Polymerization of methylmethacrylate initiated by hydrogenation catalysts

Abstract

RANEY metals (Ni, Fe, Co), URUSHIBARA metals (Ni, Co) and ULLMA" copper initiate the polymerization of methylmethacrylate. Diamines, diols or organic halides enhance their reactivity.I n the presence of CCl,, the polymerization rate (Rp) is proportional to the square root of the amount of both metals and CCl,, and to the first power of the monomer concentration, but R, becomes constant and independent of the concentration of CCl, when there is a great excess of CCl,.We conclude that this polymerization follows the free radical mechanism and the participation of a zero-valent metal atom in the initiation reaction including complex formation between metal and CCl, is suggested. ZUSAMMENFASSUNG:RAkEY-Metde (Ni, Fe, co), URUSHIBARA-Metaue (Ni, Co) und ULLMANN-Kupfer konnen die Polymerisation von Methylmethacrylat einleiten, wobei die Anwesenheit von Diaminen, Diolen oder organischen Halogenverbindungen die Reaktivitat der genannten Metalle erhoht. I n Gegenwart von CCl, ist die Reaktionsgeschwindigkeit (R,) einerseits proportional der Quadratwurzel der Menge der Metalle und des CCl,, andererseits der ersten Potenz der Konzentration des Monomeren; jedoch wird R, konstant und unabhangig von der Konzentration des CCI,, wenn dieser in groDem OberschuD vorliegt.Es wird geschlossen, dal3 die vorliegende Polymerisation iiber freie Radikale verlauft. E s wird angenommen, daD ein nullwertiges Metallatom bei der Initiierung beteiligt ist, wobei eine Komplexbildung zwischen Metall und CCl, erfolgt.

Single-Electron Transfer Living Radical Polymerization Platform to Practice, Develop, and Invent

“…The Otsu laboratory claimed the first living radical polymerization (LRP) for St and MMA with the Ni(0)/R-X system as a redox iniferter catalyst . As already suggested by Olivé, Iwatsuki, and Otsu, the redox initiation was considered to occur through a SET mechanism where the complex formed between the metal and the organic R-X halide facilitates the ET from the metal donor to the C-X bond of the halide acceptor to produce the primary radical responsible for the initiation of the polymerization.…”

“…Interestingly, under these conditions, MA polymerized in a few minutes at ambient temperature. After these pioneering publications, in addition to Cu(0), − many other zerovalent metals such as V, Cr, Co, ,− Ni, − ,− Sn, , Mn, Ti, and Fe − were reported to serve as redox radical catalytic systems for the initiation of the radical polymerization of vinyl monomers when combined with organic halides. Most of these studies were performed either in bulk or in the presence of nondisproportionation solvents such as benzene or toluene.…”

Single Electron Transfer in Radical Ion and Radical-Mediated Organic, Materials and Polymer Synthesis

“…Raney metals (Ni, Fe, Co) with organic halides including CCl 4 , BnCl, n- C 4 H 9 NCl 2 , t- C 4 H 9 OCl, C 6 H 5 SCl, and CH 3 SiCl 3 were also effective in the polymerization of MMA and Sty . Diamines, diols, and organic halides increase the polymerization rate . Commercially available metals were also used in the polymerization and were compared to activated metals .…”

“…379 Diamines, diols, and organic halides increase the polymerization rate. 380 Commercially available metals were also used in the polymerization and were compared to activated metals. 381 It was found that commercial metals were ineffective in polymerization of MMA or Sty with organohalides in benzene.…”

Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles

“…Raney metals (Ni, Fe, Co) were found to promote the polymerization of MMA in the presence of CCl 4 via a radical intermediate [38]. Otsu and coworkers reported that certain activated metals (e.g., Raney Co, reduced Ni) combined with organic halides (CCl 4 , CHBr 3 , CHI 3 , etc) could induce radical polymerizations of MMA [39][40][41].…”