Acid Polyester

A sample of polyester (ca. 1 g, exactly weighed) is dissolved in 20 mL toluene-ethanol mixture (1/1 vol.) and titrated by a solution of KOH in ethanol (0.05 mol/L) using a potentiometric titrator. A blank titration must be performed under the same conditions. Hardly soluble polyesters (e.g., PET) must be dissolved in an o-cresol-chloroform mixture or in hot benzyl alcohol.417 The result (acid content) is normally expressed in mmol COOH/g polyester but may also be given as the acid number, defined as the number of milligrams of KOH required to neutralize 1 g of polyester. [Acid number = (number of mmol COOH/g polyester) x 56.106.]... 

Anionic Wool, nylon Cotton Polyester Acid Direct Disperse... 

Polyester polyols, 25 464 468 Polyester resin(s), 11 302 coating resins, 7 104-106 cyclopentadiene and dicyclopentadiene applications, 8 230 flammability of, 20 115-116 properties in powder coating, 7 43t standard test methods for, 20 11 It unreinforced, 10 187t weathering of, 20 116 Polyester resin-based powder coatings, organic titanium compounds in, 25 125 Polyester resin composites, 26 762-763 Polyester resin formulations ingredients of, 20 96t unsaturated, 15 511-512 Polyesters, 10 185-189, 497 12 655-656. See also Thermoplastic polyesters Unsaturated polyesters acid resistance of, 20 7-8 antioxidant applications, 3 121 aromatic ionic, 23 722 based on 1,4-cyclohexanedimethanol, 12 674-675... 

T50I(NPG)/PMDA was of particular interest because of its adhesive characteristics, oxidative stability, and polymer cost. Table III shows the improvement in adhesion obtained when various substrates were coated with blends containing this polyester (acid number 39). As indicated in the table, the ease of obtaining adhesion on the different substrates decreased approximately in the following order brass > steel > copper > chrome-coated steel > aluminum > nylon 66 > poly (ethylene terephthalate). In spite of the wide differences in structure and polarity of the various polymers, the carboxylated polyester significantly improved the adhesion of the coatings. 

The hydrolysis susceptibility of a polyester or a polyester-based PU depends on the concentration of ester bonds, on the polyester polyol acidity, on the hydrophobicity of the glycol or dicarboxylic acid used for polyester synthesis, and on the steric hindrance around the ester groups. Low concentration of the ester bonds, low polyester acidity, high comonomer hydrophobicity and high steric hindrance around the ester groups confer hydrolysis resistance to the polyester-based PU. 

High barrier polymers, such as polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), polyester, acid copolymers and ionomers have been proposed and are under evaluation as a replacement for PE. However, they present some drawbacks in terms of scalability and/or mechanical properties and/or outgassing rates. Cost of these polymers is also generally higher. 

Tailoring drug delivery without additives through polyester acidic end groups... 

Unmodified polyesters Alcohol-modified polyester Acid-modified polyester Chlorinated paraffins Basic lead silicates Barium salts Cadmium salts Cadmium soaps Zinc soaps Di-n-alkyltin mercaptide Di-n-alkyltin dilaurates Dibutyltin dimaleate Epoxy resins Hydroxybenzo phenones Benzotriazoles Lead stearate... 

Alkyd resins cured with low molecular weight epoxy resins show excellent adhesion to metal, improved gloss and colour retention and excellent water and chemical resistance. Curing of carboxyl functional polyester (acid number 90) with an epoxy resin enhances the weatherability of the epoxy resins. Basic curing processes involve the reaction of—CO2H or —OH groups with epoxy groups. These reactions will be discussed later in Section 6.3.6. 

Chem. Descrip. Combination of phosphoamino compds, and surfactants Uses Wetting agent for treated silicates flatting agent used for flat varnishes based on NC, NC-alkyds, polyester, acid curing resins Properties Lt, yel, liq, sp,gr, 0,85 flash pt, 15 C pH 6,0 28% solids contains ethanol... 

Polyester Acids, common organic solvents. 100 Good strength and flexibility. Not suitable for alkalis. 

HOCHj CHjOH. Colourless, odourless, rather viscous hygroscopic liquid having a sweet taste, b.p. 197 C. Manufactured from ethylene chlorohydrin and NaHC03 solution, or by the hydration of ethylene oxide with dilute sulphuric acid or water under pressure at 195°C. Used in anti-freezes and coolants for engines (50 %) and in manufacture of polyester fibres (e.g. Terylene) and in the manufacture of various esters used as plasticizers. U.S. production 1979 1 900 000 tonnes. 

Condensation polymerization differs from addition polymerization in that the polymer is formed by reaction of monomers, each step in the process resulting in the elimination of some easily removed molecule (often water). E.g. the polyester polyethylene terephthalate (Terylene) is formed by the condensation polymerization (polycondensation) of ethylene glycol with terephthalic acid ... 

H02C(CH2)2C02H. Colourless prisms m.p. 182 C, b.p. 235°C. Occurs in amber, algae, lichens, sugar cane, beets and other plants, and is formed during the fermentation of sugar, tartrates, malates and other substances by a variety of yeasts, moulds and bacteria. Manufactured by the catalytic reduction of maleic acid or by heating 1,2-dicyanoethane with acids or alkalis. Forms an anhydride when heated at 235°C. Forms both acid and neutral salts and esters. Used in the manufacture of succinic anhydride and of polyesters with polyols. 

Polyesters from polybasic acids and polyhydric alcohols. Alkyd resins. The condensation of polyhydric alcohols and polybasic acids or anhydrides leads to polj esters known as alkyd resins. The most common member of the group is a glycerol - phthahc acid polymer, and this has led to the term glyptal resins being frequently apphed to the whole group. 

Polyesters from diols and dicarboxylic acids (polyester fibres). 

Polymerisation of a diol with a dicarboxybe acid is exemplified by the production of a polyester from ethylene glycol and terephthabc acid either by direct esterification or by a catalysed ester-interchange reaction. The resulting polyester (Terylene) is used for the manufacture of fibres and fabrics, and has high tensile strength and resibency its structure is probably ... 

The carboxylic acid produced m the greatest amounts is 1 4 benzenedicarboxylic acid (terephthahc acid) About 5 X 10 Ib/year is produced m the United States as a starting material for the preparation of polyester fibers One important process converts p xylene to terephthahc acid by oxidation with nitric acid... 

Polyesters are a second class of condensation polymers and the principles behind their synthesis parallel those of polyamides Ester formation between the functional groups of a dicarboxylic acid and a diol... 

Alkyds are formulated from polyester resins, cross-linking monomers, and fillers of mineral or glass. The unsaturated polyester resins used for thermosetting alkyds are the reaction products of polyfunctional organic alcohols (glycols) and dibasic organic acids. 

Unsaturated Polyesters. Unsaturated polyesters are produced by reaction between two types of dibasic acids, one of which is unsaturated, and an alcohol to produce an ester. Double bonds in the body of the unsaturated dibasic acid are obtained by using maleic anhydride or fumaric acid. 

Just as it is not necessary for polymer chains to be linear, it is also not necessary for all repeat units to be the same. We have already mentioned molecules like proteins where a wide variety of different repeat units are present. Among synthetic polymers, those in which a single kind of repeat unit are involved are called homopolymers, and those containing more than one kind of repeat unit are copolymers. Note that these definitions are based on the repeat unit, not the monomer. An ordinary polyester is not a copolymer, even though two different monomers, acids and alcohols, are its monomers. By contrast, copolymers result when different monomers bond together in the same way to produce a chain in which each kind of monomer retains its respective substituents in the polymer molecule. The unmodified term copolymer is generally used to designate the case where two different repeat units are involved. Where three kinds of repeat units are present, the system is called a terpolymer where there are more than three, the system is called a multicomponent copolymer. The copolymers we discuss in this book will be primarily two-component molecules. We shall discuss copolymers in Chap. 7, so the present remarks are simply for purposes of orientation. 

Those polymers which are the condensation product of two different monomers are named by applying the preceding rules to the repeat unit. For example, the polyester formed by the condensation of ethylene glycol and terephthalic acid is called poly(oxyethylene oxyterphthaloyl) according to the lUPAC system, as well as poly (ethylene terephthalate) or polyethylene terephthalate. 

Batzer has reported the following data for a fractionated polyester made from sebacic acid and 1,6-hexanediol ... 

Condensation polymers prepared with some monomer of functionality greater than 2, for example, a polyester formed with some glycerol or tricarboxylic acid. 

The preceding discussions of the kinetics and molecular weight distributions in the step-growth polymerization of AB monomers are clearly exemplified by the esterification reactions of such monomers as glycolic acid or co-hydroxydecanoic acid. Therefore one method for polyester synthesis is the following ... 

The presence of the unsaturated substituent along this polyester backbone gives this polymer crosslinking possibilities through a secondary reaction of the double bond. These polymers are used in paints, varnishes, and lacquers, where the ultimate cross-linked product results from the oxidation of the double bond as the coating cures. A cross-linked polyester could also result from reaction (5.J) without the unsaturated carboxylic acid, but the latter would produce a gel in which the entire reaction mass solidified and is not as well suited to coatings applications as the polymer that crosslinks upon drying. ... 

Acid chlorides are generally more reactive than the parent acids, so polyester formation via reaction 5 in Table 5.3 can be carried out in solution and at lower temperatures, in contrast with the bulk reactions of the melt as described above. Again, the by-product molecules must be eliminated either by distillation or precipitation. The method of interfacial condensation, described in the next section, can be applied to this type of reaction. 

The discussion of polyamides parallels that of polyesters in many ways. To begin with, polyamides may be formed from an AB monomer, in this case amino acids ... 

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. 

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