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Synthetic Fibres 12.7 Synthetic fibres 12.7.1 Introduction polymeric materials is specified using the count; in other words the mass of the thread relative to a given Obtaining more valuable products from cheap length of it. The mass in grammes of 9,000 m (1,000 materials has always been one of mankind’s goals. yards) of thread is known as the denier count or Enormous interest was therefore aroused when Hilaire denier; another way of describing the thickness of a Bernigaud de Chardonnet presented the first samples continuous thread is to specify the tex, in other words of his rayon at the International Exhibition in Paris in the weight in grammes of 1,000 m of yarn (or the 1889; as shiny and silky as natural silk, this was the decitex, dtex, referring to 10,000 m of yarn). In first artificial fibre ever made by man. addition to the fracture load and (percentage) Although as early as 1913, 1931 and 1932 deformation at break, other important mechanical processes to obtain filaments from poly(vinyl properties of fibres are their tenacity, or better, the chloride) and threads from poly(vinyl alcohol) and maximum energy that they can absorb without polystyrene were patented in Germany, the era of breaking, and resilience, or the maximum energy that synthetic fibres began in 1935 at the laboratories of they can absorb without suffering permanent the DuPont Experimental Station, Pure Science deformation. Section, Wilmington, Delaware, (USA). Here, Gerard The development of synthetic fibres progressed Berchet, one of Wallace Hume Carothers’ assistants, side by side with that of organic chemistry, and obtained just over 10 g of polyhexamethylene especially petrochemistry, which, with some extremely adipamide, subsequently commercialized in 1938 with rare exceptions, provides the base compounds for the the name nylon, the first totally synthetic industrial synthesis of monomers. In 1936, ICI (Imperial fibre. Chemical Industries) patented the manufacture of In theory, all organic polymeric materials fibres from polyethylene in Great Britain; in 1937 the consisting of linear macromolecules with a sufficiently first polyurethane bristles were made; in 1938 Paul high molecular weight can be turned into fibres, in Schlack of IG Farbenindustrie (Germany) synthesized other words long filaments whose axial ratio tends to poly(e-caprolactam), whose fibres were infinity. However, only a small number of these commercialized in 1943 with the name Perlon; in provide filaments with physical and mechanical 1941, John Rex Whinfield and James Tennant Dickson properties allowing for practical applications. The of the Calico Printers Association of Manchester arrangements in which the fibres are found, (Great Britain), synthesized polyethylene independently of their origin, are the single fibre, a terephthalate, whose fibres were commercialized with group of several single fibres to form a thread, and the the names Terylene (ICI, Great Britain), Dacron interlacing of numerous threads to form textiles. A (DuPont, USA), Terital (Montecatini, Italy); in 1942 it characteristic property of any fibre, in addition to its was discovered that N-dimethylformamide was a chemical, physical and mechanical properties, is its solvent of polyacrylonitrile, thus making it possible to size perpendicular to its axis or to that of a group of obtain fibres commercialized by E.I. DuPont de fibres forming a thread. In practice, the radial Nemours (USA) with the name Orlon; in 1960 the dimension, and thus the thickness, of all continuous same company commercialized the new elastomeric fibres including silk and those made of synthetic polyurethane fibre with the trade name Lycra. Also in VOLUME II / REFINING AND PETROCHEMICALS 917 POLYMERIC MATERIALS 1960, Polymer of Terni (Montecatini group) perfected not unlikely that third generation fibres, given their the fibres obtained from isotactic polypropylene better mechanical performance, will replace metals in (Meraklon); in 1971 Kevlar (E. I. DuPont de Nemours, many of their applications in the not too distant future. USA) entered the market, the first of the polyaramids, Synthetic fibres can be classified according to the obtained with the interfacial condensation of polar functional group repeated in their chain (for terephthalic acid and p-phenylenediamine, giving those made by polycondensation) or on the basis of the fibres with exceptional mechanical and thermal structural unit for those made by addition properties. polymerization. They are listed below in chronological Today, synthetic fibres are not merely an order of synthesis: alternative to natural and artificial fibres, but form • Polyamide fibres, obtained by condensation classes of high performance materials which play an polymerization and characterized by the regular extremely important role in the field of high recurrence along the macromolecular chain of the technology. The 5 denier of the first nylon filaments amide group ϪNHCOϪ. These include aliphatic have fallen to today’s 0.5 for polyamide or polyester polyamides such as 66 (Nylon 66), 6 (Nylon 6, monofilaments; fabrics made from these are superior Perlon) 11 (Nylon 11, Rilsan) and others of minor in appearance, softness and sheen to those in natural interest, and aromatic polyamides (polyaramids). silk (2 denier). These fibres are known as high added • Polyester fibres, obtained by condensation value fibres, as are those used to make special purpose polymerization and characterized by the regular fabrics (thermochromic fabrics which change colour recurrence along the macromolecular chain of the depending on temperature, photochromic fabrics ester group ϪCOOϪ. In addition to polyethylene which change colour depending on light, iridescent terephthalate (Terylene or Dacron), they include fabrics which change colour depending on how they the fibres obtained from wholly aromatic are hit by light, etc.). Also worth remembering are the polyesters. high technology fibres deriving from the application • Polyvinyl fibres, obtained by addition of the latest developments in the science and polymerization and characterized by a structural technology of fibre manufacturing (biodegradable unit deriving from vinylic or vinylidenic fibres for sutures; fibres which absorb and accumulate monomers; of these fibres the most important are solar energy such as Solar-a of 1988, made by the those made from acrylonitrile (Orlon), from vinyl Japanese firm Unitika, and similar products made by chloride (Leavin, Thermovil, Movil, etc.) and from Descente of Japan, widely used for sports wear; fibres tetrafluoroethane. for haemodialysis, fibres for the oxygenation of blood • Polyolefin fibres, obtained by addition in the artificial respiration machines known as polymerization, such as polyethylenes from mechanical lungs; fibres used for fabrics to make ethylene and polypropylenes (Meraklon) from space suits for extra-vehicular activities, fibres which propylene. absorb humidity and sweat for sports wear, fibres with • Polyurethane fibres, formally obtained by low friction with air, etc.) and finally superfibres, in condensation polymerization and characterized by other words fibres with exceptional mechanical the regular recurrence along the macromolecular properties (elasticity coefficient over 55 GPa and chain of the urethane group ϪOCONHϪ (Lycra). tenacity above 2.5 GPa), such as those made of high • Carbon fibres, included in this classification as tenacity polyethylene, para-aramids, and derivatives of polyacrylonitrile. polyacrylonitrile carbon. Natural fibres (and their derivatives) can be considered first generation fibres. Synthetic fibres 12.7.2 Polyamide fibres (aliphatic polyamides, polyesters, polyacrylonitrile, etc.), which appeared between the 1930s and 1960s, Polyamide fibres are generally known as nylon, the are second generation fibres, created to replace first trade name of the first wholly synthetic textile fibre of generation fibres. Today’s high performance fibres industrial importance. They are obtained with the (polyethylene, polyaramide, polyarylate, carbon fibres, condensation polymerization of aliphatic or aromatic etc.), which do not represent an alternative to natural diamines and aliphatic or aromatic organic diacids, or fibres as did those of the second generation, can be with the ring-opening polymerization of w-aminoacids classified as third generation fibres. These are used (Nylon 11 and Nylon 6). Polyamides are when fibres with low density, excellent mechanical conventionally named according to the number of performance and heat resistance are required (in carbon atoms in the diamine and the diacid, or the sectors such as sport, transportation, space technology w-aminoacid alone, and appear as corneous solids, etc.) or to reinforce other materials (composites). It is non-transparent, with a melting temperature over 918 ENCYCLOPAEDIA OF HYDROCARBONS SYNTHETIC FIBRES 200°C. Their density ranges between 1.00 and 1.20 a polyamide. In the salt, the two monomers are found g/cm3. They are all insoluble in water, and can be in the exact ratio of 1 to 1, an essential condition to dissolved cold in anhydrous acids (formic, sulphuric, obtain high degrees of polymerization. Since the glacial acetic acid) and phenols (phenol, p-cresol) at polymers made using this method sometimes had a 80°C and above. They can be hydrolysed by hot degree of polymerization too high for them to be spun, mineral acids in an aqueous solution. The high at the beginning of 1935 it was discovered that small stability of aliphatic polyamide fibres,
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