Thermally stable

A unique but widely studied polymeric LB system are the polyglutamates or hairy rod polymers. These polymers have a hydrophilic rod of helical polyglutamate with hydrophobic alkyl side chains. Their rigidity and amphiphilic-ity imparts order (lyotropic and thermotropic) in LB films and they take on a F-type stmcture such as that illustrated in Fig. XV-16 [182]. These LB films are useful for waveguides, photoresists, and chemical sensors. LB films of these polymers are very thermally stable, as was indicated by the lack of interdiffusion up to 414 K shown by neutron reflectivity of alternating hydrogenated and deuterated layers [183]. AFM measurements have shown that these films take on different stmctures if directly deposited onto silicon or onto LB films of cadmium arachidate [184]. 

Shutt J D and Rickert S E 1989 Thermally stable high-field molecular multilayer dielectrics formed from an amphiphilic 2-ring phthalocyanine J. Moi. Eiectron. 5 129-34... 

The processes of distillation and sublimation are closely related. There are three ways in which the vaporisation of a thermally stable substance may take place on heating —... 

In contrast to the 4-hydroxy isomers, the thermally stable 5-hydroxy-THISs add to the C=C bond of cyclopropenylidenes (4. 18, 27. 28). The adducts eliminate carbonyl sulfide, and the strained bond breaks resulting in ring-expansion with formation of pyridin-4-ones. -thiones, or -imines. or 4-alkylidenedihydropvridines (20, X = 0. S.NR. or CRR ) (Scheme 19). 

The main criteria for selecting a stationary phase are that it should be chemically inert, thermally stable, of low volatility, and of an appropriate polarity for the solutes being separated. Although hundreds of stationary phases have been developed, many of which are commercially available, the majority of GLC separations are accomplished with perhaps five to ten common stationary phases. Several of... 

The main difference between field ionization (FI) and field desorption ionization (FD) lies in the manner in which the sample is examined. For FI, the substance under investigation is heated in a vacuum so as to volatilize it onto an ionization surface. In FD, the substance to be examined is placed directly onto the surface before ionization is implemented. FI is quite satisfactory for volatile, thermally stable compounds, but FD is needed for nonvolatile and/or thermally labile substances. Therefore, most FI sources are arranged to function also as FD sources, and the technique is known as FI/FD mass spectrometry. 

Gyclodextrins. As indicated previously, the native cyclodextrins, which are thermally stable, have been used extensively in Hquid chromatographic chiral separations, but their utihty in gc appHcations was hampered because their highly crystallinity and insolubiUty in most organic solvents made them difficult to formulate into a gc stationary phase. However, some functionali2ed cyclodextrins form viscous oils suitable for gc stationary-phase coatings and have been used either neat or diluted in a polysiloxane polymer as chiral stationary phases for gc (119). Some of the derivati2ed cyclodextrins which have been adapted to gc phases are 3-0-acetyl-2,6-di-0-pentyl, 3-0-butyryl-2,6-di-0-pentyl,... 

Furfural is very thermally stable in the absence of oxygen. At temperatures as high as 230°C, exposure for many hours is required to produce detectable changes in the physical properties of furfural, with the exception of color (17). However, accelerating rate calorimetric data shows that a temperature above 250°C, in a closed system, furfural will spontaneously and exothermically decompose to furan and carbon monoxide with a substantial increase in pressure. The pressure may increase to 5000 psi or more, sufficient to shatter the container (18). 

Acetal resins are generally stable in mildly alkaline environments. However, bases can catalyse hydrolysis of ester end groups, resulting in less thermally stable polymer. 

Properly end-capped acetal resins, substantially free of ionic impurities, are relatively thermally stable. However, the methylene groups in the polymer backbone are sites for peroxidation or hydroperoxidation reactions which ultimately lead to scission and depolymerisation. Thus antioxidants (qv), especially hindered phenols, are included in most commercially available acetal resins for optimal thermal oxidative stabiUty. 

L. J. Bement, "AppHcation of Temperature Resistant Explosives to NASA Mission," in Symposium on Thermally Stable Explosives, NOL, White Oaks, Md.,June 1970. 

C2HgNg H4O2P2 (60). The pyrophosphate is reported to be only soluble to the extent of 0.09 g/100 mL water, whereas melamine orthophosphate is soluble to 0.35 g/mL. The pyrophosphate is the most thermally stable. Melamine orthophosphate is converted to the pyrophosphate with loss of water on heating. AH three are available as finely divided soflds. AH are used commercially in flame-retardant coatings (qv) and from patents also appear to have utihty in a wide variety of thermoplastics and thermosets. A detaHed study of the thermal decomposition of the these compounds has been pubHshed (61). 

Antiblaze 1045 contains a larger amount of [42595-49-9]. Both materials are water-soluble thermally stable low volatihty hquids having about 20% phosphoms content and no halogen. 

Photoresist appHcations in the microelectronics industry have also been disclosed (340). Thermally stable ben2yl sulfonate esters based on 2-methyl-3-nitroben2otrifluoride [6656-49-1] can serve as nonionic photoacid generators to promote a cascade of reactions during irradiation of the resist. 

Coloring and Decorating. Commercial pigments that are thermally stable at the resin processing temperature maybe used. Pigments maybe dry-blended with the resin, or ETFE pellets may be blended with color concentrates, which are available ia pellet form. 

Stripes may be appHed to wire coated with ETEE fluoropolymer over DuLite 817-5002 fluoropolymer clear enamel or other bases. Thermally stable pigments are required. Stripes may be appHed by gravure-wheel-type appHcators and oven-cured in-line. 

PVF is more thermally stable than other vinyl halide polymers. High molecular weight PVF is reported to degrade in an inert atmosphere, with concurrent HF loss and backbone cleavage occurring at about 450°C (71,72). In air, HF loss occurs at about 350°C, followed by backbone cleavage around 450°C. 

The synthesis of the high molecular weight polymer from chlorotrifluoroethylene [79-38-9] has been carried out in bulk (2 >—21 solution (28—30), suspension (31—36), and emulsion (37—41) polymerisation systems using free-radical initiators, uv, and gamma radiation. Emulsion and suspension polymers are more thermally stable than bulk-produced polymers. Polymerisations can be carried out in glass or stainless steel agitated reactors under conditions (pressure 0.34—1.03 MPa (50—150 psi) and temperature 21—53°C) that require no unique equipment. 

Catalysis is usually accompHshed through the use of tertiary amines such as triethylenediamine. Other catalysts such as 2,4,6-/m(/V,/V-dimethylaminomethyl)phenol are used in the presence of high levels of cmde MDI to promote trimerization of the isocyanate and thus form isocyanurate ring stmctures. These groups are more thermally stable than the urethane stmcture and hence are desirable for improved flammabiUty resistance (236). Some urethane content is desirable for improved physical properties such as abrasion resistance. 

The ideal high level heat-transfer medium would have excellent heat-transfer capabiUty over a wide temperature range, be low in cost, noncorrosive to common materials of constmction, nondammable, ecologically safe, and thermally stable. It also would remain Hquid at winter ambient temperatures and afford high rates of heat transfer. In practice, the value of a heat-transfer medium depends on several factors its physical properties in relation to system efficiency its thermal stabiUty at the service temperature its adaptabiUty to various systems and certain of its physical properties. 

Synthetic fluids are safe, noncorrosive, essentially nontoxic, and thermally stable when operated under conditions recommended by the manufacturers. Generally, these fluids are more expensive than petroleum oils, but the synthetics can usually be reprocessed to remove degradation products. There are several classes of chemicals offered permitting a wide temperature range of appHcation. Any heat-transfer fluid in use should be examined periodically to monitor degradation or contamination. 

A number of thermally stable polymers have been synthesized, but in general the types of stmctures that impart thermal resistance also result in poor processing characteristics. Attempts to overcome this problem have largely been concentrated on the incorporation of flexible groups into the backbone or the attachment of stable pendent groups. Among the class of polymers claimed to be thermally stable only a few have achieved technological importance, some of which are polyamides, polyimides, polyquin oxalines, polyquinolines, and polybenzimidazoles. Of these, polyimides have been the most widely explored. 

Polyimides (PI) were among the eadiest candidates in the field of thermally stable polymers. In addition to high temperature property retention, these materials also exhibit chemical resistance and relative ease of synthesis and use. This has led to numerous innovations in the chemistry of synthesis and cure mechanisms, stmcture variations, and ultimately products and appHcations. Polyimides (qv) are available as films, fibers, enamels or varnishes, adhesives, matrix resins for composites, and mol ding powders. They are used in numerous commercial and military aircraft as stmctural composites, eg, over a ton of polyimide film is presently used on the NASA shuttle orbiter. Work continues on these materials, including the more recent electronic apphcations. 

Poly(phenylquinoxaline—arnide—imides) are thermally stable up to 430°C and are soluble in polar organic solvents (17). Transparent films of these materials exhibit electrical insulating properties. Quinoxaline—imide copolymer films prepared by polycondensation of 6,6 -meth5lene bis(2-methyl-3,l-benzoxazine-4-one) and 3,3, 4,4 -benzophenone tetracarboxyUc dianhydride and 4,4 -oxydianiline exhibit good chemical etching properties (18). The polymers are soluble, but stable only up to 200—300°C. 

A large variety of bisimides and polymers containing maleimide and citraconimide end groups have also been reported (21—26). Thus polymers based on bisimidobenzoxazoles from the reaction of maleic anhydride and citraconic anhydride with 5-aniino-2-(p-aniinophenyl)benzoxazole and 5-aniino-2(y -aniinophenyl)benzoxazole are found to be thermally stable up to 500°C in nitrogen. 

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