Application of the copper(II)-aminosilane catalysts in the oxidative polymerization of 2,6-dimethylphenol

The aim of this work was to examine the aminosilane ligands for the copper(II) salts and their application as catalysts for the oxidative polymerization of 2,6-dimethylphenol leading to poly(2,6-dimethyl-1,4-phenylene ether) (PPE) [also known as poly(phenylene oxide) (PPO)] formation. As aminosilane ligands, silane derivatives containing primary and/or secondary amino groups were tested. Among aminosilanes used, PPE was only obtained when N-methylaminopropyltrimetoxysilane (MAPTMS) as a ligand for copper(II) was used. CuCl sub(2) and CuBr sub(2) were compared as catalyst precursors for 2,6-dimethylphenol polymerization and influence of N/Cu molar ratio in the range from 80 to 160 on PPE yield and its Mw was tested. It was observed, that with increasing N/Cu molar ratio from 80 to 120, both PPE yield and Mw increased. PPE with the highest Mw was obtained when CuBr sub(2)-MAPTMS as a catalyst was used. At N/Cu molar ratio equal to 160, a decrease in PPE Mw obtained with use of both precursors and decrease in PPE yield for CuCl sub(2)-MAPTMS catalyst were noticed. The condensed nanoorganosilicon particles of spherical shape well dispersed in PPE were determined in the polymer matrix. The UV-Vis studies showed that, strong ligand field of the aminosilane ligand easier electron transfer from monomer to Cu(II) and thus polymerization facilitate.Original Abstract: Silany zawierajace pierwszorzedowa lub/i drugorzedowa grupe aminowa zastosowano w charakterze ligandow w kompleksach soli miedzi(II), ktore nastepnie uzyto w polimeryzacji utieniajacej 2,6-dimetylofenolu (2,6-DMP), w wyniku ktorej otrzymano poli(eter 2,6-dimetylo-1,4-fenylenu) (PPE) znany tez jako poli(tlenek fenylenu) (PPO). Sposrod przebadanych aminosilanow, jedynie N-metyloaminopropylotrimetoksysilan (MAPTMS) - jako ligand Cu(II) - wykazywal aktywnosc w reakcji syntezy PPE. Porownano aktywnosc CuCl sub(2) i CuBr sub(2) jako prekursorow katalizatora polimeryzacji 2,6-dimetylofenolu i zbadano wplyw stosunku molowego N/Cu, w zakresie 80-160, na wydajnosc reakcji otrzymywania PPE i na jego wagowo sredni ciezar czasteczkowy (Mw). Stwierdzono, ze zwiekszenie stosunku molowego N/Cu w zakresie 80-120 powoduje zarowno wzrost wydajnosci polimeryzacji utleniajacej 2,6-DMP, jak i ciezaru czasteczkowego PPE. Polimer o najwiekszym Mw otrzymano przy uzyciu katalizatora CuBr sub(2)-MAPTMS. Przy stosunku molowym N/Cu = 160 zaobserwowano spadek ciezaru czasteczkowego PPE uzyskanego za pomoca obydwu prekursorow oraz, w