An efficient, heterogeneous, reusable atom transfer radical polymerization catalyst

Abstract

Melamine based porous polymer (MPP) was prepared as a template solid to incorporate Cu(I) cations into the framework through chelating with nitrogen groups of the melamine. The copper integrated porous material (Cu(I)@MPP) was used as a heterogeneous catalyst and displayed high activity in copper catalyzed atom transfer radical polymerization of methyl methacrylate. The characterization of the Cu(I)@MPP was performed using nitrogen adsorption experiments and wide-angle X-ray and Fourier transform infrared spectroscopies. The atomic absorption spectroscopy measurements confirmed that the catalyst is practically non-leaching and Cu(I) was found to be below 20 ppb after each atom transfer radical polymerization. Moreover, the catalyst showed reusability without any significant change in its activity.

Atom transfer coupling reactions performed with benign reducing agents and radical traps

“…Additional metal reducing agent, often copper metal, is also needed to regenerate the Cu(I) in a disproportionation reaction between copper(0) and Cu(II) . Such issues have led to studies that examine various methods of removing or recycling these metal catalysts . Synthetically, “greener” alternatives have been described that either use markedly smaller quantities of metal or none at all …”

A Process for Well-Defined Polymer Synthesis through Textile Dyeing Inspired Catalyst Immobilization

“…28,29 Silica gel, 30−33 polymeric materials, 32,34,35 and nanoparticles 36,37 have been studied as the supporting matrix for catalyst immobilization, through either physical adsorption or covalent attachment. More recently, porous materials, including metal−organic frameworks 38 and melamine-based porous system, 39 were reported for catalyst incorporation, and they showed good catalytic performance in ATRP. Furthermore, our recent work reported metalloporphyrins supported on cellulosic materials and eosin Y supported on silica nanoparticles as highly efficient heterogeneous catalysts for photoinduced electron/energy transfer reversible addition−fragmentation chain transfer (PET-RAFT) polymerization.…”

“…In controlled/“living” radical polymerization, especially atom transfer radical polymerization (ATRP), transition-metal complexes were largely employed as catalysts. , To recover and recycle the catalyst and prevent coloration of the final polymer caused by the transition metals, supported catalysts have been comprehensively investigated. , Silica gel, − polymeric materials, ,, and nanoparticles , have been studied as the supporting matrix for catalyst immobilization, through either physical adsorption or covalent attachment. More recently, porous materials, including metal–organic frameworks and melamine-based porous system, were reported for catalyst incorporation, and they showed good catalytic performance in ATRP. Furthermore, our recent work reported metalloporphyrins supported on cellulosic materials and eosin Y supported on silica nanoparticles as highly efficient heterogeneous catalysts for photoinduced electron/energy transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. − Despite the promising catalytic performance and recyclability of the immobilized catalysts, the supporting materials and immobilization methodologies are still associated with high preparation costs.…”

High Molecular Weight Poly(methyl methacrylate) Synthesis Using Recyclable and Reusable Zeolitic Imidazole Framework‐8 Catalyst

“…[31] Both homogeneous and heterogeneous catalytic systems have been used for MMA polymerization. [32][33][34][35][36][37][38] However, due to the contamination of the polymer products by homogeneous catalysts, this limits the practical applications of the assynthesized polymer product. [38] Also, 2,2′-Azobis (2-methylpropionitrile), benzoyl peroxide, etc.…”