Abstract
The heat capacity of a linear polyethylene with dimethyl branches, at every 21st backbone atom was analyzed by differential scanning calorimetry (DSC) and quasi‐isothermal temperature‐modulated DSC. This novel copolyethylene (PE2M) is relatively difficult to crystallize from the melt. On subsequent heating, a first, sharp melting peak is followed by a sharp cold‐crystallization and crystal perfection and a smaller endotherm, before reaching the main melting at 315–320 K, close to the melting temperatures of eicosane and tetracontane. The low‐temperature melting is sensitive to the cooling rate and disappears below 1.0 K min^−1^. The cold crystallization can be avoided by heating with rates faster than 80 K min^−1^. The PE2M exhibits some reversing and reversible melting, which is typical for chain‐folded polymers. The glass transition of semicrystalline PE2__M__ is broadened and reaches its upper limit at about 260 K (midpoint at about 0.355 K). Above this temperature, the crystals seem to have a heat capacity similar to that of the liquid. A hypothesis is that the melting transition can be explained by changes in crystal perfection without major alteration of the crystal structure and the lamellar morphology. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3461–3474, 2006