Journal of Colloid and Interface Science, Vol.336, No.1, 59-66, 2009
A humic-acid-like polycondensate produced with no use of catalyst
The synthesis and physicochemical characterization of a water Soluble humic-acid-like polycondensate (HALP), which mimics fundamental physicochemical and spectroscopic properties of natural humic acids is presented. The polymer can be synthesized under ambient O-2 by oxidative co-polymerization of gallic (GA) and protocatechuic (PA) acid at pH >9, with no need for a catalyst. Solid state C-13 NMR spectra for GA-PA-HALP show that ring-opening reactions of CA, PA monomers are involved in GA-PA-HALP formation. EPR spectroscopy shows that GA-PA-HALP contains stable phenol-based radicals, with pH-dependent concentration. The H-binding profile of GA-PA-HALP follows the NICA-Donnan model, with two sets of distributed pK(a), values in the range 4-6 corresponding to carboxyl groups, and 7-9 corresponding to phenolic groups, as in natural HA. GA-PA-HALP bears a permanent negative charge Q(0) = -2.3 equiv kg(-1) which is higher than the literature Q(0) values of -1 to -2 equiv kg(-1) observed for natural HAs. A critical comparison of the present data with literature data is provided. (C) 2009 Elsevier Inc. All rights reserved.
Keywords:Synthetic humic acid;HALP;H-binding;NMR;EPR;Gallic acid;Protocatechuic acid;Polymerization;O-2;Radical;Polyphenol;Ring opening