【作者】 杨涛；

【导师】 夏正斌； 陈海洪；

【作者基本信息】 华南理工大学 ， 化学工程， 2014， 硕士

【摘要】 随着人们环境保护及能源节约意识的增强，环境友好型水性涂料的应用已是大势所趋。相比于传统的溶剂型涂料，水性涂料大大减少了易挥发性有机化合物（VOCs）的排放，具有安全环保、成本低、施工灵活多变等优点。水性醇酸树脂以可再生的植物油或脂肪酸为主要原料，以水为溶剂，原料易得，价格便宜，漆膜综合性能优异，被广泛应用于各个领域。但是，水性醇酸树脂涂料本身也存在一些缺陷，如漆膜干燥缓慢、硬度低、耐水性及户外耐候性不佳等。因此，水性醇酸树脂涂料的合成及改性研究具有重要的实际意义。本论文采用溶剂法和醇解法，以亚麻油（L.O.）、三羟甲基丙烷（TMP）、邻苯二甲酸酐（PA）、偏苯三酸酐（TMA）等为主要原料，合成了水性醇酸树脂（WAR）。结果表明：当油度为45~50%，醇超量为7~10%左右，初酸值在7~10mgKOH·g-1，终酸值为55mgKOH·g-1时，树脂的硬度、柔韧性、光泽等性能可达到最佳值。为了提高水性醇酸树脂的干燥速率、硬度、耐水性及其对PET基材的附着力等性能，本论文对水性醇酸树脂的改性进行了深入研究。（1）环氧树脂改性水性醇酸树脂的合成研究：在植物油的醇解过程中加入环氧树脂，环氧基团与多元醇反应生成醚醇，最后得到澄清、透明、附着力优异的环氧改性水性醇酸树脂。红外光谱谱图表明环氧基团参与了反应；凝胶渗透色谱（GPC）结果表明环氧改性后的水性醇酸树脂分子量明显增大；马尔文粒径分析仪测得改性后的粒径及分布都有一定程度的增大，这都可以证明环氧树脂成功接入到水性醇酸树脂分子链中。实验还发现：当环氧树脂E-20的用量在6~10%时，树脂稳定性好，且在PET膜上的附着力优良。（2）TDI改性水性醇酸树脂的合成研究：选用L.O.、TMP、PA为主要原料，采用醇解法合成了端羟基醇酸树脂预聚物，再与甲苯二异氰酸酯（TDI）、二羟甲基丙酸（DMPA）等原料反应，合成了TDI改性的水性醇酸树脂分散体。探讨了DMPA含量、NCO/OH摩尔比、扩链剂乙二胺（EDA）的用量等因素对分散体的外观、粘度、粒径及涂膜的硬度、柔韧性、光泽等性能的影响。采用傅里叶变换红外光谱仪（FT-IR）表征了产物的结构，采用热重分析（TG）研究了DMPA含量、NCO/OH摩尔比对涂膜耐热性的影响。结果表明：TDI参与了反应，亲水基团COOH成功引入到树脂分子中；DMPA含量、NCO/OH摩尔比对涂膜耐热性有一定影响，当DMPA%=7%，以及NCO/OH=1.4时，树脂所形成的胶膜的硬度、耐水性、光泽、柔韧性等性能均能达到最佳。为了制备一种可涂覆于PET薄膜之上的、具有良好附着力和耐溶剂性能的快干型水性醇酸树脂涂料，本论文将自制的环氧改性水性醇酸树脂与氨基树脂复配，得到了综合性能优异的环氧改性水性醇酸氨基烤漆。优化的主要工艺参数及实验条件如下：氨基树脂选用高度甲基醚化的三聚氰胺树脂（HMMM），WAR：HMMM=3：1（质量比），选用H2O：丙二醇甲醚：乙酸乙酯=2:1:2（质量比）的混合溶剂为稀释剂，成膜时烘烤温度控制在160~180℃之间。实验所制得的涂料澄清、透明、稳定性好、180℃烘烤8s可固化、漆膜的硬度可达3H、附着力1级、耐水性好，可以满足实际应用要求。更多还原

【Abstract】 As people’s awareness of environmental protection and energy saving is becomingincreasingly intensive, the application of environmentally friendly waterborne coatings hasbeen the development trend of coatings industry in recent years. The waterborne coatingshave greatly reduced the emission of VOCs compared with the traditional solvent coatings.The waterborne coatings are more safty, lower cost and more flexible construction.Waterborne alkyd resins are synthesized by using renewable vegetable oils or fatty acids asthe main raw materials which are easy to get and their price is cheap. The comprehensiveperformances of the paint film based on alkyd resins are good. However, the waterborne alkydresin also has a lot of weakness, such as the slow drying rate, low hardness, poor waterresistance and outdoor weatherability, etc. Therefore, the study on the synthesis andmodification of waterborne alkyd resin coatings has an important practical significance.The waterborne alkyd resin (WAR) was synthesized by using linseed oil (L.O.),trimethylolpropane (TMP), phthalic anhydride (PA), trimellitic anhydride (TMA) as the mainmaterials in this thesis. The results showed that when the oil length, excess alcohol, initialacid value, final acid value were45~50%,7~10%,7~10mgKOH·g-1,55mgKOH·g-1respectively, the resin possessed excellent hardness, flexibility and gloss.In order to improve the drying rate, hardness, water resistance and adhesion to PETsubstrate of WAR, the modification of WAR was further studied.(1) The study of epoxy resin modified WAR. The epoxy resin was added in thealcoholysis process, the ether glycol was generated by the reaction between epoxy groups andpolyols, and finally a clear, transparent epoxy modified WAR with excellent adhesion wassynthesized. The Fourier infrared spectrometer (FT-IR) showed that the epoxy groups werereacted. Gel permeation chromatography proved that the molecular weight of epoxy modifiedWAR increased significantly. Marvern particle size analyzer showed that the particle size anddistribution of the modified WAR had a certain increase. These mean that epoxy resin wassuccessfully introduced into the molecular chain of WAR. It was also found that when thedosage of epoxy resin E-20was6~10%, the resin had a good stability, and a enhancedadhesion on PET.(2) The study of toluene diisocyanate (TDI) modified WAR. The terminal hydroxyl alkydresin prepolymer was firstly synthesized by using L.O., TMP and PA, and then reacted withTDI as well as dimethylol propionic acid (DMPA) to produce the TDI modified WAR. Theinfluences of DMPA content, and NCO/OH mole ratio, ethylenediamine (EDA) content on the appearance, viscosity, and particle size of the dispersion, as well as the hardness,flexibility, luster properties of the film were discussed. The structure of the product wascharacterized by the FT-IR. Effects of DMPA content and NCO/OH mole ratio on the heatresistance of the film was also studied by Thermogravimetric Analysis (TG). The researchresults showed that TDI was involved in the reaction, the hydrophilic group COOH wassuccessfully introduced to the resin chain; DMPA content and NCO/OH mole ratio haveeffects on heat resistance of the film. when the DMPA content, NCO/OH mole ratio were7%,1.4respectively, the hardness, water resistance, gloss, flexibility of the resin were excellent.For the sake of preparing a kind of quick-drying waterborne alkyd resin coatings withgood solvent resistance and excellent adhesion on PET films, the epoxy resin modified WARwas mixed with amino resin, and waterborne alkyd-amino coatings with excellentperformance were obtained. The formulation and synthetic technology were optimized,CYMEL303(HMMM) was elected as amino resin. When the baking temperature was about160~180℃, WAR: HMMM=3:1(the mass ratio of solids), the mixed solvent H2O:propanediol methyl ether: ethyl acetate=2:1:2(the mass ratio), the coating was clear,transparent, good stability. The hardness and adhesion of film was3H, level1respectively.The cured and dried film with excellent water resistance can be obtained within8seconds at180℃. The performance can meet the requirements of practical application.更多还原