Anionic Polymerization: Mechanisms and Applications

This lecture by the instructor covers the concept of anionic polymerization, focusing on the differences between anionic and cationic polymerization. It explains the initiation process using nucleophilic initiators and electron transfer. The lecture delves into the living and controlled polymerization, emphasizing the importance of fast initiation and exchange among propagating species. Practical aspects of anionic polymerization, such as high vacuum conditions and macromolecular engineering, are also discussed. The lecture concludes with a detailed explanation of the kinetics of living anionic polymerization and the factors affecting the reaction medium.

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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.

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.

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.

Ring-opening polymerization

In polymer chemistry, ring-opening polymerization (ROP) is a form of chain-growth polymerization, in which the terminus of a polymer chain attacks cyclic monomers to form a longer polymer (see figure). The reactive center can be radical, anionic or cationic. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight polymers by using metal catalysts. ROP is a versatile method for the synthesis of biopolymers. Ring-opening of cyclic monomers is often driven by the relief of bond-angle strain.

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.

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