Polymerization of conjugated 5-[(5-ethynyl-1-naphthyl)ethynyl]-N,N-dimethylnaphthalen-1-amine with rhodium and palladium complexes

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2007-05, Vol.45 (10), p.2038-2047
• Main Authors: Rodríguez, J. Gonzalo, Tejedor, Jose Luis
• Format: Article
• Language: English
• Subjects: 5-[(5-ethynyl-1-naphthyl)ethynyl]-N; 5-diene) catalyst; 5‐[(5‐ethynyl‐1‐naphthyl)ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine; Applied sciences; bis(rhodium chloride cycloocta-1; bis(rhodium chloride cycloocta‐1,5‐diene) catalyst; catalysis; Exact sciences and technology; fluorescence; N-dimethylnaphthalen-1-amine; Organic polymers; Pd/Me3SiCl; Physicochemistry of polymers; polyaromatics; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Sonogashira reaction; structure of the polymers
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.21969

The monomer 5‐[(5‐ethynyl‐1‐naphthyl)ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine was satisfactory obtained through the heterocoupling reaction of 5‐ethynyl‐N,N‐dimethylnaphthalen‐1‐amine and 4‐(5‐iodo‐1‐naphthyl)‐2‐methyl‐3‐butyn‐2‐ol catalyzed by a palladium–copper system, followed by acetone elimination. Poly{5‐[(5‐ethynyl‐1‐naphthyl)ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine} was obtained through the reaction of the acetylene monomer with homogeneous rhodium and palladium catalyst complexes. The structure of the polymers always showed a trans–cisoidal chain configuration on the basis of IR and NMR spectra. Moreover, only for the rhodium catalyst complex in methanol was a dimeric product isolated in a very low yield, having a conjugated terminal ene–yne structure, which permitted the consideration of a metallated chain‐transfer intermediate in the polymer propagation. The mass determination of the polymers, by osmometry and gel permeation chromatography techniques, showed low average molecular weights. The kinetics of the catalyzed polymerization were analyzed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2038–2047, 2007 The monomer 5‐[(5‐ethynyl‐1‐naphthyl)ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine was satisfactory obtained through the heterocoupling reaction of 5‐ethynyl‐N,N‐dimethylnaphthalen‐1‐amine and 4‐(5‐iodo‐1‐naphthyl)‐2‐methyl‐3‐butyn‐2‐ol catalyzed by a palladium–copper system, followed by acetone elimination. Poly{5‐[(5‐ethynyl‐1‐naphthyl) ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine} was obtained through the reaction of the acetylene monomer with homogeneous rhodium and palladium catalyst complexes. The structure of the polymers always showed a trans–cisoidal chain configuration on the basis of IR and NMR spectra. Moreover, only for the rhodium catalyst complex in methanol was a dimeric product isolated in a very low yield, having a conjugated terminal ene–yne structure, which permitted the consideration of a metallated chain‐transfer intermediate in the polymer propagation. The mass determination of the polymers, by osmometry and gel permeation chromatography techniques, showed low average molecular weights. The kinetics of the catalyzed polymerization were analyzed.