| Abstract: | Three poly(ethylene oxide-co-ethylene sulfide)s with oxygen to sulfur ratios of 2/1, 2/2, and 1/2 were prepared by phase-transfer catalyzed polycondensations of (1) sodium sulfide and 1,2-bis (2-chloroethoxy)ethane, (2) 1,2-ethanedithiol and 1,2-bis(2-chloroethoxy)ethane, and (3) 1,2-ethanedithiol and 2-chloroethyl ether, respectively. A buffered solution with pH between the pKa of the monothiol (RSH) and the pKa2 of the dithiol (HS–R–SH), or H2S, was needed to obtain high molecular weight polymers, which suggests that nucleophiles transfer and react as monoanions rather than dianions. These poly(ethylene oxide-co-ethylene sulfide)s were oxidized completely to poly(ethylene oxide-co-ethylene sulfone)s using 3-chloroperoxybenzoic acid as oxidant. Both the final polymers and the precursors have regular sequenced structures and are semicrystalline. As expected, their glass transition temperatures and melting points increase and solubilities decrease with the decrease of ether oxygen to sulfur ratio. © 1994 John Wiley & Sons, Inc. |
