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1988•Makromolekulare Chemie Macromolecular SymposiaRequires access

Covalent and ionic species in cationic polymerizations: Rates of exchange

Stanisław Penczek, Ryszard Szymański

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Abstract

Abstract The general kinetic scheme of simultaneous propagation on covalent and ionic species is discussed. There are a few ways of interconversion of covalent and ionic species, and at least two different modes of covalent propagation. This is either a direct inclusion with reformation of covalent species or reaction of covalent species with a monomer, giving ionic species, collapsing then into the covalent species and/or propagating ionically. Significance of these processes for the overall kinetics is discussed; rates of exchange covalent ⇌ ionic and covalent + monomer ⇌ ionic are discussed in more detail on the basis of trityl chloride ionization and ester‐ion equilibria in the polymerization of THF and oxepane.

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Abstract The general kinetic scheme of simultaneous propagation on covalent and ionic species is discussed. There are a few ways of interconversion of covalent and ionic species, and at least two different modes of covalent propagation. This is either a direct inclusion with reformation of covalent species or reaction of covalent species with a monomer, giving ionic species, collapsing then into the covalent species and/or propagating ionically. Significance of these processes for the overall kinetics is discussed; rates of exchange covalent ⇌ ionic and covalent + monomer ⇌ ionic are discussed in more detail on the basis of trityl chloride ionization and ester‐ion equilibria in the polymerization of THF and oxepane.

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Available abstract

Abstract The general kinetic scheme of simultaneous propagation on covalent and ionic species is discussed. There are a few ways of interconversion of covalent and ionic species, and at least two different modes of covalent propagation. This is either a direct inclusion with reformation of covalent species or reaction of covalent species with a monomer, giving ionic species, collapsing then into the covalent species and/or propagating ionically. Significance of these processes for the overall kinetics is discussed; rates of exchange covalent ⇌ ionic and covalent + monomer ⇌ ionic are discussed in more detail on the basis of trityl chloride ionization and ester‐ion equilibria in the polymerization of THF and oxepane.

Key concepts: Covalent bond, Ionic bonding, Chemistry, Cationic polymerization, Monomer, Polymerization, Dynamic covalent chemistry, Ion

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