Photochemical reactions Polymerization, photo

The role of the isomers of 2,4,6-trimethyl-l,3,5-trithiane as co-initiators in benzophenone-induced photopolymerizations was pursued by studying the primary photochemical reactions by nanosecond laser-flash photolysis <2001JPH133> it was found that the polymerization efficiency of the co-initiator did not follow the efficiency of photo induced formation of the initiating radicals however, detailed mechanisms of the various stages of polymerization were proposed <1998JPH21, 1999MM2173, 2001JPH133>. 

Photochemical, Electrochemical, and Radiation Initiation.— In contrast to conventional chemically-induced cationic polymerizations, photo-polymerizations, electro-polymerizations and radiation polymerizations require the application of energy from a source external to the reaction medium. 

Maleic anhydride monomer cont.) oxime adducts, 228 palladium complexes, 213 peracid formation, 246 phenols photochemical reaction, 180 phosphine reactions, 230 phosphite reactions, 206 photo-adduct applications, 213 photo-adduct sterochemistry, 182, 183, 192-194 photochemical dimerization, 188 photochemical polymerization, 195, 239, 241-243, 247, 248... 

Another field of application is the design of polymeric imaging systems. The lithographic potential of a photochemical reaction is based on the possibility of dissolving selectively either the exposed or the unexposed areas of a polymer film. Because aU the photo-Fries products are phenols, the irradiated polyester should be easily dissolved in aqueous base, while the unchanged starting material should remain undissolved. The key photochemical step of this sequence is shown above for the conversion of poly(p-acetoxystyrene) (34) into (35) (Scheme 9). ... 

Chiral crystals generated from non-chiral molecules have served as reactants for the performance of so-called absolute asymmetric synthesis. The chiral environments of such crystals exert asymmetric induction in photochemical, thermal and heterogeneous reactions [41]. Early reports on successful absolute asymmetric synthesis include the y-ray-induced isotactic polymerization of frans-frans-l,3-pentadiene in an all-frans perhydropheny-lene crystal by Farina et al. [42] and the gas-solid asymmetric bromination ofpjp -chmethyl chalcone, yielding the chiral dibromo compound, by Penzien and Schmidt [43]. These studies were followed by the 2n + 2n photodimerization reactions of non-chiral dienes, resulting in the formation of chiral cyclobutanes [44-48]. In recent years more than a dozen such syntheses have been reported. They include unimolecular di- r-methane rearrangements and the Nourish Type II photoreactions [49] of an achiral oxo- [50] and athio-amide [51] into optically active /Mactams, photo-isomerization of alkyl-cobalt complexes [52], asymmetric synthesis of two-component molecular crystals composed from achiral molecules [53] and, more recently, the conversion of non-chiral aldehydes into homochiral alcohols [54,55]. 

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