything a Woman Could Ask For (New York: McCall Corp., 1953) Cited in Miekle, p. 174.
(j) Weaver, Paul H., “On the Horns of the Vinyl Chloride Dilemma,” Fortune 90 (October, 1974): 150. Quoted in Meikle, p. 244.

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Alternative Energy Institute, Inc., www.altenergy.org
The Society of the Plastics Industry, www.plasticsindustry.org (Special Thanks to Tommy Southall, Director, Industry Information Services)
Caveman Chemistry, <a href="
The Dow Chemical Company, <a href="
American Plastics Council, Year in Review (2002)
6. http://www.plastiquarian.com/thiourea.htm

Originally published in:
OIL-INDUSTRY HISTORY, Volume 5, Number 1, 2004, Petroleum History Institute, Meadville, PA