Synthesis of poly(2,6-dimethyl-1,4-phenylene oxide) derivatives in water using water-soluble copper complex catalyst with natural ligands

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) was synthesized by oxidative polymerization of 2,6-dimethylphenol (DMP) using a water-soluble copper complex catalyst under oxygen and with natural ligands in alkaline water. Arginine, guanine, adenine, cytosine, histidine, and folic acid were used as ligands for the copper complex. Arginine performed the best, with a yield of 72%, a number-average molecular weight (Mn) of 4400, and a molecular weight distribution (Mw/Mn) of 1.7. It was then used to optimize reaction conditions. Surfactants, temperature, and sodium hydroxide concentration were varied in copolymerization of DMP and 2-allyl-6-methylphenol (AMP) to produce allyl-containing PPO with 77% yield (Mn = 4500; Mw/Mn = 1.8). The optimum conditions were applied to copolymerization of DMP, AMP, and bisphenol A, leading to dihydroxyl PPO analogs containing thermally cross-linkable allyl groups. The thermal properties of these thermosetting PPOs were studied by differential scanning calorimetry, thermogravimetric analysis, and Fourier-transform infrared spectroscopy.