Radiation-initiated

Usually, free-radical initiators such as azo compounds or peroxides are used to initiate the polymerization of acrylic monomers. Photochemical (72—74) and radiation-initiated (75) polymerizations are also well known. At a constant temperature, the initial rate of the bulk or solution radical polymerization of acrylic monomers is first order with respect to monomer concentration and one-half order with respect to the initiator concentration. Rate data for polymerization of several common acrylic monomers initiated with 2,2 -azobisisobutyronittile (AIBN) [78-67-1] have been determined and are shown in Table 6. The table also includes heats of polymerization and volume percent shrinkage data. 

Chlorine Addition. Chlorine addition and some chlorine substitution occurs at normal or slightly elevated temperatures in the absence of catalysts. The chlorination of molten naphthalene under such conditions yields a mixture of naphthalene tetrachlorides, a monochloronaphthalene tetrachloride, and a dichloronaphthalene tetrachloride, as well as mono- and dichloronaphthalenes (35). Sunlight or uv radiation initiates the addition reaction of chlorine and naphthalene resulting in the production of the di- and tetrachlorides (36). These addition products are relatively unstable and, at ca 40—50°C, they decompose to form the mono- and dichloronaphthalenes. 

Anionic polyacrylamide was prepared by gamma radiation-initiated copolymerization of acrylamid with sodium acrylate in aqueous solution at optimum conditions for the copolymerization [17]. The copolymerization process produces water-soluble poly (acrylamide-sodium acrylate [pAM-AANa] of high molecular weight [17,54]. 

Poly(acrylamide-diallylethylamine-HCl) (cationic polyacrylamide pAM-HCl) was prepared by gamma radiation-initiated copolymerization of acrylamide with di-allylethylamine-HCI in aqueous solution at the optimum composition for copolymerization of acrylamide with diallylamine derivatives [61]. 

The y-radiation-initiated sulfoxidation was extensively investigated too, but also in this case there was no further commercial development. 

Beams of electromagnetic radiation of appropriate wavelength ate scattered when they interact with the gradients inherent in stractuied materials. By measuring the ways in which the intensity of scattered radiation varies as a function of the angle at which the radiation initially strikes the sample, the wavelength of the radiation, and the time, many aspects of the stmcture of materials can be inferred. 

Physical properties of carbon black-filled EPR and EPDM elastomers have been found to be comparable with the suUur-cured analogues [372]. Aromatic oils increase the optimum dose requirement for these compounds due to the reaction of the transient intermediates formed during radiolysis of the polymer with the oil as well as energy transfer which is particularly effective when the oil contains aromatic groups. The performance and oxidative stability of unfilled EPDM as well as its blend with PE [373], and the thermal stabdity and radiation-initiated oxidation of EPR compounds are reported by a number of workers [374,375]. 

REMPI provides high detection sensitivity for free radicals similar to that of LIF.4 In the REMPI method, one or more photons typically from a focused laser radiation initially excite the free radicals to an intermediate excited electronic state. The radicals are further excited and ionized by another photon in the same laser pulse (one-color REMPI) or by a photon of different wavelength from another laser beam overlapping in space and time... 

This kind of reaction can proceed in solution by a carbocation mechanism, but in the radiation-induced case, it proceeds almost exclusively by a radical mechanism. In most cases, the radiation initiates reactions that are of chain character. 

Photochemical reactions are initiated by the interaction of a molecule with the local radiation field, perhaps from an embedded star. In cold dark clouds the radiation field may be rather small but as stars begin to form and emit radiation, initially at low energy but of every-increasing energy, photochemistry becomes important in generating a wide variety of reactive species to add to the diversity of species available for the chemical networks. 

The 7-radiation-initiated oxidation of PE at 295 K was accompanied by the formation of both hydroperoxy (1.4 x 10-2 mol kg ) and carbonyl (1.6 x 10-2 mol kg-1) groups [95], The most likely mechanism of their formation is through the consecutive intramolecular isomerization of secondary peroxyl radicals (see Chapter 2). 

The most probable fate of a photon with an energy higher than the binding energy of an encountered electron is photoelectric absorption, in which the photon transfers its energy to the electron and photon existence ends. As with ionization from any process, secondary radiations initiated by the photoelectron produce additional excitation of orbital electrons. 

Chojnowski and co-workers have studied the polymerization of octamethyltetrasila-l,4-dioxane, a monomer more basic than cyclosiloxanes, which is capable of forming more stable oxonium ions, and thus being a useful model to study the role of silyloxonium ions.150-152 In recent work, these authors used Olah s initiating system and observed the formation of oxonium ion and its transformation to the corresponding tertiary silyloxonium ion at the chain ends.153 The 29Si NMR spectroscopic data and theoretical calculations were consistent with the postulated mechanism. Stannett and co-workers studied an unconventional process of radiation-initiated polymerization of cyclic siloxanes and proposed a mechanism involving the intermediate formation of silicenium ions solvated by the siloxane... 

Radiation initiated or photodegradation - free radical reactions (see Chapter 18 on photodegradation and photostabilization of poly (ethylene terephthalate)). 

COP functions on the basis of radiation-initiated crosslinking reactions that result in the formation of interchain linkages which generate a crosslinked, three-dimensional network that is insoluble. The chemistry... 

Therapeutic irradiation is known to have multiple interactions with the vasculature of the irradiated tissue (12). Radiation has direct cytotoxic effects on the vascular endothelium, likely due to induction of oxidative injury. Radiation-induced injury stimulates inflammation and influx of inflammatory cells in addition to creating aprocoagulant state in the vascular space by the transcriptional induction of tissue factor with the subsequent activation of coagulation factors as well as von Willebrand factor and platelets. Experimental evidence suggests that the mechanism by which radiation initiates these responses is in part through the induction of cell-adhesion molecules including ICAM-1, E-selectin, and P-selectin and in part through local cytokine production and release (13). 

The kinetics of radiation-initiated polymerizations follow in a relatively straightforward manner those of photolytic polymerization. The initiation rate is determined by the radiation intensity and the concentration and susceptibility of the compound that radiolyzes to yield the initiating species (ionic and/or radical). The final expression for Rp is determined by the exact details of the initiation, propagation, and termination steps. 

High pressure can have appreciable effects on polymerization rates and polymer molecular weights. Increased pressure usually results in increased polymerization rates and molecular weights. Figure 3-17 shows these effects for the radiation-initiated polymerization of styrene [Moore et al., 1977]. 

Fig. 3-17 Effect of pressure on the polymerization rate (o) and polymer molecular weight (A) of radiation-initiated polymerization of styrene at 25° C. After Moore et al. [1977] (by permission of Wiley-Interscience, New York.)...

The copolymerization of carbonyl monomes with alkenes has been even less studied than that between different carbonhyl monomers. The radiation-initiated copolymerization of styrene with formaldehyde proceeds by a cationic mechanism with a trend toward ideal behavior, r = 52 and r2 = 0 at —78°C [Castille and Stannett, 1966]. Hexafluoroacetone undergoes radiation-initiated copolymerization with ethylene, propene, and other a-olefins [Watanabe et al., 1979]. Anionic copolymerizations of aldehydes with isocyanates have also been reported [Odian and Hiraoka, 1972]. 

Xerogels Ag, Au Two steps (1) gamma radiation initiation of metal-particle growth in a solution containing metal ions and multifunctional silanes (2) xerogels with metal clusters grafted on an oxide network prepared via hydrolysis and condensation 76... 

Trradiation provides a powerful method for modifying polymers, and radiation-initiated processes such as crosslinking and graft coply-merization have attracted considerable interest in past years. Although only a few irradiation processes are currently used in industry, it seems most likely that this field will grow and expand actively in the not-too-distant future. 

The basic mechanisms of radiation-initiated transformations in polymers are far from being completely understood. Most reactions are commonly interpreted on the basis of free radical processes, but other species—e.g., ions, and other reactive intermediates—may play a significant role. A better understanding of the basic reactions occurring in irradiated polymers is required, and this would undoubtedly spur further developments and industrial applications. This paper is devoted to a survey of the different species found in irradiated polymers. Atten-... 

Fernandez, M., L Haridon, J., Gauthier, L. Zoll-Moreux, C. (1993) Amphibian mieronueleus test(s) a simple and reliable method for evaluating in vivo genotoxic effects of freshwater pollutants and radiations. Initial assessment. Mutat. Res., 292, 83-99... 

Wellons, J. D., A. Schindler, and V. Stannett Molecular weight distributions of the side chains of radiation initiated graft copolymers. Polymer 5, 499... 

Usually, free-radical initiators such as azo compounds or peroxides are used to initiate the polymerization of acrylic monomers. Photochemical and radiation-initiated polymerizations are also well known. Methods of radical polymerization include bulk, solution, emulsion, suspension, graft copolymerization, radiation-induced, and ionic with emulsion being the most important. 

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