Simple tertiary amines as promotors in oxygen tolerant photochemically induced ATRP of acrylates

Systematic Review on the Effects, Roles and Methods of Magnetic Particle Coatings in Magnetorheological Materials

“…The ATRP process is mainly composed of a monomer, organic halide initiator/retarder, and a catalyst that consists of transition metal species and solvents. Monomers used in ATRP are structural unit compounds that can withstand propagating radicals such as styrenes [ 47 , 75 , 76 , 77 ], (meth)acrylates [ 20 , 70 , 78 , 79 , 80 ], acrylates [ 48 , 81 , 82 , 83 ] acrylonitrile [ 84 , 85 ] and acrylamides [ 86 , 87 ].…”

“…Although there are a few studies that used copper chloride as the catalyst, the former is used more extensively due to higher reduction potentials compared to the latter, which can be attributed to a stronger Cu–Br bond in comparison to the Cu–Cl bond. These catalysts are complex, with aliphatic amine, imine or pyridine based ligand such as sparteine [ 47 , 48 , 76 ], bipyridine [ 79 , 88 , 89 ] or N,N,N’,N”,N”-pentamethyldiethylenetriamine (PMDETA) [ 70 , 81 , 82 , 87 , 90 , 91 ] which improve its solubility in a polymerization mixture and fine-tune its catalytic efficiency.…”

“…Therefore, the molecular weight control is the best when bromine or chlorine is used [ 72 ]. Commonly used initiators are ethyl α-bromoisobutyrate (EBiB) [ 20 , 70 , 78 , 81 , 82 , 89 ], α-bromoisobutyryl bromide (BiBB) [ 70 , 87 , 92 ], methyl 2-bromopropionate [ 48 , 75 , 89 ] and phenylethyl bromide [ 75 , 88 ]. Additionally, it is noted that there could be more than one initiator used in a single polymerization of ATRP.…”

“…The solvent is the final component of the ATRP coating method, which is also important in this polymerization, especially when the obtained polymer is insoluble in its monomer such as polyacrylonitrile. ATRP can be conducted in bulk or in solution with the usage of non-polar solvents, such as toluene, xylene and anisole (methoxybenzene) or polar solvents such as dimethylformamide (DMF) [ 77 , 81 , 84 , 86 ], acetonitrile [ 75 , 81 , 85 ] and dimethyl sulfoxide (DMSO) [ 79 , 81 , 84 ] which are some of the most commonly used solvents in ATRP. However, the type of solvent used must be taken into consideration to minimize the chain transfer to solvent.…”

Oxygen‐Tolerant Photochemically Induced Atom Transfer Radical Polymerization of the Renewable Monomer Tulipalin A

“…Our group showed for the first time that the photoATRP of methyl methacrylate (MMA), and subsequently also methyl and n-butyl acrylate, can be performed using common catalyst/ligand ATRP system without the removal of oxygen from the polymerization mixture, while retaining excellent control over the molecular characteristics. [23] We have described that the mechanism of the oxygen consumption is based on reaction of the tertiary amines with oxidized Cu(II), formed after reaction of reduced copper catalyst with oxygen. The polymerization can then start after some induction period during which all the oxygen is consumed (see Scheme 1).…”