Phase transition temperatures oligomers

Fig. 9. Phase transition temperatures Tc, T, and Tk of monodisperse oligomers as function of the degree of polymerization r ( phase transformation crystalline to isotropic)...

The temperature dependence of Tj (Fig. 13) points to a noticeable effect of the nature of adsorbent (phenolic oligomer) on the properties of adsorbed water. Firstly, the value of Ti (1-1.2 s) is nearly half that of free water (in 0.5 1). Secondly, relaxation curves sharply differ in 20- and 400-oersted fields. In the 20-oersted field the dependence Ti = f (T) is stepwise and the steepest part is observed near temperatures corresponding to the phase transition water - ice . The authors suggest that the minimum observed between 0 to -2 °C is connected with the dispersion of the relaxation time distribution. In order to confirm this assumption a classical relaxation analysis using deuterated water and the temperature dependence of longitudinal relaxation time is required. 

Thus, it is possible to use this reaction to obtain new macromolecules (di-ols or diamines) with low glass-transition temperature (Tg) and no crystalline phase. Earlier works suggested the synthesis of hydroxy-telechelic oligomers by radical addition of thiol onto dienes. But, the products obtained showed poor solubility in organic solvents and a high melting point. Our process, however, improves the properties of diol compounds (better solubility and decrease of the melting point). 

It must be noted that the process of seeded emulsion polymerization does not lead to an equilibrium structure. Hence, the sharp interface between PS and PMMA observed in the above core-shell particles cannot be explained by thermodynamic arguments. A possible mechanism maybe sought in the adsorption of oligo(methylmethacrylate) radicals from the water phase onto the PS-seed particles [45]. The temperature of the seeded emulsion polymerization (80 °C [45]) is well below the glass transition temperature of polystyrene and the adsorbed chains bear a sulfate endgroup. The adsorbed oligomers will therefore remain at the surface of the core particles and in consequence there is no extended interface between PS and PMMA in these. particles. 

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