Effect of ferrocene moieties on the copper‐based atom transfer radical polymerization of methyl methacrylate

The atom transfer radical polymerization (ATRP) of methyl methacrylate catalyzed by copper–tripodal complexes with ferrocene moieties (CuX/TRENFcImine, where X is Br or Cl, and TRENFcImine is tris‐[2‐(ferrocenylmethyleneimino)ethyl]amine) was investigated to understand the effect of redox active moieties on the performance of ATRP catalysts. The CuBr/TRENFcImine system was highly active, with 82% conversion in 2 h. However, the polymerization became slower at higher molar ratios of monomer to catalyst. The polydispersity index was broad, and the initiation efficiency was relatively low. On the basis of the conformational analysis, the highly active and less controlled polymerization was probably caused by the electronic effect rather than the steric effect on the ferrocene moieties, which led to the higher and lower values in the activation and deactivation steps, respectively. The polydispersity index was improved by the addition of CuBr₂, but this led to slower rates of polymerization. The effect of halide groups on ATRP caused a faster rate in the CuBr/TRENFcImine polymerization system than in the CuCl/TRENFcImine system. The higher molar ratio of monomer to catalyst had no significant effect on the CuCl/TRENFcImine system. Nonetheless, the trace of water in the CuCl₂·2H₂O system accelerated the rate of propagation, which led to a higher molecular weight. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The Tracking of a Moving Object by a Mobile Robot Following the Object’s Sound

The tracking of a moving object with a mobile robot has been implemented based on the detected sound from the moving object using a microphone array. The difference between the travel times of the sound source to each of the three microphones mounted to the robot has been used to calculate the distance and orientation of the sound source. The cross-correlations between the received signals have been used to detect the individual sound signal from the object and to calculate the time difference between two signals. This provides reliable and precise time differences among the sound signals arrived at the microphones compared to the conventional method. In order to determine the tracking direction to the sound source, Fuzzy rules have been applied; the results are used for real-time control of the mobile robot. The efficiency of the proposed algorithm has been demonstrated through real-world experiments and compared to the conventional approach.     

Tripodal “click” ligands for copper‐catalyzed ATRP

A series of tris(R‐methyltriazolylmethyl)amines [R = C₆H₅ ( 1 ), 4‐FC₆H₄ ( 2 ), 4‐MeOC₆H₄ ( 3 ), Fc ( 4 )] were prepared and used as ligands for catalytic ATRP of methyl methacrylate (MMA). Despite a lower activity, the CuBr/ 4 catalyst promoted relatively well controlled polymerization compared to CuBr/ 1 , as evidenced by narrower polydispersity indices. Meanwhile, no polymerization activity was observed with CuBr/ 2 and CuBr/ 3 under the catalytic conditions investigated. The CV measurements of CuBr₂ complexes supported 1 and 4 in DMSO showed E_1/2 values of –0.206 and –0.224 V, respectively, confirming the more electron‐rich nature of CuBr/ 4 . Although both CuBr/ 1 and CuBr/ 4 catalysts were only partially soluble in several organic solvents used, kinetic studies revealed a pseudo first order linear plot of ln[M]₀/[M]_t versus time. Addition of CuBr₂ into the polymerization systems led to a decrease in polymer polydispersities and the observed rate constants (k_obs). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013