One-Pot Syntheses of PET-Based Plasticizer and Tetramethyl Thiuram Monosulfide (TMTS) as Vulcanization Accelerator for Rubber Production

Abstract

Styrene-butadiene (SBR) and acrylonitrile-butadiene (NBR) rubber blends with tetramethyl thiuram disulfide (TMTD) and tetramethyl thiuram monosulfide (TMTS) accelerators and environmentally friendly plasticizers, obtained from PET recycling and biobased resources (LA/PG/PET/EG/LA), were prepared. The mechanical properties of the obtained rubber products were tested and compared with those of commercial dioctyl terephthalate (DOTP). TMTS was prepared by simple and efficient one-pot synthesis from dimethylamine, carbon disulfide, potassium cyanide, and ammonium chloride as catalysts in recycled isopropanol/water azeotrope as solvent. In a comparative study, methoxide, ethoxide, iodide, and amide ions were also used. The two-step reaction mechanism of TMTS synthesis involves the oxidation of the amine salt of dimethyldithiocarbamic acid to TMTD by hydrogen peroxide and sulfur elimination from the TMTD disulfide bond. Potassium cyanide appears to be the most efficient nucleophile. The simplicity of operation, mild reaction conditions, solvent recycling, high yields, and applicability to the industrial level are the advantages of this process. Shore hardness, tensile strength, and compression test results of vulcanized blends before and after aging showed similar properties for both accelerators, while somewhat better results were obtained with LA/PG/PET/EG/LA plasticizer.