Polyetherification kinetics

What will phase transfer catalysis provide polymer chemistry within the near future It is apparently still to early to predict this. We are not yet in the possession of many elemental mechanistic and kinetic understandings in order to answer questions like, for example, why not "living polyetherification "... 

It has been shown in Section 3.3 that the initiated polyetherification should be described by the kinetic theory and that a simplification is possible, if groups of independent reactivity in polyfunctional monomers participate in the curing reaction. The results of the treatment of an ideal postetherification following the epoxyamine addition are summarized below. 

Fig. 14. Dependence of the critical value of the conversion of excess epoxy groups available for polyetherification, in diepoxide-diamine systems on the initial molar ratio of epoxy to amino groups 1 dependence calculated using the kinetic theory, 2 dependence calculated using the kinetic theory.

Figure 14 shows that the difference in the result obtained by the combination of the kinetic and statistical method and by the purely statistical method is rather large. In real systems, the polyetherification reaction may be complicated by termination reactions e.g. by chain transfer, so that the mechanism may deviate from the... 

Polymer Synthesis. The polymers were made by a phase-transfer-catalyzed Williamson ether synthesis as described in the literature (15-201. and one reason for this choice of polyetherification method was that only electrophilic chain ends are produced (15.20-221. which gives the polymer a well-defined structure. This was important for die transition kinetics measurements presented later in this paper. 

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