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eliminations of dialkyl sul de and hydrogen halide [Cho, 2002; Kraft et al., 1998; Lenz et al., 1988; van Breemen et al., 2001]. PPV can also be synthesized by the Heck coupling of aryl halides with alkenes (Eq. 2-231).
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The corresponding azomethine polymers (LIX) have been synthesized by the reaction of the appropriate diamine and dialdehyde [Farcas and Grigoras, 2001; Gutch et al., 2001; Morgan et al., 1987].
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2-15
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The drive for heat-resistant polymers has led to an exploration of polymers based on inorganic elements since bond energy considerations indicate that such polymers should be superior to organic polymers in thermal stability [Allcock et al., 2003; Archer, 2001; Manners, 1996; Nguyen et al., 1999; Ray, 1978]. Both inorganic and organometallic polymers have been studied. Inorganic polymers are polymers containing no organic groups, while organometallic polymers contain a combination of inorganic and organic groups. Inorganic and organometallic polymers would have potential for a variety of uses as partial or complete substitutes for organic bers, elastomers, and plastics where ame and heat resistance are important; as marine antifoulants, bactericides, medicinals, fungicides, adhesives, photoresists, photosensitizers, photostabilizers; and as conducting polymers. in general much of this potential is unrealized, although signi cant exceptions exist the polysiloxanes (Secs. 2-12f and 7-11a), poly(p-phenylene sul de) (Sec. 2-14d), polyphosphazenes (Sec. 7-11b), and polysilanes (Sec. 2-15b-3) are commercial polymers. 2-15a Inorganic Polymers
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The synthesis of high-molecular-weight inorganic polymers is more dif cult than that of organic polymers. Chain polymerization through multiple bonds is routinely used for organic monomers such as ethylene. This route is not readily available for inorganic polymers because monomers with multiple bonds between inorganic elements are generally unstable. Chain polymerization of cyclic monomers (ring-opening polymerization) offers more promise and is discussed in Chap. 7. Step polymerization using monomers with two different functional groups, relatively easy to accomplish with organic molecules, is more dif cult for synthesizing inorganic polymers. The chemistry of inorganic functional groups is not well understood, and monomers of high purity are dif cult to prepare. Thus, it is dif cult to achieve the polymer molecular weights needed to obtain materials with suf cient mechanical strength for fabrication into plastic, elastomers, and bers. With almost no exceptions attempts to synthesize inorganic polymers that can directly substitute for organic polymers have been unsuccessful. Although the intrinsic thermal stability is often good, a variety of dif culties must be overcome before a usable polymer is obtained. Inorganic polymers typically suffer from various combinations of poor hydrolytic stability, low polymer molecular weights, and low chain exibility. For example, inorganic polymers with high molecular weights and good hydrolytic stability are often highly in exible. A large de ciency for many polymers is their intractability to current techniques of fabricating polymers into products such as lm, ber, tubing, and other objects. This does not mean that inorganic polymers are useless. Inorganic polymers comprise many of the materials that are employed at home, industry, and elsewhere. Let us brie y consider some of those materials. [Several wholly inorganic polymers, polysulfur, polyselenium, polythiazyl, and poly(dichlorophosphazene), are discussed in Chap. 7.] 2-15a-1 Minerals
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A variety of mineral-type materials are inorganic polymers [Ray, 1978]. Silica [(SiO2)n] is found in nature in various crystalline forms, including sand, quartz, and agate. The various crystalline forms of silica consist of three-dimensional, highly crosslinked polymer chains composed of SiO4 tetrahedra where each oxygen atom is bonded to two silicon atoms and each silicon atoms is bonded to four oxygen atoms. Silicates, found in most clay, rocks, and
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soils, are also based on SiO4 tetrahedra. However, they differ from silica in having Si : O ratios under 1 : 2 (compared to 1 : 2 for silica) and contain Si groups with associated O metal cations. Single-strand, double-strand (ladder), sheet (composed of multiple-doublestrand sheets analogous to graphite), and three-dimensional polymer chains occur depending on the Si : O ratio, cation : Si ratio, and charge on the cation. Talc contains magnesium and possesses a sheet silicate structure. Tremolite, an asbestos mineral, has a double-strand structure and contains calcium and magnesium. The silicates, similar to silica itself, are highly rigid materials because of their ladder, sheet, and three-dimensional structure. Even the single-strand chains are rigid since the cations act to hold together adjacent polymer chains. 2-15a-2 Glasses
Silicate glasses are produced by melting and rapidly cooling silica or a mixture of silica with other materials [Thornton and Colangelo, 1985]. The product is an amorphous glass since molten silica has a strong tendency to supercool. (Special procedures with regard to heating and cooling rates are required to achieve crystallization.) Silica glass differs from crystalline silica in that there is less than full coordination of all silicon and oxygen atoms; that is, not every silicon is coordinated to four oxygens, and not every oxygen is coordinated to two silicons. Fused-silica glass, consisting of virtually pure silica, is the most chemically resistant of glasses and exhibits the maximum continuous service temperature (900 C). Its relatively high cost limits its use to special applications such as the ber optics used in information and image transmission and medical berscopes for internal examination of humans and animals. The most commonly encountered glass, referred to as soda-lime glass, is made by incorporating various amounts of calcium, sodium, and potassium into the silicate by adding the appropriate compounds, such as sodium and calcium carbonates or oxides, to molten silica. The properties of the glass (e.g., hardness, softening temperature) are varied by varying the relative amounts of the different cations. This is the glass used for windows, lightbulbs, bottles, and jars. Optical glass is similar to soda-lime glass but is much harder because it contains less sodium ad more potassium. Colored glasses are obtained by the addition of appropriate compounds; for example, chromium(III) and coblat(II) oxides yield green and blue glasses, respectively. Photochromic glasses, which darken reversibly on exposure to light, are obtained by including silver halide in the glass formulation. Vitreous enamels on metal objects and glazes on pottery are glass coatings obtained by covering the item with a paste of the appropriate oxides and heating to a high temperature. Borosilicate and aluminosilicate glasses are produced by adding B2O3 (borax) and Al2O3 (alumina), respectively, to molten silica. This produces a structure where boron and aluminum atoms, respectively, replace some silicon atoms in the silicate polymer chain. Laboratory glassware is manufactured from borosilicate glass, which additionally contains sodium and calcium (trade name: Pyrex). The very low coef cient of thermal expansion of borosilicate glasses makes them far less prone to breakage on heating and cooling and especially useful for volumetric glassware. This glass also has very good chemical resistance. Greater chemical resistance, when required, is obtained by using borosilicate glasses with a very high (99.6%) silica content. Pyrex-type borosilicate glasses contain 70 80% silica. (Quartz glassware is used for very special applications.) Aluminosilicate glasses containing calcium and magnesium are used for cookware. There are many naturally occurring aluminosilicate minerals, such as feldspars and zeolites, which contain various combinations of sodium, potassium, and calcium. A variety of other glassy inorganic polymers are known [Ray, 1978]. Polymetaphosphates are linear polymers produced by heating an alkali dihydrogen phosphate (Eq. 2-232).