“Nascent” Cu(0) nanoparticles‐mediated single electron transfer living radical polymerization of acrylonitrile at ambient temperature

Abstract

Zn(0)/ppm concentrations of CuBr2 from 10 to 50 ppm was firstly used to catalyze radical polymerization of acrylonitrile at ambient temperature. The polymerization displayed typical living radical polymerization (LRP) characteristics, as evidenced by pseudo first‐order kinetics of polymerization, linear increase of number‐average molecular weight, and low polydispersity index (PDI) value. Effects of solvent, copper concentration, and initiator concentration on the polymerization reaction and molecular weight as well as PDI were investigated in detail. EC excelled NMP, DMF, and DMSO in terms of rate of polymerization as well as control of molecular weight and PDI. The increase of the copper concentration from 2.5 to 50 ppm leads to a higher rate of polymerization and a better control over the polymerization reaction. 1H NMR and GPC analyses as well as chain extension reaction confirmed the very high chain‐end functionality of the resultant polymer. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Ex situ Cu(0) nanoparticle mediated SET-LRP of methyl methacrylate/styrene-methyl methacrylate in a biphasic toluene–water system

“…5), there is a peak shi to higher molecular weight aer the extended chain of PMMA (M n , GPC ¼ 76 566 g (Table 1d). Cheng et al 30 observed that there was no polymerization occurred when the concentration of Cu(0) decreases to 2.5 ppm but in the present study, we observed polymerization with monomer conversion of 25 wt% and Đ 1.29 at 0.15 ppm of Cu(0) nanoparticles concentration (Table 1e). Overall by using Cu(0) nanoparticles of 5 nm, polymerization is very fast with good conversion of monomer by using PMDETA and TMHDA as ligands.…”

“…Similar trend was observed when concentration of Cu(0) nanoparticles reduced to 0.75 ppm (Table 1d). Cheng et al 30 observed that there was no polymerization occurred when the concentration of Cu(0) decreases to 2.5 ppm but in the present study, polymerization with monomer conversion of 25 wt% and dispersity (Đ) 1.29 at 0.15 ppm of Cu(0) nanoparticles concentration (entry 1, Table 1e) was observed. Overall by using Cu(0) nanoparticles The results shows that the molecular weight of PMMA increases linearly with conversion, whereas, polydispersity decreases from 1.6 to 1.4 with increasing conversion at 25 C (Fig.…”

“…Among the different N-based ligands such as PMDETA, TMHDA, TMEDA, and DMHA, PMDETA has been considered for the detailed study. 30 The selection of a suitable solvent in SET-LRP is crucial since solvent exerts a strong inuence on the polymerization kinetics. It is well known that dipolar aprotic solvents such as DMSO, DMF, NMP etc.…”

Synthesis of well-defined polyacrylonitrile by ICARATRP with low concentrations of catalyst

“…Procedures employing lower catalyst concentrations for PAN synthesis, including activators regenerated by electron transfer (ARGET), initiators for continuous activator regeneration (ICAR), and supplemental activators and reducing agents (SARA) ATRP ‐ were previously used. For example, the synthesis of PAN by ARGET ATRP resulted in high MW PAN ( M n = 161,300) with a narrow MWD ( M w / M n = 1.18) .…”

Rapid ambient temperature living radical polymerization of methyl methacrylate and styrene utilizing sodium hypophosphite as reducing agent

“…To further follow the polymerization kinetics as well as the evolutions of the molecular weight and molecular weight distributions, the polymerizations of MMA and St mediated by NaH 2 PO 2 ·H 2 O/CuSO 4 ·5H 2 O in DMSO at 25°C were investigated in more detail (Figures and ). Obviously, the polymerization kinetics curves of MMA (Figure a) and St (Figure a) are of first order in monomer conversions, implying the constant radical concentration throughout the polymerization . Moreover, the reactions display rapid rates of polymerizations.…”