Supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) of acrylates, methacrylates, styrene and vinyl chloride was successfully performed in sulfolane/water mixtures using ppm amounts of soluble copper.

Inorganic sulfites as reducing agents were successfully used in combination with typical reversible addition-fragmentation chain transfer (RAFT) agents, for the controlled DET-RAFT (DET: dissociative electron transfer) of methacrylates, methyl acrylate (MA) and styrene (Sty) near room temperature (30 °C). The polymerizations were first-order in respect to monomer conversion and polymers with narrow molecular weight distributions (Ð < 1.2) and "living" features were obtained. MALDI-TOF experiments demonstrate the integrity of the chain ends and clearly show the absence of SO2 in the polymer chains. Kinetic studies revealed that an increase of either temperature or concentration of sulfites provided faster reactions, without loss of control. Ab initio quantum chemistry calculations suggested that in the presence of the reducing agent, the RAFT agent undergoes one electron reduction to a stable radical anion that can then undergo fragmentation to yield the initiating carbon-centered radical. The new metal-free DET-RAFT developed proved to be versatile and robust, as it could be also used for the polymerization of different relevant monomers, such as glycidyl methacrylate (GMA), 2-(diisopropylamino)ethyl methacrylate (DPA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA).

Cyclopentyl methyl ether (CPME) was successfully used as an environmentally friendly alternative to regularly employed organic solvents (e.g., THF, DMSO, DCM and DMF) for the RAFT and NMP polymerizations of vinyl chloride (VC) and styrene (S).

A new green solvent, cyclopentyl methyl ether (CPME), is used for the first time in solvent mixtures for the successful supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) of both activated and non‐activated monomers. The SARA ATRP of methyl acrylate (MA), glycidyl methacrylate (GMA), styrene (Sty), and vinyl chloride (VC) in CPME‐based mixtures is studied and presents similar features to those reported in the literature using other SARA ATRP systems. Moreover, CPME‐based mixtures are suitable solvents for the controlled SARA ATRP of MA using different SARA agents, such as Fe(0), Cu(0), or Na2S2O4. The chemical structure and the retention of the chain‐end functionality of the polymers are confirmed by 1H NMR and MALDI‐TOF analyses and the preparation of a well‐defined PMA‐b‐PVC‐b‐PMA triblock copolymer. The method reported here presents an additional improvement in the search for new ecofriendly ATRP systems. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2722–2729

The supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) of methyl acrylate (MA) in DMSO/ BMIM-PF 6 /glycol mixtures (DMSO, dimethyl sulfoxide; BMIM-PF 6 , 1-butyl-3-methylimidazolium hexafluorophosphate) near room temperature (30 °C), using different SARA agents, is reported. The unusual "hyperpolarity" effect within the solvent mixture allowed very fast and controlled polymerizations (Đ < 1.1) during the entire reaction time. Remarkably, the replacement of DMSO by water in the reaction mixture led to a "flash" polymerization with monomer conversion reaching 92% in only 11 min (degree of polymerization, 222), yet still affording good control over the polymerization.

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The supplemental activator reducing agent atom transfer radical polymerization (SARA ATRP) with catalytic system composed of Cu(0) and CuBr2/Me6TREN at room temperature using different sulfolane/co‐solvent‐based mixtures is reported. Three different co‐solvents were studied: 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIM‐PF6), water, and tetraethylene glycol (TEG). The results revealed a synergistic effect between sulfolane and BMIM‐PF6, which enhanced the polymerization rate several times while maintaining a stringent control over the polymerization. The catalytic system was used as proof‐of‐concept for the SARA‐ATRP of methyl methacrylate (MMA), styrene (Sty), and vinyl chloride (VC). The addition of 10% of water (or TEG) to the sulfolane/BMIM‐PF6 mixture resulted in fast polymerization rates. The results presented in this manuscript highlight the importance of the sulfolane as an universal industrial solvent for SARA‐ATRP of different monomer families. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1322–1328

A new solvent mixture, based on ethanol/reline (EM: eutectic mixture), was investigated for the supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) of methyl acrylate (MA) near room temperature, for the first time, affording complete catalyst recovery and reuse. The kinetic results revealed that the polymerizations were controlled, with polymers having narrow molecular weight distributions ( -D < 1.2). The "living" character of the resultant PMA was confirmed by the synthesis of a welldefined PMA-b-PBA block copolymer. Remarkably, it was demonstrated that the Cu(0)/CuBr 2 /Me 6 TREN (Me 6 TREN: tris[2-(dimethylamino)ethyl]amine) could be recovered from the final reaction mixture and reused for new successful SARA ATRP of MA, suggesting that the reported system could be very attractive from both the economic and environmental perspectives.