Controlled Radical Polymerization of Styrene by Quinone Transfer Radical Polymerization (QTRP)

Abstract

Radical polymerization of styrene falls under control when conducted at 100 °C in the presence of an ortho-quinone, e.g., phenanthrenequinone (PhQ), and a catalytic amount of cobalt(II) acetylacetonate. Criteria for a controlled chain polymerization are fulfilled at least until 50% of monomer conversion, i.e., molar mass increasing with monomer conversion, molar mass predictable from the styrene/quinone molar ratio, linear time dependence of ln([M]0/[M]), and effective resumption of styrene polymerization by preformed oligopolystyrene. A tentative mechanism is proposed for this new system designated as quinone transfer radical polymerization (QTRP).

Mechanistic Insights into the Cobalt‐Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(III) Adducts as Initiators

“…Three main techniques of controlled radical polymerization (CRP) have emerged: atom-transfer radical polymerization (ATRP), [2,3] reversible addition-fragmentation chain transfer (RAFT), [4][5][6][7][8] and stable free-radical polymerization (SFRP). [9][10][11][12] Other systems must also be mentioned, [13][14][15][16][17][18] with special emphasis on the so-called "organometallic radical polymerization" (OMRP). [19] In this context, cobalt complexes [20][21][22][23][24][25] proved highly efficient in mediating the radical polymerization of vinyl monomers, particularly of "nucleophilic" monomers, the radical polymerization of which is not prone to control.…”

Hip bone density predicts breast cancer risk independently of Gail score

“…Up to date, several CRP methods have been well developed, includes atom transfer radical polymerization (ATRP),4–7 nitroxide‐mediated polymerization,8, 9 and degenerative transfer with dithioesters via reversible addition‐fragmentation chain transfer polymerization 10, 11. Some novel CRP methods have been invented, such as iodine transfer polymerization,12, 13 Te‐, Sb‐, and Bi‐mediated radical polymerizations,14, 15 quinone transfer radical polymerization,16 reversible chain transfer catalyzed polymerization,17 and single electron transfer‐living radical polymerization (SET‐LRP) 18–34. Among them, SET‐LRP has shown distinct advantages over other CRPs since its emergence in 2006 by Percec et al,18 including mild reaction conditions (room temperature or below), a small quantity of catalyst, ultrafast polymerization, and resultant of high‐molecular weight polymers with low polydispersity.…”

Synthesis and Evaluation of New Dicarboxylic Acid Functional Trithiocarbonates: RAFT Synthesis of Telechelic Poly(n-butyl acrylate)s

“…Of particular note is the discovery and development of the controlled/living free radical polymerization techniques. For example, stable free radical polymerization (SFRP), best exemplified by nitroxide-mediated systems (NMP), − atom transfer radical polymerization (ATRP), , reversible addition−fragmentation chain transfer (RAFT) polymerization, − tellurium-mediated radical polymerization (TERP), − and quinone transfer radical polymerization (QTRP), are all versatile techniques for the preparation of well-defined polymers in a controlled fashion, although both TERP and QTRP have not yet been widely evaluated. Of these techniques, RAFT is arguably the most versatile, at least with respect to monomer choice.…”