Timeline

2.0 Natural original plastics (see also the link above)

Many ancient peoples worldwide used naturally occurring plastics for a range of decorative and functional purposes. These included materials such as bitumen, amber, waxes, lac and rubbers and especially horns of different types were moulded or shaped, some being filled and used as coatings (ref. 8.4). In the last millennium more systematic developments and commercial applications led to increasingly rapid changes.

2.1 Some notable steps

1284 The Horners Company was recorded and it was awarded a Royal Charter in 1638. By 1725 London was a major centre for moulding of horn.

1850s Shellac compounded with wood flour was patented in the USA (S. Peck, J. Critchlow) and moulded into union cases, picture frames, etc.

1855 Bois durci was patented by Francois Lepage, being hard dark mouldings of albumen or blood with wood flour capable of durable fine replication under heat and pressure.

1880 Phonograph records (Berliner) based on shellac compounds were introduced and continued until PVC was used in the 1950s.

1897 Casein plastics derived from milk patented by Adolph Spitteler (Bavaria). This important material was developed by Erinoid (1909) for a range of pastel and coloured items.

2.2 Gutta Percha (GP) (reference 8.6)

This plastic material made contributions in many fields over a long time period and is worthy of particular reference.

1656 John Tredescant introduced gutta percha from the Far Eastern Palaquium ree bark. This produced a hard material mouldable by heat to soften and rovide products which proved to have unique properties.

1843 Dr William Montgomerie introduced GP to the Royal Society of Arts and illustrated its moulding properties. Excellent electrical and chemical resistances underpinned technical progress, whilst imitation wood mouldings provided artistic outlets. Montgomerie used GP for handles and golf balls which, in 1846, revolutionised the game.

1845 Gutta Percha Co. (C. Hancock, H. Bewley) was founded in London and developed an extrusion process for rods and tubing. Bewley, 1845-50, designed the first extruder for applying GP and rubber insulation to copper cables used in submarine telegraph links. The company became The Telegraph Construction and Maintenance Co. Ltd. (Telcon) which continued manufacturing submarine cable for over a century.

1846 R. and J. Dick Ltd., founded in Glasgow, are still making belting from GP.

1849 The first temporary dental filling compound employed GP.

1851 The Great Exhibition featured over 100 applications of GP.

3.0 Rubber and derivatives (reference 8.6)

1730 Charles Marie de la Condamine reported long established rubber uses in the Amazonian basin, e.g. bottles. Imports to Europe developed from his work with Francois Fresneau.

1770 Joseph Priestly (of oxygen fame) gave rubber its name because of its ability to rub out charcoal marks on paper (India Rubber).

1820-43 Thomas Hancock investigated intensively the moulding of masticated rubber and its many uses.

1839 Charles Goodyear (USA) revealed vulcanisation of rubber with sulphur, allowing formulation variables to provide a wide range of resilience in mouldings.

1843 Hancock refined and patented vulcanisation, establishing the UK rubber industry with products including boats, springs, hoses and bands. Vulcanite (hard rubber or ebonite) was an important innovation.

1846 Charles Macintosh bought Alexander Parkes’ ‘cold cure’ vulcanisation process which allowed production of brightly coloured fabrics using organic dyes.

1851 Nelson Goodyear (USA) patented ebonite primary thermosetting material for demanding applications, e.g. battery boxes, pumps, telephones, dental plates and fountain pens.

1861 Francis Shaw introduced the first screw extruder for rubber production.

1920 Peter Schidrowitz prepared prevulcanized latex, leading to the 'dipped rubber goods' industry.

4.0 Modified Natural Plastics (reference 8.2, 8.4, 8.5)

This section refers essentially to plastics based on chemical modifications of natural polymers, especially cellulose where improved controlled products preceded the more modern eras following. (Sulphur modified rubbers covered in Section 3.2. related.)

1846-68 Alexander Parkes followed Schonbein’s earlier work with detailed studies of nitro-cellulose as a thermoplastic base material. A great stride forward was made with Parkesine moulded from doughs to resemble ivory or horn. New products in controlled volume outputs became possible. Over 20 patents were filed. Parkesine was introduced at the 1862 London Exhibition.

1869-70 John Wesley Hyatt (USA) patented Celluloid - a camphor modified cellulose nitrate - a readily mouldable material for billiard balls, spectacle frames, photographic film, etc.

1877-84 Extensive legal actions between Hyatt and Spill established Parkes as the true inventor of camphor modified cellulose nitrate. In 1878 J. W. Hyatt was granted US Patent 202441 for injection moulding thermoplastics.

1880 Cellulose nitrate combs began to be mass produced by BXL which by the 1890s caused a decline in the crafting of tortoiseshell and horn products. By 1920 celluloid replaced such combs and its use continued until the 1950s.

1887 The Revd. Hannibal Goodwin patented celluloid film for photographic and other uses.

1892 Cross, Bevan and Beadle patented cellulose acetate regenerated from chemically treated wood pulp for fibres and threads. This was followed by Cross and Bevan producing tough, fire resistant thermoplastic products many colours for applications spanning some 50 years.

1905 J. Edwin Brandenberger (USA) invented cellophane used in thin films for fabrics and packaging providing major applications for many years.

5.0 Early synthetic plastics era

This era provided progress from initial fully synthesised plastics where the physics and chemistry were not fully understood but which led to the basis and development of later ‘designed’ molecular plastics. Great impetus came from coal and oil developments and particularly the industrial demands of the Great War such as urgent volume replacements of natural material sources.

5.1 Synthetic rubbers

1900 J. Kondakov (Ger.) synthesised methyl rubber poly(dimethylbutadiene).

1910 S. V. Lebedev (USSR) produced (BR) rubber from poly (1, 3 butadiene).

1915 Synthetic methyl rubber production began in Leverkusen.

1930 E. Tschunker developed nitrile rubbers (BUNA) produced in 1939 in the USA.

1931 W. Carothers et al (Du Pont USA) produced polychloroprene rubber (Neoprene).

1937 O. Bayer (Ger.) developed urethane rubbers introduced in the same year by R. M. Thomas ((USA).

1939-40 Waldo Semon (Goodrich) developed viable polybutadiene and styrene-butadiene rubbers which made major contributions to World War II.

1943 Silicone polymers were introduced by Dow Corning Corporation following much earlier work by Frederick Kipping on organo-silicon compounds.

Many rubber and elastomer variants were later developed using controlled molecular (block) structures.

5.2 Synthetic plastics

1899 Arthur Smith patented phenol-formaldehyde resins to replace ebonite for electrical insulation.

1904 The Fireproof Celluloid Syndicate (later became the Damask Lacquer Co. Ltd. - Sir James Swinburne) developed phenol-formaldehyde lacquers for metal.

1907 Leo Baekeland (USA) formed phenol-formaldehyde resins (p/f) and produced over 100 patents.

1909 Leo Baekeland patents Bakelite, the first major thermoset material to replace wood, ivory, ebonite, etc.

1910 Formica electrical insulation laminate was produced by H. Faber and D O’Conor (USA) using p/f resin impregnated paper plies.

1912 I. Ostromislensky (Russ.) patented the polymerisation of vinyl chloride to give unstable PVC polymer (unstable when not modified).

1913 Klatte produced polyvinyl acetate.

1918 Hans Johns patented urea-formaldehyde resins.

1922 Herman Staudinger (Ger.) proposed long chain molecular structures for polymers and synthesised rubber.

1924-28 Edmund Rossiter developed water-white transparent mouldings from thiourea-formaldehyde resins (marketed as Beetle resins from 1928).

1926 The first truly successful commercial injection moulding machine was produced in 1926 by Eckert and Ziegler (German Patent 495362).

1927 Otto Rohm (Ger.) developed poly (methyl methacrylate) clear plastic.

1927-37 Wallace Carothers headed major Du Pont team into ‘designed’ macromolecules, e.g. Neoprene rubber introduced in 1931 followed in 1934 with Nylon fibre (Nylon 66; Hill).

1931 Heidrich (Germany) produced the first screw extruder specifically for thermoplastic processing.

1938 Nylon 6 fibre (Schlack, I. G. Farben) commercially produced as Perlon.

1932 J. Crawford, R. Hill, ICI, introduced PMMA - Perspex, followed by others.

1933-40 Henkel patented melamine production for melamine formaldehyde resins. Developed by Ciba, American Cyanamid as basis for moulding powders (Melaware) and M-F surfaced laminates (Formica).

1933 W. Semon produced stable PVC polymer (Goodrich).

1933 R. Whiley (Dow) discovered polyvinylidene chloride (Saran).

1933 First injection moulded polystyrene articles produced following earlier work by BASF and Dow Chemicals (produced in scale in 1937).

1933 Fawcett and R. O. Gibson (ICI) discovered low density polythene, full commercial production in 1939.

1933 Carlton Ellis patented unsaturated polyester resins, introduced commercially into the USA 1941. (Cold-cured styrenated polyesters introduced in 1946 for fibre reinforced plastics.)

1937 Hans Kellerer (Austria) introduced a fully automatic injection moulding machine capable of continuous operation. R. Colombo and C. Pasquetti (Italy) produced the first twin screw extrusion machines.

1938 R. Plunkett (Du Pont) discovered PTFE.

1939 Bayer, I. G. Farben introduced polyurethane systems.

6.0 Pre- and post space age plastics

1939 Castan in Ciba (Swiss) produced foundation epoxy resins. 1945 Ciba produced epoxy resins following pre-cursor work by Schlack (Ger.) using bisphenol A/glycidyl ethers.

1940 Du Pont introduced Polyacrylonitrile (PAN) polymer, an early engineering product.

1940 PET - poly(ethylene-terephthalate) synthesised by J. R. Whitfield and J. T. Dickson at Calico Printers Association. ICI Terylene fibres and Melinex films followed (also Dacron and Mylar from Du Pont). In 1977 oriented blow moulded drinks containers were launched based on PET polymers and other types, e.g. PBT – poly(butyl-terephthalate).

1947 Formica melamine faced decorative p/f laminates were introduced to the UK.

1953 Karl Ziegler with E. Holzkamp produced high molecular weight, low pressure poly(ethylene) using organo-metallic catalysts; a major step forward.

1953 Drs H. Schnell (Bayer) and D. Fox (General Electric) independently produced polycarbonate pioneering engineering polymer. Industrial production after 1958 provided the basis of optical discs and high impact resistant applications.

1954 Isotactic polypropylene discovered by Guilo Natta, Montecatini, using Ziegler type catalysts. ICI produced ‘Propathene’ used in high volumes for demanding domestic and engineering applications.

1955 Du Pont patented EVA (ethylene-vinyl acetate copolymer) with the Elvax range launched in 1960. This is a versatile range of products.

1959 Du Pont launched Delrin - polyformaldehyde polymer based on work under Robert McDonald since 1947. This proved to be a valuable light engineering polymer.

1961-62 Du Pont introduced polyimide films (Kapton) and varnishes and later foams for composite structures. The resins are capable of high insulation, fire resistant and mechanical properties.

1964 Polyphenylene oxide (PPO) polymers were patented by General Electric (USA) and introduced as the Noryl range in 1966. These were widely used as high performance engineering thermoplastics.

1965 Union Carbide, 3M and ICI produced polysulphone thermoplastic engineering polymer.

1965 PEEK - Poly(ether.ether ketone) resistant chemical and engineering polymer produced by ICI.

1966 Fekete et al synthesised vinyl ester polymers (bisphenol A/acrylic variants). Produced by Dow Chemical Co. as the Derakane series.

7.0 Later developments

Further modified polymers and composites followed for high performance applications. The advent and development of fibres, e.g. glass, carbon, polyaramid, ceramics, etc., have provided the key backbones for fibre reinforced polymer matrix systems of outstanding performance levels. The greater understanding of control, manufacture, design and test techniques has allowed for fine tuning in space and electronic age applications. Military and civilian applications have also used selected properties such as mechanical and heat resistance to achieve high levels of performance. Coatings and adhesive systems have been vital contributors and cannot be ignored.

Recommendations for further reading

Some contributory references are given on the following page (Section 8).

Readers are referred to the proceedings of the Plastics Historical Society - journals, newsletters and compact discs.

8.0 Some contributory references

8.1 www.plastiquarian.com. See ‘Who’s who in polymers’.

8.2 The First Century of Plastics - Celluloid and its Sequel; Morris Kaufman 1961; (Fundamental landmark publication.)

8.3 Paint Technology Manuals series - Oil and Colour Chemists Association; Chapman and Halley (c.1962).

8.4 Early Plastics; Sylvia Katz; Shire Publications Ltd., 1994. (Illustrated guide to plastics and design.)

8.5 Early Plastics - Perspectives 1850-1950, ed. Susan Mossman, Leicester University Press 1997.

8.6 Tears of the Tree; John Loadman; Oxford University Press, 2005. (Definitive rubber history and technology.)

8.7 The Technology of Adhesives; Delmonte; Reinhold Publishing Corp., 1947. (Wide ranging details of many thermoplastic/thermosetting polymers.)

8.8 Developments in Reinforced Plastics; ed. G. Pritchard; Applied Science Publishers, 1980. (Reviews of many resin/reinforcement systems.)

8.9 Fibre Composite Hybrid Materials; ed. N. L. Hancox; Applied Science Publishers, 1981. (High performance polymers, adhesives and reinforcements etailed for design and moulding of composites for demanding applications, e.g. prosthetics.)

8.10 ‘Plastics- The Layman’s Guide by James Maxwell, IOM Communications Ltd., 1999.

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