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Fig. 2-13 Schematic representation of industrial process for synthesis of poly(hexamethylene adipamide). After Taylor [1944] and Jacobs and Zimmerman [1977] (by permission of WileyInterscience, New York).

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steering reservoirs, valve covers, lamp housings, roof-rack components, light-duty gears for windshield wipers and speedometers), electrical/electronics (toggle switches, plugs, sockets, antenna-mounting devices, terminal blocks), industrial (self-lubricated gears and bearings, antifriction and snap- t parts, parts for food and textile-processing equipment, valves, vending machines, pumps), lm (meat and cheese packaging, cook-in-pouches, multilayer nylon polyole n protective barrier materials for oil and moisture resistance), and consumer (ski boots, racquet frames, kitchen utensils, toys, power tool housings). Nylons 6/6 and 6 comprise more than 90% of the polyamide market. The two have similar properties but nylon 6 has a lower Tm (223 C). Small amounts of nylons 6/9, 6/10, 6/12, 11, 12, 12/12, and 4/6 are produced as specialty materials. Those with more methylene groups than nylons 6/6 and 6 have better moisture resistance, dimensional stability, and electrical properties, but the degree of crystallinity, Tm , and mechanical properties are lower. Specialty nylons made from dimerized fatty acids nd applications as hot-melt adhesives, crosslinking agents for epoxy resins, and thermographic inks. The synthesis of aromatic polyamides (referred to as aramid polymers) is dif cult to carry out using diacid and diamine reactants because of the lower reactivity of aromatic amines compared to aliphatic amines [Lenk, 1978]. The aromatic ring decreases the electron density of nitrogen through resonance interaction. The elevated temperatures required to achieve polymerization are generally too high, resulting in extensive side reactions that limit polymer molecular weight.

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class SortComparer<T> : IComparer<T> {

Aromatic polyamides are produced by using the faster reaction of a diamine with a diacid chloride, for example, for poly(m-phenylene isophthalamide) or poly(imino-1,3-phenyleneiminoisophthaloyl) (trade name: Nomex). The polymerization is carried out in solution at temperatures under 100 C with a tertiary base present to react with the liberated hydrogen chloride. Highly polar aprotic solvents such as dimethylacetamide, 1-methyl-2-pyrrolidinone (NMP), tetramethylurea, and hexamethylaphosphoramide have been used to prevent premature precipitation of the growing polyamide chains. This is a signi cant problem in the synthesis of aromatic polyamides, since the reaction temperature is much lower than for aliphatic polyamides. The presence of LiCl or CaCl2 promotes solubilization of the polymer, probably by coordination of the metal ion with the amide carbonyl, which decreases the hydrogenbonding between amide groups [Kwolek and Morgan, 1977]. The resulting polymer solutions from these polymerizations are often used directly to spin bers.

30 40 50 zenith angle [deg] (a)

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2 10

private ListSortDescriptionCollection m_SortCollection = null;

There have been efforts to form aromatic polyamides directly from diacids at moderate temperatures by using various phosphorus compounds for in situ activation of the carboxyl groups [Arai et al., 1985; Higashi and Kobayashi, 1989; Krigbaum et al., 1985]. A useful agent is diphenyl(2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, which probably activates the carboxyl group by forming a mixed carboxylic-phosphoric anhydride [Ueda, 1999; Ueda et al., 1991]. Poly(imino-1,4-phenyleneiminoterephthaloyl) (XIV) (trade names: Kevlar, Twaron) is synthesized from the corresponding para-substituted diamine and diacid chloride. Poly (iminocarbonyl-1,4-phenylene) (XV) (also known as Kevlar) is based on p-aminobenzoic acid.

The totally aromatic structures of the aramid polymers give them exceptional heat and ame resistance, very high melting points (generally above their decomposition temperature, which are !500 C), ultrahigh strength, and better resistance to solvents, chemicals, and oxidizing agents compared to aliphatic polyamides. Kevlar has higher strength and modulus properties compared to Nomex. The para structure of the former gives a rodlike extendedchain structure that forms liquid crystal solutions. (Liquid crystal solutions are solutions in which there is a high degree of ordering of solute molecules; see Sec. 2-14g.) Polymer crystallization from liquid crystal solutions results in a highly oriented, extended-chain morphology in the bulk polymer, resulting in high strength and high modulus.

ionization density = 10%, 20% Wave frequency [MHZ]=32

private PropertyDescriptor m_PropDesc = null; private ListSortDirection m_Direction = ListSortDirectionAscending; public SortComparer(PropertyDescriptor propDesc, ListSortDirection direction)

Aramid polymers are much more expensive than the aliphatic polyamides. The use of aramid polymers is limited to those applications that justify the high cost. The present U.S. market is about 20 million pounds per year. The applications are those where one needs very high ame resistance (clothing for re ghters and welders, welder s protective shield, upholstery and drapes), heat resistance (ironing board covers, insulation lm for electrical motors and transformers, aerospace and military), dimensional stability ( re hose, V- and conveyor belts), or strength and modulus (circuit boards, bulletproof vests, ber optic and power lines, ship mooring ropes, automobile tire cord, puncture-resistant bicycle tires).

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