This paper describes the room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator. The disproportionation reaction 2CuI + L --> Cu0 + CuII(L) is the crucial step, as it continuously provides the active species for both the initiation (Cu0) and the reversible termination step (CuII). Mn was found to increase linearly with conversion and is in good agreement with Mth, with the Mw/Mn being approximately 1.5.

The first example of living radical polymerization of vinyl chloride carried out in water at 25 °C is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu0 produced by the disproportionation of CuI in the presence of strongly CuII binding ligands such as tris(2‐aminoethyl)amine or polyethyleneimine. The resulting poly(vinyl chloride) was free of structural defects, had controlled molecular weight and narrow molecular weight distribution, contained two ∼CHClI active chain ends, and had a higher syndiotacticity (62%) than the one obtained by conventional free‐radical polymerization at the same temperature (56%). This novel polymerization proceeds, most probably, by a combination of competitive pathways that involves activation by single electron transfer mediated by nascent Cu0 and degenerative chain transfer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3283–3299, 2003

Non‐transition metal‐catalyzed living radical polymerization (LRP) of vinyl chloride (VC) in water at 25–35 °C is reported. This polymerization is initiated with iodoform and catalyzed by Na2S2O4. In water, S2O dissociates into SO that mediates the initiation and reactivation steps via a single electron transfer (SET) mechanism. The exchange between dormant and active propagating species also includes the degenerative chain transfer to dormant species (DT). In addition, the SO2 released from SO during the SET process can add reversibly to poly(vinyl chloride) (PVC) radicals and provide additional transient dormant ∼SO radicals. This novel LRP proceeds mostly by a combination of competitive SET and DT mechanisms and, therefore, it is called SET‐DTLRP. Telechelic PVC with a number‐average molecular weight (Mn) = 2,000–55,000, containing two active ∼CH2CHClI chain ends and a higher syndiotacticity than the commercial PVC were obtained by SET‐DTLRP. This PVC is free of structural defects and exhibits a higher thermal stability than commercial PVC. SET‐DTLRP of VC is carried out under reaction conditions related to those used for its commercial free‐radical polymerization. Consequently, SET‐DTLRP is of technological interest both as an alternative commercial method for the production of PVC with superior properties as well as for the synthesis of new PVC‐based architectures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6267–6282, 2004

Sodium dithionite in the presence of NaHCO 3 in water acts as a singleelectron-transfer agent and facilitates the single-electron-transfer/degenerative-chaintransfer mediated living radical polymerization (SET-DTLRP) of acrylates initiated with iodoform at room temperature. The resulting ␣,-di(iodo)polyacrylates can be used as macroinitiators for the SET-DTLRP of other acrylates. Ultrahigh-molar-mass poly-(tert-butyl acrylate) can be synthesized via the SET-DTLRP of tert-butyl acrylate and has a very low weight-average molecular weight/number-average molecular weight ratio of 1.15.

The new generation of catalytic systems for Controlled/"Living" Radical Polymerization (CLRP) of vinyl monomers should be non-toxic, inexpensive and provide fast polymerizations in environmentally friendly media. Herein, we report the successful ambient temperature ATRP of several vinyl monomers (MA, n-BA, MMA and DMAEMA) catalyzed by inorganic sulfites (Na S O and Na S O) and small amounts of a Cu(II)Br /Me TREN system in alcohol-water mixtures. The