Free-radical copolymerization of α-olefins with ethylene

Ethylene was polymerized at 15,000–25,000 psi at 130–220°C. with free-radical initiators in the presence of 0–10% of C¹⁴-labeled propylene, butene-1, and octene-1. Polymer composition was determined by scintillation counting. Molecular weight measurements and polymer unsaturation as detected by infrared analysis gave independent estimates of chain transfer. It was concluded that the major reaction of all α-olefins is copolymerization: chain transfer is a minor reaction. For all α-olefins, r₁ (where ethylene is monomer 1) is 3.2–3.3 uncorrected, or 3.4–3.6 corrected for chain transfer.