Ferrocenyl methacrylate, polymer

The properties of a number of vinyl, acrylate, and methacrylate polymers that incorporate ferrocenyl groups in their sidechains were also examined. " The incorporation of ferrocene moieties into these classes of polymers resulted in materials with glass transition temperatures much higher than that of their organic analogs.For example, radical polymerization of ferrocenyl methylacrylate (16) allowed for the isolation of polymer 17, whose glass transition temperature (Tg) was 197-210°C versus only 3°C for poly(methyl acrylate) (18). 

Gallei M (2014) The renaissance of side-chain ferrocene-containing polymers scope and limitations of vinylferrocene and ferrocenyl methacrylates. Macromol Chem Phys 215 699-704... 

Other ferrocene pendant-containing polymers include polymers such as poly(ferrocenyl methyl acrylate) and poly(ferrocenyl methyl methacrylate) [23]. These polymers have been prepared from the free-radical polymerization of the corresponding ferrocenyl acrylate monomers (Fig. 8.3) [23]. 

There have also been many studies of the polymerization kinetics of organoiron monomers these have shown that such polymerizations often do not follow the same rate laws as organic monomers. Ferrocene-substituted polymethacrylates possessing nonlinear optical (NLO) properties were reported by Wright and coworkers." The copolymerization of the ferrocenyl-fimctionalized monomer (5mol%) 14 with methyl methacrylate 15 yielded the organometaUic polymer 16, as shown in scheme 4." This polymer displayed second-harmonic-generation activity and possessed... 

Sidechain ferrocene-based polymers possessing nonlinear optical properties have been described by Wright and coworkers as shown in Scheme The copolymerization of 5 mol% of the ferrocenyl functionalized monomer 28 with methyl methacrylate 29 resulted in an organometallic polymer (30) displaying second-harmonic-generation activity. The Tg and T values of this organometallic polymer were 120 and 225°C, respectively, which are similar to those of poly(methyl methacrylate). 

Monomer Reactivity and Polymer Synthesis. Monomers la-d were copolymerized with methyl methacrylate (MMA) by free-radical initiation. The monomers were incorporated into the copolymers 6 at the same level as the feed-stock ratio of ferrocenyl monomer/LOlA. The copolymers each had an identical as the respective starting monomer, indicating the NLO-phore was indeed intact. 

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