SynopsisObservations obtained by other techniques were confirmed by DSC analyses. As the length of the methylene chain increased, T, decreased, and crystallinity, heat capacity, and heat of fusion increased. The T, and crystallinity of the isophthalate esters were lower than for the corresponding terephthalate esters. The values for an odd-numbered methylene sequence were lower than for the adjacent even-numbered members. A model was used to calculate the heat of fusion of theoretically 100% crystalline poly(hexamethy1ene isophthalate) and poly(decamethy1ene isophthalate).
SynopsisThe 0-relaxation at Tg of the terephthalate and isophthalate series is due to molecular motions of the backbone chains in the amorphous region, but differs for the isophthalate series in that the p-phenylene group does not exhibit the free rotation possible for the rn-phenylene group. Consequently, the relaxation times of the terephthalate series are longer than for the isophthalate series. The y-relaxation (T,) for the higher homologues of the terephthalate series cannot be explained in terms of the poly(ethy1ene terephthalate) analogy. For poly(ethy1ene terephthalate) and poly(tetramethy1ene terephthalate), an induced cooperative type of motion of all the moieties is possible, whereby overlapping processes caused by "rocking vibrations" are observed as one y-peak. The resolution of the y-loss peaks for the above-mentioned polyesters into components is not possible at the experimental frequency of 110 Hz. For poly(hexamethylene terephthalate) and poly(decamethy1ene terephthalate), the "rocking vibrations" between the moieties of the skeletal chain are reduced so that even at a test frequency of 110 Hz, the yloss peaks could be resolved into two or three components. In the case of poly(decamethy1ene terephthalate), three components are resolved; the lowest temperature peak y1 is attributed to hindered motions of the methylene portions, the yz peak is attributed to motions of the carbonyl group in the gauche conformation, and the y3 peak is attributed to the carbonyl group in the trans conformation of the skeletal chain in the amorphous region. The general observations obtained by other techniques were confirmed by the forced vibration analyses. As the length of the methylene chain increased, Tg decreased. As crystallinity increased, the 0-relaxation moved to higher temperatures and the damping peak was smaller and broader. The damping peak moved to lower temperatures and increased in size as the length of the methylene chain increased. The damping peak was larger for the isophthalate homologue than for the corresponding terephthalate polyester.
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