Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.

Alkenes undergo polymerization via a free-radical mechanism involving three steps: initiation, propagation, and termination. 

Radicals are generated in the initiation step by heating a small quantity of free-radical initiators such as benzoyl peroxide. The benzoyloxy radical loses CO₂ and forms a phenyl radical (Ph·), which adds to the double bond of the alkene to initiate the polymerization process. One of the electrons of the alkene π bond pairs with one electron from the phenyl radical to form a new C–C bond.

In the propagation step, the carbon radical generated in the initiation step adds to another molecule of alkene to generate a new radical. The continuous addition of alkene monomers at the radical site yields the polymer.

The termination step of the free-radical mechanism occurs via recombination or disproportionation. In a recombination step, two growing chains form a bond at their radical sites.

In termination by disproportionation, a β-hydrogen atom is transferred from one radical to another radical center, resulting in two non-radical products.

The free-radical polymerization of ethylene yields low-density polyethylene (LDPE), where the low density is a consequence of significant branching in the polymer chains. Articles made from polymers surround us in various forms, such as food packaging materials, plastic bags, bottles, stationery, and automotive parts.