【作者】 林彩萍；

【导师】 孙维林；

【作者基本信息】 浙江大学 ， 高分子化学和物理， 2003， 硕士

【摘要】 随着社会的进步，科学的发展以及高新技术的应用，对磁性材料不断提出更高的要求。有机或高分子铁磁性材料越来越引起科技工作者的重视。有机磁体在超高频装置、高密度存贮用的磁光材料、新型微波吸收剂、电子工业的微型化、空间动力系统、宇宙航行系统等方面具有较大的应用前景。同无机磁性材料相比，有机或高分子磁性体结构多样，磁性可在分子水平上调整，另外有机磁体还有密度小、易加工等特点，因此合成新型有机铁磁体在磁性材料领域具有重大的意义。 含2,2’—二氨基—4,4’—联噻唑（DABT）芳杂环系列的聚西佛碱，能与金属离子配位，生成配位化合物。经先前研究探索表明，这一类型金属配合物具有良好的铁磁性能。为了进一步的探寻高性能，更优异的新型有机磁性材料，丰富有机磁性理论，研究结构与磁性能的关系，为开拓有机磁性高分子材料的应用打下坚实的基础，本文系统地概述了分子磁体和有机高分子磁性材料的结构和磁性能。本工作设计并合成了三个新型结构的芳杂环聚西佛碱，并且制备其相应的金属配合物7个，测定了它们中一部分的磁性能，结果表明含噻唑及吡啶环的芳杂环聚西佛碱金属离子配合物，具有软磁性能；用原位共混的方法，由PVA和聚酰胺金属配合物制备成均相PVA磁性复合膜，并考察共混前后的磁性能变化。为改善含噻唑类金属配合物的加工性能探索了一种可行方法。 具体的工作如下： （1）合成了三个新型结构的芳杂环聚西佛碱（PBTAP，PBTMP，PBTPP），并与金属离子配合，得到其金属配合物并研究它们的磁性能。 经磁性测量表明：PBTAP-Fe²⁺单金属配合物，在2K时，最高磁饱和强度（Ms）为6.2emu／g，顺磁居里温度（T_p）达88K，S型的磁滞回线表明此配合物在低温下是有机软磁体。对于PBTMP-Fe²⁺，Ms=4.8emu／g，顺磁居里温度为负值，表明未成对电子之间有相互作用，呈反铁磁性。2K时观察到PBTMP-Fe²⁺的磁滞回线，剩磁为0.08emu／g，矫顽力（H_c）可达300Oe。这些磁性数据表明：PBTMP-Fe²⁺配合物在低温下呈铁磁性，当温度升高后，表现反铁磁性。PBTMP-Cu²⁺：Ms=5.1emu／g，其剩磁为0.009emu／g，H_c=42Oe，因此，PBTMP-Cu²⁺是一个软的有机聚合物铁磁体。PBTPP-Fe²⁺的磁饱和强度为3.4emu／g，顺磁居里温度为负值，低温下同样可观察到磁滞回线。此配合物的磁 浙江人学硕士学位论文件与 pBTW不／“配合物的磁性很相似。也是一个低温下呈铁磁性，随着温度升高，呈反铁磁性。 （2 ） 由 PVA和聚合物配合物原位共混，使得配合物溶解在溶剂中，制备成PVA a合膜、复合膜颜色比配合物自身颜色法，且均相透明。通过电镜观察PVA复合吸的微相结构，发现：作为分散相的配合物在 PVA中分布很均匀，而且配合物札PVA的相界面也不明显，证实了配合物和PVA之间是存在相互作用，不只是简单的共混。 配合物PVA复合膜的磁性测试表明：DCIAIfe》配合物PVA复合膜，在二SK时，MS＝0尸8 Cio山g，T。＝80K，表明此复合膜在低温下发生部分磁有序，从而表现出一定的铁磁性。复合版的磁性与纯DCIAI不e》配合物的磁性相比，可发现：共混前后配合物的磁性能基本不变，复合膜中含配合物数量的减少导致复合膜的各磁性特征数值的减少。同时也测定了＊＊＊PA(UDPw复合膜的磁性能。ZK日寸，Ms二1．15 emu／g，H。二0刀olemu／g，矫顽力为20Oe。其乘余磁场羽1矫心UJ都很小，是一个非常软磁性物质。 J沂究中用FTIR、NAUI等来确定配合物的结构，通过多功能材料物理狈u量系统（PPMS：P卜yslC81 PfopCrty MC。sUrCmC川SystCffi）测定配合物的磁性营。更多还原

【Abstract】 With the advancement of society, development of science and application of high-tech there is need for magnetic materials with the better performance. The organic or polymeric magnetic materials which have a prospect application in many areas such as magnetic-optic materials, novel absorbents of microwave, micromation of electron products, space kinetics systems and universe sail systems have interested more and more scientists and engineers. Compared with inorganic ferromagnet, the organic ferromagnet exhibits the characteristics of structural diversities, low density, and readily processing. The magnetic feature of organic or polymeric ferromagnet can be revealed in the submolecular level. So the synthesis of novel organic magnets was significant in the field of magnetic materials.A serial of bithiazole-containing heteroaromatic poly (schiff base) s and their metal complexes have been synthesized. The previous research showed that these compexes are ferromagnetic materials. In order to find the new organic magnetic materials with the better performance, enrich the organic magnet theories, study the relationship between the structure and property, lay down a basement for the application of these magnetic materials as well, we syntheses three new poly (schiff base) s and their metal complexes. The magnetic property of some compexes has also been measured. The results show: the metal comolexes of heteroaromatic poly (schiff base) are soft magnets. Novel homogeneous composite films were prepared by in-silu blending the metal complexes of polyamides with polyvinyl alcohol (PVA). The magnetic properties of the compexes and their related PVA composite film are also studied. This method provides a way to synthesize soluble magnetic materials.The material work is followed:(1) Three poly(schiff base)s (PBTAP, PBTMP, PBTPP) and their compexes were synthesized by condensation and comlexation. The magnetic properties of complexes were measured as well.It was found: PBTAP-Fe2+ has a relative high saturation magnetization (Ms) (6.2 emu/g). The curie-temperature (Tp) of PBTAP-Fe2+ is 88 K and there is a magnetic hysteresis loop at low temperature. It is show PBTAP-Fe2+ is a soft ferromagnet in low temperature. To PBTMP-Fe2", the saturation magnetization is 4.8emu/g. The value of curie-temperature is negative and means there are some interaction between the unpaired electrons. The hysteresis loop of PBTMP-Fe2+ is observed in 2K. The coercivity (Hc) of PBTAP-Fe2+ is 3000e, and the remanence magnetization is 0.08emu/g. All the data show: PBTAP-Fe2+shows ferromagnetism at low temperature and antiferromagnetism at the relative high temperature. The magnetic property of PBTMP-Cu2’ is similar with that of PBTAP-Fe2". Ms=5.1 emu/g, H.^42 Oe, and the remanence magnetization is 0.009emu/g. PBTMP-Cu2+ is a soft polymeric magnet. The relative saturation magnetization of PBTPP-Fe2+ is lower than that of PBTMP-Fe2+. The value of Tp is negative. To PBTPP-Fe2+ there is also a hysteresis loop at 2K. The magnetic property of PBTPP-Fe2+ resembles of that ofPBTMP-Fe2".(2) The composite films synthesized by in-situ blending the metal complexes of polyamides with polyvinyl alcohol (PVA) are homogeneous, transparent. The micro structure of the film observed by SEM shows the compex destribted in PVA evenly and the interface between the PVA and complex is not apparent. This means there exist some interaction between the comlex and PVA.The magnetic properties of PVA composite films were measured. To DClAl-Fe2+ PVA composite film, the saturation magnetization is 0.78 emu/g at 2.5 K and the curie-temperature is 80 K. The magnetic property of the composite film is similar with magnetic property of pure DClAI-Fe2+. The characteristic value of composite is lower than that of the complex only because there is a little content of complex in composite film. The magnetic property of DTTPA-Cu2+ PVA composite film is also measured. At 2 K the saturation magnetization is 1.15 emu/g. The hysreresis loop shows the coercivity is 20 Oe and the reman更多还原