Amides polyamides

There are two different oligomer series present in all spectra. The oligomer series can be identified by calculating the masses of the end groups and assigning them to specific chemical structures (Pasch and Schrepp, 2003 Weidner et al., 2004). In the present example, the two species are the propionic amide-acid (R-am-ac) and the propionic amide-propionic amide polyamides (R-am-am-R). The use of MALDI-TOF MS as a structure-sensitive detector allows the resolution to be indirectly enhanced since several species coelute, as shown in Fig. 17.21. The polarity of the... 

The polymeric amides, polyamides, are an especially important class of condensation polymers. Nylon is the best known polyamide. It is prepared by heating anhydrous hexa-methylenediamine with anhydrous adipic acid, a dicarboxylic acid. This substance is often called nylon 66 because the parent diamine and dicarboxylic acid each contain six carbon atoms. 

The thermoplastic variety of polyimides with enhanced melt processabihty is obtained by combining the basic imide stmcture with more flexible aromatic groups such as aromatic ethers or amides. Polyamide-imides are produced by condensing trimellitic anhydrides with aromatic diamines, while polyetherimides are made by the reaction between bisphenol A, 4,4 -methylene dianiline, and 3-nitrophthalic anhydride. 

Polyamide TPEs are usually polyester-amides, polyetherester-amide block copolymers, or polyether block amides. Polyamide TPEs are characterized by then-high service temperature under load, good heat aging, and solvent resistance. The copolymers are used for waterproof/breathable outerwear, air conditioning hose, under-hood wire covering, automotive bellows, flexible keypads, decorative watch faces, rotationally molded sports balls, and athletic footwear soles. Producers include Elf Atochem (Pebax). 

The leader of DuPont s effort was Wallace H Carothers who reasoned that he could reproduce the properties of silk by constructing a polymer chain held together as is silk by amide bonds The neces sary amide bonds were formed by heating a dicar boxylic acid with a diamine Hexanedioic acid adipic acid) and 1 6 hexanediamme hexamethylenedi-amine) react to give a salt that when heated gives a polyamide called nylon 66 The amide bonds form by a condensation reaction and nylon 66 is an example of a condensation polymer... 

Polyamide (Section 20 17) A polymer in which individual structural units are joined by amide bonds Nylon is a syn thetic polyamide proteins are naturally occurring polyamides... 

Properties Polyamide Poly(amide- imide), unfilled... 

Polyamides. The next two compounds are the amide counterparts of the esters listed under item (4). Although the values of AH j are less for the amides than for the esters, the values of T j, are considerably higher. This is a consequence of the very much lower values of AS j for the amides. These, in turn, are attributed to the low entropies of the amide in the liquid state owing to the effects of hydrogen bonding and chain stiffness arising from the contribution of the resonance form... 

Amide interchange reactions of the type represented by reaction 3 in Table 5.4 are known to occur more slowly than direct amidation nevertheless, reactions between high and low molecular weight polyamides result in a polymer of intermediate molecular weight. The polymer is initially a block copolymer of the two starting materials, but randomization is eventually produced. 

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

As a class of compounds, nitriles have broad commercial utility that includes their use as solvents, feedstocks, pharmaceuticals, catalysts, and pesticides. The versatile reactivity of organonitnles arises both from the reactivity of the C=N bond, and from the abiHty of the cyano substituent to activate adjacent bonds, especially C—H bonds. Nitriles can be used to prepare amines, amides, amidines, carboxyHc acids and esters, aldehydes, ketones, large-ring cycHc ketones, imines, heterocycles, orthoesters, and other compounds. Some of the more common transformations involve hydrolysis or alcoholysis to produce amides, acids and esters, and hydrogenation to produce amines, which are intermediates for the production of polyurethanes and polyamides. An extensive review on hydrogenation of nitriles has been recendy pubHshed (10). 

Amidation. Heating of the diammonium salt or reaction of the dimethyl ester with concentrated ammonium hydroxide gives adipamide [628-94-4] mp 228°C, which is relatively insoluble in cold water. Substituted amides are readily formed when amines are used. The most industrially significant reaction of adipic acid is its reaction with diamines, specifically 1,6-hexanediamine. A water-soluble polymeric salt is formed initially upon mixing solutions of the two materials then hea ting with removal of water produces the polyamide, nylon-6,6. This reaction has been studied extensively, and the hterature contains hundreds of references to it and to polyamide product properties (31). 

Copoly(amide-imides) comprise an important class of copolyimides that have been developed into a commercial product. Incorporating the amide linkage into the PI makes the polymer more tractable than simple Pis, but involves a loss in thermal stabiUty. However, copoly(amide—imides) still possess quite good thermal stabiUties, intermediate between those of polyamides and Pis (12). They are relatively inexpensive to synthesize. 

Carboxyhc acids react with aryl isocyanates, at elevated temperatures to yield anhydrides. The anhydrides subsequently evolve carbon dioxide to yield amines at elevated temperatures (70—72). The aromatic amines are further converted into amides by reaction with excess anhydride. Ortho diacids, such as phthahc acid [88-99-3J, react with aryl isocyanates to yield the corresponding A/-aryl phthalimides (73). Reactions with carboxyhc acids are irreversible and commercially used to prepare polyamides and polyimides, two classes of high performance polymers for high temperature appHcations where chemical resistance is important. Base catalysis is recommended to reduce the formation of substituted urea by-products (74). 

Polyamides, often also lefeiied to as nylons, are liigli polymers which contain the amide repeat linkage in the polymer backbone. They are generally characterized as tough, translucent, semicrystalline polymers that ate moderately low cost and easily manipulated commercially by melt processing. 

However, significant exceptions to all these attributes occur. The regularity of the amide linkages along the polymer chain defines two classes of polyamides AB and AABB. 

The nomenclature (qv) of polyamides is fraught with a variety of systematic, semisystematic, and common naming systems used variously by different sources. In North America the common practice is to call type AB or type AABB polyamides nylon-x or nylon-respectively, where x refers to the number of carbon atoms between the amide nitrogens. For type AABB polyamides, the number of carbon atoms in the diamine is indicated first, followed by the number of carbon atoms in the diacid. For example, the polyamide formed from 6-aminohexanoic acid [60-32-2] is named nylon-6 [25038-54-4], that formed from 1,6-hexanediamine [124-09-4] or hexamethylenediamine and dodecanedioic acid [693-23-2] is called nylon-6,12 [24936-74-1]. In Europe, the common practice is to use the designation "polyamide," often abbreviated PA, instead of "nylon" in the name. Thus, the two examples above become PA-6 and PA-6,12, respectively. PA is the International Union of Pure and AppHed Chemistry (lUPAC) accepted abbreviation for polyamides. 

Because the rules for organic nomenclature determine the priority of naming different carbon chains from their relative lengths, the systematic names for type AABB polyamides depend on the relative length of the carbon chains between the amide nitrogens and the two carbonyl functions of the polymer for aUphatic nylon-Ayy, when x < the lUPAC name is poly[imino-R imino(l2y-dioxo-R )]. When x > then the name is... 

Fig. 3. Alignment of amide dipoles in polyamide crystals (a) for a two-dimensional array of an odd nylon, nylon-7, (b) for a one-dimensional array of an odd—odd nylon, nylon-5,7 (c) for one-dimensional arrays of polyamides containing even segments an even nylon, nylon-6 an even—even nylon, nylon-6,6 ...

Direct Amidation. The direct reaction of amino acids to form Type AB polyamides (eq. 1) and diacids and diamines to form type AABB polyamides (eq. 2) ate two of the most commonly used methods to produce polyamides. The... 

Direct amidation is generally carried out ia the melt, although it can be done ia an iaert solvent starting from the dry salt (46). Because most aUphatic polyamides melt ia the range of 200—300°C and aromatic-containing polyamides at even higher temperatures, the reactants and products must be thermally stable to be polymerized via this method. 

Other Preparative Reactions. Polyamidation has been an active area of research for many years, and numerous methods have been developed for polyamide formation. The synthesis of polyamides has been extensively reviewed (54). In addition, many of the methods used to prepare simple amides are appHcable to polyamides (55,56). Polyamides of aromatic diamines and aUphatic diacids can also be made by the reaction of the corresponding aromatic diisocyanate and diacids (57). 

Grafting can also occur in the amide nitrogen, either through an anionic-type mechanism which is beheved to operate when ethylene oxide [75-21 -8] and similar copolymers are grafted to polyamides, or through a polycondensation mechanism when secondary amides are formed as graft copolymers (70). 

The mechanism for photodegradation at short wavelengths is generaUy beUeved to be initiated by the photolytic cleavage of the amide bond (eq. 17), which has the lowest bond strength in aUphatic polyamides (220 kj/mol (53 kcal/mol))... 

Nylon-6,6 and nylon-6 have competed successfully ia the marketplace siace their respective commercial iatroductioas ia 1939 and 1941, and ia the 1990s share, about equally, 90% of the total polyamide market. Their chemical and physical properties are almost identical, as the similarity of their chemical stmcture might suggest the amide functions are oriented ia the same directioa aloag the polymer chain for ayloa-6, but are altematiag ia directioa for ayloa-6,6. 

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