Radical Chain Polymerization

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Description

This lecture covers the mechanism, rate, molecular weight, and chain transfer in radical chain polymerization. It explains the differences between step and chain polymerization, the general mechanism, and considerations for polymerizability of vinyl monomers. The lecture also delves into electrical effects, inductive and resonance effects, and the structural arrangement of monomer units. It discusses the industrial importance of radical chain polymerization, initiation, propagation, and termination steps. Additionally, it explores the rate of polymerization, initiation methods, and the kinetics of thermally initiated radical polymerization. The lecture concludes with discussions on chain transfer, control of molecular weight, molecular weight distribution, and the complexities involved in determining molecular weight in radical chain polymerization.

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Related lectures (14)

Related concepts (50)

Radical polymerization

In polymer chemistry, free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the successive addition of free-radical building blocks (repeat units). Free radicals can be formed by a number of different mechanisms, usually involving separate initiator molecules. Following its generation, the initiating free radical adds (nonradical) monomer units, thereby growing the polymer chain. Free-radical polymerization is a key synthesis route for obtaining a wide variety of different polymers and materials composites.

Polymerization

In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many forms of polymerization and different systems exist to categorize them. In chemical compounds, polymerization can occur via a variety of reaction mechanisms that vary in complexity due to the functional groups present in the reactants and their inherent steric effects.

Anionic addition polymerization

In polymer chemistry, anionic addition polymerization is a form of chain-growth polymerization or addition polymerization that involves the polymerization of monomers initiated with anions. The type of reaction has many manifestations, but traditionally vinyl monomers are used. Often anionic polymerization involves living polymerizations, which allows control of structure and composition. As early as 1936, Karl Ziegler proposed that anionic polymerization of styrene and butadiene by consecutive addition of monomer to an alkyl lithium initiator occurred without chain transfer or termination.

Chain transfer

Chain transfer is a polymerization reaction by which the activity of a growing polymer chain is transferred to another molecule. P• + XR' → PX + R'• Chain transfer reactions reduce the average molecular weight of the final polymer. Chain transfer can be either introduced deliberately into a polymerization (by use of a chain transfer agent) or it may be an unavoidable side-reaction with various components of the polymerization.

Living polymerization

In polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar (i.e.