Synthetics and the Triumph and Transition of Petrochemicals

Compiled and Drafted by Rod Handeland July 2004

 

With the emergence of computers over the past half-century combined with telecommunication advances, we are tempted to think of those industries as ones that have most changed our lives. However, if we reflect on what we wear each day and is everywhere around us in our homes, workplaces and communities as well as vehicles we use to move us around, we might conclude that petrochemical based materials play an even larger role in our lives.

 

I. Petrochemicals in Our Products of Today

The synthetic fibers in the apparel we wear as well as the coverings of nearly all components, furnishings and appliances of our homes, workplaces and vehicles are derived from petrochemicals that have been commercialized over the past century. This story and what can be learned from the business ramifications of this evolution is little unknown. And it involves some of the most colorful and intriguing individuals, extraordinary discoveries and commercialization processes of the past century. With the titanic shifts that resulted from the migration to petroleum for fuel to move vehicles and generate electricity, follow the even more magical transformation of hydrocarbons into the daily products that surround us wherever we go. It is the wizardry of this transformation that brings us:

 

The 1960’s film The Graduate is best know for its most remembered word, which is as insightful today as it was then: ‘Plastics. There’s a Great future in plastics’. The only change is, who’s future? In the intervening years, the world of petrochemicals have evolved from the dominance of great US firms like DuPont, Dow, Carbide, Monsanto and the petrochemical groups of major oil companies to DuPont’s announcement that all nylon and synthetic fiber businesses will be spun off to a separate public company. At the same time, we use more of petrochemical-based products than ever. Worldwide growth continues at the rapid rate of the days when petrochemicals in America were the equivalent of today’s high tech businesses.

 

II. Magic of Synthetics to Extend the Textile Industrial Revolution

To answer the question of where did it all go, it may be best to follow this fascinating tale from where it all began. To do this is to trace the tales of the great streams of advancement of fibers and plastics that explain how we live today. Each encompasses stunning breakthroughs and catastrophes as well as dramatic evolution. Ultimately, DuPont was correct in its long used slogan of ‘Better Living through Chemistry’. But what a trail it took along the way.

 

Synthetic Dyes to Launch the Petrochemical 20 th Century

By the 1850’s in England, the industrial revolution of the late 1700’s, which revolutionized textiles and iron through steam and machinery innovation, had spawned great mills and factories. Transportation dominance had shifted from sea to canal to rail. Petroleum discoveries in far away Pennsylvania were still several years away. A.W. Hoffman had left Germany to head London’s Royal College of Chemistry. He was a student of Justus Liebig, whose deep commitment to coal tar and world famous methods launched organic chemistry.

Since petroleum had not yet been found and commercialized, Hoffman encouraged his assistant William Perkin to experiment with coal tar as a potential source for quinine to cure malaria. On Easter 1856, the 18 year old Perkin failed to produce quinine after attempting to prepare quinine by oxidizing aniline. His experiment gave him a dirty brown solid, rather than the shiny white crystals he expected. He tried extracting with benzene and then with alcohol. This gave him a deep purple solution, which he found would dye silk a bright purple color. P erkin had accidentally produced the first ever synthetic dye, aniline purple which he called mauve. He set up a factory on the banks of the Grand Union Canal in 1857 to produce it and by age 35 retired as a very wealthy man.

However, it was the Germany of his professor that captured the industry and future. They trained more chemists and spent more on research and development than England. Despite Perkin’s triumph in innovation and brilliance in overcoming process and product acceptance limitations, it was German industry that built dominance in synthetic dyes and organic chemistry by 1900. This was led by the great firms such as:

 

The accident of Perkin’s discovery of a synthetic purple dye combined with the exploding textile industry need for dyes far in excess of those produced from natural sources, led to a rainbow of colors of synthetic dyes. The turning point in the shift in dominance from Britain to Germany was 1869 when Graebe & Lieberman of BASF synthesized alizarin, a red dye. Perkin also synthesized and produced alizarin, but sold his company a few years later to devote the remainder of his life to pure research.

The greatest triumph of the German dye industry came when BASF introduced the synthetic blue dye indigo in 1880. Initially it proved impossible to produce on a commercial scale. After an unprecedented 17 year $3.5 million effort, it led to the collapse of Britain’s indigo production in India from 640,000 to 114,000 acres between 1896 and 1909.

German leadership in coal tar research also led to breakthroughs in pharmaceuticals and explosives. Painkillers before 1870 were either herbs or natural opiates, which were addictive. Salicylic acid was an improvement, but was also addictive. It took a Bayer program to develop acetominophen or tylenol and then the blockbuster acetylsalicylic acid, which was aggressively marketed under the Bayer trademark Aspirin until WWI.

 

Birth of Synthetic Fibers from Cellulose

As important as synthetic dyes were in the emergence of German chemical dominance, the main link to the marvels of petrochemical derived products of the 20 th century is through the precedent dyes set in establishing organic chemistry processes and their importance to the exploding world of textiles. For textile fibers rather than dyes became the key to weave petrochemicals into apparel and fabrics.

 

In 1839 Charles Goodyear mixed India rubber with sulfur and found that when heated it made the rubber durable. Later tests ensured that this blend would not become brittle in cold or melt in heat. Goodyear had improved the properties of a natural polymer. The next logical step was to use a natural polymer such as cellulose as the basis of a new material. This opens the world of both synthetic fibers and plastics.

To focus on the synthetic fiber track first, we find that in 1884, a French chemist, the Comte de Chardonnay, introduced a cellulose-based fabric that became known as Chardonnay silk. In 1889, his fabrics of artificial silk caused a sensation at the Paris Exhibition. Two years later he built the first commercial rayon plant at Besancon, France, and secured his fame as the father of the rayon industry. Chardonnay silk was an attractive cloth, but like celluloid it was very flammable, a property completely unacceptable in clothing. After some ghastly accidents, it was withdrawn from the market.

In 1894, three British inventors, Charles Cross, Edward Bevan, and Clayton Beadle, patented a new artificial silk that was much safer. The three men sold the rights for the new fabric to the French Courtalds Company, a major manufacturer of silk, which put it into production in 1905, using cellulose from wood pulp as the feedstock material.

Several attempts to produce artificial silk in the United States were made during the early 1900's but none were commercially successful until the American Viscose Company, formed by Samuel Courtaulds and Co., Ltd., began production of rayon in 1910. The growth of rayon is one of the phenomena of our industrial age. Its success in the US is credited largely to the perseverance and confidence displayed by Samuel Salvage.

After landing in New York from England in 1893, young Salvage worked for a glass and china merchant in Cincinnati and then a yarn merchant. In 1897 he started his own small business as an importer and salesman of cotton yarns. Among the goods he imported was some artificial silk from Germany. He found a market for it in the braid and trimming trade, but no one else wanted it. Deliveries from Germany were poor, but Salvage believed in the product. When Samuel Courtald & Co. started to make artificial silk, Salvage acquired some found it satisfactory and secured the US agency for it in 1908.

It was the next year that Salvage wrote Courtalds to suggest that they buy the viscose patents for the United States and build a plant here. The proposition, said to have been sent on a postcard, was accepted. The American Viscose Co. was formed, and Marcus Hook was chosen as the site for the plant. U.S. rayon production grew to meet increasing demand. By the mid-1920's, textile manufacturers could purchase the fiber for half the price of raw silk. So began manufactured fibers' gradual conquest of the American fiber market. This modest start in the 1920's grew to nearly 70% of the national market for fibers by the last decade of the century.

In the same year of 1910 that Salvage began US rayon production, five years of chemical research by two Swiss brothers Camille and Henri Dreyfus culminated in a commercial process and plant to manufacture cellulose acetate. By 1913 the Dreyfus brothers produced excellent laboratory samples of continuous filament acetate yarn. On Christmas day 1924, Camille’s long and persistent efforts culminated in the first acetate yarn spun in the US at the Cumberland, Maryland Celanese plant.

 

DuPont Path to Nylon

By 1913 DuPont had begun to shift funds from explosives to industrial research labs and chemicals. From the enormous munitions profits of WWI, DuPont acquired rights of Chardonnet viscose rayon process and set up DuPont Fibersilk in Buffalo NY. William Church and Karl Prindle developed cellophane there in 1924 and commercialized it in 1926, revolutionizing packaging.

However, it was DuPont’s commitment in 1927 to fund pure research and hire brilliant Harvard chemist Wallace Carothers to lead the effort that led to the most significant breakthroughs in synthetic fibers. Carothers had DuPont’s promise that he could pursue basic research, specifically looking at polymers, molecules with long, repeating chain structures.

In one remarkable month, April 1930, Carothers’ team discovered neoprene synthetic rubber and synthesized the first polyester superpolymer, the forerunner of nylon. A lab assistant working with esters, compounds which yield an acid and an alcohol or phenol in reaction with water, discovered a very strong polymer that could be drawn into a fiber. This polyester fiber had a low melting point, however. Carothers changed course and began working with amides, which were derived from ammonia. In 1935 Carothers found a strong polyamide fiber that stood up well to both heat and solvents. He evaluated more than 100 different polyamides before choosing one for development. With this the world of synthetic fibers would move from a base of plant cellulose to petrochemicals.

 

Nylon was commercialized remarkably quickly, in part due to DuPont's experience with rayon at Fibersilk. After determining that low-cost production was possible and settling on silk stockings as a target market, DuPont produced a preliminary batch of nylon staple. To confirm that the nylon hose would be practical, the staple was delivered to a commercial knitting mill under conditions of extreme secrecy. It took two test runs and further development to convince DuPont to build a pilot plant in Wilmington and, finally, a full-scale production facility in Seaford, Delaware. Commercial production began in late 1939 after nylon stocking introduction at the World’s Fair.

DuPont’s $27 million twelve-year investment to refine and commercialize nylon ultimately resulted in one of the most profitable returns of the 20 th century. Carothers suicide in 1937 didn’t him allow to see any of this. This tragic loss may have also delayed the development of the even more important polyester fiber Eric Spanagel identified in the Carothers lab, as well as progress on Carothers’ 1935 hypothesis that proteins are made by joining amino acids together in long chains. Carothers suggested that proteins are built when amino acids are held down on a surface and forced to join together. These revolutionary biochemistry ideas turned out to be not only how proteins are made from an RNA template, but how DNA and RNA are themselves replicated.

 

Polyester and a World of New Blends

Returning to our fiber tales, we find that in England, J. T. Dickson and J. R. Whinfield produced a polyester fiber by condensation polymerization of ethylene glycol with terephthalic acid. ICI patented Terylene polyester, to which DuPont purchased the U.S. rights in 1945 for further development. In 1950, a pilot plant at the Seaford, Delaware, facility produced Dacron polyester fiber with modified nylon technology. DuPont subsequently acquired the patent rights for the United States and Imperial Chemical Industries for the rest of the world.

And there were other synthetic fiber advances after World War II: BASF with metalized fibers; Union Carbide with modacrylic; Hercules with olefins and DuPont with the wool like acrylic. But it was DuPont’s commercialization of polyester in 1953 that launched the wash and wear revolution and led to synthetics and blends with natural fibers and their dominance today.

 

Synthetic Fiber Applications

With the majority of the 20th century's basic manufactured fibers now had been discovered, industry engineers turned to refining their chemical and physical properties to extend their use across the American economy. In the 1960's and 1970's consumers bought more and more clothing made with polyester. Clotheslines were replaced by electric dryers, and the wash and wear garments they dried emerged wrinkle free. Ironing began to shrink away on the daily list of household chores. Fabrics became more durable and color more permanent. New dyeing enhancements were implemented and shape-retaining knits offered new comfort and style.

 In the 1960's, manufactured fiber production accelerated as it was spurred on by continuous fiber innovation. The revolutionary new fibers were modified to offer greater comfort, provide flame resistance, reduce clinging, release soil, achieve greater whiteness, special luster, easier dyeability and better blending qualities. New fiber shapes and thicknesses were introduced to meet special needs. Among these were Spandex, the high-temperature-resistant polyamide aramid, bullet resistant Kelvar and a range of microfibers.

Applications of these fibers spread from apparel to carpets, furniture and other household necessities such as towels, sheets and draperies. The original cellulose based rayon and cellulose acetate were shifted from being based on natural materials to petrochemicals. The final petrochemical inroad to this chain of fiber innovations that originated with dyes and carried on through the fiber materials themselves ended with what we used to keep our wash and wear apparel clean.

Detergent alkylates swept the laundry field as the active cleaning ingredient after World War II. From 1950-65 half the world’s detergents were petrochemical based. By then foaming in streams and taps had also been discovered and biodegradability of detergent alkylates identified as cause. This first major biodegradable issue was resolved by a shift to linear alkyl benzene as the petrochemical basis rather than the propylene tetramer benzene used in early detergent alkylates. This was the start of many biodegradable, toxic and safety issues petrochemical based products would need to face in coming years.

 

III. Plastics as the Moniker of Our Times

In parallel with the triumphs in synthetic fibers, were equally giant leaps in a range of similar materials, which also would become based on petrochemicals and which we know as plastics. We have already alluded to some of the links between synthetic fibers and plastics by noting that one of breakthroughs of DuPont’s Fibersilk operation was cellophane. But long before then, the web of ties between fiber and plastic was extensive.

 

Cellulose Path to Plastics

At the same time Perkin was revolutionizing dyes in the 1850’s, his fellow English inventor Alexander Parkes observed that the solid residue left after the evaporation of the solvent of photographic collodion was hard, horny elastic and waterproof. In 1856, he patented the process of waterproofing woven fabrics with this substance. In 1862, at the Great Exhibition in London, Parkes introduced a new material that was obtained by dissolving cellulose nitrate in a minimum of solvent. The mixture was then put on a heated rolling machine from which some of the solvent was then removed. While still in the plastic state, the material was then shaped by dies or pressure. Parkes tried to commercialize this through a company he founded in 1866, but it failed by 1868. This may be partially due to inferior products resulting from his production cost reduction efforts.

In the United States during the 1860s, John Wesley Hyatt experimented with cellulose nitrate. In 1865, Hyatt became involved in devising a method for producing billiard balls from materials other than ivory. Hyatt and his brother Isaiah took out a patent in 1870 for a process of producing a horn-like material using cellulose nitrate and camphor. The Hyatt brothers recognized the value of camphor as a plasticizer for cellulose nitrate. In 1872, the term celluloid was coined by Isaiah to describe the Hyatts’ commercially successful product.

They established the Celluloid Manufacturing Company, changed its name to the American Cellulose Chemical Corporation, which was eventually absorbed by the Celanese Corporation to rejoin our fiber stream. We will also recall that the Dreyfus brothers initially focused on cellulose acetate film, which was then widely used in celluloid plastics and motion picture film before they commercialized cellulose acetate as a fiber.

Next to cellulose nitrate, the most important material in the early history of plastics was formaldehyde. Around 1897 there was a demand in German schools for a white chalkboard. Efforts to obtain such a product resulted in the discovery of casein plastics, produced by reacting milk protein casein with formaldehyde. The material soon became established under the trade names of Galalith and Erinoid. Today, casein still is used by the button industry.

 

Bakelite Phenolic Resins

As early as 1872, German chemist Adolf von Baeyer was investigating the recalcitrant residue that gathered in the bottom of glassware. This was from reactions between phenol, a turpentine-like solvent distilled from coal tar, which the gas-lighting industry produced in bulk, and formaldehyde, an embalming fluid distilled from wood alcohol. Von Baeyer set his sights on new synthetic dyes. To him the ugly, insoluble gunk in his glassware was a sign of a dead end. In 1899, Arthur Smith took out a British Patent dealing with phenol-formaldehyde resins for use as an ebonite substitute in electrical insulation. But during the next decade, the phenol-formaldehyde reaction was investigated mainly for academic interest.

Leo Hendrik Baekeland was educated in his native Belgium. By age 21, he had received his Doctor of Science degree and was a professor at Ghent University. He moved to the US and formed a Yonkers company where he developed the first photographic paper which could be used in artificial light. After selling this as Velux to Eastman Kodak, he had sufficient funds to experiment on what ever he found of interest. Initially Elon Hooker requested that he cooperate with Clinton Townsend on commercialization of Townsend’s new electrolytic cell at Brooklyn Edison. This success led Hooker to found Hooker Chemical at Niagara Falls which is today part of Occidental Chemical. The Durez Plastics unit of Hooker later used the results of Baekeland’s next great breakthrough, Bakelite.

After Velux and electrochemistry, Baekeland turned his attention to the resinous product formed when phenol and formaldehyde are reacted together. He discovered techniques to control and modify the reaction so that useful products resulted and phenolics became the first fully synthetic resins to become commercially successful. After several years work, he secured the patents in 1907 for his process, which when mixed with fillers, produced a hard and moldable plastic which quickly replaced the very flammable celluloid products.

Since this Bakelite could be easily colored and shaped, it was applied to phonograph records and billiard balls by 1912 as well as camera cases and telephone receivers by 1915. The radio cases of the 1920’s were of Bakelite, and it spread from there to furniture, automobile equipment and a wide range of coating, jewelry and other applications. Baekeland’s initial plant in Perth Amboy and expanded facilities in Bound Brook, NJ produced large volumes and profits up through the 1927 patent expiration.

After patent expiration, Bakelite’s use grew even more rapidly as competition brought costs down with new processes. The streamlined design and styling of the 1930’s expanded Bakelite applications to many new areas. Since labor needed in production was very small, user costs remained low and phenolic resins replaced wood and steel in many applications. In 1939 Baekeland sold his General Bakelite Company to Union Carbide and retired a very wealthy man.

 

IV. Thermoplastics

Prompted by the success of phenolic moldings, research began on reacting other materials, such as urea and thiourea, with formaldehyde. These materials were used to manufacture molding powders. Unlike phenolics, they could be molded into light-colored articles and rapidly achieved commercial success as molding powders, adhesives, and textile and paper finishing, while the related melamine-formaldehyde resins are used in decorative laminates. Cellulose acetate, a thermoplastic, was developed about the same time as the urea-based resins. Similar in structure to cellulose nitrate, it was found to be safer to process and use. Cellulose acetate was introduced as a molding compound in 1927.

 

Polyvinyl Chloride

The 1930’s saw the initial commercial development of today’s major thermoplastics: polyvinyl chloride, low-density polyethylene, polystyrene, and polymethyl methacrylate. PVC was first created by the German chemist Eugen Baumann in 1872. However, it was never patented until 1913 when inventor Friedrich Heinrich August Klatte initiated the polymerization of vinyl chloride with sunlight.

Commercial application was led by Waldo Semon, a B.F. Goodrich organic chemist who was attempting to bind rubber to metal, when he stumbled across PVC. Semon later discovered it was inexpensive, durable, fire-resistant, and easily molded. Vinyl found its place as an upholstery material that would last for years in the average family's living room.

 

Polystyrene and Styrofoam

Polystyrene is a strong plastic created from ethethylene and benzene that can be injected, extruded or blow molded, making it a very useful and versatile manufacturing material. Its Styrofoam form has become foam polystyrene packaging. Polystyrene is used in electrical appliance light switches and plates as well as other household items.

Polystyrene’s long history begins in 1839 when a German apothecary called Simon discovered it by isolating it from natural resin. It took another German organic chemist, Hermann Staudinger, to realize that Simon's discovery, comprised of long chains of styrene molecules, was a plastic polymer.

In 1922, Staudinger published his theories on polymers, stating that natural rubbers were made up of long repetitive chains of monomers that gave rubber its elasticity. He went on to write that the materials manufactured by the thermal processing of styrene were similar to rubber. They were the high polymers including polystyrene. In 1930, the scientists at BASF developed a way to commercially manufacture polystyrene and Dow Chemical introduced it to the US market.

In 1954, Ray McIntire invented Styrofoam for the Dow Chemical Co. McIntire said his invention of foamed polystyrene was accidental. He was trying to find a flexible electrical insulator around the time of World War II. Polystyrene, which already had been invented, was a good insulator but too brittle. McIntire tried to make a new rubber-like polymer by combining styrene with isobutylene, a volatile liquid, under pressure. The result was a foam polystyrene with bubble, 30 times lighter than regular polystyrene.

 

Saran Wrap and Teflon

Another Dow chemist, Ralph Wiley, in 1933, accidentally discovered polyvinylidene chloride, which became better known as Saran. It was first used to protect military equipment, but it was later discovered that it was perfect for food packaging. Saran would cling to almost any material. For this it became the perfect tool for maintaining the freshness of food at home.

A DuPont chemist named Roy Plunkett discovered Teflon in 1938. Plunkett discovered the material accidentally by pumping Freon gas into a cylinder left in cold storage overnight. The gas dissipated into a solid white powder. Teflon is unique because it is impervious to all acids in addition to both cold and heat. It is best known for its slipperiness, which makes it effective in pots and pans for easy cooking and cleaning.

 

Polyethylene

In 1933, two organic chemists working for the Imperial Chemical Industries Research Laboratory were testing various chemicals under highly pressurized conditions. In their wildest imaginations, the two researchers E.W. Fawcett and R.O. Gibson, had no idea that their work would discover polyethylene, nor imagine its enormous impact. The researchers set off a reaction between ethylene and benzaldehyde, utilizing two thousand atmospheres of internal pressure. The experiment went askew when their testing container sprung a leak and the pressure escaped. Upon opening the tube, they were surprised to find a white waxy substance that greatly resembled plastic.

When the experiment was carefully repeated and analyzed the scientists discovered that the loss of pressure was only partly due to a leak; the greater reason was the polymerization process that had occurred, leaving behind polyethylene. In 1936, Imperial Chemical Industries developed a large-volume compressor that made the production of vast quantities of polyethylene possible. This high-volume production of polyethylene actually led to some history-making events during World War II as an underwater cable coating and then as a critical insulating material for such vital military applications as radar insulation. It was so light and thin that it made placing radar onto airplanes possible. And it was this lightweight radar system, capable of being carried onboard planes that allowed the out-numbered Allied aircraft to detect German bombers under such difficult conditions as nightfall and thunderstorms.

It was not until after the war that the polyethylene became a tremendous hit with consumers. From that point on, its rise in popularity has been unprecedented. It became the first plastic in the United States to sell more than a billion pounds a year, and it is currently the largest volume plastic in the world. It is used to make such common items as soda bottles, milk jugs and grocery and dry-cleaning bags in addition to plastic food storage containers.

 

Synthetic Rubber

The advent of World War II in 1939 brought plastics into great demand, largely as substitutes for materials in short supply, such as natural rubber. In the United States, the crash program leading to large-scale production of synthetic rubbers resulted in extensive research into the chemistry of polymer formation and, eventually, to the development of more plastic materials.

We recall Carothers initial discovery of neoprene in his polymer work, which led to nylon. Because neoprene was more resistant to water, oils, heat and solvents than natural rubber, it was ideal for industrial uses such as telephone wire insulation and gasket and hose material in automobile engines. DuPont improved both the manufacturing process and the end product throughout the 1930s. Elimination of the disagreeable odor that had plagued earlier varieties of neoprene made it popular in consumer goods like gloves and shoe soles.

World War II removed neoprene from commercial applications as the military claimed it all. DuPont purchased a government-owned neoprene plant in Louisville, Kentucky to keep up with increasing demand after the war. Essentially unchanged since 1950, neoprene continues to be essential in the manufacture of adhesives, sealants, power transmission belts, hoses and tubes. Since 1996, it has been produced in joint venture with Dow Chemical.

 

Polypropylene

The first decade after World War II saw the development of polypropylene and high-density polyethylene and the growth of the new plastics in many applications. Paul Hogan and fellow research chemist Robert Banks were working for Phillips Petroleum in 1951 when they invented crystalline polypropylene and high-density polyethylene (HDPE). Together, the plastics were marketed under the brand name Marlex®, which has since made its way into every corner of American life. Banks and Hogan began working together in 1946.

 

More Polyethylene

Low-density polyethylene already existed, but manufacturing it required extremely high pressures. While working on another project to improve yields of high-octane gasoline--the two chemists discovered crystalline polypropylene. They experimented further and found they were able to produce HDPE in a low-pressure situation. Their discoveries launched multi-billion dollar applications from the over 50 billion pounds of HDPE manufactured each year for milk jugs, laundry baskets, indoor-outdoor carpeting, and artificial turf.

 

Polyurethanes

Otto Bayer and co-workers discovered the chemistry of polyurethanes in 1937. In the mid 1930s, chemists already knew about polymerization and co-polymerization of vinyl compounds and dienes to yield synthetic rubbers and important polymers such as polystyrene and polyvinylchloride. Carothers in the United States had also just discovered the polycondensation reaction of adipic acid and hexamethlyenediamine to form Nylon 66.

Convinced that the future belonged to plastics, Otto Bayer had his own ideas of how to get involved in this burgeoning market. The discovery of diisocyanate chemistry and their polyaddition products, which were polyurethanes, seemed a lock to gain Otto Bayer worldwide recognition. But success did not come quickly. For more than one and a half decades, Otto Bayer remained dedicated to his polyurethane chemistry. In spite of all the criticism and cynical smiles of the experts, he involved more and more of his co-workers on the project.

By the time of Otto's death in 1982, the world production of polyurethanes amounted to 3 million tons, with a total value of approximately $6 billion. Today, world production has increased to about 9 million tons for: cushioning, insulation, shoe soles, and automotive coatings, as well as endcaps for dialysis filters, and encapsulated time-release fertilizer.

 

Polyester

English chemists, John Rex Whinfield and James Tennant Dickson, of the Calico Printer's Association of Manchester, patented polyethylene terephthalate (PET) in 1941, after advancing the early Carothers' research which had not investigated the polyester formed from ethylene glycol and terephthalic acid. Polyethylene terephthalate is the basis of synthetic fibers such as polyester, Dacron, and terylene. Even though the polymer that became polyester has roots in the 1929 writings of Wallace Carothers, DuPont chose to concentrate on the more promising nylon research.

When DuPont resumed its polyester research, ICI had patented Terylene polyester, to which DuPont purchased the U.S. rights in 1945 for further development. In 1950, a pilot plant at the Seaford, Delaware, facility produced Dacron [polyester] fiber with modified nylon technology. Dupont's polyester research lead to a whole range of trademarked products, such as Mylar in1952, an extraordinarily strong polyester (PET) film that grew out of the development of the fiber Dacron in the early 1950s. PET is also manufactured as a plastic for videotape, high quality packaging, professional photographic printing, X-ray film and floppy disks. And it becomes another unifier of our fiber and plastic story threads.

Linear low-density polyethylene was introduced in 1978. Large-scale production reduced cost dramatically. These new materials began to compete with the older plastics and even with the more traditional materials such as wood, paper, metal, glass, and leather. The introduction of alloys and blends of various polymers made it possible to tailor properties to fit certain performance requirements that a single resin could not provide. The demand for plastics has increased steadily; plastics are now accepted by designers and engineers as basic materials along with the more traditional materials. The automotive industry relies on plastics to reduce weight and thus increase energy efficiency.

 

V. Chemical Engineering as Catalyst to Commercialization

Beyond the alchemy of all the innovators who discovered the materials that made the 20th century of synthetics, it was another group that led to the vast commercial success. This story could wind its way back to George Davis at the end of the 19 th century in England. Industrial chemistry books already existed for each industry, such as alkali manufacture, acid production, brewing, and dyeing. However, Davis organized his work by basic operations common to many industries, such as: transporting solids, liquids, and gases; distillation; crystallization; and evaporation, to name a few. And with this approach, Davis became the father of chemical engineering.

 

MIT and Unit Operations Approach

In the US, MIT had become a leader in chemistry through the German type basic physical chemistry research lab established by Alfred Noyes. But it was the approach of unit operations patterned after Davis and promoted by William Walker and Arthur D. Little that dominated at MIT by 1915. It became the crucible for the process engineering that made possible the commercial success of all the brilliant chemical breakthroughs.

In transforming matter from inexpensive raw materials to highly desired products, chemical engineers became very familiar with the physical and chemical operations necessary in this metamorphosis. Examples of this include: filtration, drying, distillation, crystallization, grinding, sedimentation, combustion, catalysis, heat exchange, extrusion and coating. These unit operations repeatedly find their way into industrial chemical practice.

The unit operations concept had been latent in the chemical engineering profession ever since George Davis had organized his original 12 lectures around the topic. However, it was Arthur Little who first recognized the potential of using unit operations to separate chemical engineering from other professions. While mechanical engineers focused on machinery, and industrial chemists concerned themselves with products, and applied chemists studied individual reactions, no one, before chemical engineers, had concentrated upon the underlying processes common to all chemical products, reactions, and machinery.

 

Commercial Application of Unit Operations Approach

As innovative and practical as the unit operations approach was at MIT and other universities, it was applications in industry that made the petrochemical revolution of early synthetic chemicals. These applications also influence control of this industry as it evolved. To understand how, it is important to realize the enormity of change in innovation at the beginning of the 20 th century. The lone chemical inventors, like the Hyatts, Dreyfus brothers and Baekeland, who went on to build plants and found companies were being superseded by industrial research labs of large corporations with the resources to bring innovations to market. A critical catalyst for this transformation were the unit operation focused chemical engineers who developed the great industrial plants and processes that provided the scale and volumes to reduce costs dramatically and produce vast quantities of chemical products.

Arthur D. Little, Warren Lewis and William Walker moved between MIT and industry to both influence how chemical engineers were trained and how the unit operations approaches they learned were actually applied to commercialize products. After publishing in 1923 with Lewis and William Adams The Principles of Chemical Engineering which became the standard text for chemical engineering instruction for decades, Walker returned to consulting. From his faculty position Lewis also maintained close connections with industry, consulting most frequently for Standard Oil Company of New Jersey.

Lewis’s most famous industrial contribution was a collaboration with his colleague, Edwin R. Gilliland. Working for several years before World War II with a company research team, they developed fluidized-bed catalytic cracking of petroleum. These breakthroughs solved many of the problems posed by the Houdry process and played a large part in supplying the vast quantities of gasoline needed during World War II.

 

Petrochemical Building Blocks

After the war other chemical engineers led the process revolutions which shifted the sources of supply for synthetic plastics and films from natural fibers like cellulose to hydrocarbons. This was accomplished through increasingly sophisticated distillation and refining technologies. It was speeded up with the introduction of catalysts for the petrochemical conversions and reactions. The result was replacement of natural materials like cellulose with petroleum and natural gas as the building blocks for all synthetic fibers, films and plastics and development of new synthetics from these hydrocarbon sources.

Leading these enormous transformations made possible by chemical engineering and unit operation process improvements were chemists like Donald Othmer whose patents cover methods, processes, and equipment for the manufacture and processing of chemicals, solvents, synthetic fibers, acetic acid, and methanol. Other leaders such as Ralph Landau founded and guided successful specialized engineering and design firms, which developed and commercialized the many new processes for producing petrochemicals while other chemists led Universal Oil Products and similar firms in commercialization of new catalysts to make the processes and chemical reactions efficient.

This materials transformation was something akin to petroleum replacing coal in ships and rail at the start of the 20 th century. And it illustrated the flexibility of petroleum as a chemical building block source. This same petroleum flexibility was illustrated with gasoline for the burgeoning automobile fuel demands replacing the kerosene illumination business, which for the forty years since it’s inception had dominated the oil business, but was by then being supplanted by Edison’s electricity revolution as autos rose.

 

VI. Business Ramifications of Petrochemical Evolution

As fascinating as were the individuals and their innovations and process improvements that made the exploding market demands of the synthetic petrochemical based materials revolution of the 20 th century, the business ramifications are even more phenomenal. In the first fifty years, the shift was made from the time of lone inventors to the large industrial research labs of corporations like General Electric, DuPont and other chemical and oil company giants. In this same period the enormous sophistication of chemical and petroleum feedstock processing that arose from the unit operations approaches and innovations spawned at MIT spread to industry to make reliable and low cost petrochemical processes the foundation of our synthetic century.

 

Specialized Engineering Firms

In the last fifty years the unit operations process improvements and innovations were led by specialized engineering firms like UOP, Kellogg, Lummus, Foster Wheeler and Stone & Webster. With the devastation of Europe and Asia industry after World War II, the great chemical and oil firms of the United States dominated the manufacture and sale of petrochemicals based fibers, films and plastics.

 

US Chemical and Petrochemical Giants

Based on corporate industrial research programs, Dupont discovered neoprene and nylon. DuPont’s success led to other innovations from other labs such as those of Dow, Union Carbide, Eastman, Monsanto, Celanese, Hercules and Rohm & Haas. Exxon and the Standard Oil offshoot labs helped ensure building blocks would be from petroleum and natural gas and along with Gulf, Phillips, Occidental and Arco petrochemical units were the bridge to consumer products based on new plastics, fibers, films and other synthetics.

These chemical and oil firms controlled patents on technologies from their research labs. They formed cross licensing agreements and other joint ventures that led to market domination. And they shared the explosive growth and new petrochemical product introductions throughout the decades of the 1950’s and 1960’s. But they did not control all the commercialization processes. These were the property of the specialized engineering and catalyst firms. Along with other major changes, this would determine the business evolution of the synthetic petrochemical based industries in recent decades.

 

Shift from US Corporate Dominance

The rise of OPEC pricing power combined with the nationalizations in the MidEast and other worldwide producing locations during the 1970’s set in motion a shift in dominance in petrochemicals and their products. Oil producing countries looked at petrochemicals as ways to increase their returns from petroleum as well as use natural gas, which was being flared. And they had the financial resources to buy the plants from the specialized engineering firms to make the petrochemical feedstocks and products. Other OECD and newly industrialized countries also wanted their own petrochemical plants, as they saw the explosive growth in demand for petrochemical-based products in their rapidly growing domestic markets.

Meanwhile in the US, environmental, toxicity and safety issues associated with the great petrochemical plants became of increasing concern and burden to the US firms that had dominated the business here and abroad. The added costs of the environment and other issues that required expensive reformulation such as with alkylates and then phosphates in detergents reduced petrochemical profitability. Legal liability of biodegradable and toxic disposal from disasters like Love Canal, Bhopal and Gulf Coast plants added a further overhang of potential liability to the US companies.

Finally, the vast capacity expansion and dramatically lowered feedstock costs in oil producing countries resulted in lower prices and reduced profit margins for the large US corporations. Over time these enormous changes led to the great US firms gradually selling or spinning off petrochemical businesses. Some went to private US firms, more willing to face the environmental and toxicity risks and liabilities. Others were sold to foreign chemical firms, as the Japanese and European chemical giants recovered and restructured after the War. Finally by the end of 20 th century, petrochemicals were no longer growth and profit vehicles even at DuPont as attention shifted to more profitable specialized chemicals and the hopeful future of life sciences and genetic engineering.

 

As we begin the 21 st century, this epochal industrial shift is sealed and complete with DuPont's announcement that its entire fiber business will be spun off under separate public. We still wear more apparel than ever from the synthetic fibers of the 20 th century, even though they are more likely to be blends with natural fibers and the newer microfibers that have evolved to supplement nylon and polyester. We still launder them with petrochemical based detergents and other cleaning agents. Our homes, cars and offices are still covered by the paints, laminates and other petrochemical based finishes. We ship all our products with the packaging materials of petrochemicals as well as encase most of the food we buy. And we still encase all our consumer electronic, computer and telecommunication equipment in the plastics of The Graduates one word for the future: plastics.

But we can no longer directly associate everything we see around us with the great chemical and oil firms that had made true DuPont’s long used slogan of ‘Better Living through Chemistry’. Perhaps this isn’t very different from other past tectonic industrial shifts that doomed the railroads. In the 19 th century railroad companies were the first US big businesses. They dominated at the start of the 20 th century, until Ford and other automobile manufactures perfected a better idea.

The shifts in who dominates synthetics may also not be much different from other examples of industry shifts, as we have seen in steel and other metals. We may be seeing today the same transitions in the computer, information technology and telecommunications industries that replaced petrochemical synthetics at the end of the 20 th century as growth industries. Older computer manufacturers and telecommunication companies struggle to compete at the same time as forecasts of continued growth remain attractive.

But these are stories that are better known and documented. Is it time for the same story to be told of petrochemicals, the industry that was today’s high tech for much of the 20th century?