【作者】 张良；

【导师】 孙培勤； 赵科；

【作者基本信息】 郑州大学 ， 工业催化， 2014， 硕士

【摘要】 近年来，玻璃纤维复合材料GFRP开始广泛应用于建筑领域。由于其具有施工方便、强度高和质量轻等优点，得到了工程领域的广泛关注。但国内外诸多研究表明， GFRP筋材的耐碱性能并不理想，其在碱性环境中容易受到腐蚀从而影响自身力学性能。水性环氧树脂是一种性能优异的水性涂料，由于其体系中有大量在碱性环境中可以稳定存在的醚键，所以具有耐碱稳定性。不过由于生产原料和方法不同，水性环氧树脂的种类也不尽相同。此外，水性环氧树脂本身难以固化，需要加入固化剂。查阅相关文献知道，醚化三聚氰胺树脂可以作为水性环氧树脂交联剂，使其固化成膜。本文实验合成了性能较好的水性环氧树脂和甲丁醚化三聚氰胺缩甲醛树脂。研究了反应物配比，反应温度、反应时间和pH对甲丁醚化三聚氰胺缩甲醛树脂性能的影响。并对甲丁醚化三聚氰胺缩甲醛树脂与水性环氧树脂的复配成膜进行了研究。结果如下：在催化剂过硫酸钾作用下，聚乙二醇4000和环氧树脂会发生聚合反应生成乳化剂。然后将环氧树脂与合成的乳化剂复配，通过相反转法合成水性环氧树脂。结果表明，聚乙二醇4000和环氧树脂摩尔比为1:1，催化剂为过硫酸钾，180℃下反应3.5h，合成的乳化剂性能较好。然后在搅拌速度800r/min、水浴温度50℃时合成的水性环氧树脂具有较好的稳定性。采用两步法，使用不同摩尔比的甲醇丁醇同步改性方法合成了3种高度甲丁醚化三聚氰胺缩甲醛树脂。使用单因素法研究了反应物摩尔比，羟甲基化反应的时间、温度和pH,以及醚化反应的时间、温度和pH等对合成树脂性能的影响。优化出了较好的合成工艺：羟甲基化反应阶段，温度为70℃，pH为8.5，反应时间为体系澄清之后20min；醚化反应阶段，醚化温度为50℃，pH为4.5，醚化时间为60min。合成的树脂甲醛含量较低，储存稳定性高。本文将合成的交联剂与实验室自制的水性环氧树脂进行固化交联,对复配的比例、固化温度和固化时间进行了优化,考察了以上因素对涂膜性能的影响。结果表明，固化剂采用甲醇丁醇摩尔比为（8:2）的甲丁醚化三聚氰胺缩甲醛树脂，交联剂同水性环氧树脂固化交联的质量比例为1:2，固化温度为200℃，固化时间为10min时，涂膜完全固化，硬度为6H，附着力0级，成膜均匀性良好，具有较好的耐碱性，涂膜性能良好。在上述最佳固化条件下，对GFRP筋表面进行处理，然后进行快速耐碱实验。结果表明经过处理的GFRP筋弯曲强度下降率明显小于未经处理的GFRP筋的弯曲强度下降率，且经过长时间的碱液腐蚀，经过处理的筋材弯曲性能优于未处理的筋材。这说明筋材表面的固化涂层起到了较好的耐碱作用。因此，本文合成的甲丁醚化三聚氰胺缩甲醛树能够作为水性环氧树脂的交联剂。二者复配所成膜具有良好的硬度、附着力、均匀性和耐碱性，可以应用于FRP筋材表面增加筋材的耐腐蚀性能，增加建筑结构的使用寿命。更多还原

【Abstract】 In recent years, the glass fiber reinforced polymer has been widely used in theconstruction sector. Because of its easy construction, high strength and light weightetc., it has been widespread concern in the field of engineering. However, manydomestic and foreign research reports indicate that alkali resistance of GFRP is notideal, it is easy to be corroded by base, which would to affect their mechanicalproperties. Waterborne epoxy resin is a water-based paint which has excellentperformance. It has a lot of ether bond in the system, this makes it possible to stablyexist in the base. However, due to different raw materials and production methods,there are many types of water-based epoxy resin. In addition, it is difficult forwater-based epoxy resin to cure without curing agent. We know that etherifiedmelamine resin can be used as water-based epoxy resin cross-linking agent fromrelevant literatures.We synthesize waterborne epoxy resin and methanol-butanol etherifiedmelamine resins.And both of them have better performance.This paper study onseveral factors which would effect the properties of methanol-butanol etherifiedmelamine resin,the factors include reactant ratio, reaction temperature, reaction timeand pH. The paper also studies cross-linking of the two resins. The results are asfollows:In the role of potassium persulfate catalyst, emulsifier is synthesized bypolymerization between polyethylene glycol4000and epoxy E-44.Then waterborneepoxy resin is synthesized by inversion method. The results show that, when themolar ratio of polyethylene glycol4000and the epoxy resin is1:1, the catalyst ispotassium persulfate, the reaction temperature is180℃, reaction time is3.5h, theemulsifier has better performance. Then, when the stirring speed is800r/min, waterbath temperature is50℃, the composite waterborne epoxy resin has good stability.The methanol-butanol etherified melamine-formaldehyde resin is synthesized intwo steps and used as a curing agent of water borne paint. The best reaction condition is investigsted in ferms of the influence of temperature, time and pH. The resultsshow that, in the reaction stage of hydroxyl methylation, when the temperature is70℃, time is20min and pH is8.5, the methylol content is high and the content of freeformaldehyde is low in the system. In the etherification stage, when the temperatureis50℃,time is60min and pH is4.5, the resin have excellent storage performance.Formaldehyde content of the synthetic resin is low,and the resin has high storagestability.The paper studies cross-linking of the two resins. Several factors which wouldeffect the coating performance have been studied,such as reactant ratio, reactiontemperature, reaction time. The results show that, if curing agent usesmethanol-butanol etherified melamine-formaldehyde resin that molar ratio ofmethanol, butanol is8:2in the preparation, the mass ratio of crosslinking agent andWaterborne epoxy resin is1:2, curing temperature is200℃,and curing time is10min,the coating performance is better, its hardness is6H, adhesion is0, simultaneously ithas better uniformity and alkali.GFRP is processed under the best condition.Then the paper does quick alkaliexperiment. The results show that, flexural strength decreased rate of treated GFRP isless than the untreated GFRP. After a long period of lye corrosion, flexural strength oftreated GFRP is better than the untreated GFRP. This indicates that cured coating onthe reinforcement surface playes the role of better alkali.So, the methanol-butanoletherified melamine-formaldehyde resin synthesized in this paper can be used as acrosslinking agent of waterborne epoxy resin. The solidified membrane has somegood performance,such as hardness, adhesion, uniformity and alkali resistance,and itcan be used on the surface of GFRP to increase its corrosion resistance. It is helpfulto increase the life of the building structure.更多还原