Brominated polyethylene single crystals show unique melting and annealing behavior. Given that a Br substituent has such a marked effect on properties, it was of interest to examine the effects of a much larger substituent. This was accomplished by replacing Br with a toluene group via a Friedel-Crafts reaction. Neutron activation analysis, Fourier transform infrared spectroscopy and thermal analysis were used to examine the reaction products. There techniques show that Br had indeed been replaced by toluene. Further substitution is primarily in the 1,4 (para) position with some 1,3 (meta) substitution. The presence of bulky substituents modifier the melting behavior of the lamellae. However the heat of fusion remains unchanged. The major effect on the melting process is the suppression of any reorganizational annealing behavior.