Crystallization and Melting of Model Polyethylenes with Different Chain Structures

The crystallization and melting of three model polyethylenes of different chain structures have been studied. The polymers studied were a linear copolymer, hydrogenated poly(butadiene); a hydrogenated poly(butadiene)-atactic poly(propylene) diblock copolymer; and a three-arm star hydrogenated poly(butadiene). An important feature of this work was that the crystallizing portions of the copolymers all have the same molecular lengths.It was found that the overall crystallization rate decreases steadily from a linear to a diblock to the star copolymer. The differences in crystallization rates are related primarily to the activation energy for segmental transport. The non-crystallizable structure affects the segmental mobility to different degrees. An estimation of this effect is presented from the analysis of the overall crystallization rates using classical nucleation theory. In spite of thedifferences in their molecular structure, there are no major differences in the supermolecular structure of samples crystallized rapidly or slowly cooled.The melting process followed by DSC of the isothermally crystallized linear and star copolymers shows two endothermic peaks at intermediate undercoolings. The double melting is associated with a partitioning of crystallizable ethylene sequences during crystallization. The longest sequences are preferentially selected in the early stages of the crystallization. Single melting peaks are obtained for high and very low undercoolings for the linear and the star copolymers as well as for the diblock in the whole range of temperatures. The lack of the second, lower melting endotherm in the diblock could be associated with the influence in the crystallization process of the amorphous block in the microphase segregated melt.This revised version was published online in November 2005 with corrections to the Cover Date.