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Lecture

Controlled free radical polymerization

In course

MSE-437: Polymer chemistry and macromolecular engineering

Know modern methods of polymer synthesis. Understand how parameters, which determine polymer structure and properties, such as molecular weight, molecular weight distribution, topology, microstructure can be controlled by proper choice of polymerization me ...

Description

This lecture covers the concept of controlled radical polymerization, discussing initiation, propagation, and termination steps. It explores the challenges of achieving precise control over molecular weight, composition, and topology in polymer synthesis. Different polymer architectural forms and living polymerization techniques are presented, including ATRP, SFRP, and RAFT. Mechanistic consequences, characteristics, and strategies for achieving living polymerization are explained, emphasizing the need for fast and quantitative initiation and long-lived polymer chains. The lecture concludes with a comparison of NMP, ATRP, and RAFT systems, highlighting their features, conditions, and limitations.

Instructor

Harm-Anton Klok

Official source

Ontological neighbourhood

Chemistry

Organic chemistry: Polymer chemistry

Related concepts (23)

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.

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.

Polymer

A polymer (ˈpɒlᵻmər; Greek poly-, "many" + -mer, "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function.

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