The oriented gamma form of isotactic polypropylene

A structural analysis of the oriented gamma form of isotactic polypropylene (iPP) is presented. The X-ray diffraction intensity distribution in the or iented gamma form is quantitatively evaluated for the first time. The struc tural analysis is performed on a new, poorly stereoregular ([mmmm] = 35%) p olypropylene material, prepared with a novel C-2-symmetric zirconocene base d catalytic system, showing elastomeric properties. The sample, initially a morphous, partially crystallizes upon aging. In the oriented crystalline ma terials, obtained by stretching the aged sample, the crystallites tend to a ssume a preferred orientation with the chain axes parallel to the draw dire ction. Disorder is present in the structure. For low draw ratios (less than twice the initial length) disordered crystalline modifications, very close to the gamma form of iPP, are obtained; increasing the draw ratio, crystal line modifications, closer to the alpha form of iPP, are observed. The stru ctural disorder occurring in our stretched samples originates from the rand om succession of bilayers of chains with chains parallel (like in the alpha form) or tilted approximate to 81 degrees each other (like in the gamma fo rm). The results of this analysis are the follows. For the sample stretched at a low draw ratio, approximate to 75% of the bilayers of chains are face d each other like in the gamma form so that the fraction of bilayers with c hain axes pointing preferentially along the draw direction is on the order of 60-65% (the remaining 35-40%, being oriented with the chain axes tilted approximate to 81 degrees to the draw direction). For the samples stretched at higher draw ratios, the fraction of bilayers facing each other like in the gamma form is reduced to 20-30%, so that only 10-15% of the bilayers re sults oriented with the chain axes nearly normal to the draw direction. Thi s is as if, in all cases, the regions of the crystals with chains arranged like in the alpha form tend to br oriented with the chain axes parallel to the stretching direction rather than tilted approximate to 81 degrees. A co ntinuum of disordered modifications intermediate between the pure gamma and alpha forms could exist. The possible inclusion in the crystalline domains of stereo defects (mainly of the kind mrrm), which would favor the gamma - like packing situations on the local scale, is discussed.