【作者】 俞剑峰；

【导师】 周晓东；

【作者基本信息】 华东理工大学 ， 化学工程， 2013， 博士

【摘要】 卷材涂料与一般工业涂料不同,它采用先涂装后加工的生产工艺,因此该涂层不但要有较高的硬度,以防止加工和使用时的擦伤和划伤,而且要防止加工时涂层的开裂,由此决定了卷材涂料需要具有十分优异的综合性能。涂装后的涂层要有极佳的稳定性,经久耐用,能满足用户不同的需求。目前,卷材涂料以溶剂型涂料为主,由于其含有大量的有机挥发物,不符合环保要求,因此水性卷材涂料关键技术的研究在欧美已成为卷材涂料领域研究的热点。本文主要论述了开发一套水性卷材涂料,包括水性底漆和水性面漆,以满足目前环保技术的要求。在底漆的研究中,合成了一种水性丙烯酸改性环氧复合乳液,并成功应用于卷材底漆。采用红外及DSC等测试手段,研究了丙烯酸酯单体与高分子量环氧树脂接枝反应的规律。研究表明,当丙烯酸类单体的用量占大分子环氧树脂质量的40%时,其应用在卷材涂料底漆中的漆膜综合性能最佳。对环氧树脂进行磷酸酯改性,其对金属基板的附着力随着磷酸用量的增加而增加。通过筛选,脲醛类R578氨基树脂可成功应用于上述改性树脂的固化交联,由此所得到的漆膜具有优异的综合性能。在面漆研究方面,目前溶剂型的聚酯卷材涂料以其均衡的硬度、T弯、耐候性等综合性能,在市场应用中占据了绝对的地位,水性聚酯卷材涂料的报道却很少见。采用间苯二甲酸-5-磺酸钠(5-SSIPA)对聚酯树脂进行改性,合成了一种水性改性聚酯树脂,并对合成工艺及影响涂层性能的因素进行了研究。结果表明,通过两步法的工艺,将亲水性功能单体5-SSIPA引入到聚酯分子中,亲水性功能单体5-SSIPA的用量影响聚酯树脂的亲水性,用量越大其树脂的亲水性越好,但是用量太大,表面固化反应太快,影响漆膜的性能；采用对羧基封端的方法能明显提高水性聚酯树脂的存储稳定性。为了获得储存稳定性优良的水性卷材面漆,我们探索了一种新型改性丙烯酸树脂的制备方法。水性丙烯酸酯树脂的制备可以采用乳液聚合和相反转型聚合方法,与乳液聚合得到的产品相比,相转变型乳液聚合具有显著的优点,这些乳液与颜料的亲和性优良,而且机械稳定性很好,在制备色漆时可以直接作为研磨树脂,操作方便。丙烯酸树脂的改性主要采用两种方式,一种是采用叔碳酸缩水甘油酯(E10p)对丙烯酸树脂进行改性,另一种是聚酯聚氨酯对丙烯酸酯进行改性。E10p是具有活泼的环氧基团的化合物,该基团可用作树脂和聚合物改性的中间体应用,由于E10p的特殊反应特征和性质,在聚酯、丙烯酸和环氧树脂涂料中得到广泛应用。E10p能降低树脂黏度、提高涂料固含量、提高树脂对颜料的润湿性,提供了更好的抗结晶性和抗化学性,具有优异的光泽和保光性,改善其应用性和瓷漆的丰满度。采用叔碳酸缩水甘油酯E10p、丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯等为原材料,制备了一系列的丙烯酸乳液。研究表明,反应温度不仅对自由基聚合有影响,同时也影响E10p中环氧基团接枝到大分子链的接枝方式,反应温度低于120℃是比较合适的,有利于合成窄分布、低酸值的水性丙烯酸树脂,从而获得综合性能优异的水性卷材涂料。增加E10p的用量能有效提高涂料漆膜的耐酸碱性、人工老化等性能。此外,在卷材涂料品种中,聚酯聚氨酯型涂料具有优异的柔韧性,是溶剂型卷材涂料面漆改进柔韧性的重要方法。本文采用聚酯多元醇和丙烯酸羟基酯,通过与异氰酸酯架桥,生成带有双键的聚酯型聚氨酯预聚物,预聚物与其他丙烯酸类单体一起进行自由基聚合,乳化后得到了核壳型丙烯酸／聚酯(聚氨酯)复合乳液。用所合成的乳液制得的涂料其性能与水性E1Op改性的丙烯酸树脂的漆膜性能相当,目前深入的研究还在进行中。更多还原

【Abstract】 Coil coating is obviously different from other general industrial coatings. It is usually coated on metal substrates before shaping, which need coil coating has excellent overall performance. The coil coatings should have high hardness in order to prevent abrasion and scratch, and also have good toughness to resist the cracking in the processing of shaping. Today, the main type of coil coating is the solvent-borne coil coating, due to they contain a large amount of volatile organic compounds (VOC), this system does’t comply with the requirements of environmental protection. Therefore, the research of the aqueous coil coating is the key work in the field of the coil coating in the future. In this thesis, water-borne coil coatings were developed, including water-brone primer and water-brone topcoat, to follow up the requirements of environmental protection.In the investigation of the primer system, several water-borne acrylic modified epoxy (PEA) hybrid emulsions were synthesized, and successfully applied to the primer of coil coating. The grafting reaction of the acrylate to epoxy molecular was tested by IR and DSC. The main results were represented as following:In the emulsion system, the dosage of the acrylate monomers about amount40%by epoxy weight was more suitable for the primer. Phosphate-modification was used to enhance adhesion of the primer on metal, the adhesion on metal was enhanced by increasing of the amount of the phosphoric acid.By comparison, the R578urea amino resin was successfully used for curing crosslinking of the above-mentioned modified resins. The coating film obtained from the above system had excellent overall performance.Now, the solvent-based top coil coating based on polyester resins occupy the dominant market in order to balance the hardness, T-bend, weather resistance, and the overall performance. However, the reports of water-borne polyester coil coatings are very rare due to the poor resistnce of the hydrolysis. In this study, a series of water-borne polyesters were synthesized using5-SSIPA, and many influence factors were studied which affected on the properties of the coatings.In this experiment, it found that the polyester resins containing5-SSIPA hydrophilic functional monomer were more hydrophilic prepared by the process of the two-step method than that of by one-step method. The more dosage of5-SSIPA, the more hydrophilic was. However, if the amount of5-SSIPA was too large, the surface of the curing reaction was too fast, which would reduce the performance of the film. End-blocking of the hydroxyl-terminated improved the storage stability of the aqueous polyester resin.Besides, water-borne acrylic resins were used in top coil coatings in order to obtain the coating with excellent storage stability. In this study, El Op was used for modification of acrylic resins. This study showed that the reaction temperature not only affected the free radical polymerization, also affected the El Op epoxy groups grafting onto the macromolecular chains. When the reaction temperature was lower than120℃, the resin had a relative narrow molecular weight distribution and lower acid value, which was benefit to the overall performance of water-based coil coatings. Increasing the amount of E10p can effectively improve the acid and alkali resistance and artificial aging performance of the film.Furthermore, polyurethane was used to modify the polyester to improve the flexibility, which was very important for the solvent-borne top coil coatings. In this study, a new kind of core/shell emusion was prepared by using polyester polyol, isocyanate and acrylate monomers. The property of the coating using this kind of emusion was tested and the depth investigation is still in progress.更多还原