In polymer chemistry, polymerization, or polymerisation, 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 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. Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups.
In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer are emulsified in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.
In chemistry, the cage effect (also known as geminate recombination) describes how the properties of a molecule are affected by its surroundings. First introduced by James Franck and Eugene Rabinowitch in 1934, the cage effect suggests that instead of acting as an individual particle, molecules in solvent are more accurately described as an encapsulated particle. The encapsulated molecules or radicals are called cage pairs or geminate pairs. In order to interact with other molecules, the caged particle must diffuse from its solvent cage. The typical lifetime of a solvent cage is 10-11 seconds. Many manifestations of the cage effect exist.
Chain-growth polymerization (AE) or chain-growth polymerisation (BE) is a polymerization technique where monomer molecules add onto the active site on a growing polymer chain one at a time. There are a limited number of these active sites at any moment during the polymerization which gives this method its key characteristics.
In polymer chemistry, step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Many naturally-occurring and some synthetic polymers are produced by step-growth polymerization, e.g. polyesters, polyamides, polyurethanes, etc. Due to the nature of the polymerization mechanism, a high extent of reaction is required to achieve high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is a group of people reaching out to hold their hands to form a human chain—each person has two hands. There also is the possibility to have more than two reactive sites on a monomer: In this case branched polymers production take place.
End groups are an important aspect of polymer synthesis and characterization. In polymer chemistry, they are functional groups that are at the very ends of a macromolecule or oligomer (IUPAC). In polymer synthesis, like condensation polymerization and free-radical types of polymerization, end-groups are commonly used and can be analyzed by nuclear magnetic resonance (NMR) to determine the average length of the polymer. Other methods for characterization of polymers where end-groups are used are mass spectrometry and vibrational spectrometry, like infrared and raman spectroscopy. These groups are important for the analysis of polymers and for grafting to and from a polymer chain to create a new copolymer. One example of an end group is in the polymer poly(ethylene glycol) diacrylate where the end-groups are circled.
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. 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.
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.
Atom transfer radical polymerization (ATRP) is an example of a reversible-deactivation radical polymerization. Like its counterpart, ATRA, or atom transfer radical addition, ATRP is a means of forming a carbon-carbon bond with a transition metal catalyst. Polymerization from this method is called atom transfer radical addition polymerization (ATRAP). As the name implies, the atom transfer step is crucial in the reaction responsible for uniform polymer chain growth. ATRP was independently discovered by Mitsuo Sawamoto and by Krzysztof Matyjaszewski and Jin-Shan Wang in 1995.
Reversible addition−fragmentation chain-transfer or RAFT polymerization is one of several kinds of reversible-deactivation radical polymerization. It makes use of a chain-transfer agent (CTA) in the form of a thiocarbonylthio compound to afford control over the generated molecular weight and polydispersity during a free-radical polymerization. Discovered at the Commonwealth Scientific and Industrial Research Organisation (CSIRO) of Australia in 1998, RAFT polymerization is one of several living or controlled radical polymerization techniques, others being atom transfer radical polymerization (ATRP) and nitroxide-mediated polymerization (NMP), etc. RAFT polymerization uses thiocarbonylthio compounds, such as dithioesters, thiocarbamates, and xanthates, to mediate the polymerization via a reversible chain-transfer process. As with other controlled radical polymerization techniques, RAFT polymerizations can be performed under conditions that favor low dispersity and a pre-chosen molecular weight. RAFT polymerization can be used to design polymers of complex architectures, such as linear block copolymers, comb-like, star, brush polymers, dendrimers and cross-linked networks.
In polymer chemistry, chain transfer is a polymerization reaction by which the activity of a growing polymer chain is transferred to another molecule:
Solution polymerization is a method of industrial polymerization. In this procedure, a monomer is dissolved in a non-reactive solvent that contains a catalyst or initiator.
In polymer chemistry, the kinetic chain length of a polymer is the average number of units called monomers added to a growing chain during chain-growth polymerization. During this process, a polymer chain is formed when monomers are bonded together to form long chains known as polymers. Kinetic chain length is defined as the average number of monomers that react with an active center such as a radical from initiation to termination.
Bulk polymerization or mass polymerization is carried out by adding a soluble radical initiator to pure monomer in liquid state. The initiator should dissolve in the monomer. The reaction is initiated by heating or exposing to radiation. As the reaction proceeds the mixture becomes more viscous. The reaction is exothermic and a wide range of molecular masses are produced.
Living free radical polymerization is a type of living polymerization where the active polymer chain end is a free radical. Several methods exist. IUPAC recommends to use the term "reversible-deactivation radical polymerization" instead of "living free radical polymerization", though the two terms are not synonymous.
In polymer chemistry, cationic polymerization is a type of chain growth polymerization in which a cationic initiator transfers charge to a monomer, which then becomes reactive. This reactive monomer goes on to react similarly with other monomers to form a polymer. The types of monomers necessary for cationic polymerization are limited to alkenes with electron-donating substituents and heterocycles. Similar to anionic polymerization reactions, cationic polymerization reactions are very sensitive to the type of solvent used. Specifically, the ability of a solvent to form free ions will dictate the reactivity of the propagating cationic chain. Cationic polymerization is used in the production of polyisobutylene and poly(N-vinylcarbazole) (PVK).
Plasma polymerization uses plasma sources to generate a gas discharge that provides energy to activate or fragment gaseous or liquid monomer, often containing a vinyl group, in order to initiate polymerization. Polymers formed from this technique are generally highly branched and highly cross-linked, and adhere to solid surfaces well. The biggest advantage to this process is that polymers can be directly attached to a desired surface while the chains are growing, which reduces steps necessary for other coating processes such as grafting. This is very useful for pinhole-free coatings of 100 picometers to 1-micrometer thickness with solvent insoluble polymers.
In polymer chemistry, reversible-deactivation radical polymerizations (RDRPs) are members of the class of reversible-deactivation polymerizations which exhibit much of the character of living polymerizations, but cannot be categorized as such as they are not without chain transfer or chain termination reactions. Several different names have been used in literature, which are:
Single Chain Cyclized/Knotted Polymers are a new class of polymer architecture with a general structure consisting of multiple intramolecular cyclization units within a single polymer chain. Such a structure was synthesized via the controlled polymerization of multivinyl monomers, which was first reported in Dr. Wenxin Wang's research lab. These multiple intramolecular cyclized/knotted units mimic the characteristics of complex knots found in proteins and DNA which provide some elasticity to these structures. Of note, 85% of elasticity in natural rubber is due to knot-like structures within its molecular chain.
An intramolecular cyclization reaction is where the growing polymer chain reacts with a vinyl functional group on its own chain, rather than with another growing chain in the reaction system. In this way the growing polymer chain covalently links to itself in a fashion similar to that of a knot in a piece of string. As such, single chain cyclized/knotted polymers consist of many of these links, as opposed to other polymer architectures including branched and crosslinked polymers that are formed by two or more polymer chains in combination.
