Synthesis of poly(4‐vinylpyridine) by reverse atom transfer radical polymerization

Abstract

Controlled radical polymerization of 4‐vinylpyridine (4VP) was achieved in a 50 vol % 1‐methyl‐2‐pyrrolidone/water solvent mixture using a 2,2′‐azobis(2,4‐dimethylpentanitrile) initiator and a CuCl2/2,2′‐bipyridine catalyst–ligand complex, for an initial monomer concentration of [M]0 = 2.32–3.24 M and a temperature range of 70–80 °C. Radical polymerization control was achieved at catalyst to initiator molar ratios in the range of 1.3:1 to 1.6:1. First‐order kinetics of the rate of polymerization (with respect to the monomer), linear increase of the number–average degree of polymerization with monomer conversion, and a polydispersity index in the range of 1.29–1.35 were indicative of controlled radical polymerization. The highest number–average degree of polymerization of 247 (number–average molecular weight = 26,000 g/mol) was achieved at a temperature of 70 °C, [M]0 = 3.24 M and a catalyst to initiator molar ratio of 1.6:1. Over the temperature range studied (70–80 °C), the initiator efficiency increased from 50 to 64% whereas the apparent polymerization rate constant increased by about 60%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5748–5758, 2007

Zinc (II), palladium (II) and cadmium (II) complexes containing 4‐methoxy‐N‐(pyridin‐2‐ylmethylene) aniline derivatives: Synthesis, characterization and methyl methacrylate polymerization

“…Similarly, compared with previous Zn (II) complexes with N ‐(pyridin‐2‐ylmethylene) aniline and N ‐phenyl‐(pyridin‐2‐yl)methanimine, current Zn (II) systems effectively catalyzed MMA polymerization. The Cd (II) complexes, [(L‐c)Cd(μ ‐ Br)Br] 2 and [(L‐c)Cd(μ ‐ Br)Br] 2 , exhibited lower activities compared with our previously reported Cd (II) complexes bearing N , N ‐di(2‐picolyl) amine ligand, but resulted in high molecular weight PMMA with improved T g (Table ). Moreover, the PDIs of the resultant PMMA ranged from 2.40 to 2.96, which is in agreement with the fact that the PDI range narrowed with increasing molecular weights .…”

Synthesis and structural characterisation of tetrahedral zinc(II) and trigonal bipyramidal cadmium(II) complexes containing N′-cyclohexyl substituted N,N-bispyrazolyl ligand

“…The PDI range was slightly narrow when the molecular weight of PMMA increased. These results are explained by the narrower PDI range of the highermolecular-weight polymer [63,64].…”

Quaternary Ammonium Compounds

“…Poly(vinyl pyridines) are particularly studied in the academia to demonstrate the applicability of polycations in antimicrobial coatings [ 40 ] . They are readily accessible via alkylation of commercially available poly(vinyl pyridine), forming poly(vinyl pyridinium chloride) (Scheme 15.3 ).…”