Acceleration of the single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride in water at 25 °C

Abstract

The accelerated single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride (VC) in H2O/tetrahydrofuran (THF) at 25 °C is reported. This process is catalyzed by sodium dithionite (Na2S2O4)‐sodium bicarbonate (NaHCO3). Electron transfer cocatalysts (ETC) 1,1′‐dialkyl‐4,4′‐bipyridinum dihalides or alkyl viologens were also employed in this polymerization. The resulting poly(vinyl chloride) (PVC) has a number‐average molecular weight (Mn) = 2,000–12,000, no detectable amounts of structural defects, and both active chloroiodomethyl and inactive chloromethyl chain ends. The molecular weight distribution of PVC obtained is Mw/Mn = 1.5. The surface active agents afford the final polymers as a powder and provide an acceleration of the rate of polymerization. The role of ETC is to accelerate the single electron transfer (SET) step, whereas THF enhances the degenerative chain transfer (DT) step. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6364–6374, 2004

Impact of Competitive Processes on Controlled Radical Polymerization

“…[44][45][46][47] In light of the theory proposed here it may be as a result of the reduced transient radical lifetime that defects, which for vinyl chloride polymerization are largely caused by transfer to polymer, are reduced. In addition, similar polymerizations conducted in aqueous media suggested that chain transfer to the poly(vinyl alcohol) stabilizer employed does not occur.…”

Non‐Oxidative Conversion of 1,2‐Dichloroethane in a Non‐Thermal Plasma and Characterisation of the Polymer Formed

“…A combination of NMR experiments and techniques was undertaken in order to interpret the peaks disclosed in the a) b) [36] The peaks in the region of 3.7-3.9 ppm can be attributed to the CH 2 Cl which is a component of the CH 2 ClCH 2 -group. [36] This group may be introduced in the polymer by the initiator radical or as a result of branching of the polymer.…”

“…[36] This group may be introduced in the polymer by the initiator radical or as a result of branching of the polymer. The peaks in the region of 4.2-4.8 ppm correspond to the main chain CHCl group.…”

Thermal characterization of poly(vinyl chloride) samples prepared by living radical polymerization: Comparison with poly(vinyl chloride) prepared by free radical polymerization

“…5 Nevertheless, the stringent conditions associated to some of these methods have limited the perspectives for widespread of commercial products. After several years of the development, Percec et al discovered a new strategy to polymerize-activated [6][7][8] and nonactivated monomers, [9][10][11] under controlled/ living mechanism in aqueous medium. In addition, this method requires only industrially consumed compounds and lead to a polymer that does not need to be purified.…”