Sequential reordering in condensation copolymers, 1. Melting‐ and crystallization‐induced sequential reordering in immiscible blends of poly(ethylene terephthalate) with polycarbonate or polyarylate

Abstract

AbstractUnlike previous attempts, the entire cycle of melting‐ and crystallization‐induced reordering is realized in binary polymer blends in the following order: two homopolymers → block copolymer → random copolymer → block copolymer. Blends of poly(ethylene terephthalate)Systematic IUPAC name: poly(oxyethyleneoxyterephthaloyl). (PET) and bisphenol‐A/polycarbonate (PC) as well as PET/polyarylate (PAr) blends, are annealed directly in a differential scanning calorimeter at 280°C for various times. Scanning the samples in the heating mode reveals the complete disappearance of crystallization or melting in the blends where the ratio of PET/PC repeating units is less than 5.7/1.0. Such an amorphization is attributed to the formation of random copolymers. This statement is confirmed by NMR measurements, by the observation of one glass transition temperature Tg in the range between the initial two Tgs, and by solubility tests. Once randomized, annealing the samples at 235°C and 245°C, i. e., below melting of PET, results in a Tg shift toward the Tg of PET as well as in reappearance of melting. This effect is accompanied by an eight‐fold crystallinity increase in the equimolar blend, as compared to the randomized sample. The regenerated crystallization ability is explained by restoration of the blocks. According to previous findings, it is concluded that the considerable enthropy increase is the main driving force of randomization. The rival trend to the formation of a block copolymer by sequential reordering is driven by the crystallization of PET blocks formed. The conclusion that the observed changes in the crystallization ability and Tg‐values are based on sequential reordering is supported by experiments with samples containing increased amounts of transesterification catalyst leading to a much faster appearance of these changes. No randomization is observed with the blend composition ratio of repeating units PET/PC > 5.7/1.0. When the annealing is performed for 300 min at 165°C, where no significant exchange reactions are expected to occur, no restoration of the crystallization ability is observed.