Preparation Of Aromatic Heterocyclic Polymers With Pendent Thiazolylazo Groups And The Magnetic Properties Of Their Metal Complexes

The development and status in quo of organic magnetic materials have been summarized in this paper. The main task, which includes the synthesis of acrylate-type polymer with pendent 4-(2-thiazolylazo)phenyl group, 4-(2-thiazolylazo)-1,3-benzene polyester and their metal complexes, the relationship between their structures and magnetic properties, has been proposed on the basis of the introduction. The aim of these studies is supposed to contribute to the theoretical research of organic magnetic materials.The acrylate-type monomer, 4-(2-thiazolylazo)phenyl methacrylate, was synthesized and copolymerized with methyl methacrylate by a free radical route to obtain a novel copolymer, poly(TPMA-co-MMA), in good yields. FT-IR, 1H NMR and Elemental Analysis were applied to characterize these materials. The copolymer was also determined through gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and glass transition temperature (Tg) methods. 4-(2-thiazolylazo)-resorcin (TAR) was prepared and condensed with succinyl chloride, adipoyl chloride and sebacoyl chloride respectively, and resulted in three kinds of novel polyesters (PTABAn). The viscosity of these polymers was measured, and the structure of them was characterized, too.Twelve novel polymer-metal complexes were prepared by reacting the polyesters with transition metal ion Cu (â…¡), Fe (â…¡) and Ni(â…¡), and PTABA06 with rare earth ions Nd (â…¢), Pr (â…¢), Sm (â…¢). FT-IR was applied to characterize their structures and the metal contents were determined by complexometric titration.The magnetic properties, which include magnetization versus temperature, magnetization versus applied field, magnetic susceptibility versus temperature and magnetic hysteresis, of five kinds of these polymer-metal complexes were measured by a PPMS-9T magnetometer (QUANTUM DESIGN). The temperature is ranged from 4 to 300 K and the intensity of magnetic field is ranged from -50 to 50 kOe. According to the measurement, it can be concluded that PTABA04-Ni2+, PTABA06-Cu2+, and PTABA06-Nd3+ were soft magnets, PTABA10-Fe2+and PTABA10-Fe2+ were antiferromagnets under certain temperatures.At the end of this paper we designed and synthesized two new 2-thiazolylazo-containing monomers, 2-(2-thiazolylazo)-4-cresolyl arylates (TACA) and 2-(2-thiazolylazo)-4-cresolyl metharylates (TACMA). FT-IR and 1H NMR were used to confirm the structure of the monomers. Further investigations concerning polymerization and properties of these monomers are in progress.