• Srinivas Darbha

      Articles written in Journal of Chemical Sciences

    • Solid, double-metal cyanide catalysts for synthesis of hyperbranched polyesters and aliphatic polycarbonates

      Joby Sebastian Srinivas Darbha

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      Fe-Zn and Co-Zn double-metal cyanide (DMC) complexes exhibit highly efficient and selective catalytic activity for synthesis of hyperbranched polyesters (glycerol-succinic acid (G-SA) and glycerol-adipic acid (G-AA)) and aliphatic polycarbonates (via., alternative co-polymerization of cyclohexene oxide and CO2), respectively. The influence of method of preparation of DMC, in particular the mode of addition of reagents, on its physicochemical and catalytic properties was investigated. Co-Zn DMC was found highly selective for polycarbonate (than polyethers) formation. Catalysts prepared using tert-butanol and PEG-4000 as complexing and co-complexing agents, respectively, were found superior to those prepared without these agents. Apart from its role as a coordinating ligand, tert-butanol activated the Lewis acidic Zn2+ sites for reactions in polyester and polycarbonate formation. Hydrophobicity, micro-mesoporosity, acid strength and the amount of coordinated complexing agent are some of the crucial factors influenced the catalytic activity of DMC complexes.

    • Synthesis of fatty monoester lubricant base oil catalyzed by Fe-Zn double-metal cyanide complex

      Ravindra K Raut Mehejabeen Shaikh Srinivas Darbha

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      Fatty monoester lubricant base oils as high as 96.7 mol% were prepared by reacting methyl oleate with long-chain alcohols viz., 2-ethyl-1-hexanol (C8−OH), 1-decanol (C10OH) and 1-dodecanol (C12OH) in the presence of a solid Fe-Zn double-metal cyanide (DMC) complex catalyst. Unlike many other acid catalysts, DMC doesn't produce undesired ether side products. The catalyst was reusable in four recycling experiments with little loss in catalytic activity and ester yield. The long-chain esters prepared in the study have the desired physical properties for their application as lubricant base oils.

    • Direct synthesis of dimethyl carbonate from CO2 and methanol over CeO2 catalysts of different morphologies

      UNNIKRISHNAN P SRINIVAS DARBHA

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      The direct synthesis of dimethyl carbonate (DMC) from carbon dioxide CO2 and methanol is an attractive approach towards conversion of the greenhouse gas - CO2 into value-added chemicals and fuels.Ceria CeO2 catalyzes this reaction. But the conversion efficiency of CeO2 is enhanced when the byproductwater in the reaction medium is separated by employing trapping agents like 2-cyanopyridine (2-CP). In thiswork, the influence of morphology of CeO2 on the direct synthesis of DMC in presence of 2-CP is reported.CeO2 catalysts of cube, rod, spindle and irregular morphology (Ce - C, Ce - R, Ce - S and Ce - N, respectively)were prepared, characterized and studied as catalysts in the said reaction conducted in a batch mode. Amongall, Ce - S shows superior catalytic performance with nearly 100 mol% of DMC selectivity. Catalytic activitycorrelates with the concentration of acid and base sites of medium strength as well as defect sites. Ce - S has anoptimum number of these active sites and thereby shows superior catalytic performance.

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