Historical Development of Industrial Polymers

Like most other technological developments, polymers were first used on an empirical basis, with only a very incomplete understanding of the relationships between structure and properties. The first polymers used were natural products that date back to antiquity, including wood, leather, cotton, various grasses for fibers, papermaking, and construction, wool, and protein animal products boiled down to make glues and related material. 

Then came several semisynthetic polymers, which were natural polymers modified in some way. One of the first to attain commercial importance was cellulose nitrate plasticized with camphor, popular around 1885 for stiff collars and cuffs as celluloid, later most notably used in Thomas Edison s motion picture film (11). Cellulose nitrates were also sold as lacquers, used to coat wooden staircases, and so on. The problem was the terrible fire hazard existing with the nitrates, which were later replaced by the acetates. 

Other early polymer materials included Chardonnet s artificial silk, made by regenerating and spinning cellulose nitrate solutions, eventually leading to the viscose process for making rayon (see Section 6.10) still in use today. 

The first truly synthetic polymer was a densely cross-linked material based on the reaction of phenol and formaldehyde see Section 14.2. The product, called Bakelite, was manufactured from 1910 onward for applications ranging from electrical appliances to phonograph records (16,17). Another early material was the General Electric Company s Glyptal, based on the condensation reaction of glycerol and phthalic anhydride (18), which followed shortly after Bakelite. However, very little was known about the actual chemical structure of these polymers until after Staudinger enunciated the Macromolecular Hypothesis in 1920. 

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