Polymerization of Glycidyl Phenyl Ether with Phosphonic Acid Esters as Novel Thermally Latent Initiators

Abstract

Novel phosphonic acid esters, O,O-di-1-phenylethyl phenylphosphonate (1), O,O-di-tert-butyl phenylphosphonate (2), and O,O-dicyclohexyl phenylphosphonate (3), were synthesized from phenylphosphonic dichloride and the corresponding alcohols. The phenylphosphonic esters 1−3 decomposed into phenylphosphonic acid and the corresponding olefins by heating at 150−170 °C. Their initiator activities were examined in the cationic polymerization of glycidyl phenyl ether (GPE). They converted GPE only 4% even at 190 °C in the absence of ZnCl2. In the presence of ZnCl2 along with 1−3, GPE did not convert below 90 °C in the case of 1 and 2, and below 140 °C in the case of 3, but it rapidly converted to afford polyGPE with Mn of 2000−7000 above those temperatures. It was found that 1−3 served as thermally latent initiators in the polymerization of GPE in the presence of ZnCl2.