Free‐radical homopolymerization and copolymerization of vinylferrocene

Abstract

The benzene solution homopolymerization of vinylferrocene, initiated by azobisisobutyronitrile, gave a series of benzene‐soluble homopolymers. Thus, free‐radical copolymerization studies were performed with styrene, methyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and isoprene in benzene. With the exception of vinyl acetate and isoprene, which did not give copolymers with vinylferrocene under these conditions, smooth production of copolymers occurred. The relative reactivity ratios, r1 and r2, were obtained for vinylferrocene–styrene copolymerizations by using the curve‐fitting method for the differential form of the copolymer equation, by the Fineman‐Ross technique, and by computer fitting of the integrated form of the copolymer equations applied to higher conversion copolymerizations. In styrene (M2) copolymerizations, the curve‐fitting and Fineman‐Ross methods both gave r1 = 0.08, r2 = 2.50, while the integration method gave r1 = 0.097, r2 = 2.91. Application of the integration method to methyl acrylate and methyl methacrylate (M2) gave values of r1 = 0.82, r2 = 0.63; r1 = 0.52, r2 = 1.22, respectively. The curve‐fitting method gave r1 = 0.15, r2 = 0.16 for acrylonitrile (M2) copolymerizations. From styrene copolymerizations, vinylferrocene exhibited values of Q = 0.145 and e = 0.47.

Styrene-vinylferrocene random and block copolymers by TEMPO-mediated radical polymerization

“…This results in low molecular weights in a conventional radical polymerization initiated with AIBN (M -n above 12 000 g/mol is rarely described in literature). Also the double bond of vinylferrocene is electron richer, which results in considerably different e-values (e-value (vinylferrocene) = -2.1; evalue (styrene) = -0.8 25) leading to non-ideal/non-azeotropic copolymerization parameters (r vinylferrocene = 0.08; r styrene = 2.63; (r vinylferrocene 6r styrene ) = 0.21; at 70 8C, initiated by AIBN in benzene 25,26) . In summary, the deviations from a controlled radical polymerization observed for the homo-and copolymerization of vinylferrocene in the presence of TEMPO are most likely due to the fact that the vinylferrocene monomer can act as a transfer agent.…”

Grafting of Polymers onto Carbon Microcoil Surface by Ligand-Exchange Reaction of Ferrocene Moieties of Polymer with Polycondensed Aromatic Rings of the Surface

“…22,23 The number-average molecular weight of poly(VFE-co-MMA) and poly(VFE-co-St) was estimated to be 6:5 Â 10 4 and 4:2 Â 10 4 , respectively. The content of ferrocene moieties of poly(VFE-co-MMA) and poly-(VFE-co-St) were determined to be 14 mol % and 7 mol %, respectively.…”

A Vinylanthracene and Vinylferrocene‐Containing Copolymer: A New Dual pH/Sulfide Sensor

“…The electroactive but pH insensitive vinylferrocene (VFc) has been polymerized by cationic [33], anionic [34], free radical polymerization [35], and more recently by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated free radical polymerization [36]. Numerous studies have been reported on the copolymerization of VFc, using 2,2'-azobisisobutyronitrile (AIBN) in organic solvent, with a variety of monomers, such as styrene, methyl methacrylate and isoprene [35].…”