Supported nickel bromide catalyst for Atom Transfer Radical Polymerization (ATRP) of methyl methacrylate

Abstract

A new supported catalytic system, i.e. nickel bromide catalyst ligated by triphenylphosphine (TPP) ligands immobilized onto crosslinked polystyrene resins (PS-TPP) is reported. Per se, this catalyst does not allow any control over the polymerization of methyl methacrylate (MMA) initiated by ethyl 2-bromoisobutyrate but, in the presence of a given amount of purposely added free TPP, it promotes controlled ATRP of MMA. Indeed colorless PMMA chains of low polydispersity indices are readily recovered, the molecular weight of which linearly increases with monomer conversion and agrees with the expected values. Recycling of the supported catalyst is evidenced and does not prevent the polymerization from being controlled.

“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

“…Various supported ATRP catalysts have been utilized. [158][159][160][161][162][163][164][165][166] Often, the support is silica or polySty cross-linked with divinylbenzene, but JandaJel-supported pyridinemethineimine-and DETA-type ligands were also used in the ATRP of Sty, MMA, and DMAEMA. 131,146 JandaJel resins (polySty that is cross-linked with flexible oligoTHF-type linkers) have an improved swellability and site accessibility compared to their poly(Sty-co-divinylbenzene) counterparts.…”

Structural and Mechanistic Aspects of Copper Catalyzed Atom Transfer Radical Polymerization

“…Use of biphasic systems such as fluorous solvents [152,153] 3. Solid supported catalysts [154,155,156,157,158,159,160,161] 4. Development of highly active catalysts based on ligand design [86,87] Perhaps the most significant solution to the problem of catalyst recycling and regeneration in ATRP relies on the use of reducing agents that effectively regenerate copper(I) complex during polymerization [162,163,164,165,166,167] .…”

Cu-based atom transfer radical polymerization of methyl methacrylate using a novel tridentate ligand with mixed donor atoms

“…The study of catalysts has been carried out to develop new ATRP catalysts and understand their catalytic activities using various combinations of transition metals and ligands. Up to now, many transition metals such as Ti (Kabachii et al, 2003), Mo (Le Grognec et al, 2001), Ru (Haas et al, 2006), Ni (Duquesne et al, 2004), Fe (Zhu et al, 2011) and Cu (Sarbu & Matyjaszewski, 2001;Xu et al, 2004;Lee et al, 2005;Pintauer & Matyjaszewski, 2009;Lu et al, 2010) have been successfully used in ATRP of methyl methacrylates Cheng et al, 2013), styrenes (Rusen & Mocanu, 2013), acrylates (Datta et al, 2006), acrylonitriles (Chen et al, 2009) and acrylamides (Wever et al, 2012). However, copper is widely used and intensively studied as copper based ATRP catalysts are found superior in terms of activity, adaptability and cost .…”