Halogenation of polyethylene single crystals

The halogenation of melt‐crystallized and solution‐crystallized linear polyethylene indicated that halogen atoms have no effect on the fold length on recrystallization. At temperatures of 60°C. or higher, reaction of the crystal lattice with chlorine proceeded to completion. Extremely thin layers of both solution and melt crystallized polyethylene exhibited no difference in reactivity with chlorine, but the reactivity of molded polyethylene films to chlorine was apparently limited by chemically combined chlorine occupying the free volume in the surface layer of the polymer. There was a coexistence of highly halogenated and essentially unreacted phases during chlorination of individual crystal layers. Finally, this phase separation involved dimensions of about 100 A. and may well be related to some inherent structural feature of single crystals.