【作者】 牛宗；

【导师】 卞凤玲；

【作者基本信息】 兰州大学 ， 高分子化学与物理， 2012， 硕士

【摘要】 近些年来,随着人们对环境保护的日益重视和环保法规的逐渐加强,世界上各国对于传统的溶剂型涂料中所含有的挥发性有机物(VOC)的排放越来越加以限制。因此,开发低污染甚至无污染环境友好型涂料经成为涂料研制的主要方向。紫外光引发的水性涂料结合了水性技术和紫外光聚合技术的优点,具有引发速度快、环境友好、节能以及涂膜性能优良等优点,在最近20多年得到了迅猛发展,是新一代的绿色化工产品。本论文研究的主要内容是紫外光引发的水性聚氨酯的制备,并通过KH550,环氧树脂,丙烯酸酯等对水性聚氨酯进行改性,从而得到涂膜性能较好的环境友好型涂料：(1)以异佛尔酮二异氰酸酯(IPDI)、聚乙二醇(PEG)、二羟甲基丙酸(DMPA)、季戊四醇三丙烯酸酯(PETA)为原料合成了一系列紫外光固化水性聚氨酯丙烯酸酯树脂(UV-WPUA),并进一步研究了UV-WPUA的合成条件与树脂水溶性以及涂膜性能之间的关系。研究结果表明：当DMPA用量为6.0-8.0%,双键含量在0.873-1.558mmol/g,光引发剂的质量分数(以乳液的质量分数计)为3%,n(-NCO)：n(-HO)在1.3-1.4之间时,紫外光固化水性聚氨酯丙烯酸酯树脂的综合性能较好。(2)用硅烷偶联剂(KH550)的伯胺基团对双酚A型环氧树脂(E51)的环氧基进行开环得到KH550-E51,再将其引入到聚氨酯预聚物的主链中,制备了一系列多重交联的紫外光固化水性聚氨酯(UV-PUDs)。研究结果表明：随着KH550-E51用量的增加,乳液的平均粒径增大,透明度下降,当KH550-E51引入量为10.0%,稳定性变差；KH550-E51的引入提高了涂膜的耐水性,耐热性以及机械强度。当KH550-E51的引入量为9.1%时,涂膜的综合性能达到最佳。(3)通过在聚氨酯预聚物末端引入乙烯基得到聚氨酯乳液(WPU),然后以WPU为种子,使用紫外光引发的无皂乳液聚合方法与丙烯酸酯类的单体共聚,制备了一系列具有互穿网络结构的聚氨酯／含氟聚丙烯酸酯聚合物(PU/PALIPNs).研究结果表明：紫外光引发聚合达到和热引发聚合相同的产率时需要的温度更低,时间更短；含氟单体的引入赋予了涂膜良好的耐水性和耐热性；当PU/PA为1/1时,涂膜有着较好的耐水性、耐热性以及机械性能。更多还原

【Abstract】 In recent years, with people increasingly attach importance to environmental protection and environmental regulations have been gradually strengthened, the emission of volatile organic compounds (VOC) from traditional solvent-based paints has been limited in the world. Therefore, the development of low pollution and even non-polluting paint become one of the main direction of coating developed.UV-initiated waterborne coatings combine the advantages of waterborne technology and UV technology. Owing to fast curing speed, environmental friendliness, energy saving and excellent film properties, UV response waterborne coatings has been developing rapidly in the last20years and become a new generation of green chemicalproducts.The main content of this thesis is to synthesize and modify UV-initiated waterborne polyurethane with KH550, epoxy resin, acrylate, and get environment friendly paint with good film properties.(1) A series of ultraviolet curable waterborne polyurethane acrylate resins (UV-WPUA) had been synthesized from isophorone diisocyanate (IPDI), poly (ethylene oxide) glycol (PEG), dimethylol propionic acid (DMPA), pentatry thritol triacrylate (PETA). The effects of the different conditions on resin water-soluble and performance of the film was investigated. The results showed that when the content of DMPA, double bond, photoinitiator and n(-NCO)/n(-HO) were6-8%,0.873-1.558mmol/g and3%(mass ratio) and1.3-1.4respectively, the UV-WPUA exhibited good properties.(2) We used3-aminpropyltriethoxysilane (APTES) to open the epoxy ring of bisphenol-A-based epoxy resin (APTES-E51) and incorporated it into the chains of polyurethane to synthesize a series of multiple cross-linking UV-curable waterborne polyurethane dispersions (UV-PUDs). The average particle size increased with increasing the APTES-E51content and the stability of the UV-PUD storage became poor when the content of APTES-E51was10.0%. After modification with APTES-E51, the water resistance, thermal stability and tensile strength of films were all raised. We can obtain good storage stability, satisfied water resistance, high thermal stability and tensile strength when the APTES-E51content is9.1%.(3) A series of polyurethane (PU)/fluorine-containing polyacrylate (PA) latex interpenetrating networks (LIPNs) were synthesized in two stages. Firstly PU dispersion was synthesized by self-emulsification polymerization. Then the PU/fluorine-containing PA LIPNs using PU dispersion as a seed were prepared by ultraviolet (UV)-initiated soap free emulsion polymerization. Compared to the corresponding thermal-initiated polymerization, UV-initiated polymerization could be accomplished at a higher speed and a lower temperature. The incorporation of fluorine-containing groups markedly improved the water resistance and the thermal stability of the LIPN film. We could obtain satisfied water resistance, high thermal stability and mechanical property when the PU/fluorine-containing PA weight ratio reached1/1.更多还原