Starch xanthate–polyethylenimine reaction mechanisms

The chemical nature of starch xanthate (SX)–polyethylenimine (PEI) reaction products has been studied because of their effectiveness as wet‐end additives for improving strength properties of paper. Model compounds, in conjunction with ultraviolet, infrared, and chemical analyses, served to elucidate SX–PEI reaction mechanisms. Aqueous solutions of SX (degrees of substitution 0.1–0.5) were titrated with PEI at pH 5–7 (25–30°C) to form SX–PEI flocculent precipitates that were determined to be polyelectrolyte complexes. However, when solutions of SX–PEI were kept at pH 10–12, products were formed that included dithiocarbamic acid salts in major quantities, PEI thioureas, and minor quantities of O‐starch PEI thinocarbamate. Acid precipitation of these SX–PEI polymeric reaction products from their alkaline solutions, which contained residual xanthate and PEI, also yielded polyelectrolyte complexes. Model systems suggest that PEI thiuram disulfide and starch xanthide, possible products of air oxidation, could be present in minor amounts and would react rapidly with PEI to yield thioureas and thioncarbamates, respectively. Apparently, mixtures of xanthate and amine gave (1) dithiocarbamic acid salts from both xanthate groups and CS2 (decomposition from xanthate), (2) thioureas from both dithiocarbamic acid salts and thiuram disulfide, and (3) thioncarbamates, principally from xanthate as opposed to xanthide.