Plastics Timeline

Whilst plastics are thought of as 'new' materials there is nothing further from the truth. Polymers have a long and full history and the following is simply a snapshot of some of the important events. Many of the discoveries were accidental but took great men to turn from accident to reality.

If there are any events that you would like recorded on the Timeline then please let me know - amusing stories are always welcome but serious ones have to be really interesting!

 

c.1000 BC	Lacquer work - A resin from a lacquer tree (Rhus vernicflua) this has been used by the Chinese since 1000 BC to form waterproof and durable coatings and until the 1950s used to coat domestic tableware.
c.23-79	Amber - Amber is a thermoplastic resin from fossilized trees and is found mainly on the Baltic Coast. The material can be mixed into lacquers or small pieces pressed into compression moulds to produce small articles. Amber is described by Pliny the Elder (23 - 79) in the work Natural History.
c.0	Horn - This behaves like a typical thermoplastic sheet and can be split and moulded into shape after heating in hot water. Layers can also be laminated together to build thicker products or pressed into wooden moulds to form snuff boxes or buttons. The raw material can also be ground up and mixed with a binder (such as blood) before being compression moulded for buttons and other products.
c.400	Tortoiseshell - This is actually the shell of a turtle but it can be cut and shaped, similar to horn, to keep an attractive pattern for a variety of articles.
c.800	Gutta percha - A natural resin from the bark of Malayan trees.
1284	First recorded mention of the Horners Company. The Horners Company of London (one of the Royal Livery Companies) is regarded as the first plastics trade association and even today retains links with the British Plastics Federation via the annual Horners Award.
c.1550	Valdes describes first reference to natural rubber in reports of expeditions to Central America. The native Indians used the material for sports and waterproofing.
1596	John Huyglen von Linschoeten, after visiting India, describes the use of shellac.
1638	Horners Company receives Royal Charter.
c.1650	John Tradescant introduces gutta percha to the West after his travels in the East collecting plants. Gutta percha was used to make products from garden hoses to furniture for many years after the introduction to the West and was only replaced for undersea cable insulation in the 1940's.
1725	London is established as an important horn moulding centre with metal dies being manufactured for snuff boxes.
1731	Charles Marie de la Condamine reports natives in Amazon basin using rubber for waterproofing and flexible bottles. Rubber imported into Europe in 1736 but evidence suggests that it was in use by the natives for several thousand years.  la Condamine led an expedition to Peru (now part of Ecuador) to measure the size and shape of the Earth, he was scarred by smallpox and shy of women but led an expedition of French scientists into the jungles to 'advance the art of doing science' - in the process they introduced rubber to Europe, investigated the uses of quinine and discover platinum as well as advocating the standard measure that would lead to the metre - true heroes in the jungle.
1820	Thomas Hancock (Britain) discovers that if strongly processed (masticated) then rubber became plastic and could be made to flow and develops the method of milling rubber.
1823	Scottish chemist Charles Macintosh begins using rubber to waterproof fabrics - the Macintosh is born!
1835	Regnault reports first production of vinyl chloride monomer.
1831	First description of styrene.
1835	Pelouze first produces cellulose nitrate.
1839	Charles Goodyear (USA) discovers the process of mixing natural rubber with sulphur to make a stronger and more resilient product, the process was later termed 'vulcanisation'. As with many discoveries in plastics this was an accident. Goodyear had been trying to find a method of preventing rubber from softening at high temperatures for many years and in 1839 he dropped accidentally dropped a mixture of rubber and sulphur onto a hot stove - a Eureka moment! Payen (France) isolates cellulose as the principal constituent of wood.
1843	Thomas Hancock (Britain) patents 'vulcanisation' process for rubber. Dr W Montgomerie introduces Gutta-Percha to the West (initially used for cutlery handles).
1844	Charles Goodyear (USA) patents 'vulcanisation' process for rubber.
1845	Robert William Thompson invents the rubber tyre.
1851	Ebonite is patented and commercialised by Nelson Goodyear (USA). Charles Goodyear and Thomas Hancock both find that excess sulphur during vulcanisation leads to ebonite. Ebonite is a hard, dark and shiny material used for jewellery, fountain pens, pipe stems and is the basis for most dental plates (with pink colouring) for nearly 100 years. The material can also be inlaid with metals or painted to produce very decorative objects. Ebonite is a milestone because it is the first thermosetting material and because it involves modification of the natural material.
1854	Shellac (mixed with woodflour) patented as a moulding material by Samuel Peck (USA) for use in frames and carrying cases.
1855	François Lepage patents an animal polymer composite based on albumen (from blood or egg white) with wood powder as filler. The material is known as Bois Durci and is used for moulding small items.
1856	First of many patents granted to Alexander Parkes (Britain) for nitrocellulose products. Parkes was to register over 20 patents on nitrocellulose products as the processes and products were developed. Cellulose nitrate is an explosive (guncotton), highly flammable and is brittle - but despite this it is a major development in plastics technology. The use of 'Parkesine' for the waterproofing of fabrics was patented in the same year by Parkes.
1859	Butlerov describes formaldehyde polymers.
1861	First of Parkes patents for 'Parkesine' - a cellulose nitrate based product that forms a mouldable dough which looks like ivory or horn.
1862	Parkes shows 'Parkesine' at the Great International Exhibition in London.
1863	Phelan and Collander, a billiard ball manufacturer, offers prize of $10,000 to anyone who can produce a substitute for ivory in billiard balls
1865	Parkes obtains a major patent for 'Parkesine' that describes how the samples for the Great International Exhibition were made.  Cellulose acetate discovered.
1869	John Wesley Hyatt and his brother Isaiah (USA) develop 'Celluloid' (a commercialised form of cellulose nitrate or nitrocellulose made less brittle by the addition of camphor) to try to win a prize of $10,000 in a competition to find a better billiard ball. Celluloid replaces Parkesine in many applications and is used to make spectacle frames, knife handles and photographic film.
1870	Hyatt brothers patent the use of cellulose nitrate and camphor to form a horn-like material (Celluloid).
1872	Adolph Bayer (Germany) reports reactions of phenols and aldehydes to give resinous substances. Hyatt brothers patent the first injection moulding machine. Celluloid registered as trademark by Hyatt.
1876-77	Seeds of Brazilian rubber trees smuggled out of Brazil by Sir Henry Wickham and later sent to Asia where they form the basis of the worlds rubber industry.
1877-84	Series of legal cases between Hyatt and Spill (a collaborator of Parkes) over the invention of 'Celluloid'. The eventual result is that Parkes had mentioned the use of both camphor and alcohol in his patents and was therefore the true inventor - the result is that there was no restriction on the use of the processes.
1879	Carbon fibres first used by Edison as filaments in electric light bulbs. Gray obtains patent for first screw extruder.
1880	Shellac used by the Berliner label to produce phonograph records because of the ability to reproduce fine detail - shellac was used until 1952 when PVC was first introduced for this purpose.
1884	Louis Bernigaud (Count of Chardonnet) produces 'artificial silk' fibres from cellulose (later to be termed Rayon).
1885	George Eastman Kodak patents machine for producing continuous photographic film and will become renowned for photographic products.
1887	Goodwin invents celluloid photographic film and production process.
1894	Cross and Bevan develop industrial process for cellulose acetate after research into cellulose esters to avoid flammability concerns with 'Celluloid' (cellulose nitrate).
1899	Kritsche and Spitteler (Barvaria) discover and patent casein plastics (probably by accident). Casein is made from skimmed milk curdled with rennet which is cured by immersion in formaldehyde. Casein plastics become available as 'Galalith'. Arthur Smith (Britain) patents phenol-formaldehyde resins to replace ebonite as electrical insulation.
1903	Stern and Charles Topham develop method for producing artificial silk (viscose).
1905	J. Edwin Brandenberger invents 'Cellophane' after dining at a restaurant and noticing that tablecloths absorbed moisture. He set about producing an waterproof material by applying a flexible film to the cloth to prevent soiling of materials.
1907	Leo Baekeland (USA) mixes phenol and formaldehyde to produce phenol formaldehyde resins and obtains the first of 117 patents on phenol-formaldehyde resin systems.
1908	Charles Frederick Cross invents 'Cellophane' (cellulose acetate and viscose rayon).
1909	Leo Baekeland (USA) patents Bakelite, the first widely used thermoset to replace traditional materials such as wood, ivory and ebonite. The trade name 'Bakelite' will later become synonymous with the materials.
1910	Rayon stockings for women are first manufactured in Germany. 'Formica' first produced by Herbert Faber and Daniel O'Conor (American researchers) as an electrical insulator. Formica is layers of paper impregnated with phenolic and melamine resins and pressed into sheets.
1912	I. Ostromislensky (Russia) patents polymerisation of vinyl chloride to give PVC but decomposition during processing prevents commercial development.
1915	First production of synthetic methyl rubber at Leverkusen.
1918	Hans John prepares resins by reacting urea with formaldehyde and patents the urea-formaldehyde resin systems.
1920	Fashion for long hair with women leads to Celluloid replacing horn as the material of preference for hair combs. Fashions change but even in 1944 most toilet goods are still made from Celluloid.
1922	Hermann Staudinger (Germany) synthesises rubber.
1924	Edmund Rossiter (Britain) develops urea thiourea formaldehyde for the British Cyanides Co. to give the first water-white transparent thermosetting moulding powder. Marketed from 1928 onwards as 'Beetle'. Discovery of polyvinyl alcohol.
1926	Hermann Staudinger (Germany) starts work on 'macromolecules' that will eventually show that polymers are long chains of monomers joined together (polymerised). Previously it was widely believed that plastics were composed of rings of linked molecules. Eckert and Ziegler patent first commercial injection machine in Germany but automatic production was not possible until 1937.
1927	Discovery of suitable plasticisers for cellulose acetate leads to rise of the material as a replacement for the more flammable celluloid. Otto Rohm (Germany) develops poly(methyl methacrylate) and limited production begins at Darmstadt (the aptly named Intestine Town).
1928	Ziegler becomes interested in organo-metallic chemistry and starts to lay the foundations for polyethylenes and polypropylenes. Wallace Hume Carothers (1896 - 1937) starts work on polymers and polymerisation as head of a research group at Du Pont - this was to be one of the most successful groups in the history of polymer science.
1929	Dunlop Rubber Co. (Britain) produces the first foam rubber.
1930	BASF / I.G.Farben (Germany) develops polystyrene and Dow Chemical Co. (USA) starts to develop polystyrene but commercial production takes another 7 years. W.L.Semon of B.F.Goodrich (USA) modifies PVC to improve processing and give more commercially processable material.
1931	Carothers develops Neoprene. Imperial Chemical Industries - ICI (Britain) develops polyethylene almost by accident when E.W.Fawcett and R.O.Gibson notice a small amount of a waxy solid produced during experiments with ethylene. This was later isolated to produce polyethylene which had excellent chemical resistance and insulation properties.
1932	Improvements to urea thiourea formaldehyde products at British Cyanides Co. give urea formaldehyde resins.
1933	ICI workers (R.Hill and J.W.C. Crawford) start to develop commercial synthesis of poly(methyl methacrylate) or PMMA - later to be commercialised under the names 'Perspex', 'Lucite', 'Plexiglas' and many others. Ralph Wiley (Dow Chemical) accidentally discovers polyvinylidene chloride (Saran). Wiley was a college student cleaning glassware in the Dow labs when he found some glassware that he couldn't clean. The result was the discovery of polyvinylidene chloride or Saran. First injection moulded polystyrene articles produced.
1934	Wallace Hume Carothers at Du Pont (USA) develops nylon, originally as a fibre. First commercial production of Perspex (PMMA).
1935	Carothers and Du Pont patent nylon. Henkel patent the production of resins based on melamine.
1936	ICI patents polymerisation of ethylene to give polyethylene and develop large volume compressor to commercially produce polyethylene.
1937	Wallace Carothers commits suicide only three weeks after applying for a patent for nylon and before nylon is released to the public (1938/9) as 'Exton'. Unfortunately he never has a chance to see how much he did for mankind. The frightening thing is that Carothers committed suicide because he felt that he was a failure - would that we could all fail as brilliantly as Carothers. Otto Bayer starts development of polyurethanes at I.G.Farben. Polystyrene first commercially produced. Germany starts to commercially produce synthetic rubbers, styrene-butadiene (called Buna S) and butadiene-acrylonitrile (called Buna N).
1938	Roy Plunkett (Du Pont) accidentally discovers PTFE whilst looking for a reason that a cylinder of TFE was empty. Allegedly, Plunkett was working with tetrafluoroethylene when he found that a full cylinder of the gas had nothing in it - when the cylinder was cut up a white residue (polytetrafluoroethylene) was found on the inside of the cylinder and PTFE was born. P Schlack develops 'perlon'.
1939	ICI patents chlorination of polyethylene to give PE-C. ICI (Britain) commercialises production of polyethylene. Plastics magazine complains of 'cheap, low-grade moulding powders, skimped designs and faulty moulding techniques' and of the 'wild scramble to exploit every available, and sometimes unsuitable market'. It is good to see that nothing has changed.
1940	PMMA becomes widely used for aircraft glazing. First production of PVC in the UK.
1941	I.G.Farbenindustrie (Germany) starts to produce polyurethanes. PTFE patented by Kinetic Chemical Ltd. First commercial PET polymer announced. The work of Wallace Carothers on aliphatic polyesters is extended to cover aromatic polyesters by J.R.Whinfield and J.T.Dickson at the Calico Printers Association in Britain and poly(ethylene terephthalate) is developed. PET is initially used as a fibre (Terylene and Dacron - shirt makers of the world rejoiced) and later as a film (Melinex - ICI and Mylar - Du Pont).
1942	'Super Glue' (methyl cyanoacrylate) first discovered by Dr Harry Coover (working for Eastman Kodak) during research into transparent materials for use as gun sights. The material polymerises and acts as an adhesive by extracting water vapour from the surfaces and the air. The potential adhesive qualities were not realised until 1951 and it was not until 1958 that the product was actually marketed as an adhesive. After accidentally sticking lots of fingers together one of the first applications was as a wound dressing in the Vietnam War.
1943	First pilot plant for PTFE, later to be marketed under the name 'Teflon' comes on stream. Commercial production takes another 7 years until 1950. Investigations into using woven glass fibres as reinforcement begins. A large quantity of woven glass fibre went missing at the Royal Aircraft Establishment in Farnborough in the early stages. It is thought that the soft 'feel' lead the thief to think that it was the new material 'nylon', then in great demand for ladies underwear. It is amusing to think of what happened to any ladies wearing glass fibre underwear as the glass fibres tend to get into the skin and cause great irritation. Glad it wasn't me!
1947	Formica first introduced to the British market.
1948	George deMestral (Switzerland) invents Velcro after seeing burrs in his socks and dogs hair after a walk in the Swiss woods. Velcro is later patented in 1955.
1949	'Silly Putty' invented by James Wright (GE engineer) after mixing silicone oil with boric acid. 'Silly Putty' acts like a rubber but can also be stretched and formed but will revert to a 'blob' after a short period of time. 'Lycra' invented by Joe Shivers (a chemist) working for DuPont. Shivers was looking for a material to improve girdles and came up with the polyurethane based 'Lycra'. This changed the shape (literally and pun intended) of fashion wear throughout the world.
c.1950	High impact polystyrene introduced as commercial plastic.
1952	First long-playing records and singles manufactured from PVC appear - replacing shellacs and phenolics previously used.
1953	High density polyethylene (Du Pont trade name of 'Polythene') first produced. Karl Ziegler (Germany) develops metal ion catalysts for regular polymerisation of polyethylene. Giulio Natta (Italy) who had worked independently but also with Ziegler develops metal ion catalysts for production of isotactic polymers such as polypropylene. Ziegler and Natta had collaborated for some time before Natta filed a patent on polypropylene before informing Ziegler of its existence. Ziegler felt this breached their agreement to share their research and the partnership split in anger. Reconciliation was only achieved in 1963 in Stockholm when they received a joint Nobel prize. Hermann Staudinger wins Nobel Prize for Chemistry for the study of polymers. Herman Schnell at Bayer first synthesises polycarbonate at Bayer Uerdingen plant. The initial discovery attracted little attention because carbonates were thought to be thermally unstable - how wrong they were!
1955	High density polyethylene (manufactured using the Phillips - metal oxide catalysts - or Zeigler - aluminium alkyl catalysts - processes) produced and marketed.
1956	Patent filed by DuPont for first acetals (POM).
1957	Polypropylene commercially produced and marketed by Montecatini as 'Moplen' using Zeigler-Natta catalysts to control the structure of the polymer and to polymerise products that had previously been impossible.
1958	Commercial production of polycarbonate resins produced from bis-phenol A in both Germany (Bayer) and USA (General Electric Co.). Acetals (POM) introduced by Du Pont (USA) under the trade name 'Delrin™' for conveyor applications.
1962	Polyimides introduced by Du Pont (USA).
1963	Ziegler and Natta share Nobel Prize for Chemistry for the synthesis of polymers.
1965	Polysulphones introduced by Union Carbide (USA). PPO introduced by General Electric Co. (USA) and Aku (Holland). Aromatic polyesters, ionomers introduced. First glass-filled grades of acetals (Delrin™) introduced by DuPont
1974	Oil crisis strikes! Crude oil prices increase by 300%, ethylene prices increase by 200% and most other petrochemical based polymers increase by between 50% and 100%. Strangely enough interest in reprocessing waste and reducing materials use also grows! Prior to this it was normal to have processors pay you to take away their scrap. After 1974 you had to pay them.
1976	DuPont releases Zytel ST (PA 6,6). Montedison patents on PP (see Zeigler and Natta above) are about to run out and plant is being built throughout Europe to produce PP (later to be called 'the new mild steel').
1977	PEEK first prepared by ICI (Britain).
1980	PE-LLD introduced.
1983	ICI and Bayer launch PEEK, PES and PPS as the new engineering thermoplastics. The costs are enormous but specialist applications create a lasting market even after ICI retreats from the plastics market.
1990	Warner Lambert develops Novon - a starch which is also an injection mouldable plastic, ICI launches Biopol. Both are bio-degradeable plastics.
2000	New commercially important polymers are unlikely to be developed from scratch and the emphasis is now on compounding existing polymers to create composites with improved properties. Some of the most exciting developments are in the use of cellulose fillers (wood flour, flax and many others) to extend and improve the plastics properties. Polypropylene described as 'the new mild steel' by Alan Griffiths.
2002	'Formica' company seeks Chapter 11 protection in USA. The end of an era?

Acknowledgments: We would like to thank Colin Williamson of the Plastics Historical Society for permission to use some key dates for this timeline. All Trade Marks and Copyrights are acknowledged.

For more detailed information look at the The Plastics Historical Society: www.plastiquarian.com

 

Last edited: 30/12/06

© Tangram Technology Ltd. 2001

Our standard disclaimer regarding Internet data applies.