Abstract
Polycarbonate block copolymers were prepared by phosgenating pyridine solutions of polyether glycol-bisphenol-A mixtures. Copolycarbonates derived from poly(oxyethylene) glycols (Carbowaxes) were studied in detail for property-structure effects as a function of glycol molecular weight (1000–20,000) and copolymer composition (5–70 weight per cent or 0.3–10.0 mole per cent of a 4000 molecular weight glycol). Remarkable strength (>7000 psi) and snappy elasticity (>90 per cent immediate recovery) were observed at poly(oxyethylene) block concentrations greater than 3 mole per cent. These thermoplastic elastomers also exhibited high softening temperatures (>180° C) and tensile elongations up to about 700 per cent. Both Tg and softening temperature varied linearly with comonomer mole ratio over the composition range studied, with Tg displaying much greater polyether concentration sensitivity. It is suggested that the observed property effects result to a large extent from the variation in poly(bisphenol-A carbonate) block length that accompanies the changing of copolymer composition. An initial increase in flexural modulus (stiffness) was observed at low polyether concentrations (0–1 mole per cent). This phenomenon is considered to be related to similar modulus effects found in plasticized rigid thermoplastics at low plasticizer concentrations. A moderate degree of molecular order, due to bisphenol carbonate segments rather than the normally crystalline polyether, was detected by x-ray analysis. Elastomeric carbonate-carboxylate tetrapolymers were also prepared by partial replacement of carbonate with isophthalate, terephthalate or adipate linkages in polyether-bisphenol systems. The dramatic softening temperature depression observed in this class of polymers is attributed to the disruption of long bisphenol carbonate block sequences that exist in the simpler polyether glycol-bisphenol carbonate copolymers.
