Radical Chain-Growth Polymerization: Chain Branching

The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the abstraction site to the end of the chain becomes a branch.

In intermolecular hydrogen abstraction, the radical site abstracts hydrogen from another growing polymer chain and terminates its chain growth. A new branch grows in the other chain where the hydrogen was removed. Figure 1 demonstrates the intermolecular hydrogen abstraction and the consequent chain growth from the middle of the polymer chain.

Figure 1: The intermolecular hydrogen abstraction (top) and the subsequent addition of the newly formed radical site to a monomer (bottom).

The radical site abstracts hydrogen from the same growing chain in intramolecular hydrogen abstraction. The length of the branch depends on the distance between the radical site and the abstraction site. Intramolecular 1,5-hydrogen abstraction frequently occurs due to the relatively stable six-membered transition state, resembling the chair conformation of cyclohexane. The resultant butyl branches are commonly found in branched polymers. Figure 2 shows the intramolecular hydrogen abstraction and the formation of the butyl branch.

Figure 2:  The intramolecular hydrogen abstraction (top) and subsequent addition of the newly formed radical site on a monomer (bottom).

In general, intramolecular hydrogen abstraction is more probable than intermolecular hydrogen abstraction. Also, short-chain branching is more common than long-chain branching, as the ends of the chains are more accessible.