Insoluble, characterization

Because pyrrole is so reactive and its homopolymers and copolymers are insoluble, characterization of its graft copolymers is a formidable problem for researchers preparing these materials. 

Alkylselenazoles are oily alkaline liquids possessing a smell similar to that of the corresponding thiazole or pyridine derivatives. The crystalline picrates or 3-methylselenazolium iodides have been used for the purpose of characterization. Alkyl derivatives are partially soluble in water aryl derivatives are insoluble. 

Several early interpretations of the polymerization mechanism have been proposed (1,17,29—31). Because of the complexity of this polymerization and insoluble character of the products, key intermediates have not ordinarily been isolated, nor have the products been characterized. Later work, however, on the resinification of furfural (32,33) has provided a new insight on the polymerization mechanism, particularly with respect to thermal reaction at 100—250°C in the absence of air. Based on the isolation and characterization of two intermediate products (9) and (10), stmcture (11) was proposed for the final resin. This work also explains the color produced during resinification, which always is a characteristic of the final polymer (33). The resinification chemistry is discussed in a recent review (5). 

Bulk Polymerization. The bulk polymerization of acryUc monomers is characterized by a rapid acceleration in the rate and the formation of a cross-linked insoluble network polymer at low conversion (90,91). Such network polymers are thought to form by a chain-transfer mechanism involving abstraction of the hydrogen alpha to the ester carbonyl in a polymer chain followed by growth of a branch radical. Ultimately, two of these branch radicals combine (91). Commercially, the bulk polymerization of acryUc monomers is of limited importance. 

AppHcations of soHd-state nmr include measuring degrees of crystallinity, estimates of domain sizes and compatibiHty in mixed systems from relaxation time studies in the rotating frame, preferred orientation in Hquid crystalline domains, as weU as the opportunity to characterize samples for which suitable solvents are not available. This method is a primary tool in the study of high polymers, zeoHtes (see Molecular sieves), and other insoluble materials. 

In the United States, Hquid HLW from the reprocessing of defense program fuels was concentrated, neutralized with NaOH, and stored in underground, mild steel tanks pending soHdification and geologic disposal (see Tanks AND PRESSURE VESSELS). These wastes are a complex and chemically active slurry. Suspended in the supernatant Hquid are dissolver soHds which never went into solution, insoluble reaction products which formed in the tank, and salts which have exceeded their solubiHty limit. The kinetics of many of the reactions taking place are slow (years) so that the results of characterization... 

Secondary Structure. The silkworm cocoon and spider dragline silks are characterized as an antiparaHel P-pleated sheet wherein the polymer chain axis is parallel to the fiber axis. Other silks are known to form a-hehcal (bees, wasps, ants) or cross- P-sheet (many insects) stmctures. The cross-P-sheets are characterized by a polymer chain axis perpendicular to the fiber axis and a higher serine content. Most silks assume a range of different secondary stmctures during processing from soluble protein in the glands to insoluble spun fibers. 

Mesophase formation in coal-tar pitch is encouraged by a reduction of the natural quinoline-insoluble matter content, which resembles carbon black but is not optically anisotropic and is characterized by an atomic carbon hydrogen ratio of 4 1. In contrast, the atomic carbon hydrogen ratio of mesophase is about 2 1. 

The reddish brown pentachloride, uranium pentachloride [13470-21 -8], UCl, has been prepared in a similar fashion to UCl [10026-10-5] by reduction—chlorination of UO [1344-58-7] under flowing CCl, but at a lower temperature. Another synthetic approach which has been used is the oxidation of UCl by CI2. The pentachloride has been stmcturaHy characterized and consists of an edge-sharing bioctahedral dimer, U2CI2Q. The pentachloride decomposes in H2O and acid, is soluble in anhydrous alcohols, and insoluble in benzene and ethers. 

Emulsion polymerizations of vinyl acetate in the presence of ethylene oxide- or propylene oxide-based surfactants and protective coUoids also are characterized by the formation of graft copolymers of vinyl acetate on these materials. This was also observed in mixed systems of hydroxyethyl cellulose and nonylphenol ethoxylates. The oxyethylene chain groups supply the specific site of transfer (111). The concentration of insoluble (grafted) polymer decreases with increase in surfactant ratio, and (max) is observed at an ethoxylation degree of 8 (112). 

A large number of polymeric substances, (RAs) or (ArAs), are also known (113). They are usually prepared by the reduction of arsonic acids with hypophosphorous acid (100,114) or sodium dithionite (115). Most of these polymers have not been well characterized. An insoluble, purple material, poly(methylarsinidene) [26403-94-1], (CH As), prepared by the interaction of methylarsine and a dihalomethylarsine, however, has been shown by an x-ray investigation to have a ladderlike polymeric stmcture in which the inter-mng distances correspond to one-electron bonds (116) ... 

The only components in a coating powder which might cause the waste to be classified as hazardous are certain heavy-metal pigments sometimes used as colorants. Lead- (qv) and cadmium-based pigments (qv) are seldom used, however, and other potentially hazardous elements such as barium, nickel, and chromium are usually in the form of highly insoluble materials that seldom cause of the spent powder to be characterized as a hazardous waste (86). 

Hydrogels are water-containing polymers, hydrophilic in nature, yet insoluble. In water, these polymers swell to an equiUbrium volume and maintain thek shape. The hydrophilicity of hydrogel is a result of the presence of functional groups such as —NH2, —OH, —COOH, —CONH2, —CONH—, —SO H, etc. The insolubihty and stabiUty of hydrogels are caused by the presence of a three-dimensional network. The scope, preparation, and characterization of hydrogels has been reviewed (107). 

Polyanilines. Initial preparations of polyaniline (PANI) led to insoluble materials that were difficult to characterize. Use of model compounds and polymers (124,125) allowed for definitive stmctural analysis. Poly( phenylene amineimine) (PPAI) was synthesized directiy to demonstrate that PANI is purely para-linked (126). The synthesis was designed so as to allow linkage through the nitrogen atoms only (eq. 9). Comparison of the properties of PPAI and PANI showed PPAI to be an excellent model both stmcturaHy and electronically. 

By far the largest source of phosphorus is phosphate rock, with some use of phosphatic iron ore, from which phosphorus is obtained as a by-product from the slag. Phosphate rock consists of the insoluble tricalcium phosphate and other materials. For use as a fertilizer, phosphate must be converted to the water soluble form, phosphoric acid (H3PO4) which has three hydrogen atoms, all of which are replaceable by a metal. Tricalcium phosphate, is converted to soluble monocalcium phosphate and to superphosphate, A fertilizer factory, typically, a large installation, characterized by large silos produces year round, but peaks with the demands of the growing season. Phosphorus has many uses other than for fertilizer. 

Most niobates and tantalates, however, are insoluble and may be regarded as mixed oxides in which the Nb or Ta is octahedrally coordinated and with no discrete anion present. Thus KMO3, known inaccurately (since they have no discrete MO3 anions) as metaniobates and metatantalates, have the perovskite (p. 963) stmcture. Several of these perovskites have been characterized and some have ferroelectric and piezoelectric properties (p. 57). Because of these properties, LiNb03 and LiTa03 have been found to be attractive alternatives to quartz as frequency filters in communications devices. 

Iodide ions reduce Cu to Cu , and attempts to prepare copper(ll) iodide therefore result in the formation of Cul. (In a quite analogous way attempts to prepare copper(ll) cyanide yield CuCN instead.) In fact it is the electronegative fluorine which fails to form a salt with copper(l), the other 3 halides being white insoluble compounds precipitated from aqueous solutions by the reduction of the Cu halide. By contrast, silver(l) provides (for the only time in this triad) 4 well-characterized halides. All except Agl have the rock-salt structure (p. 242). Increasing covalency from chloride to iodide is reflected in the deepening colour white yellow, as the... 

The literature of polyimines is extensive [164-173]. A number of researchers have tried to synthesize high molecular weight polymers but failed due to poor solubility in organic solvents. Polyimines are of great interest because of their high thermal stability [174-176], ability to form metal chelates [174-177], and their semiconducting properties [178-181]. Due to insolubility and infusibility, which impeded characterization of the molecular structure, the application of these polymers is very limited and of little commercial importance. 

Unsubstituted poly(/ -phenylene) PPP 1 as a parent system of a whole class of polymers is an insoluble and intractable material, available by a variety of synthetic methods [3, 4]. The lack of solubility and fusibility hinders both unequivocal characterization and the processing of PPP 1. Moreover, the intractability of unsubstituted PPP materials has thwarted any serious commercial development of the polymer. 

Unsubstituted OPV5 (u-OPV5) was synthesized in a Wittig-Horncr reaetion from 4-styrylbcnzaldchydc and tetraethyl-11,4-phenylene-bis(melhylene) -biphosphonate in DMF/THF (see Fig. 16-6). The yellow crystalline solid obtained appeared to be insoluble in common solvents. It was characterized by mass spectrometry M+=486.64. 

This compound has been investigated by several groups,379- 384 but due to its practical insolubility it has not been fully characterized. Another approach to obtain phthalocyanine network polymers is with the use of crown ethers385 or other groups like di oxy -para-p h enyle n e3 8 6 as bridging units between the macrocycles. Some attempts to obtain metal phthalocyanine substructures arranged as ladder polymers have also been proposed (see below).344... 

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