Addition ferrocene-containing vinyl monomer

Addition polymerization of ferrocene-containing vinyl monomers is probably the earliest preparation method that has been widely studied. Vinylferrocene 1 [5], the first organometallic monomer, was synthesized in 1955 and its polymerization behavior has been extensively studied under radical [5, 6], cationic [7], and Ziegler-Natta conditions [7] it is inert to anionic initiation [8]. 

In addition to samples containing 1% and 5% vinyl ferrocene and a BA/S/MAA control, two additional samples were prepared containing 1% and 5% ferrocene additive (added as solution in monomer mix) since this represented a substantial cost savings in the use of the ferrocene moiety ( 85/lb. for vinyl ferrocene - 5/lb. for ferrocene). All systems processed without difficulty and were carried to 100% conversion within 2-3 hours. No oxidation of the ferrocene moiety was observed, nor were there any conversion rate differences among the five systems. Table I summarizes the five emulsions prepared for this study. 

The attachment of cymantrene groups to polymers has attracted interest for other reasons. Studies have shown, for example, that adherent, abrasion-resistant coatings are formed on metals when thin films of the Mn-containing polymer are subjected to irradiation with UV light. The polymerization of styrene tricarbonylchromium 47 has also been studied.This species is available from the reaction of styrene with Cr(CO)3(NH3)3. Although the Cr monomer 47 resisted attempts at homopolymerization, co-polymerizations with styrene, methyl acrylate, as well as with 41 to yield bimetallic polymers 48 were possible (Equation (17)). In addition, co-polymerization with vinyl-ferrocene afforded co-polymers of low molecular weight (Mn = ca. 4,000). A variety of other organometallic vinyl momomers 49 has been successfully polymerized to yield polymers 50 that contain pendant Gr, W, and Ir carbonyl moieties (Equation (18)). ... 

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