Ferrocene-functionalized polymer copolymer

Graphical representation of the preparation of ferrocene-functionalized polymer brushes grafted on gold nanoparticles via SI-ROMP. (Reprinted with permission from Watson et at. 1999. Hybrid nanoparticles with block copolymer shell structures. Journal of the American Chemical Society 121 (2) 462-463, copyright (1999) American Chemical Society.)... 

Pittman and coworkers reported a number of ferrocene-functionalized polymers in the 1960s and 1970s that not only included the synthesis but also the properties of these polymers. " In particular, the bulk and solution polymerization of vinylferrocene along with the physical, chemical, and electrical properties of many polymers and copolymers were studied. The copolymerization of vinyl-ferrocene with styrene was reported by Frey and co-workers in 1999, using living radical initiator 2,2,6,6-tetramethyl-l-pyperidinyl-l-oxy (TEMPO). The polymers obtained by this method were block copolymers with narrow polydis-persities. 

Ferrocene-containing polymers with long spacers have been prepared as new nonlinear optical (NLO) materials for second harmonic generation (SHG) applications (e. g. frequency doubling) [10], The use of ferrocene derivatives in this area is attractive as a result of their demonstrated large hyperpolarizability values combined with their thermal and photochemical stabilities [11], These factors make polyferrocenes desirable candidates for use as processable NLO materials. The polyurethane copolymer 4.4 was synthesized using a functional ferrocene monomer (Eq. 4.1) and has been well-characterized the molecular weight was estimated by GPC to be Mn=7600. The two possible orientations of the ferrocene NLO chromophore monomer unit, which correspond to opposite dipole orientations, were both present in the main chain. 

Copolymerization reactions with ferrocenophanes using transition metal catalysts have also been accomplished. The self-assembly of block copolymers has been examined, and polymers with dimethylsiloxane or ethyleneoxide blocks have been found to be soluble in aqueous solution. These ferrocene-based polymers have been found to self-assemble in solution, and their morphologies have been investigated. A number of water-soluble anionic (26) and cationic (27) polyelectrolytes have also been produced by sidechain functionalization. 

Polyphosphazenes with simple alkyl and aryl substituents directly attached to the backbone by P-C linkages can be prepared by the condensation polymerization of N-silylphosphoranimine precursors. These simple polymers can then be converted to a variety of functionalized polyphosphazenes by derivatization reactions. In this paper, the synthesis and characterization of some derivatives of poly(methylphenyl-phosphazene), [Me(Ph)P=N]and the copolymer, [Me(Ph)P=N]j [Me2P=N)y, are discussed. These polymers include grafted copolymers, water soluble carboxylated polymers, and polymers with silyl, vinyl, alcohol, ester, ferrocene, phosphine, thiophene, and/or fluoroalkyl groups. 

---