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Poly(3,4-ethylenedioxythiophene) (PEDOT) plays a key role in the field of electrically conducting materials, despite its poor solubility and processability. Various molecules and polymers carrying sulfonic groups can be used to enhance PEDOT’s electrical conductivity. Among all, sulfonated polyarylether sulfone (SPAES), prepared via homogenous synthesis with controlled degree of sulfonation (DS), is a very promising PEDOT doping agent. In this work, PEDOT was synthesized via high-concentration solvent-based emulsion polymerization using 1% w/w of SPAES with different DS as dopant. It was found that the PEDOT:SPAESs obtained have improved solubility in the chosen reaction solvents, i.e., N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone and, for the first time, the role of doping agent, DS and polymerization solvents were investigated analyzing the electrical properties of SPAESs and PEDOT:SPAES samples and studying the different morphology of PEDOT-based thin films. High DS of SPAES, i.e., 2.4 meq R-SO3−g−1 of polymer, proved crucial in enhancing PEDOT’s electrical conductivity. Furthermore, the DMSO capability to favor PEDOT and SPAES chains rearrangement and interaction results in the formation of a polymer film with more homogenous morphology and higher conductivity than the ones prepared from DMAc, DMF, and NMP.

The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used as easily accessible monomers for the synthesis of polylactic acid (PLA), is described here. An optimization of reaction conditions was carried out, with p-toluensulfonic acid emerging as the most efficient Br&oslash, nsted acid catalyst. The reactivity of the monomers in the tested conditions was studied following the monomer conversion by 1H NMR and the molecular weight growth by SEC analysis. A double activation polymerization mechanism was proposed, pointing out the key role of the acid catalyst. The formation of acetal bridges was demonstrated, to different extents depending on the nature of the aldehyde or ketone employed for lactic acid protection. The polymer shows complete retention of stereochemistry, as well as good thermal properties and good polydispersity, albeit modest molecular weight.