History

CASEIN PLASTICS - 1897 Adolph Spitteler

When Celluloid first became available it was primarily viewed as a substitute for ivory and tortoiseshell. Being prepared from readily available natural raw materials, cotton linters and camphor was a major factor in its commercial success. Naturally enough, this inspired much research into basic substances and reactive chemicals. 

In 1897, a cat, a saucer of milk, a bottle of formaldehyde and a chemist are supposed to have conspired together to create a new moulding material. A German Chemist, Dr. ADOLPH SPITTELER of Hamburg, first made the material in association with fellow researcher, W. Krische in a competition to produce a white marker board.

CASEIN was widely known as a protein component of milk obtained from skim milk by the addition of an enzyme, RENNET, derived from the stomachs of calves. Casein substances could be plastisized with glycerine and blended with water in an ordinary dough mixer to form a material which could be shaped and formed.
Spitteler found that an article moulded with the Casein hardened when immersed in a FORMALDEHYDE solution. Further research went into the product, (patented 1899) and it was released in Germany by 1904 and in England as LACTOID shortly after. It was produced as ALADDINITE in the USA during 1919.

Early uses were for buttons and buckles replacing horn and natural Brazilian ivory nut products. It became known as "artificial horn" which it closely resembled. It could be produced in a wide range of colours and finishes and polished to a brilliant lustre. It was made in rod, sheet and tube from 1927.

In 1908, Eastman-Kodak introduced a Cellulose Triacetate film and by 1910, the DREYFUS plant produced a true Acetate film and won a major contract with French motion picture pioneer, Pathe Freres. Replacing the scratchy and flammable Nitrate film, acetate production rapidly expanded to cover the whole motion picture market.

The next big DREYFUS success was for an Acetate "dope" for the fabric coating of early aeroplanes. Wartime demand saw a major expansion of their interests with plants in England and USA. After the war, production switched to Acetate yarns with the successful CELANESE fibre introduced to the UK in 1919 and the USA in 1924.

By 1924, the Dreyfus enterprises were offering Cellulose Acetate in sheet, rod and tube forms. Experimental moulding of Cellulose Acetate using the injection moulding process had commenced in 1922 and was firmly established by 1936 after which it was widely available as a Thermoplastic moulding material.

BAKELITE - 1909 Dr. Leo Hendrick Baekeland

Early researchers into plastic materials had attempted to imitate nature developing artificial silk, ivory and horn. A Belgian scientist, Dr. LEO BAEKELAND settled in America and quickly made a substantial sum from the sale of an earlier invention, the VELOX Photographic Paper to Eastman-Kodak.

Baekeland settled into research on new substances and set out to make his fortune producing a substitute for Shell Lacca which was still widely used in lacquer and in moulding formulas. Following the work of BAYER (1872), KLEEBURG (1891) and SMITH (1900), he started inquiries into PHENOL and ALDEHYDE chemicals.

While originally attempting a solvent type product on established chemical principles for a lacquer, Baekeland was to abandon this idea for a resin type moulding material and succeeded in 1907, reacting his basic ingredients in a sealed kettle to produce a solid spheroid of resin which resembled natural amber but was a great deal harder.

Like Hyatt before him, Baekeland set out to learn as much about moulding this new material as possible. Preparing the resin for moulding proved difficult, it was a tough solid after all, however with US patents issued in February 1909, he registered the product name BAKELITE and started producing the material in small quantities. 

An earlier phenol-formaldehyde compound product, marketed as 'Fireproof Celluloid' lacquer in England circa 1904 appears to have been solvent based and not a reacted product. The DAMARD LACQUER CO. of London was formed in 1910 to exploit this. Later agreements with Dr. Baekeland established Bakelite Ltd. (UK).

Moulders of the day usually made their own compounds and the Bakelite resin was only cautiously tried by moulders of electrical, telephone and automotive parts. As a thermosetting resin, Bakelite needed high temperatures and high pressure and Baekeland found his greatest problem was to get moulders to use new techniques. 

With perseverance, Bakelite was well established by 1922 in a wide range of moulded products and a major expansion of plant capacity took place with the establishment of the BAKELITE CORPORATION. The descendants of Bakelite are still widely used as PHENOL-FORMALDEHYDE under the generic name of PHENOLIC Plastics.

UREA FORMALDEHYDE - 1923 Frits Pollack

In the years following the release of the synthetic Bakelite, plastic materials became very big business and as a result, future developments were in the domain of the large chemical companies. Large scale production of these resins required big plants with enormous capital costs and ready sources of chemical raw materials.

Experiments with Urea reactions on Aldehydes had produced several patented surface coatings and synthetic glues by 1920. The first Urea moulding powder called POLLAPAS appeared after 1923 patents to FRITS POLLACK. British Cyanides Co. produced their famous BEETLE range of THIOUREA moulding powders from 1928.

To prepare a ready-mixed moulding material, the resin was usually compounded with Cellulose or wood flour and then ground to a powder. Further development was slow as synthetic UREA was available only in Germany until 1935 when ICl Ltd. produced it in England. Production in the USA commenced in 1936.

UREA plastics could be brightly coloured and moulded on existing compression moulding equipment. They were a minor sensation in both Europe and the USA in the years before World War II and helped plastic moulders expand their interests into consumer product markets, light fittings and other household products.

The compression moulding process was the established technique and readily available resins such as Bakelite and Urea led to the widespread abandonment of 'home-made' moulding compounds. The trend had a slight set back during the war years when the 'witches brew' moulding formulas helped maintain production.

The 'home made' compounds of the 40's were a deal more sophisticated that wood flour and glue and included cold setting bituminous compounds such as Gilsonite (a type of Asphalt) which had been compounded with Mica and Asbestos fibres, gums and resins to produce electrical components from about 1908.

These required substantial oven curing and produced dimensionally variable results. Successful use of Phenolic and Urea resins prompted research into Aldehyde reactions with Soybean Flour, Corn Gluten and Furfural (Oat Hulls), for moulding compounds. Furfural-aldehyde was widely used in the U.S. during WW II.

POLYVINYL CHLORIDE (PVC) - circa 1927 B. F. Goodrich and others

Following Regnault's initial discovery of Vinyl Chloride in 1838, little work was done on chemical analysis of the monomer until 1872 when BAUMANN succeeded in obtaining polymerized substances. Russian Professor IVAN OSTROMISLENSKY, worked on synthetic rubbers in 1912, producing'rubber-like' polymerized materials.

His analytical work between 1912 and 1916 has been described as outstanding, demonstrating the potential of PVC and detailing polymerization techniques. Rubber had become a 'strategic war material' and the idea of creating a synthetic product was eventually to become an urgent priority for a number of European governments.

Laboratory research into vinyl polymers soon involved all the big names in plastics chemistry as well as major rubber processors. With a focus on rubber synthesis, it was not until after 1927 that Carbide and Carbon (USA) marketed polymerized vinyl materials, mainly as plastisols for lacquer and waterproofing bases. 

Dr. WALDO SEMON of the B.F. GOODRICH Co. first commercialized the polymers with a plasticised PVC developed between 1927 and 1933. The first Goodrich PVC moulding compound was called KOROSEAL, marketed with processing support from 1930. (Dr. Semon is also remembered for putting the 'bubble' into bubble gum.)

The versatile Vinyls appeared in every form from toothbrushes to book bindings and were first injection moulded around 1937. The rubber-like structure of the polymer, noted by Ostromislensky and studied by German chemists from 1929 resulted in parallel development of materials, with PVC compounds widely available after 1938.

Unplasticised PVC (UPVC) progressively became a major commodity resin after 1958 following its successful introduction in Europe for pipe for town water services replacing cast iron systems. Chlorinated PVC (CPVC), Polyvinylidene Chloride (PVDC) and Polyvinylidene Fluoride (PVDF) are derivatives.

POLYSTYRENE - circa 1929 I. G. Farben/Dow Chemical

Styrene as a monomer was first obtained by distilling the gum resin of a tree, liquidamber orientalis. German apothecary, Simon, had noted its polymerization on exposure to sunlight in 1839 but did not understand the reaction. A synthetic styrene was first prepared by M. Berthelot in 1869 (Berthelot invented the word 'synthesis').

By 1900, the German, Kronstein had developed polymers of styrene and in 1911, English Chemist Mathews took out a patent describing a similar process. In Europe, I. G. Farbenindustrie had commenced experiments on styrene after 1924 with full scale production commencing in 1929. Their main interest was rubber synthesis.

I. G. Farben's highly secret work on Buna-S rubber for which styrene was the CO-MONOMER with Butadiene led to other research on the thermoplastic properties of the polymer. Trial injection moulding of styrene polymer was conducted by Dynamit A.G. in 1930 and it found its way into a number of applications before 1935.

Experimental work on Styrene commenced in the US at DOW CHEMICAL with Drs. Dreisbach & Grebe before 1930, with small scale production in 1937. Increasing tension between the major powers prompted the US Government to explore Styrene Monomer for the production of synthetic rubber and during the war, DOW, UNION CARBIDE and MONSANTO CHEMICALS commenced production.

The investigation of Styrene and its derivative polymers and COPOLYMERS in the 1920's and 30's was the main vehicle for testing the revolutionary theories and experiments of German Chemist, HERMAN STAUDINGER who was the first to use the term MACRO-MOLECULES in his May 1922 paper on rubber.

Staudinger's "Macromolecules" helped explain the chemical nature of plastic materials and laid the foundations for future commercial exploitation of polymers. It took many years of work to convince fellow experimenters of the correctness of his theories. His outstanding work was rewarded with a NOBEL PRIZE in 1953.

Another great name in plastics, OSTROMISLENSKY (Vinyls) was to play a significant role in early research into Styrenes during the 1920's. His work centred on different reaction (polymerisation) results with different conditions and provided additional clarification and independent confirmation of Staudinger's work.

Polystyrene was a commodity resin by 1949 and remains in the top ten Plastics by production volume. Later Styrenic derivatives STYRENE ACRYLO-NITRILE (SAN) and ACRYLONITRILE BUTADIENE STYRENE (ABS) contributed to development of extremely tough engineering plastics.

ACRYLIC - 1931 Rohm & Haas A. G.

Acrylic Acid and its derivatives were well known by the 1890's. The basis for modern polymers of Acrylic was the work of Dr. OTTO ROHM, in Germany in 1901. ROHM produced solid transparent polymers of Acrylic Acid in laboratory experiments and observed some of their characteristics. 

Acrylic monomers, METHYL ACRYLATE and ETHYL ACRYLATE were both colourless liquids which could be polymerised into transparent solids. This was a handy discovery but many years of effort went into developing a commercial product. Like many plastics, a viable source of bulk monomers took time to emerge.

By 1927, ROHM & HAAS A.G. produced POLYMETHYL ACRYLATE as ACRYLOID and PLEXIGUM Moulding Powder, although full scale production did not commence until 1931 when PLEXIGLAS sheeting was added. From around 1929, ICI Ltd. (UK) conducted major research into the properties of Acrylic Plastics.

This resulted in a commercial process for POLYMETHYL METHACRYLATE for cast sheet in 1932. This went into production in 1934, marketed as PERSPEX. ICI's major competitor, Plexiglas, took licences to produce the cast sheet in Germany and Acrylic plastics in sheet, profiles, granules and moulding powder were available by 1937.

Further investigations by KLEIN and PEARCE, I.G. Farben, Du Pont and others from 1936 indicated potential for aqueous dispersions of acrylic polymers for use in surface coatings, artificial leathers, fabric finishing as distinct from casting resins. The acrylic based paints have now substantially replaced oil based paints for domestic use.

MELAMINES - 1933 CIBA/Cyanamid

Moulding compounds, based on Melamine resins, were developed from commercial processes for Melamine synthesis patented between 1933 (CIBA) and 1946 (Du PONT). German and British interests had simultaneously developed Melamine resins for glues and fabric impregnation and forms of moulding compounds by 1940.

Palmer Griffith, an employee of AMERICAN CYANAMID, produced a resin of this type in 1933 adding FORMALDEHYDE which was offered as a moulding compound from 1937. Like Urea, the resin or syrup was compounded with Alpha-Cellulose, hardened and ball-milled to produce a powder.

War-time production absorbed much of the new moulding compound which produced articles with superior chemical resistance, good electrical characteristics and required no special alteration to compression moulding techniques. They became very popular for use in kitchenware and other household appliances.

Formaldehyde already had a history of association with the development of long chain polymers as a very reactive chemical. The commercial success of Melamines encouraged experimentation and this played a significant role in the development of engineering plastics when the science of polymer chemistry was better understood.

Du Pont commenced studies on formaldehyde after World War II, leading to the production of an ACETAL resin, DELRIN in 1959. A German researcher, H. SCHNELL, also enquiring into formaldehyde identified POLYCARBONATE in 1956 with BAYER resins and the G.E. LEXAN products were released in 1959.

POLYVINYL ACETATE (PVA) - 1937 I. G. Farben/Monsanto

Vinyl Acetate was discovered in Germany by Dr. FRITZ KLATTE in 1912 with patents for its preparation from acetylene gas. It was readily polymerized to give dense solid materials but had greater potential as a copolymer due to its ability to combine with other monomers described by Klatte in 1917.

Production of Vinyl Acetates on a commercial scale commenced after 1937 at I.G. FARBEN, going mainly into adhesives, laminate glues and paints. Experimental production in the U.S.A. began in the same year at MONSANTO where the main interest was for safety glass in the lucrative automobile industry.

POLYAMIDES - 1938 E.I. Du Pont de Nemours

Dr. WALLACE H. CAROTHERS joined the Du PONT research team at Wilmington, Delaware, in 1928 after a brilliant academic career at HARVARD UNIVERSITY in theoretical and analytical chemistry which advanced the work begun by Staudinger and established the principles of poly-condensation of long chain polymers.

CAROTHERS conducted fundamental research into polymers, his first commercial research being with forms of synthetic rubber. This work led to the first practical all-purpose synthetic rubber, NEOPRENE, developed by colleague, lra Williams. The research team a Wilmington produced many giant linear molecules in this period. 

Between 1929 and 1931, the Wilmington research team had expanded and Du Pont executive, Dr. E.R. BOLTON directed Carothers to continue fundamental research while keeping an eye on any new polymers which could have potential as fibres. The most significant developments of this period were the POLYESTER resins.

In 1932, Carothers, continuing work on POLYESTERS, joined with Dr. JULIAN W. HILL to experiment with a "Molecular Still" which enabled polymerization of "Super-Polymers". At Bolton's request, Carothers examined the AMIDE group of chemicals and produced interesting Amide polymers in 1935 which could be drawn into fibres.

Exhausting research of these by a team of over forty chemists was to produce the original "Fiber #66" as the best for future commercial development. It led to a string of Du Pont patents between 1937 and 1942. Extensive trials of processing operations followed and commercial production of NYLON commenced in 1938.

Tragically, Carothers did not witness the worlds' astonishment at the new fibre made from 'coal', taking his own life in 1937. As a product from a totally non-related material source, NYLON was a 'media miracle' (encouraged by Du Pont) leading to an unheard of investment of US$ 8 MILLION on a plant in Delaware to produce NYLON FIBRES.

Nylon was the first totally synthetic fibre. The Delaware plant was commissioned on December 15th, 1939 and first deliveries of the amazing fibre reached hosiery mills in January 1940. Demand for NYLON forced DU Pont to built a second, larger plant only six months after NYLON STOCKINGS hit store shelves.

NYLON was first moulded in 1941. At the start of the war in Europe, it was classified as a strategic war material and the process heavily guarded. Nylon was first produced on commercial scales in the U.K. by I.C.I. Ltd. in the early 1950's was widely available after that. It revolutionised thermoplastic moulding with tough and durable products.

POLYETHYLENE - 1939 ICI Limited

Imperial Chemical Industries Ltd., was one of the major British companies to lead experimental development of plastic polymers during the 1930's. Like their German and US competitors, they had committed significant resources to research during the late 20's and had independently determined that high heat and high pressure polymerization techniques (Carother's "Molecular Still") merited investigation.

From 1931, Dr. E.W. FAWCETT and a large team of scientists commenced a program to systematically explore the technique. At the time, ETHYLENE gas was being considered for a synthetic petrol, a major objective for European chemists and proved suitable for high pressure experiments on polymerization.

In 1935, Fawcett and the senior researchers, Gibson, Paton, Perrin and Williams had succeeded in isolating a waxy, white solid substance, the Polymer of Ethylene, so titled POLYETHYLENE. Gearing up to full scale production was a major chemical engineering challenge which concluded with the release of ALKATHENE in 1939.

A true thermoplastic, Polyethylene (or Polythene as it is often incorrectly termed) could be injection moulded, extruded, cast and powder coated. In this period, thermoplastic processing techniques were still developing but it was recognised that the new plastic was ideally suited for converters using injection moulding and for cable insulation.

High Density Polyethylene (HDPE) was developed in Germany during 1953 after the work of Dr. KARL ZIEGIER on catalytic reaction. Both HOECHST and PHILLIPS PETROLEUM released HDPE products in 1956. The Ultra High Molecular Weight Polyethylene (UHMWPE) was pioneered by U.S. company ALLIED CHEMICAL.

POLYURETHANES - circa 1940 I.G. Farben

Polyurethanes were first produced in Germany by I.G. Farben., with early experiments (from 1937) closely parallel to Carothers' studies of the 'super polyamides'. War time research was clouded in secrecy due to their rubber-like (elastomeric) properties, but POLYURETHANES were certainly in use from 1940.

From 1947, BAYER offered two main polyurethane formulas; IGAMID, for plastics and PERION for synthetic fibres. Interest developed in their use as adhesives for rubber but also in their foaming reaction with isocyanate chemicals. Seperate research was conducted into possible applications in surface coatings and as contact glues. 

A BAYER/MONSANTO joint venture developed elastomeric casting urethanes in 1955. Flexible polyurethane foams were developed in Germany and became widely available during the 1960's. The injectable polyurethane moulding compounds were introduced after 1980 and further development continues today.

POLYTETRAFLUOROETHYLENE - 1941 EI. Du Pont de Nemours

Major scientific discoveries by accident are rare but the discovery of PTFE is among the more unusual. High temperature, high pressure polymerization was the research focus for new plastic resins by the late 30's but Du Pont's Dr. Roy PLUNKETT had a small team assigned to work on Flurocarbon refrigerants.

Whilst experimenting with a Tetrafluoroethylene gas which had showed promise as a replacement for FREON, Plunkett stored some reacted gases in steel gas cylinders. One particular experiment in 1938 seemed to have gone astray when a gas bottle inspected by an assistant showed no pressure, yet retained its fully charged weight.
The offending bottle was immediately cut open, revealing a strange white powder which looked like a polymerized substance but did not behave like any thermosetting or thermoplastic material known at the time. It was PTFE, the first high temperature plastic, later commercialized and known as TEFLON.
Experimental production began in 1941 with research on adapting its useful anti-friction characteristics and unique electrical properties to wartime use. Processing technologies developed in the 1960's and it was to become widely used in industrial applications but is better known for use in non-stick fry-pans and cooking utensils.

SILICONE PLASTICS - 1943 Dow-Corning
Silicone materials originate with glass manufacturing. In 1904, English experimenter F.S. KIPPING determined that Silicone molecules, the main ingredient of glass, were analogous to the carbon molecules common to most polymers. He proved that organic radicals could be attached to silicone to create an entirely new base for polymerization.

CORNING GLASS experimented with Silicone-polymers in 1931, joining with DOW CHEMICAL to produce Silicones in 1943. The basic 'monomers' or SILANOLS prepared from Silicone offered an almost infinite variety of NEW polymers from liquids to thermoplastic solids and even rubber-like Elastomers.

The complex chemistry of Silicone polymers retarded progress, though the GENERAL ELECTRIC Co. had also commenced development in 1943, engaging Dr. E.G. RACHOW who developed a new direct reaction chemical process. DOW's SILASTIC material was fully commercialized by the late 1950's.

Development of SYNTHETIC RUBBER materials based on SILICONE was also the a high priority for research due to the inherent 'toughness' of the materials and was the subject of a string of patents in the 1960's and 1970's. Silicone Rubbers are now widely used in commercial and industrial applications.

POLYPROPYLENE - 1954 Prof Guillo Natta
If Ethylene gas was capable of being polymerized to form plastic substances, it was reasonable to suspect that PROPYLENE, its near chemical cousin, could also do so. The growing community of theoretical chemists involved in polymer research at least had this expectation in the 1950's due to significant advances in polymer science.

At the MILAN POLYTECHNIC Institute, Professor NATTA had been examining Propylene reactions attempting to find a new commercial polymer. The best efforts of researchers had yielded only soft, gummy substances which showed no promise when thermoplastics of high durability were required.

Noting ZIEGLER's work with the use of catalysts, Natta conceived a desirable polymer structure requiring the use of a specific catalyst which he went on to develop. His work was of great importance as it represented the first attempt to engineer a molecule to a predetermined specification using a designed polymerization technology.

The first "molecular mechanic" succeeded in 1954, building a long chain molecule ideal for thermoplastic materials. Polypropylene went into production in 1957 and is now a commodity plastic. Extensive research has also taken place on modifications and derivative materials of Polypropylene and this continues today.

Professor Natta was awarded the 1964 NOBEL PRIZE for Chemistry.