Radiation-induced polymerization free-radical chain initiation

Polymerization of monomer-impregnated concrete was initially carried out with 60Co gamma radiation. A principal advantage of using radiation is that free radical chain reactions can be induced at ambient temperature. This limits vaporization loss and may produce a better concrete-polymer bond. The disadvantages are the dose requirements and the relatively high initial investment required for the radiation source and facility. 

Radiation-Induced Polymerization. Polymerization induced by irradiation is initiated by free radicals and by ionic species. On very pure vinyl monomers, D. J. Metz demonstrated that ionic polymerization can become the dominating process. In Chapter 12 he postulates a kinetic scheme starting with the formation of ions, followed by a propagation step via carbonium ions and chain transfer to the vinyl monomer. C. Schneider studied the polymerization of styrene and a-methylstyrene by pulse radiolysis in aqueous medium and found results similar to those obtained in conventional free-radical polymerization. She attributes this to a growing polymeric benzyl type radical which is formed partially through electron capture by the styrene molecule, followed by rapid protonation in the side chain and partially by the addition of H and OH to the double vinyl bond. A. S. Chawla and L. E. St. Pierre report on the solid state polymerization of hexamethylcyclotrisiloxane by high energy radiation of the monomer crystals. 

Radiation-induced polymerization, which generally occurs in liquid or solid phase, is essentially conventional chain growth polymerization of a monomer, which is initiated by the initiators formed by the irradiation of the monomer i.e., ion radicals. An ion radical (cation radical or anion radical) initiates polymerization by free radical and ionic polymerization of the respective ion. In principle, therefore, radiation polymerization could proceed via free radical polymerization, anionic polymerization, and cationic polymerization of the monomer that created the initiator. However, which polymerization dominates in an actual polymerization depends on the reactivity of double bond and the concentration of impurity because ionic polymerization, particularly cationic polymerization, is extremely sensitive to the trace amount of water and other impurities. 

As described above, the radiolysis of olefinic monomers results in the formation of cations, anions, and free radicals. It is possible for these species to initiate chain polymerizations. Whether radiation-induced polymerization is initiated by radicals, cations, or anions depends on the monomer and the reaction conditions. However, in most radiation-initiated polymerizations, initiating species are radicals [4]. It is usually only at low temperatures that ions are stable enough to react with a monomer [5]. At ambient temperatures... 

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... 

Radiation-induced grafting is a process where, in a first step, an active site is created in the preexisting polymer. This site is usually a free radical, where the polymer chain behaves like a macroradical. This may subsequently initiate the polymerization of a monomer, leading to the formation of a graft copolymer structure where the backbone is represented by the polymer being modified, and the side chains are formed from the monomer (Fig. 1). This method offers the promise of polymerization of monomers that are difficult to polymerize by conventional methods without residues of initiators and catalysts. Moreover, polymerization can be carried out even at low temperatures, unlike polymerization with catalysts and initiators. Another interesting as-... 

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