【作者】 王银柱；

【导师】 熊国宣；

【作者基本信息】 东华理工大学 ， 化学工艺， 2012， 硕士

【摘要】 有机高分子化合物具有许多良好的物理和化学性能，如高弹性、可塑性、耐腐蚀、电绝缘性等，因而其应用非常广泛。其中某些高分子化合物具有磁性能，可作为磁性材料，与传统的磁体相比，具有比重轻、容易加工成精度高和复杂形状的优点。近年来，设计和合成有机高分子磁性材料成为国内外研究的热点方向之一。本文阐述了噻唑衍生物的合成研究进展、含噻唑聚合物的金属配合物的合成与磁性能研究现状，研究了三种联噻唑聚合物及其金属配合物的制备与电磁性能，其主要研究内容如下：（1）以溴代正丁烷和N-甲基咪唑为原料，通过烷基化反应制备溴化1-丁基-3-甲基咪唑（[Bmim]Br）。考察反应温度、时间、物料比对[Bmim]Br产率的影响，结果表明：在70℃反应24h、溴代正丁烷与N-甲基咪唑的摩尔比为1.2:1时，[Bmim]Br产率最大，达88.5%。利用红外、核磁共振及质谱对其结构进行表征，结果表明为目标产物。（2）[Bmim]Br和液溴混合制备三溴化1-丁基-3-甲基咪唑（[Bmim]Br3），然后利用[Bmim]Br3与2,3-丁二酮通过卤化反应得到1,4-二溴-2,3-丁二酮。再以1,4-二溴-2,3-丁二酮、硫脲为原料发生成环反应制备2,2′-二氨基-4,4′-联噻唑（DABT）。研究反应温度、时间、物料比对1,4-二溴-2,3-丁二酮及DABT产率的影响，结果表明：在50℃、滴加时间为20min、2,3-丁二酮与[Bmim]Br3的摩尔比为2.2:1时，1,4-二溴-2,3-丁二酮产率最大，达79.8%；当反应温度为90℃，反应2h，硫脲与1,4-二溴-2,3-丁二酮的摩尔比为2.2:1，DABT产率最大，达78.3%。利用红外及核磁共振对其结构进行表征，结果显示为目标产物。（3）以DABT和对苯二甲酰氯为原料，在二甲基甲酰胺（DMF）中通过酰化反应制备聚联噻唑对苯二甲酰胺（PBTTA）。聚合物分别与稀土离子（Y3+）及过渡金属离子(Cu²⁺、Ni²⁺)络合制备相应的金属配合物。探索反应温度、时间和物料比对PBTTA产率的影响，结果表明：在50℃温度下反应6h、对苯二甲酰氯与DABT的摩尔比为1.3:1时，PBTTA产率最大，达81.5%。利用红外光谱仪、X射线能谱仪、元素分析仪等对它们进行了表征，结果表明为目标产物。热重分析显示聚合物具有良好的热稳定性；常温下测得聚合物的电导率为8.04×10^-5S/cm，与金属配位后电导率小一个数量级，它们都有作为半导体材料的可能；在常温下研究聚合物及其钇的配合物的磁性能，发现PBTTA和PBTTA-Y3+的磁滞回线都呈现反“S”型，表明它们都表现出反铁磁性。（4）在酸性条件下，利用DABT、多聚甲醛分别与对硝基苯胺和对硝基苯酚缩聚制备聚合物SAD和SPD。聚合物在二甲基亚砜（DMSO）分别与与过渡金属离子(Cu²⁺、Ni²⁺、Mn2+)络合制备相应的金属配合物。探讨反应温度和时间对SAD、SPD产率的影响，结果表明：在100℃温度下反应6h时，SAD产率最大，达69.9%；在100℃温度下反应5h时，SPD产率最大，达79.5%。利用红外光谱仪、X射线能谱仪、元素分析仪等对它们进行了表征，结果可知为目标产物。从热重分析结果可知聚合物及其铜的配合物都具有良好的热稳定性，且与Cu²⁺配位后热稳定性下降。常温下测得本征态的电导率的分别为2.12×10^-5S/cm、4.54×10^-5S/cm，与金属配位后电导率小一个数量级，它们都有作为半导体材料的可能；在常温下研究聚合物及其铜离子配合物的磁性能，SAD、SPD的磁滞回线表明它们表现出反铁磁性。SAD-Cu²⁺是软铁磁体，它的饱和磁场强度为0.051emu/g，矫顽力为170Oe，剩余磁场强度为0.0021emu/g；SPD-Cu²⁺也是软铁磁体，饱和磁场强度为0.029emu/g，矫顽力为66Oe，剩余磁场强度为0.00105emu/g。更多还原

【Abstract】 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.更多还原