Ambient temperature SARAATRP for meth(acrylates), styrene, and vinyl chloride using sulfolane/1-butyl-3-methylimidazolium hexafluorophosphate-based mixtures

Abstract

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

Catalytic Halogen Exchange in Supplementary Activator and Reducing Agent Atom Transfer Radical Polymerization for the Synthesis of Block Copolymers

“…A wide variety of monomers, from methyl acrylate (MA) to vinyl chloride (VC), have been polymerized by SARA ATRP. [ 32–42 ]…”

Electrochemically Mediated Aqueous Atom Transfer Radical Polymerization of N,N‐Dimethylacrylamide

“…[16][17][18][19][20][21][22][23][24][25] ATRP is catalyzed by transition metal complexes and many metals have been tested [26] but over the years the process has been refined to use small amounts of copper complexes with polydentate amine ligands. [27] Indeed, techniques such as initiators for continuous activator regeneration (ICAR) ATRP, [28,29] activators regenerated by electron transfer (ARGET) ATRP, [30][31][32][33] supplemental activator and reducing agent (SARA) ATRP, [34][35][36][37][38][39][40] photoATRP, [41][42][43][44] electrochemically mediated ATRP (eATRP), [45][46][47][48][49][50][51][52] mechanoATRP, [53] sono-ATRP [54][55][56][57][58] allowed well-controlled polymerizations with catalyst amounts down to parts per million levels relative to the monomer. Scheme 1 illustrates the mechanism of eATRP catalyzed by Cu complexes with multidentate nitrogen-based ligands (L).…”

“…ATRP is catalyzed by transition metal complexes and many metals have been tested but over the years the process has been refined to use small amounts of copper complexes with polydentate amine ligands . Indeed, techniques such as initiators for continuous activator regeneration (ICAR) ATRP, activators regenerated by electron transfer (ARGET) ATRP, supplemental activator and reducing agent (SARA) ATRP, photoATRP, electrochemically mediated ATRP ( e ATRP), mechanoATRP, sono‐ATRP allowed well‐controlled polymerizations with catalyst amounts down to parts per million levels relative to the monomer.…”

Electrochemically Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate: The Importance of Catalytic Halogen Exchange

“…Since its discovery in 1995, ATRP has witnessed a large number of developments aimed to make the process more efficient, cleaner and more cost‐effective. New techniques such as initiators for continuous activator regeneration (ICAR) ATRP, activators regenerated by electron transfer (ARGET) ATRP, supplemental activator and reducing agent (SARA) ATRP, known also as SET‐LRP, photoATRP, electrochemically‐mediated ATRP ( e ATRP), and mechanoATRP were developed, allowing well‐controlled polymerizations with catalyst amounts down to parts per million levels relative to the monomer.…”