Synthesis, Characterization and Conductivity Properties of Novel Oligomer Schiff Bases Derived from 4-Amino-3-hydrazino-5-mercapto-1, 2, 4-triazole and Their Reactions with VO(Ⅳ), Cu(Ⅱ) Ions

摘要

A new Schiff base, 4-(4-hydroxysalicylid-enamino)-3-hydrazino-5-mercapto-1,2,4-triazole (4HSAHMT), and novel Schiff base oligomers of 4-salicylidenamino-3-hydrazino-5-mercapto-1,2,4-triazole (SAHMT), 4-(2-hydro-xynaphthylidenamino)-3-hydrazino-5-mercapto-1,2,4-triazole (2HNAHMT),4-(4-hydroxysalicylidenamino)-3-hydrazino-5-mercapto-1,2,4-triazole (4HSAHMT) and 4-(5-bromosalicyli-denamino)-3-hydrazino-5-mercapto-1,2,4-triazole (BrSAHMT) were synthesized via oxidative polymerization using NaOCl as the oxidant. The structures of the oligomers were supported by FT-IR, UV-Vis, ~1H-NMR, and ~(13)C-NMR techniques. The compounds were further characterized by solubility tests, TG-DTA, and elemental analysis. The molecular weight distribution parameters of the compounds were determined by the size exclusion chromatography (SEC). According to SEC, the number average molecular weight (M_n) values of O-SAHMT, O-BrSAHMT, O-4HSAHMT and O-2HNAHMT were 2,700, 2,100, 2,700 and 1,000 g mol~(-1), respectively. The weight losses of O-SAHMT, O-BrSAHMT, O-4HSAHMT and O-2HNAHMT were 73, 76, 80 and 54 %, respectively, at 1,000 ℃. TG analyses showed that the synthesized oligomers were stable toward thermal decomposition. The synthesized oligomers were converted to metal complexes with salts of VO(Ⅳ) and Cu(Ⅱ). The doped and undoped electrical properties of oligomers and oligomer-metal complexes were determined by the four-point probe technique at room temperature and atmospheric pressure.