Radicals, radiation-induce

Effect of high energy radiation This effect is particularly important in the case of organic solids due to the formation of free radicals. Radiation induced polymerisation is also known. 

Hence, in order to ensure a relatively high rate of radiation-induced polymerization in the emulsion, low dose rates (0.1-1 Gy/s) and low absorbed doses are required. For all these reasons, radiation emulsion polymerization is particularly advantageous from an economical standpoint. Its activation energy, just as for other processes of radical radiation-induced polymerization, is 15-35 kJ/mol. The molecular weight of polymers increases with temperature, as in the case of typical free-radical processes (to a certain extent). This increase is due to an increase in kp with temperature, whereas k, does not depend on the temperature. 

A third source of initiator for emulsion polymerisation is hydroxyl radicals created by y-radiation of water. A review of radiation-induced emulsion polymerisation detailed efforts to use y-radiation to produce styrene, acrylonitrile, methyl methacrylate, and other similar polymers (60). The economics of y-radiation processes are claimed to compare favorably with conventional techniques although worldwide iadustrial appHcation of y-radiation processes has yet to occur. Use of y-radiation has been made for laboratory study because radical generation can be turned on and off quickly and at various rates (61). 

Silicone acrylates (Fig. 5) are again lower molecular weight base polymers that contain multiple functional groups. As in epoxy systems, the ratio of PDMS to functional material governs properties of release, anchorage, transfer, cure speed, etc. Radiation induced radical cure can be initiated with either exposure of photo initiators and sensitizers to UV light [22,46,71 ] or by electron beam irradiation of the sample. 

The theory of radiation-induced grafting has received extensive treatment. The direct effect of ionizing radiation in material is to produce active radical sites. A material s sensitivity to radiation ionization is reflected in its G value, which represents the number of radicals in a specific type (e.g., peroxy or allyl) produced in the material per 100 eV of energy absorbed. For example, the G value of poly(vinyl chloride) is 10-15, of PE is 6-8, and of polystyrene is 1.5-3. Regarding monomers, the G value of methyl methacrylate is 11.5, of acrylonitrile is 5.6, and of styrene is >0.69. 

Ionizing radiation is unselective and has its effect on the monomer, the polymer, the solvent, and any other substances present in the system. The radiation sensitivity of a substrate is measured in terms of its G value or free radical yield G(R). Since radiation-induced grafting proceeds by generation of free radicals on the polymer as well as on the monomer, the highest graft yield is obtained when the free radical yield for the polymer is much greater than that for the monomer. Hence, the free radical yield plays an important role in grafting process [85]. 

The creation of active sites as well as the graft polymerization of monomers may be carried out by using radiation procedures or free-radical initiators. This review is not devoted to the consideration of polymerization mechanisms on the surfaces of porous solids. Such information is presented in a number of excellent reviews [66-68]. However, it is necessary to focus attention on those peculiarities of polymerization that result in the formation of chromatographic sorbents. In spite of numerous publications devoted to problems of composite materials produced by means of polymerization techniques, articles concerning chromatographic sorbents are scarce. As mentioned above, there are two principle processes of sorbent preparation by graft polymerization radiation-induced polymerization or polymerization by radical initiators. We will also pay attention to advantages and deficiencies of the methods. 

A thorough consideration of mechanisms of formation of the organometallic products led to the conclusion " that the j5-decay itself must be the cause of the molecule formation. Neither purely mechanical collisiona substitution, nor thermal chemical reactions, nor radical reactions, nor radiation-induced reactions seem to be responsible for the synthesis reactions. 

The theory of radiation-induced grafting has received extensive treatment [21,131,132]. The typical steps involved in free-radical polymerization are also applicable to graft polymerization including initiation, propagation, and chain transfer [133]. However, the complicating role of diffusion prevents any simple correlation of individual rate constants to the overall reaction rates. Changes in temperamre, for example, increase the rate of monomer diffusion and monomer... 

The quantitative aspects of track reactions are involved some details will be presented in Chapter 7. The LET effect is known for H2 and H202 yields in aqueous radiation chemistry. The yields of secondary reactions that depend on either the molecular or the radical yield are affected similarly. Thus, the yield of Fe3+ ion in the Fricke dosimeter system and the initiation yield of radiation-induced polymerization decrease with LET. Numerous examples of LET effects are known in radiation chemistry (Allen, 1961 Falconer and Burton, 1963 Burns and Barker, 1965) and in radiation biology (Lamerton, 1963). 

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. 

Radiation-induced substitution reactions have been reviewed by Wilson (1972) with examples of nitration, nitrosation, sulfochlorination, and others. These generally proceed by a free-radical mechanism. The free radicals are generated by the action of radiation on the reagent, which is present in large excess—for example,... 

Radiation is one of the most important known environmental stimuli of cancer development. This environmental factor becomes especially dangerous for humans living in the areas affected by irradiation from nuclear accidents. Earlier we found that the administration of a mixture of vitamin E and a-lipoic acid to children living in the area of Chernobyl nuclear accident significantly and synergistically suppressed leukocyte oxygen radical overproduction [211]. Thus a-lipoic acid and a-lipoic acid + vitamin E supplements may be of interest as antioxidant preventive agents for the treatment of radiation-induced cancer development. 

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