Synthesis And Properties Of Novel Ferrocenium Salts Conttaining Phosphorus

Ferrocenium salts is one kind of cationic photoinitiators and the UV-Vis absorption peak can stretch to visible light region. Ferrocenium salts loose the uncharged arene ligand in the process of initiating polymerization. The uncharged ligand may affect the resin properties. In this paper, the novel ferrocenium salts modified by containing phosphorus flame retardant unit were designed to slove the mobility and volatility problem of lignds in resin.Four novel ferrocenium salts containing flame retardant unit9,10-dihydro-9-oxa-10-phosphaphenanthrene10-oxide (DOPO) were synthesized. They were (η6-4-(N-(1-p-hydroxybenzene-l-DOPO) methyl) aminophenoxybenzene)(η5-cyclopentadiene) iron hexafluorophosphate (FCOPH),(η-4-(N-(1-benzene-1-DOPO) methyl) aminophenoxybenzene)(η5-cyclopentadiene) iron hexafluorophosphate (FCOP),(η-4-(1-(4-hydroxyl phenylamino)1-DOPO)methylbiphenyl)(η5-cyclopentadiene) iron hexafluorophosphate (FCPH),(η6-4-(1-phenylamino-1-DOPO)methylbiphenyl)(η5-cyclopentadiene)iron hexafluorophosphate (FCP). These compounds were characterized by IR, MS,1H-NMR and31P-NMR.The cationic photopolymerization initiated by the novel ferrocenium salts containing DOPO unit with iodonium salts and the radical photopolymerization initiated by the the novel ferrocenium salts containing DOPO unit with N-methyl pyrrolidone were studied.The photoinitiating activity of the above two syetems were studied by NIR.The limited oxygen index test (LOI) and thermogravimetric test (TGA) were used to study the properties of the flame retardant and thermal stability of the cured epoxy resins and the epoxy acrylate resins with the ferrocenium salts containing DOPO. It was found the flame retardant of resin were improved only by adding1wt%Fc-P to the resins. The LOI data of epoxy resin were improved from19.2to21.5and the LOI of epoxy acrylate resin was improved from21.2to25.2. In the combustion process, the epoxy acrylate resin show self-extinguish. The char contents of two resin system were also improved.The epoxy resin and the epoxy acrylate resin initiated by Fc-P show good thermostability.(η6-cholobeneze)(η5-cyclopentadiene) iron hexafluorophosphate was found to react with the aryl boronic acid in the mild condition. This Suzuki coupling reaction was used to synthesis the compounds FCPH and FCP in this paper. As a novel reaction, the reaction conditions were optimized and diferent substituent groups of aryl boronic acids coupling with (η6-cholobeneze)(η5-cyclopentadiene) iron hexafluorophosphate werestudied.11kinds of biphenyl derivatives ligand ferrocenium salts were obtained and10kinds of ferrocenium salts were novel compounds.