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A large number of polypropylene samples, of isotacticities spanning the range 0.35 to 1.00 mm, have been examined by differential scanning calorimetry (DSC) in order to establish a calorimetric index for determining stereostructure. Crystallization studies show that the crystallization onset temperature decreases in step with reduced isotacticity. However, samples prepared with supported catalysts show significantly lower crystallization onset temperatures than those from conventional catalysts which is believed to be due to differences in the inter- or intramolecular distribution of stereodefects. Furthermore, whole and fractionated samples cannot be fitted by one calibration curve. However, the enthalpy of crystallization is found to be related to the isotacticity by an equation of the form: log ΔH = m log (isotacticity) + c. This relationship is found to be applicable to samples from all types of catalysts examined and to both whole and fractionated samples. Fusion curves have been determined for “as received” as well as conditioned and annealed samples but the melting temperatures are not found to be a reliable guide to isotacticity. The respective enthalpies of fusion are found to follow the same logarithmic relationship stated above and thus can also be used as a basis for a calorimetric isotactic index. Examination of glass transition and related heat capacity data does not provide any clear-cut alternative index.

This study examines the application of infrared (IR) spectrometry to the determination of polypropylene (PP) stereoregularity. The use of the absorption bands at 998 cm−1 and 841 cm−1 as indices of isotacticity and bands at 1167 cm−1 and 973 cm−1 as internal references have been explored. Calibration curves relating various absorption ratios to isotacticity as measured by 13C nuclear magnetic resonance are reported. The ratios A998/A973 and A841/A973 are the most useful and provide linear correlations with isotacticity. The effect of instrument type on the calibration has been investigated for both dispersive and Fourier transform type IR spectrometers. For samples annealed at room temperature the average of measurements on the same set of PP films by five instruments provide the calibrations: A998/A973 = 1.08 ± 0.02 (mm)−0.15 ± 0.03; and A841/A973 = 0.84 ± 0.06 (mm)−0.04 ± 0.02. High temperature annealing increases the crystallinity of the samples and the corresponding value of the absorption ratio but is not necessary for obtaining reproducible calibration curves.