Diacid aromatic

Reactive (unsaturated) epoxy resins (qv) are reaction products of multiple glycidyl ethers of phenoHc base polymer substrates with methacrylic, acryhc, or fumaric acids. Reactive (unsaturated) polyester resins are reaction products of glycols and diacids (aromatic, aUphatic, unsaturated) esterified with acryhc or methacrylic acids (see POLYESTERS,unsaturated). Reactive polyether resins are typically poly(ethylene glycol (600) dimethacrylate) or poly(ethylene glycol (400) diacrylate) (see PoLYETPiERs). 

A polyester backbone with two HFIP groups (12F aromatic polyester of 12F-APE) was derived by the polycondensation of the diacid chloride of 6FDCA with bisphenol AF or bisphenol A under phase-transfer conditions (120). These polymers show complete solubkity in THF, chloroform, ben2ene, DMAC, DMF, and NMP, and form clear, colorless, tough films the inherent viscosity in chloroform at 25°C is 0.8 dL/g. A thermal stabkity of 501°C (10% weight loss in N2) was observed. 

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). 

The yellow members of this pigment class are obtained by coupling a dia2oti2ed aminoben2oic acid with a bisacetoacetaryUde, followed by conversion to a diacid chloride and reaction with a substituted aromatic amine. An example is Pigment Yellow 93 [5580-57-4] (Fig. 2b). 

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). 

The diacid components for the manufacture of poly(y -phenyleneisophthalamide) and poly(p-phenyleneterephthalamide) are produced by one of two processes. In the first, the diacid chlorides are produced by the oxidation of / -xylene [108-38-3] or -xylene [106-42-3] followed by the reaction of the diacids with phosgene [75-44-5]. In the second, process m- or -xylene reacts with chlorine initiated by ultraviolet light to form the m- or Nhexachloroxylene. This then reacts with the respective aromatic dicarboxyUc acid to form the diacid chloride. 

Thermoplastic copolyester elastomers are generally block copolymers produced from short-chain aUphatic diols, aromatic diacids, and polyalkjlene ether-diols. They are often called polyesterether or polyester elastomers. The most significant commercial product is the copolymer from butane-l,4-diol, dimethyl terephthalate, and polytetramethylene ether glycol [25190-06-1J, which produces a segmented block copolyesterether with the following stmcture. 

Cellulose esters of aromatic acids, aUphatic acids containing more than four carbon atoms and aUphatic diacids are difficult and expensive to prepare because of the poor reactivity of the corresponding anhydrides with cellulose Httle commercial interest has been shown in these esters. Of notable exception, however, is the recent interest in the mixed esters of cellulose succinates, prepared by the sodium acetate catalyzed reaction of cellulose with succinic anhydride. The additional expense incurred in manufacturing succinate esters is compensated by the improved film properties observed in waterborne coatings (5). 

The diacids are characterized by two carboxyHc acid groups attached to a linear or branched hydrocarbon chain. AUphatic, linear dicarboxyhc acids of the general formula HOOC(CH2) COOH, and branched dicarboxyhc acids are the subject of this article. The more common aUphatic diacids (oxaUc, malonic, succinic, and adipic) as weU as the common unsaturated diacids (maleic acid, fumaric acid), the dimer acids (qv), and the aromatic diacids (phthaUc acids) are not discussed here (see Adipic acid Maleic anhydride, maleic acid, and fumaric acid Malonic acid and derivatives Oxalic acid Phthalic acid and OTHERBENZENE-POLYCARBOXYLIC ACIDS SucciNic ACID AND SUCCINIC ANHYDRIDE). The bihinctionahty of the diacids makes them versatile materials, ideally suited for a variety of condensation polymerization reactions. Several diacids are commercially important chemicals that are produced in multimillion kg quantities and find appHcation in a myriad of uses. 

In 1973 Du Pont commenced production of another aromatic polytunide fibre, a poly-(p-phenyleneterephthalamide) marketed as Kevlar. It is produced by the fourth method of polyamide production listed in the introductory section of this chapter, namely the reaction of a diamine with a diacid chloride. Specifically, p-phenylenediamine is treated with terephthalyl chloride in a mixture of hexamethylphosphoramide and V-methylpyrrolidone (2 1) at -10°C Figure 18.32). 

In addition to a block copolymer, a microcapsule was made from suspension interfacial polycondensation between diacid chloride having aromatic-aliphatic azo group and aliphatic triamine [70,71]. The capsule was covered with a crosslinked structure having an azo group that was thermally stable but sensitive to light so as to be applicable to color photoprinting materials. 

Polyesters are the most important class of synthetic fibers. In general, polyesters are produced by an esterification reaction of a diol and a diacid. Carothers (1930) was the first to try to synthesize a polyester fiber by reacting an aliphatic diacid with a diol. The polymers were not suitable because of their low melting points. However, he was successful in preparing the first synthetic fiber (nylon 66). In 1946, Whinfield and Dickson prepared the first polyester polymer by using terephthalic acid (an aromatic diacid) and ethylene glycol. 

The typical alkyd resin (see above) is eomprised of three basic components an aromatic diacid such as phthalic anhydride which together with a polyol such as glycerol, forms the backbone of the resin molecule and along which are distributed the fatty acids derived from vegetable oils. The solubility, film hardness and colour of alkyd resins depend on the nature of the modifying fatty acid which in most cases contributes some colour to the film. 

Various compounds Group TVB Various alcohols Aromatic diacids 68)... 

MnOz Various diols Various aromatic diacids 165... 

Solution reactions between diacid chlorides and diols or diphenols are carried out in THF or CH2C12 at —10 to 30°C in die presence of tertiary amines such as triethylamine or pyridine, which play a role of both reaction catalyst and HC1 acceptor (Scheme 2.26). This synthetic mediod is also termed acceptor-catalytic polyesterification.295-297 High-temperature solution reactions have also been reported for a number of less soluble, generally semicrystalline, aromatic polyesters.6 They yield high-molar-mass polyesters exhibiting good mechanical properties and thermal stability. 

It is also possible to prepare them from amino acids by the self-condensation reaction (3.12). The PAs (AABB) can be prepared from diamines and diacids by hydrolytic polymerization [see (3.12)]. The polyamides can also be prepared from other starting materials, such as esters, acid chlorides, isocyanates, silylated amines, and nitrils. The reactive acid chlorides are employed in the synthesis of wholly aromatic polyamides, such as poly(p-phenyleneterephthalamide) in (3.4). The molecular weight distribution (Mw/Mn) of these polymers follows the classical theory of molecular weight distribution and is nearly always in the region of 2. In some cases, such as PA-6,6, chain branching can take place and then the Mw/Mn ratio is higher. 

The partially aromatic PAs are exclusively made of die diamine-diacid type and not die amine-acid type. The aromatic diamines, similar to phenylene diamines, color easily and dieir polymers are conjugated, having a golden brown color. The aromatic diacids used in the formation of partially aromatic PAs are mainly terephthalic and isophthalic acids. Starting with the diacids, the PA salt is made first and with this the salt prepolymers are prepared. The prepolymerization is usually carried out in an autoclave to prevent die sublimation of the reactants. In a laboratory synthesis it would be preferable to avoid this autoclave step as one is not always available. It is possible to start with the more reactive esters, such as diphenyl isophtiialate, or with the acid chlorides starting with the reactive isocyanates is, in principle, also possible. The terephthalic and isophthalic acids are also used to modify PA-6,6 and PA-4,6 to more dimensionally stable copolymers.6,18... 

This method involves the direct polycondensation of aromatic diamines with aromatic diacids in the presence of an aryl phosphite (triphenyl phosphite) and an organic base like pyridine.7,9 70 71 The addition of salts improves die solubility of the polymer and, with this, the maximum attainable molecular weight.71 The concentrations are, however, lower than by the dichloride method. 

A direct route to obtain polyimides and polybenzoxazoles without diacid has been explored by using direct carbonylation of an aromatic diiodo compound.100 The reactions were performed in polar aprotic solvent. The cheaper chlorine derivative can be used instead of the iodo one when it is located on a strongly... 

The Suzuki reaction was also used to prepare the polyketone since this particular reaction tolerates the subsequent step (Scheme 6.19).135 Palladium-catalyzed cross-coupling of aromatic diacid chlorides and bis(trimethylstannane) monomers was utilized to prepare poly(arylene ether ketone)s.136... 

Aliphatic-aromatic copoly imides, 268 Aliphatic-aromatic polyesters, 18, 19 Aliphatic degradable polyesters, 41 Aliphatic diacids, polyamide synthesis from, 183-184... 

Copolyesters, from diacids and diols, 43 Copoly etheramide, 147-148 Copolymerization, wholly aromatic polyesters and, 35. See also Copolymers... 

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