Electropolymerization of 2-methacryloyloxy(ethyl) acetoacetate on aluminum using a novel initiation method

Abstract

Electropolymerization has been used as a method to form polymers on graphite fibers and metals. Most of the previous studies have involved either the use of sulfuric acid as an initiator or direct reduction or oxidation of monomers to form the polymers. In this article, ␣-bromoisobutyronitrile (BrIBN) was used as a new electrochemical initiator to form polymer coatings on an aluminum cathode. The reduction of BrIBN on a glassy carbon electrode was examined using cyclic voltammetery. It was found that BrIBN could be reduced to isobutyronitrile radicals at potentials below the reduction potential of water. The reduction behavior of BrIBN was found to be similar in aqueous, semiaqueous, and nonaqueous solutions. 2-Methacryloyloxy(ethyl) acetoacetate was then electropolymerized on aluminum using the BrIBN as the initiator and lithium perchlorate as a supporting electrolyte. Defect-free coatings were formed at half-cell potentials of less than Ϫ1.20 V. The effect of various process variables on the polymerization kinetics under potentiostatic conditions is reported. The coating thickness increased with polymerization time, monomer concentration, and initiator concentration. A strong dependence of thickness on monomer concentration was observed. As expected, there was weak dependence on the initiator concentration.

Electropolymerised acrylic coatings for polymer-metal adhesion enhancement

“…Secondly, a number of acrylic monomers are water soluble (for example, acrylamide, acrylic acid and, to a small degree, methyl methacrylate). Finally, there are a number of examples in the literature of the electropolymerisation of acrylic monomers from aqueous electrolytes [1,[14][15][16][17][18][19][20][21][22] to form cathodic coatings on metals. Despite this interest, no published work could be found on the testing of these lms as adhesion promoting tie-layers to metal substrates.…”

Pd0‐ and Au0‐Nanoparticles Catalyze the Reduction of Perchlorate by ·C(CH3)2OH Radicals

“…The maximal yield of H 2 under these conditions is: [46,47,51,52,58] where G[·C(CH 3 ) 2 OH] = G(eaq. ) + G(·H) + G(·OH); see Reactions (12)(13)(14). The somewhat smaller yields observed, mainly at low doses, are usually attributed to the reduction of oxides on the surface of the NPs and/or to nonreduced metal cations adsorbed on the NPs.…”

“…Clearly, in neutral aqueous solutions, O ·will be transformed into ·OH, and C(CH 3 ) 2 OH + will be transformed into C(CH 3 ) 2 O + H + , and these transformations will increase the free-energy gain and initiate a chain reaction, as the ·OH radicals will react with 2-propanol [Reaction (13)], which undoubtedly was not observed. Notably, the calculations indicate that ClO 4…”

“…+ ClO 4 – ) < 1 × 10 6 m –1 s –1 . Perchlorate is often used as the supporting electrolyte in systems that require significant cathodic potentials;, however, it was recently reported that perchlorate is reduced on some electrodes, and therefore, its use as a supporting electrolyte is not safe . A variety of processes to remove perchlorate from water have been developed owing to the environmental importance .…”

Enhanced electrochemical performance of Lithium-ion batteries by conformal coating of polymer electrolyte

“…It can be noted that the electrochemical-assisted polymerization process is a convenient and versatile approach. Indeed, the polymer formation can be achieved by different mechanisms involving the formation of free-radical intermediates, the activation by light, the use of initiator, and the direct oxidation or reduction of monomer as it has been reported for poly(para-phenylene)vinylene (PPV) [ 18 ], polypyrrole (PPy) [ 19 ], poly(2-methacryloyloxy(ethyl) acetoacetate) [ 20 ], and poly(sulfonated phenol) [ 21 ], respectively.…”