End unit effect on the Tg of differentiated series of perfluoro-poly (oxymethylene-co-oxyethylene) oligomers

Twelve series of linear oligomers of four different degrees of polymerization (x_n = 8.77−41.55), having a common perfluorinated random copolymeric chain as molecular body and two equal foreign end units of one of the types listed in Table 1, have been synthesized by derivatization of base samples of one of them having a diolic---CH₂OH functionality. The glass transition temperature T_g of all the series was measured and thus examined as a function of x_n. A clear end unit effect is observed, dominantly determined in every series by chemical nature and structure of the end units, quantitatively expressed at any x_n by different positive or negative T_g deviations from the common asymptotic T_g∞ value. The results are also discussed in terms of copolymer end effect and of relation between T_g and end copolymeric composition.