【作者】 郑平；

【导师】 孙维林；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2005， 硕士

【摘要】 本论文综述了有机磁性材料的发展和现状,并在此基础上提出了本论文的工作,主要包括制备含噻唑侧基的聚丙稀酰胺聚合物及其金属配合物,研究其磁性能的特点及其与结构的关系,为丰富有机磁性材料的理论研究进行了有益的探索。 文中合成了二种含噻唑侧基的丙稀酰胺单体:N-2-噻唑丙稀酰胺（NTA）和N-2-噻唑甲基丙稀酰胺（NTMA）,并通过自由基聚合的方法制备了各自的均聚物:聚（N-2-噻唑丙稀酰胺）（Poly-NTA）和聚（N-2-噻唑甲基丙稀酰胺）（Poly-NTMA）。用IR,¹H NMR等手段对单体及聚合物的结构进行了表征。测定了两种聚合物的特性粘数。 将这两种含噻唑侧基的聚丙稀酰胺聚合物分别与过渡金属离子Fe（Ⅱ）和稀土离子Nd（Ⅲ）、Pr（Ⅲ）、Sm（Ⅲ）反应,制备了8种新型的高分子-金属配合物。用IR对其结构进行了分析,并用络合滴定法测定了各种配合物的金属离子含量。 通过PPMS-9T（QUANTUM DESIGN）测定仪测定了8种金属配合物的磁性能（温度范围4～300K,磁场范围-50～50 kOe）,其中包括磁化强度与温度的关系、磁化强度与外加磁场的关系、磁化率与温度的关系以及磁滞回线。通过分析得出了各金属配合物在低温下的磁性:PolyNTA-Nd³⁺,PotyNTA-Pr³⁺,PolyNTMA-Fe²⁺为软铁磁性;PolyNTA-Fe²⁺,PolyNTMA-Pr³⁺为反铁磁性;PolyNTA-Sm³⁺,PolyNTMA-Nd³⁺,PolyNTMA-Sm³⁺各自存在一个特定的磁性转变温度,高于此温度配合物表现出抗磁性,低于此温度表现铁磁性。 最后针对单噻唑环对稀土离子的配位能力较差的问题,设计了一种新的含双噻唑结构的二烯单体:2,2’-二丙烯酰胺基-4,4’-联噻唑（DAABT）。通过IR,¹H NMR等方法确定了其结构。对DAABT的聚合进行了初探,发现通过自由基聚合的方法很难使该单体聚合。更多还原

【Abstract】 The development and status in quo of organic magnetic materials have been summarized in this paper. The main task has been proposed on the basis of the introduction, which including the synthesis of acrylamide-type polymers with pendent thiazolyl groups and their metal complexes, the relationship of their structures and magnetic properties. The aim of these studies is supposed to contribute to the theoretical research of organic magnetic materials.Two acrylamide-type monomers, N-2-thiazolylacrylamides (NTA) and N-2-th.iazolylmethacrylamides (NTMA), were synthesized and polymerized by a radical route to obtain the corresponding polymers in good yields. FTIR and ]H NMR were applied to characterize these materials. The Viscosity of the two polymers were also measured.These two acrylamide-type polymers reacted with transition metal ion Fe(II) and rare earth ions Nd(III), Pr(III), Sm(III) to produce 8 novel polymer-metal complexes. FTIR were applied to characterize their structure and the metal content was determined by complexometric titration.The magnetic properties of these polymer-metal complexes were measured by a PPMS-9T magnetometer (QUANTUM DESIGN), which include magnetization versus temperature, magnetization versus applied field, magnetic susceptibility versus temperature and magnetic hysteresis. 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 PolyNTA-Nd3+, PolyNTA-Pr3+ and PolyNTMA-Fe2+ were soft ferromagnet; PoIyNTA-Fe2+ and PolyNTMA-Pr3+ were antiferromagnet; PolyNTA-Sm3+, PolyNTMA-Nd3+and PolyNTMA-Sm3+ exhibited a special magnetic property: along with the decreasing of temperature, they changes from a diamagnet to ferromagnet with a certain transition temperature.At the end of this paper we designed a new bithiazole-containing monomer, 2,2’-diacrylamido-4,4’-bithiazole (DAABT). FTIR and lH NMR were used to confirm the structure of the monomer. It is supposed to possess greater coordinative ability compared with poly(N-2-thiazolyl(meth)acrylamides). We attempt to study the preparation of its polymer, but it is difficult for DAABT to be polymerized by a radical route.更多还原