Conformation transition and crystalline phase variation of long chain branched isotactic polypropylenes (LCB-iPP)

The changes of conformation and crystalline structure of long chain branched isotactic polypropylene (LCB-iPP) under different crystallization temperatures and the effects of their special molecular architecture on the crystallization behavior were investigated by a combination of Fourier transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). In these polymers, long chain branching was introduced via in situ polymerization of polypropylene and an asymmetric diene monomer using the metallocene catalyst technology. Through the characterization of the specific IR band variation, it was proved that the conformational orders of helical sequences of LCB-iPP show great changes in different crystallization temperature ranges. In lower crystallization temperature range (100-130 °C), the intensities of all regular helical conformation bands of LCB-iPP increase with the increasing crystallization temperature and the regular helical conformation bands with more monomer units increase faster than that with less monomer units. In higher crystallization temperature range (130-150 °C), the intensities of all regular helical conformation bands of LCB-iPP decrease with the increasing crystallization temperature and the regular helical conformation bands with more monomer units decrease faster than that with less monomer units. The results of WAXD and DSC showed that LCB-iPP crystallizes from the melt as a mixture of α and γ forms. The content of the γ form increases with the increasing crystallization temperature, reaches a maximum value at 130 °C, and then decreases with a further increase of the temperature. At the same time, the crystallization of γ form is favored by the presence of the LCB structure of iPP. Moreover, the transitional temperatures of different helical conformations and crystallization structures of LCB-iPP show obvious correlations.