Sulfur-containing polymers. Synthesis and properties of novel poly(arylene thioether)s based on 2,2-bis(4-mercaptophenyl)propane.

Novel poly(arylene thioether)s were synthesized using the one pot polymn. method from the bis(N,N-dimethyl-S-carbamate) of 2,2-bis(4-mercaptophenyl)propane and activated difluoro arom. compds. Each of the polymers, obtained in good yields and with fairly high mol. wts., were characterized by IR, GPC and NMR analyses. In particular, the NMR characterization was performed using 1H NMR, 13C NMR, DEPT, 2D COSY and 2D HSQC expts. To study the effect on the thermal properties of replacing the ethereal oxygen atoms with sulfur atoms, we have synthesized the counterparts, the poly(arylene ether)s, with similar mol. wts. We obsd. that the substitution of the ethereal oxygen atoms with sulfur atoms results in a slightly lower thermal stability for the poly(thioether ketone)s, both under nitrogen and in air, and does not modify the Tg values. For the poly(thioether sulfone), on the other hand, the thermal stability is equal to that of the poly(ether sulfone), while the Tg is 10 °C lower. Furthermore, each sample is completely amorphous, with the exception of one of the poly(thioether ketone)s (sample 1b), which shows the capacity to crystallize, even if with a very slow crystn. kinetics.