【作者】 马细柳；

【导师】 李再峰；

【作者基本信息】 青岛科技大学 ， 应用化学， 2006， 硕士

【摘要】 水性聚氨酯(PU)是一种新型以水为溶剂的聚氨酯体系。该乳液由于其优良性能和无污染被广泛应用。本论文由四部分组成：1)IPDI基阴离子水性聚氨酯树脂的制备与性能研究 2)酮亚胺的制备及其对水性聚氨酯性能的改进 3)新型丙烯酸酯改性聚氨酯水性树脂的制备与性能研究 4)活性自由基聚合大分子引发剂的制备。 第一部分系统地研究了HEA封端的水性聚氨酯树脂，讨论了DMPA用量、反应温度、引发剂种类和用量对乳液及成膜性能的影响。研究结果表明：随DMPA用量的增加，乳液粒径减小，外观由不透明变得透明；当温度为75℃，反应3h得到的乳液透明且带蓝光，外观最好；安息香乙醚引发的交联型聚氨酯漆膜与过氧化二异丙苯引发所得到的电泳膜相比，硬度明显提高。 第二部分以丙酮和乙二胺与己二胺为原料合成酮亚胺，并以其作为潜伏性扩链剂改性水性聚氨酯。实验过程中，研究了不同方式、加入不同量的酮亚胺对水性PU漆膜厚度、硬度、涂膜的耐水性、耐酸性、耐碱性、热稳定性和机械力学性能的影响。结果表明，采用丙酮缩乙二胺扩链的水性PU乳液的电泳漆膜和涂膜，在耐水性、耐酸性、耐碱性等性能都优于用丙酮缩己二胺和用水扩链的PU乳液的漆膜和涂膜，且加入过量的酮亚胺扩链效果较好，但其热稳定性并没有得到明显提高。 第三部分采用设计合成的丙烯酸酯与半封闭TDI或聚氨酯预聚物溶液共聚法对聚氨酯进行改性，合成了不同封端比例和不同封端剂的半封端异氰酸酯以及不同配方的丙烯酸酯，并对二者进行共聚研究。讨论了半封端异氰酸酯的种类与封端比、丙烯酸酯的用量、配方等对漆膜外观、凝胶含量、耐腐蚀性能和热稳定性的影响。交联后的漆膜的凝胶含量提高达10％，聚氨酯-丙烯酸酯在低温下共聚时得到的漆膜外观柔软有韧性，但是乳液不能长期稳定，而高温下共聚得到乳液虽然稳定，但是漆膜硬且脆。随丙烯酸酯软单体含量的增加，漆膜硬度下降，PUA热稳定性相对提高，但漆膜的耐水、耐酸性和耐碱性普遍下降。在MEKO封端体系中，PUA漆膜，耐水、耐酸、耐碱性均为封端比例高者较好。在HEA封端的体系中，漆膜的耐酸性为封端比例高者较好，但其耐水性和耐碱性反而为封端比例低者较好。更多还原

【Abstract】 In this dissertation, the synthesis of waterborne polyurethane resins and its relative properties were studied. It consists of four main parts of (1) study of the preparation and properties for the IPDI based waterborne polyurethane, (2) the synthesis of ketimine and modification of aqueous polyurethane, (3) modification of water-based polyurethane dispersions by polyacrylate, and (4) preparation of "living" radical macromolecule initiator.First, we discussed the effect of processes, such as contents of DMPA, temperature and initiator, on the performance of water-based polyurethane resin. The results showed that the dispersion was clear and the particle diameter became smaller with the increasing of DMPA amount. The apparent of the dispersion was best at the reaction temperature of 75 ℃ and 3 hours of reaction time. The hardness of electrophoretic film initiated by ethoxybenzoin was better.Second, ketimines were applied as potential chain-extender to modify water-based polyurethane. The ketimines were synthesized by acetone, ethylene diamine and hexamethylene diamine. The hardness, thickness of the PU electrophoretic film, the corrosion-resistance and mechanical performance of the paint film were affected by the way of adding, and the amount and kinds of ketimines. The results showed that the performance of PUD modified by ketimine from ethylenediamine was better than that of PUD modified by ketimine from 1,6-hexanediamine. However, the thermal stability of the PU paint film was not improved dramatically.Third, the self-made water-based polyacrylate containing hydroxyl group, half-capped-TDI or fine designed polyurethane prepolymer were applied to synthesize更多还原