Copolyesters of poly[ethylene terephthalate) (PET) with a liquid crystalline polymer (LCP), SBH 1:1:2, have been synthesized by the polycondensation, carried out in the melt at temperatures up to 300 degrees C of sebacic acid (S), 4,4'-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) in the presence of PET. The PET-SBH copolyesters have been characterized by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, etc., and the relationships between properties and preparation conditions are discussed. The copolyesters show a biphasic nature, which is more evident for the products synthesized with a thermal profile comprising relatively lower temperatures (220-230 degrees C) in the initial stages of the polycondensation. Another procedure, whereby the addition of PET to the monomer charge was made at a later stage of the reaction, has also been devised to prepare copolyesters with enhanced blockiness. The compatibilizing effect of the PET-SBH copolymers toward PET/SBH blends has been investigated. PET/SBH blends (75/25, w/w) have been prepared in a Brabender mixer at 270 degrees C and 30 rpm, with and without the addition of appropriate amounts (2.5, 5, and 10%, w/w) of 50-50 PET-SBH copolyesters. Different blending techniques have been used according to whether the three components were fed into the mixer at the same time, or one of them was added at a later stage. The effect of the type and the amount of added copolyester has been studied through morphological, thermal, and mechanical characterizations. The results show that the addition of small amounts similar to 5 wt% of copolyesters leads to improved dispersion and adhesion of the minor SBH phase. Moreover, while the tensile modulus of the blends is practically unaffected by the addition of the copolymer, a substantial increase of both tensile strength and elongation to break is found for a concentration of added copolyester of similar to 5 wt%. Slightly better results were apparently obtained by the use of a block copolyester
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
“Synthetic blends” of a flexible polymer forming the matrix and a liquid‐crystalline polymer (LCP) forming the dispersed phase have been prepared by transesterification of PET with a mixture of sebacic acid (S), 4,4′‐diacetoxybiphenyl (B) and 4‐acetoxybenzoic acid (H) in the mole ratio 1:1:2. A change of the synthesis conditions causes marked variations of the chemical composition and the morphology of the phases. The SEM investigation of the inner morphology of the LCP droplets of blends consisting of two phases with fairly different aromatic content has shown that the LCP macromolecules are aligned tangentially at the matrix surface boundary, and that the nematic director configuration is toroidal. When the two phases have closer chemical composition, and are therefore supposed to possess improved mutual compatibility, a perpendicular anchoring of the LCP fibrils to the matrix cavity surface, and an axial configuration of the nematic director, are observed. The expected effect of the nematic configuration of the LCP droplets on their ability to deform into fibrils under appropriate flow conditions is preliminarily discussed.
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