The Synthesis And Properties Of The Polymers Containing Bithiazole And Their Complexes

Organic polymers have many excellent physical and chemical properties, such as highelasticity, good plasticity, the resistance of corrosion, electrical insulation, etc., so that thepolymer materials have a very wide range of use. Some possess magnetic properties andcan be used as magnetic materials. Compared with traditional magnets, polymericmagnetic materials have the advantages of a light weight, easily processed into thecharacteristics of high precision and complex shapes gaining more and more attention. Inrecent years, the design and synthesis of polymeric magnetic materials becomes one of thehot subjects at home and abroad.This article reviews the progress on the synthesis of thiazole derivatives, the researchon the synthesis and magnetic properties of polymer containing thiazole and explored thepreparation of three kinds of polymers containing bithiazole and their metal complexes andthe electrical and magnetic properties, the main research content includes the following:（1）1-butyl-3-methyl imidazolium bromide （[Bmim]Br） was prepared by bromidebutane and N-methyl imidazole. The effects of the temperature, time and charge ratio ofreaction on the yield were considered and discovered on the temperature of70℃, the timeof24hours, molar ratio of bromide butane/N-methyl imidazole is1.2:1, the yield of[Bmim]Br had the maximum output is68.7%. The product were characterized by IR,NMR，MS and proved to be the target product.（2）1-butyl-3-methyl imidazolium tribromide （[Bmim]Br3） was obtained by themixture of [Bmim]Br and Br2and then reactioned with2,3-butanedione by halogenationreaction to gain1,4-dibromine-2,3-butanedione.2,2-diamino-4,4-bithiazole（DABT） wassynthesized by annelation of thiocarbamide and1,4-dibromine-2,3-butanedione. Theeffects of the temperature, time and charge ratio of reaction on the yield were investigatedand discovered on the temperature of50℃, the dropping time of20minutes, molar ratioof2,3-butanedione/Bmim]Br3is2.2:1, the yield of1,4-dibromine-2,3-butanedione had the maximum output is68.7%and the temperature of90℃, the time of2h, molar ratio ofaminothiourea/1,4-dibromine-2,3-butanedione is2.2:1, the yield of DABT had themaximum output is78.3%. Their structures were determined by IR and H-NMR, whichindicated they were the target products.（3） The polymer of PBTTA was synthesized from paraphthaloyl chloride and DABTby acylation in DMF and the metal complexes prepared from PBTTA coordinated with therare earth ion （Y3+） and transition metal ions (Cu²⁺and Ni²⁺). The effects of thetemperature, time and charge ratio of reaction on the yield were discussed and discoveredon the temperature of50℃, the time of6hours, molar ratio of paraphthaloyl chloride/DABT is1.3:1, the yield of PBTTA had the maximum output is81.5%. The products werecharacterized by IR, EDS and elementary analysis and testified to be the target products.The TGA analysis showed that it had good thermal properties. The conductivity ofpolymer measured at room temperature is8.04×10^-5S/cm, which is one order of magnitudebigger after coordination. They all can be used as semiconductor materials. The magneticproperties of PBTTA and its complex containing Y3+are examined at room temperature.The result shows that they are antiferromagnetism due to the shapes of their hysteresisloops are anti-S.（4） The polymer of SAD and SPD are synthesized by the polycondensation of DABT,paraformaldehyde and p-nitrophenol/paranitroaniline under acidity condition. Their metalcomplexes are prepared from polymers and mental ions (Cu²⁺, Ni²⁺, Mn2+) in DMSO. Theeffects of the temperature and time of reaction on the yield are studied and discovered onthe temperature of100℃, the time of6hours, the yield of SAD had the maximum outputis69.9%and the temperature of100℃, the time of5h, the yield of SPD had themaximum output is79.5%. The products were characterized by IR, EDS and elementaryanalysis and attested to be the target products. The TGA analysis showed that the polymersand their complexes with Cu²⁺have good thermal properties and the thermal propertydeclined after coordination. The conductivity measured at room temperature of SAD andSPD respectively are2.12×10^-5S/cm and4.54×10^-5S/cm, which are one order ofmagnitude bigger after coordination. They all can be used as semiconductor materials. Themagnetic properties of two polymers and their complex containing Cu²⁺are examined atroom temperature. Their hysteresis loop shows that the polymers are anti-ferromagnetisms.SAD-Cu²⁺is a soft ferro-magnetism, in which the saturation magnetization （Ms） is0.029emu/g, the observed coercive field （HC） is66Oe and the remnant magnetization （Mr）is0.00105emu/g. SPD-Cu²⁺is also a soft ferromagnetism, in which the Ms is0.029emu/g,the HCis66Oe and the Mr is0.00105emu/g.