Cationic coordination polymerization cyclic ester

Some heterocycles have both nucleophilic and electrophilic atoms in their molecule. Thus they can be opened and polymerized by the anionic, cationic or coordination mechanisms. Examples are lactams, lactones, and cyclic siloxanes. Investigations of the mechanism of lactam propagation are complicated by the occurence of side reactions. In principle, the mechanism described in Chap. 3 by the schemes (55)—(57) and (71) is accepted. Anionic polymerization of cyclic esters consists, in most cases (see Chap. 4, Sect. 2.2) of repeated reversible attacks on the carbonyl carbon by the anion 0]-. From e-caprolactone, polyester chains grow according to [315]... 

Monomers listed above polymerize by the cationic mechanism. For some groups of monomers (lactones, carbonates) anionic or coordinate mechanism also operates and, from a synthetic point of view, this is the preferred method of converting cyclic esters into linear polyesters. The cationic polymerization of lactones, glycolide and it substituted analog, lactide, as well as spiroorthoesters and bicyclic orthoesters has been studied in some detail. 

Lactones, i.e. esters of hydroxyacids and their dimers, like glycolide and lactide, are two major groups of cyclic esters used in polymerization. These compounds are used on the large scale and polymerized mostly by anionic or coordinative mechanisms. Four, six-, and seven-membered lactones polymerize by both cationic and anionic mechanisms. Polyesters prepared in this way are however only a small fraction of the polyesters prepared by polycondensation. 

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