Abstract
Group 14 (Mt = Sn, Ge, Pb) R3MtX, R4Mt, and R6Mt2 complexes (R = alkyl, aryl; X = H, halide, etc.) are introduced as novel, universal, visible and black light bulb (BLB)/UV photoinitiators for free radical photopolymerization of alkenes, including vinylidene fluoride (VDF), vinyl acetate, methyl methacrylate, styrene, and butadiene. A comprehensive solvent, ligand and metal comparison for VDF indicates progressively faster BLB photopolymerizations in acetonitrile (ACN) ∼ dimethylacetamide (DMAc) < dimethyl sulfoxide (DMSO) < butanone < propylene carbonate < acetic anhydride ∼ cyclohexanone < dimethyl carbonate and especially in the photosensitizing acetone, where Me2SnI2 ∼ Ph3SnI ∼ Bu3Sn–N3 ∼ Bu3Sn–CH2–CH═CH2 ≪ Bu3Sn–S–SnBu3 < Ph4Ge < Ph6Pb2 < Bu3Sn–I < Bu4Sn < Ph6Sn2 < Bu3Sn–Br < Ph6Ge2 < Oct4Sn < Bu4Ge < Bu3Sn–Cl < Ph4Pb < Bu3Sn–H ≪ Bu6Sn2 ≪ Me6Sn2 and where Mn is controlled by solvent chain transfer. Photoinitiation results from a combination of R3Mt·, R·, and solvent (S·, e.g., CH3–CO–CH2·) radicals, ...
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