Helical Mesophase of Syndiotactic Polypropylene in Copolymers with 1-Hexene and 1-Octene

Random copolymers of syndiotactic polypropylene (sPP) with hexene and octene comonomeric units have been synthesized in a wide range of comonomer concentrations with a single-center syndiospecific Cs-symmetric metallocene catalyst. The effects of the presence of hexene and octene on the crystallization behavior of sPP and in particular on the stress-induced transformations have been analyzed. All copolymer samples crystallize from the melt in the stable helical form I of sPP. At very low concentrations of hexene or octene (around 1-2 mol %) the behavior of these copolymers is similar to that of sPP; that is, the stable helical form I of the melt-crystallized samples transforms into the trans-planar form III by stretching at high deformations. For hexene or octene concentrations in the range 2-5 mol % the stretching produces transformation of the helical form I into the trans-planar mesophase. Finally, for hexene or octene concentrations higher than 4-5 mol%the helical form I transforms by stretching at high deformation into a different mesomorphic form, characterized by chains in the ordered 2/1 helical conformation, and disorder in the lateral packing of the chains. This is a first evidence of the crystallization of a solid mesophase of sPP with chains in 2-fold helical conformation, never observed before in the sPP homopolymer.