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The association is strongest as a covalent bond and weakest when the pair exists as free ions. [6] In cationic polymerization, the ions tend to be in equilibrium between an ion pair (either tight or solvent-separated) and free ions. [2] The more polar the solvent used in the reaction, the better the solvation and separation of the ions.
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In polymer chemistry, ionic polymerization is a chain-growth polymerization in which active centers are ions or ion pairs. [2] It can be considered as an alternative to radical polymerization, and may refer to anionic polymerization or cationic polymerization. [3] As with radical polymerization, reactions are initiated by a reactive compound.
General scheme ionic propagation. Propagating center can be radical, cationic or anionic. 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).
In polymer chemistry, chain transfer is a polymerization reaction by which the activity of a growing polymer chain is transferred to another molecule: [1] [2] + + where • is the active center, P is the initial polymer chain, X is the end group, and R is the substituent to which the active center is transferred.
Living cationic polymerization is a living polymerization technique involving cationic propagating species. [1] [2] It enables the synthesis of very well defined polymers (low molar mass distribution) and of polymers with unusual architecture such as star polymers and block copolymers and living cationic polymerization is therefore as such of commercial and academic interest.
In terms of mechanism, an ideal RAFT polymerization has several features. The pre-equilibrium and re-initiation steps are completed very early in the polymerization meaning that the major product of the reaction (the RAFT polymer chains, RAFT-P n ), all start growing at approximately the same time.
In chain-growth (or chain) polymerization, the only chain-extension reaction step is the addition of a monomer to a growing chain with an active center such as a free radical, cation, or anion. Once the growth of a chain is initiated by formation of an active center, chain propagation is usually rapid by addition of a sequence of monomers.