This miniaccount presents selective examples of our recent discoveries in the photopolymerization of vinyl derivatives using the initiators such as hydrosilanes, poly(hydroarylsilane)s, Cp2M/CX4 (M = Fe, Co, Ni; X = Cl, Br, I), benzoin silyl ethers, and thianthrene cation radical. In the photo-polymerization of vinyl monomers with silanes polysilanes, while the polymerization yields and polymer molecular weights of the poly(MMA)s containing the silyl moieties decreased, the TGA residue yields and intensities of SiH stretching IR bands increased as the mole ratio of the silanes over MMA increased. The hydroarylsilane and poly(hydroarylsilane) seemed to influence strongly on the photopolymerizaiton of olefinic monomers as both chain initiation and chain transfer agents. In the photopolymerization of vinyl monomers using Cp2M/CCl4 (M = Fe, Co, Ni), the photo-polymerization of MMA initiated by Cp2M/CCl4 (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order Cp2Fe > Cp2Ni > Cp2Co, the molecular weight decreases in the order Cp2Co > Cp2Ni > Cp2Fe. For the photohomo-polymerization and photocopolymerization of MA and AA, the similar trends were observed. Furthermore, the photopolymerizations are not living. Benzoin silyl ethers and thianthrene cation radical show the photoinitiating ability in the photopolymerization of MMA. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the miniaccount.
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