【作者】 陈钦慧；

【导师】 林金火；

【作者基本信息】 福建师范大学 ， 高分子化学与物理， 2003， 硕士

【摘要】 本研究利用我国丰富的生漆和稀土资源合成出漆酚镨聚合物，使漆酰高分子功能化和稀土原子高分子化。并用元素分析、IR、UV、XPS、TG和化学手段等研究漆酚镨聚合物的形成机理及其结构特征与性能。结果表明，漆酚酚羟基与镨离子配位后其不饱和侧链基发生聚合交联生成漆酚镨聚合物。镨元素特殊的外层电子结构赋予漆酚镨聚合物许多特殊的性能，即能催化烯类单体聚合、催化酯化反应以及吸附有害气体。由漆酚与甲醛缩合制备的漆酚甲醛缩聚物中的酚羟基同样能与镨离子配位。以X-射线荧光分析、IR、DMTA和TG等手段研究漆酚甲醛缩聚物吸附三氯化镨前后的结构变化，并分别用联苯胺、丙烯酸树脂、苯胺、硫脲和糠醛等与漆酚共聚，试验不同官能团与镨离子的配位能力。结果表明，共聚物均能与镨离子形成配位键，其中氧原子是其最好的配体。 在涂料应用方面，采用互穿网络技术制备出漆酚甲醛缩聚物/醇酸树脂的共混物，互穿网络技术改善了漆膜的抗紫外线性能和柔韧性。为了进一步研究提高漆膜耐碱性的方法，利用IR、HPLC、DSC、DMTA和其它物理及化学手段表征苯胺或二乙烯三胺改性后的漆膜的结构与性能。这种改性使得漆膜的耐碱性以及在低温时的抗冲击性能均得到了提高。而且，二乙烯三胺改性后的漆酚聚合物可作为环氧树脂的固化剂，固化所得的环氧涂膜兼具漆酚聚合物和环氧类涂料的优异性能，耐酸、耐碱和有机溶剂。本研究为克服漆酚涂膜在抗紫外线性能和耐碱性方面的缺陷提供了理论和实验依据。更多还原

【Abstract】 Chinese lacquer, named as "the King of Coating", is a kind of special local product in our country. Its film is hard, heat-resistant and anti-corruptive, so the unearthed lacquerwares still keep good for thousands of years. However, it has been still an important work to improve the lacquer because of its inherent drawbacks such as being corroded by alkali, baddish weatherability, low adhesion to metal and drying only at definite temperature and humidity. The main component forming film of Chinese lacquer is urushiol which is o-dihydroxybenzene containing an unsaturated side chain. Urushiol polymer possesses good inter-soluble capability with the other resin owed to the long side chain. Urushiol and its polymer have phenolic properties because of the hydroxy in phenylene. In the first place, the hydroxy can react withthe atoms of transition element and rare element with vacant orbits. In the second place, the ortho-carbon or para-carbon of phenylene is apt to reacting with formaldehyde and amine. The functional material as urushiol metal polymer is prepared utilizing coordination reaction between urushiol or its polymer and metal compound. It is beneficial to open up some new applications and new functional materials for Chinese lacquer.On the basis of the summarizing of father’s works, firstly, the reaction properties of urushiol or its polymer with PrCl3 is studied. Then, it is studied about the functions of urushiol praseodymium polymer (PUPr) synthesized utilizing the reaction between Pr3+ and phenolic hydroxy in catalyzing the polymerization of olefinic monomers, catalyzing esterification and absorbing toxic gases etc. Finally, the modificative methods to urushiol formaldehyde condensation (PUF) with alkyd, aniline and diethylen etriamine and the characteristic of product are also studied.It is studied about the synthetical condition of solvent kinds, reactive time, reactive temperature and reactant ratio etc of PUPr obtained by hot polymerization inAbstractnon-water medium. Its forming mechanism, structure characteristic and properties are illustrated by elemental analysis, IR, XPS, TG and chemical means etc. The results show that the forming of PUPr is owed to the coordination between phenolic hydroxy and Pr3+ and further cross-linking reaction of the unsaturated side chains of urushiol. For the especial out-shell electronic configurations of praseodymium element, rigidity of phenyl groups and the curl of side chains, the coordination number of praseodymium is unsaturated. As a result, PUPr possesses many aspects catalytic properties. Firstly, PUPr is reactive for catalyzing the polymerization of olefinic monomers such as butyl a -methacrylate in the presence of sodium sulfite even in atmosphere and without stirring. Secondly, PUPr can effectively catalyze esterification between phthalic anhydride and butanol etc. Thirdly, the PUPr shows adsorptive capability to toxic gases as 862 and HCHO etc. PUPr exhibits higher activity, better reusability and electivity than little molecular catalyst.The phenolic hydroxy of PUF can also coordinate with praseodymium. The structural difference between PUF and PUFPr obtained by soaking in PrCla ethanol solutionis studied by IR, X-ray diffraction analysis, DMTA and TG etc. The results show that PUF-Pr(HI) polymer coordination compound forms owed to coordination bonds between PUF and praseodymium. For seeing about the reactive abilities of diverse functional group with Pr3+, urushiol group polymers containing diverse functional group as -NH2, =C=S or -OH etc are synthesized by co-polymerizing with benzidine, acrylic resin, aniline, sulfourea and furfural. The result shows that oxygen is the best ligand to Pr3+.The condensation polymer of urushiol and formaldehyde (PUF) is an important production in the modificative study of Chinese lacquer in our country. PUF possesses excellent physico-mechanical properties and has been used practically. However, The phenyl and unsaturated side chains of urushiol group have influence on its tenacity and resistance to ul更多还原