Still 2 Polyesters

There are now commercially available a large range of laminated plastics materials. Resins used include the phenolics, the aminoplastics, polyesters, epoxies, silicones and the furane resins, whilst reinforcements may be of paper, cotton fibre, other organic fibres, asbestos, carbon fibre or glass fibre. Of these the phenolics were the first to achieve commercial significance and they are still of considerable importance. 

An interest has been developed in the use of vanadium naphthenates as accelerators. In 1956 the author found that if MEKP was added to a polyester resin containing vanadium naphthenate the resin set almost immediately, that is, while the peroxide was still being stirred in. Whereas this effect was quite reproducible with the sample of naphthenate used, subsequent workers have not always obtained the same result. It would thus appear that the curing characteristics are very dependent on the particular grade of resin and of vanadium naphthenate used. It was also observed by the author that the gelation rate did not always increase with increased temperature or accelerator concentration and in some instances there was a retardation. Subsequent workers have found that whilst the behaviour of the naphthenate varies according to such factors as the resin and catalyst used, certain vanadium systems are of value where a high productivity in hand lay-up techniques is desired. 

The polyols used are of three types polyether, polyester, and polybutadiene. The polyether diols range from 400 to about 10,000 g/mol. The most common polyethers are based on ethylene oxide, propylene oxide, and tetrahydrofuran or their copolymers. The ether link provides low temperature flexibility and low viscosity. Ethylene oxide is the most hydrophilic and thus can increase the rate of ingress of water and consequently the cure rate. However, it will crystallize slowly above about 600 g/mol. Propylene oxide is hydrophobic due to hindered access to the ether link, but still provides high permeability to small molecules like water. Tetrahydrofuran is between these two in hydrophobicity, but somewhat more expensive. Propylene oxide based diols are the most common. 

Polyamides are the second largest group of synthetic fibers after polyesters. However, they were the first synthetic fibers that appeared in the market in 1940. This was the result of the work of W. H. Carothers in USA who developed nylon 66. At about the same time nylon 6 was also developed in Germany by I. G. Farben. Both of these nylons still dominate the market for polyamides. However, due to patent restrictions and raw materials considerations, nylon 66 is most extensively produced in USA and nylon 6 is most extensively produced in Europe. 

Reinforced plastics (RPs) hold a special place in the design and manufacturing industry because they are unique materials (Figs. 6-11 and 6-12). During the 1940s, RPs (or low-pressure laminates, as they were then commonly known) was easy to identify. The basic definition then, as now, is simply that of a plastic reinforced with either a fibrous or nonfibrous material. TSs such as polyester (Table 6-19) and E-glass fiber dominated and still dominates the field. Also used are epoxies. 

Polyester chemistry is the same as studied by Carothers long ago, but polyester synthesis is still a very active field. New polymers have been very recently or will be soon commercially introduced PTT for fiber applications poly(ethylene naph-thalate) (PEN) for packaging and fiber applications and poly(lactic acid) (PLA), a biopolymer synthesized from renewable resources (corn syrup) introduced by Dow-Cargill for large-scale applications in textile industry and solid-state molding resins. Polyesters with unusual hyperbranched architecture also recently appeared and are claimed to find applications as crosstinkers, surfactants, or processing additives. 

The carboxy-hydroxy reaction (direct esterification) is the most straightforward method of polyester synthesis. It was first reported in the 1930s by Carothers10 12 and is still a very widely used method for the synthesis of polyesters from diacids and diols (Scheme 2.12) or from hydroxy acids (Scheme 2.13). Direct... 

Diols are applied on a multimilhon ton scale as antifreezing agents and polyester monomers (ethylene and propylene glycol) [58]. In addition, they are starting materials for various fine chemicals. Intimately coimected with the epoxidation-hydrolysis process, dihydroxylation of C=C double bonds constitutes a shorter and more atom-efficient route to 1,2-diols. Although considerable advancements in the field of biomimetic nonheme complexes have been achieved in recent years, still osmium complexes remain the most efficient and reliable catalysts for dihydroxylation of olefins (reviews [59]). 

Recently, many synthetic polymers such as urea/formalin resin, melamine/formalin resin, polyester, and polyurethane have been widely used as the wall material for the microcapsule, though the gelatin microcapsule is still used. Microcapsules using a synthetic polymer wall have several advantages over those using a gelatin wall (1) the preparation process is simple, (2) the size of the microcapsules is well balanced, (3) the microcapsule concentration can be increased twofold or more and (4) the microcapsules have a high resistance to water and many chemicals. Synthetic microcapsules are prepared by interfacial polymerization or in situ polymerization. 

An analytical solution for molecules with alkaline functionality is acid/base titration. In this technique, the polymer is dissolved, but not precipitated prior to analysis. In this way, the additive, even if polymer-bound, is still in solution and titratable. This principle has also been applied for the determination of 0.01 % stearic acid and sodium stearate in SBR solutions. The polymer was diluted with toluene/absolute ethanol mixed solvent and stearic acid was determined by titration with 0.1 M ethanolic NaOH solution to the m-cresol purple endpoint similarly, sodium stearate was titrated with 0.05 M ethanolic HC1 solution [83]. Also long-chain acid lubricants (e.g. stearic acid) in acrylic polyesters were quantitatively determined by titration of the extract. 

Even as Carothers was explaining the fundamental nature of large biological molecules, he orchestrated a miraculous two weeks in the history of industrial research. During April 1930, he and his team invented not only Neoprene, the first high-grade synthetic rubber, but also polyester, the first synthetic fiber that closely resembled silk. It was a dazzling accomplishment that can still make industrial chemists starry-eyed. 

The new fibers were scientifically interesting—and they eventually laid the foundation for the synthetic textile industry—but at the time they seemed practically worthless. The first polyester fibers resembled those produced by the lowly silk worm, but Carothers did not think that the discovery would be commercially valuable. The polymer chains made in Hill s molecular still were still not long enough to make robust fibers. The filaments melted at such a low temperature and were so soluble that they could not be ironed or washed in dry cleaning fluid or hot water. Carothers knew he would have to make longer polymers if he hoped to make a marketable fiber. Instead, Carothers dramatized the romance of Hill s discovery by quoting the seventeenth-century microscopist, Robert Hooke, who had dreamed of making synthetic silk even better than that Excrement made by silk worms. 

Although polyester is always brightened with disperse-type products, the methods of application vary. FBAs are marketed for incorporation in the polymer mass, for exhaust application with or without carrier and for use in the pad-thermosol process at a temperature within the range 160-220 °C. Most products are applicable by more than one method, although none can he applied satisfactorily by all methods and cost-effective products introduced in the 1950s still remain important today. 

Alternative reducing agents are still sometimes proposed and evaluated. A detailed comparison of five reducing agents has been reported sodium dithionite, thiourea dioxide, iron(II) chloride/gluconic acid, sodium hydroxymethanesulphinate and hydroxyacetone [123]. Results of fastness tests on black polyester dyeings variously aftertreated are given in Table 12.10. 

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