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The driving force in polymer synthesis is the search for new polymers with improved properties to replace other materials of construction. Polymers are lightweight and can be processed easily and economically into a wide range of shapes and forms. The major synthetic efforts at present are aimed at polymers with high temperature, liquid crystal, conducting, and nonlinear optical properties [Maier et al., 2001; Sillion, 1999]. There is an interrelationship between these efforts as will become apparent. 2-14a Requirements for High-Temperature Polymers
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There has been a continuing and strong effort since the late 1950s to synthesize hightemperature polymers. The terms heat-resistant and thermally stable polymer, used synonymously with high-temperature polymer, refer to a high-performance polymer that can be utilized at higher use temperatures; that is, its mechanical strength and modulus, stability to various environments (chemical, solvent, UV, oxygen), and dimensional stability at higher temperatures match those of other polymers at lower temperatures. The impetus for heatresistant polymers comes from the needs in such technological areas as advanced air- and spacecraft, electronics, and defense as well as consumer applications. The advantages of heat-resistant polymers are the weight savings in replacing metal items and the ease of processing polymeric materials into various con gurations. Lightweight polymers possessing high strength, solvent and chemical resistance, and serviceability at temperatures in excess of 250 C would nd a variety of potential uses, such as automotive and aircraft components
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(including electrical and engine parts), nonstick and decorative coatings on cookware, structural components for aircraft, space vehicles, and missiles (including adhesives, gaskets, composite and molded parts, ablative shields), electronic and microelectronic components (including coatings, circuit boards, insulation), and components such as pipes, exhaust lter stacks, and other structural parts for the chemical and energy-generating (nuclear, geothermal) plants. The synthetic routes studied have involved inorganic and semiinorganic as well as organic systems. The efforts to date have been much more fruitful in the organic systems, which will be discussed in this section. Inorganic and semiinorganic systems will be considered separately in Sec. 2-15. Both chemical and physical factors determine the heat resistance of polymers [Cassidy, 1980; Critchley et al., 1983; Hedrich and Labadie, 1996; Hergenrother, 1987; Marvel, 1975]. The strengths of the primary bonds in a polymer are the single most important determinant of the heat resistance of a polymer structure. This is especially critical with respect to the bonds in the polymer chain. Breakage of those bonds results in a deterioration of mechanical strength due to the drop in molecular weight. Bond breakages in pendant (side) groups on the polymer chain may not be as disastrous (unless it subsequently results in main-chain breakage). Aromatic ring systems (carbocyclic and heterocyclic) possess the highest bond strengths due to resonance stabilization and form the basis of almost all heat-resistant polymers. The inclusion of other functional groups in the polymer chain requires careful choice to avoid introducing weak links into an otherwise strong chain. Certain functional groups (ether, sulfone, imide, amide, CF2) are much more heat-resistant than others (alkylene, alicyclic, unsaturated, NH, OH). A number of other factors weaken or strengthen the inherent heat resistance of a polymer chain. Polymer chains based on aromatic rings are desirable not only because of the high primary bond strengths but also because their rigid (stiff) polymer chains offer increased resistance to deformation and thermal softening. Ladder or semiladder polymer structures are possible for chains constructed of ring structures. A ladder polymer has a double-strand structure with an uninterrupted sequence of rings in which adjacent rings have two or more atoms in common (see structure VII in Sec. 1-2c). A semiladder structure has single bonds interconnecting some of the rings. The ladder polymer is more desirable from the viewpoint of obtaining rigid polymer chains. Also, the ladder polymer may be more heat-resistant since two bond cleavages (compared to only one bond cleavage for the semiladder structure) in the same ring are required before there is a large drop in chain length and mechanical strength. Ladder polymers have been synthesized but have no practical utility because of a complete lack of processability. High molecular weight and crosslinking are desirable for the same reason. Strong secondary attractive forces (including dipole dipole and hydrogen bond interactions) improve heat resistance. Crystallinity increases heat resistance by serving as physical crosslinks that increase polymer chain rigidity and the effective secondary attractions. Branching lowers heat resistance by preventing close packing of polymer chains. The factors that lead to increased heat resistance also present problems with respect to the synthesis of polymers and their utilization. Rigid polymer chains lead to decreased polymer solubility, and this may present a problem in obtaining polymer molecular weights suf ciently high to possess the desired mechanical strength. Low-molecular-weight polymers may precipitate from the reaction mixture and prevent further polymerization. Polymers with highly rigid chains may also be infusible and intractable, which makes it dif cult to process them by the usual techniques into various shapes, forms, and objects. The synthesis of heat-resistant polymers may then require a compromise away from polymer chains with maximum rigidity in order to achieve better solubility and processing properties. There are two general approaches to this compromise. One approach involves the introduction of some
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