Atom-Transfer Radical Polymerization of Acrylates in an Ionic Liquid

Abstract

The atom‐transfer radical polymerization (ATRP) of acrylates in 1‐butyl‐3‐methylimidazolium hexafluorophosphate was investigated. The solubility of the acrylates in the ionic liquid depends on the substituent. The homogeneous polymerization of methyl acrylate gives polymers with M̄n close to the calculated value and relatively narrow polydispersity. In heterogeneous polymerizations of higher acrylates, with the catalyst present in the ionic liquid phase, deviations from ideal behavior are observed although the polymerization of butyl acrylate approaches the conditions of a controlled polymerization.

New ionic liquids with hydrolytically stable anions as alternatives to hexafluorophosphate and tetrafluoroborate salts in the free radical polymerization and preparation of ion-conducting composites

“…These intriguing features have stimulated interest in the application of ILs as reaction media in other types of radical polymerization, including the reversible addition-fragmentation chain transfer [28][29][30][31] process, polymerization with atom (atom transfer radical polymerization), [32][33][34][35][36][37][38][39][40][41][42][43][44] group 45 or charge 46 transfer, nitroxide-mediated polymerization 47 and some others. [48][49][50] The majority of published reports 14,15,19,23,29,30,32,34,37,39,51 devoted to polymerization in ILs as reaction media only deals with the investigation of commonly known ILs with fluorinated anions such as tetrafluoroborate, hexafluorophosphate and bis(trifluoromethylsulfonyl)imide ILs. Indeed, such ILs have proven to be very promising reaction media for radical polymerization; they readily dissolve unsaturated monomers and provide access to high molecular weight polymers in good yields.…”

Environmentally Friendly Synthesis of Polymer-Grafted Nanoparticles

“…Moreover, the polymerization product was made copper free by a simple solvent wash, which avoids the contamination of the polymer product by the catalyst. Other atom transfer radical polymerizations in ionic liquids have recently been reported (Sarbu & Matyjaszewski, 2001;Biendron & Kubisa, 2001). In an organic solvent system, after the reaction, the purification and isolation of the resulting nanoparticles was achieved by troublesome procedures, such as filtration and centrifugation as mentioned above.…”

Organostibine‐Mediated Controlled/Living Radical Polymerization of Methyl Methacrylate and Styrene in Ionic Liquidsa

“…Table 1 [16][17][18][19][20][21] or other C/LRP. [22][23][24][25][26][27][28] As the reaction kinetics and rate of DT resemble CRP, the observed acceleration was attributed to the larger rate constant of propagation (k p ), and smaller rate constant of termination (k t ), which were induced by the high polarity and high viscosity of the ionic liquids. [1,17(b), 26] The plots of M n and PDI of the resulting PMMA against conversion in ionic liquids by SBRP are depicted in Figure 2.…”

“…They had been successfully used in conventional free-radical polymerization (CRP), [16][17][18][19][20][21] as well as C/LRPs (ATRP, [22] reverse ATRP, [23] RAFT, [24,25] NMP, [26] Copper(I)-mediated LRP, [27,28] etc.). Compared with the polymerizations in volatile organic solvents (VOSs) or in bulk, polymerizations in RTILs are often affected by the special properties of RTILs, and therefore lead to higher reaction rate and higher molecular weight.…”