Functional polymers and sequential copolymers by phase transfer catalysis. 18. Synthesis and characterization of α,ω-bis(2,6-dimethylphenol)–poly(2,6-dimethyl-1,4-phenylene oxide) and α,ω-bis(vinylbenzyl)–poly(2,6-dimethyl-1,4-phenylene oxide) oligomers

A novel and convenient synthetic method for the preparation of α,ω-bis(2,6-dimethylphenol)–poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-2OH) is presented. It is based on the oxidative copolymerization of 2,6-dimethylphenol (DMP) with 2,2′-di(4-hydroxy-3,5-dimethylphenyl propane) (TMBPA) in a mixture of water–methanol or chlorobenzene–methanol. By using a 4/1 mole ratio of DMP to TMBPA and different solvent mixtures, it was possible to obtain bifunctional PPO-2OHs with number average molecular weights between 1000 and 5000. A phase-transfer-catalyzed etherification of PPO-2OH chain ends with a mixture of m- and p-chloromethylstyrene was used to synthesize α,ω-bis(vinylbenzyl)-poly(2,6-dimethyl-1,4-phenylene oxide)s (PPO-2VBs). The thermal polymerization of the PPO-2VBs was studied by differential scanning calorimetry, and has demonstrated a very high thermal reactivity for this new class of reactive oligomers.