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This article discusses the results of experimental research on the synthesis of polyether sulfones and the molten polymer filament layering 3-D printing technology. The regularities of influence of the polycondensation conditions in the synthesis of polyphenylene sulfone on the processes of cross-linking, thermal degradation of the polymer at processing temperatures, and 3-D printing were revealed. It is shown that introduction of cardo fragments increases the glass transition temperature and heat resistance of the copolymers, and the elastic-strength properties, due to the increased chain rigidity. It determined the influence of technological modes of 3-D printing by layering molten polymer filaments on the physico-mechanical properties of polyether sulfones.