Phase Transfer Catalyzed Polycondensation of α, α′-Dichloro-p-xylene with 2,2-Bis(4-hydroxyphenyl)propane II. Some Aspects of Phase Transfer Catalyzed Polycondensation Reaction in the Tetrahydrofuran-Dimethyl Sulfoxide/ Aqueous Sodium Hydroxide System

Abstract

Phase transfer catalyzed (PTC) polycondensations of α, α′-dichloro-p-xylene with 2,2-bis(4-hydroxyphenyl)propane were carried out in a THF–DMSO (3: 1)/aqueous sodium hydroxide system at 60°C in the presence of quaternary ammonium halides. For both tetra-n-butylammonium bromide and hexadecylammonium bromide, the following rate equation was obtained: polymerization rate=k[Q+X−]0.57[NaOH]2.3 where [Q+X−] and [NaOH] stand for the concentrations of a phase transfer catalyst in an organic layer and sodium hydroxide in an aqueous layer, respectively. The catalytic activity for the PTC polycondensation was in the increasing order of (CH3)4NBr<(C2H5)4NBr<C6H13(CH3)3NBr<C8H17(CH3)3NBr<C10H21(CH3)3NBr ≍ C12H25(CH3)3NBr ≍ C14H29(CH3)3NBr<C16H33(CH3)3NBr<(C3H7)4NBr<(C4H9)4NBr< (C5H11)4NBr. The counter halide anions for benzyltriethylammonium cation also affected the polycondensation rate, which decreased in the order of chloride > bromide > iodide. The addition of sodium chloride to the PTC polycondensation system in the presence of benzyltriethylammonium chloride caused little change in the polymerization rate but always gave a white, soluble polyether even when some drastic reaction conditions were applied.