Structure of syndiotactic propylene–ethylene copolymers: Effect of the presence of ethylene units on the structural transitions during plastic deformation and annealing of syndiotactic polypropylene

Syndiotactic propylene–ethylene copolymers have been synthesized with a single-center Cs-symmetric syndiospecific metallocene catalyst. A study of the effect of the presence of ethylene comonomeric units on the polymorphic behavior of syndiotactic polypropylene (sPP) and on the structural transitions occurring during stretching is reported. For copolymer samples with low ethylene contents, in the range 2–7 mol%, crystals of the helical form I, present in the melt-crystallized samples, transform into the trans-planar form III by stretching at high deformation. Form III transforms in part into the helical form II by releasing the tension, as it occurs for sPP. Samples with ethylene contents in the range 8–10 mol% are crystallized from the melt as a mixture of crystals of helical form I and form II. Both helical forms transform by stretching at low values of deformation (lower than 300%) into the trans-planar mesomorphic form, which transforms into the trans-planar form III by further stretching at higher deformations (higher than 500%). For these samples form III transforms back into the mesomorphic form, rather than into the helical forms, by releasing the tension. Unoriented samples of copolymers with ethylene content in the range 13–18 mol% are mainly crystallized in the helical form II, which transforms into the trans-planar mesomorphic form by stretching. Upon releasing the tension the mesomorphic form remains stable and no polymorphic transition is observed. The presence of ethylene comonomeric units stabilizes the trans-planar forms in fibers of the copolymer samples. This has been confirmed by the result that for high ethylene contents the trans-planar form III and the mesomorphic form do not transform in helical forms by annealing of fibers stretched at high deformations.