PTMG-g-HFP及含氟聚氨酯的合成、表征与性能研究

【作者】 葛震；

【导师】 张兴元；

【作者基本信息】 中国科学技术大学 ， 高分子化学与物理， 2006， 博士

【摘要】 聚氨酯(PU)材料因其具有良好的机械性能、可低温固化，附着强度高，以及耐水、耐溶剂、耐低温等优点，在许多领域和日常生活中得到了广泛的应用。但随着社会的迅速发展和进步，对材料的保护性能和装饰性能，尤其是耐久性提出了更高更新的要求，面对新的要求，原有的聚氨酯材料就显示出了很大的不足，限制了它的应用。而含氟聚氨酯(FPU)材料作为一类新型高分子功能材料，由于含氟基团的引入，可以使聚合物同时具有极低的表面能、优异的化学稳定性和憎水憎油性，因此很好的弥补了原有PU材料在这些性能方面的不足。本论文首次采用自由基接枝法合成出了含氟聚氨酯的中间体—含氟聚醚二醇，并对其合成工艺和反应机理进行了研究和探讨。进一步以它为软段成功制备了FPU材料，并对这种FPU的本体和表面结构进行了鉴定和分析，同时初步探讨了FPU结构和性能之间的关系。 1．采用自由基接枝法，在引发剂引发作用下，将六氟丙烯(HFP)接枝到聚四亚甲基醚二醇(PTMG)链中，从而合成出了一种新型含氟聚醚二醇(PTMG-g-HFP)。通过IR、NMR和GPC等分析手段对其结构和组成进行了鉴定和表征，进一步讨论了接枝反应的机理，同时考察了各种实验条件对接枝反应的影响。对合成出的含氟聚醚二醇的羟值进行了测定，发现低于理论值，其原因在于接枝反应中PTMG的部分羟基与HFP发生了反应，为此设计了一种方法：“保护羟基-接枝反应-脱保护恢复羟基”，通过该方法改进和完善了PTMG-g-HFP的制备方法。对乙酰化和硅烷化两种羟基保护方法进行了比较，结果发现虽然这两种方法通过优化反应条件都能完全保护PTMG的羟基，但是完全脱除乙酰化的保护基却很困难，而硅烷保护基能够完全脱除。因此采用“硅烷化反应保护PTMG羟基—接枝HFP—脱保护恢复羟基”的合成路线是制备PTMG-g-HFP的最佳方法。 2．以合成出的含氟聚醚二醇(PTMG-g-HFP)为中间体，成功制备了含氟聚氨酯(FPU)材料，通过IR、NMR测试手段对其结构进行了表征。同时比较了普通PU和FPU的热稳定性，结果发现FPU的热稳定性要高于普通PU，而且芳香族的FPU热稳定性要好于脂肪族的FPU。此外对FPU的耐化学性进行了考察，发现制备出的FPU具有优异的耐化学性能。更多还原

【Abstract】 Due to their excellent mechanical properties, curing at low temperature, high adhesion, and high resistance to water, solvents and low temperature, polyurethane（PU） have been widely applied in many fields and daily lives. However, with the development and progress of society, higher and newer requirements of protective and ornamental especially to wear have been presented. Original PU materials have showed insufficiency and their use have been limited in the face of these requirements. Fluorinated polyurethane （FPU）, as a species of novel macromolecule functional materials, owing to the introduction of fluorinated groups, have very lowest surface energy, excellent resistance to chemicals water and oils. Therefore, FPU have supplied original PU gap in the above mentioned shortages. In this dissertation, the intermediate of FPU, i.e. a novel fluorinated polyether glycol were synthesized via the radical grafting. At the same time, the synthesis technics and reaction mechanism were studied and discussed. FPU were successfully prepared with the fluorinated polyether glycol as intermediate. The bulk and surface structures of FPU and properties were investigated, and the relation between the structures and properties were discussed preliminarily.1. A new fluorinated polyether glycol （PTMG-g-HFP） was prepared by radical grafting of hexafluoropropylene （HFP） onto polytetramethylene glycol （PTMG） in the presence of different initiators by radical grfting. The structure of PTMG-g-HFP was characterized by means of IR, ¹H NMR and ¹³C NMR. The effects of the nature and amount of initiator, reaction time and temperature on the grafting HFP onto PTMG were investigated. The measured hydroxyl values of PTMG-g-HFP were lower than theoretical values. Therefore, a new protection-graft-deprotection procedure was designed. The prepartion of PTMG-g-HFP was improved and perfected via the procedure. By the comparison of acetylation and silylation protection hydroxyl methods, it was found, though the hydroxyl of PTMG had been totally protected by the optimal reaction conditions with two protection methods, the acetylated protective groups were hard to be totally deproected and the silylated protective groups were更多还原