Poly(ethy1ene terephthalate) (PET) was melt blended with several liquid-crystalline polymers (LCPs), both with and without Ti(OBu), catalyst. The LCPs, referred to as VA, LC5, LC3, and SBH, respectively, were Vectra-A950, Rodrun LC-5000, Rodrun LC-3000, and a laboratory copolyester of sebacic acid (S), 4.4'-diacetoxybiphenyl (B), and 4-acetoxybenzoic acid (H). Their degree of aromaticity decreases in that order. The phase behavior and the morphology of the blends were studied by diEerential scanning calorimetry and scanning electron microscopy. All the LCPs retard the dynamic crystallization of PET. The lower the LCPs degree of aromaticity, the more pronounced was the effect. It was not possible to obtain any evidence of ester exchange reactions by the reactive blending of PET with VA. On the contrary, appreciable changes of phase behavior and morphology were observed under comparable conditions for the other blends. With LC5 and LC3, the transesterification process predominantly involved the ET-rich phase of those polymers. Extensive transesterification occurred between PET and SBH, as proven by the gradual formation of a quasi homogeneous material, with lowered temperatures and enthalpies of fusion and crystallization. For blends with more than 25% SBH, homogenization is followed by the segregation of a new, highly aromatic phase.
The transesterification of poly(ethylene terephthalate) (PET) with a mixture of sebacic acid (S), 4,4'-diacetoxybiphenyl (B) and 4-acetoxybenzoic acid (H), carried out under conditions expectedly favoring the formation of a p(ET-SBH) random copolyester, produces biphasic materials with an isotropic matrix and a highly fibrous, liquid-crystalline dispersed phase. Spectroscopic, calorimetric, microscopic and diffractometric characterization of the fractions separated by solvent extraction has shown that the two phases consist of practically random copolyesters having different average composition. Interestingly, the degree of aromaticity of the matrix is even lower than that of PET, whereas that of the minor phase is appreciably higher than that calculated for the SBH copolyester that would be produced from the monomer mixture in the absence of FET. This unexpected result is interpreted on the basis of an enthalpy-driven progressive diffusion of aromatic-rich material toward the mesophase which segregates at an early stage of the polycondensation within the isotropic mixture of low molar mass oligomers initially produced by the PET acidolysis. Thus, an increasing differentiation, rather than an equilibration, of the composition of the two phases takes place. It is noteworthy that, despite the strong compositional difference, the two phases of these products show fairly good compatibility and interfacial adhesion
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