CN110330882B - 一种自修复聚氨酯防腐涂料及制备方法 - Google Patents
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Abstract
本发明提供一种自修复聚氨酯防腐涂料，由PPG、IPDI、DMPA为主要原料，合成水性聚氨酯；利用包封技术，以TEOS为壁材，亚麻籽油为芯材，聚多巴胺为纳米阀，设计合成纳米硅微球；将纳米硅微球添加到水性聚氨酯中，制备一级修复涂层；由PPG、IPDI、DMPA、Di‑Se、GO为主要原料，合成双硒型水性聚氨酯/GO二级修复涂层。本发明聚氨酯涂料自修复性能优异，防腐效果良好，对人体无伤害并且对环境无污染；并且制备工艺简单，成本较低。
Description
技术领域
本发明属于自修复聚氨酯防腐涂料技术领域，具体涉及一种自修复聚氨酯防腐涂料及制备方法。
背景技术
材料腐蚀会对交通运输业、水泥和混凝土制造业、金属加工和发电设备等领域产生严重影响。每年全世界材料腐蚀成本估计超过全球GDP的3％。预计2022年全球防腐涂料市场份额将达到310亿美元。适应当今环保需求，水性聚氨酯(WPU)涂料在过去几十年中的市场份额显著增加。随着WPU的广泛应用，如何使其更安全，更可靠和更耐用，以及更易于维护的方法已成为重要的课题研究方向。而具有自修复功能的聚合物涂料可以延长材料的寿命和可靠性。在聚合物中加入外在的愈合剂是延长材料寿命和降低维护和更换成本的有效方法，但会对最终产品的物理性质产生负面影响，且愈合机制不可重复。内在型自修复材料，虽然可以多次修复受损区域，但通常需要热、光等外界因素的引发，并且主要针对小尺度的修复。尝试将这两种机制的修复结合起来，将为材料自修复防腐提供新的途径。因此，将自修复、耐腐蚀和WPU三者相结合，设计对不同尺度的裂痕损伤都能够进行自修复的水性聚氨酯涂层，并通过研究其自修复协同作用机制和耐腐蚀性能，进一步研究其如何应用于各种基材，并提出产业化路线。该新型涂层材料的研发与应用将关系国计民生，具有重大意义社会效益和经济效益。
早期国外研究者重点开展外在型WPU自修复的研究，制备了各种类型微球或毛细管，并研究其添加到基材中自修复与耐腐蚀性能，其中比较典型的单层壁材有脲醛、苯甲醛、TEOS等，多层壁材结构有PU/PF/PGMA，而常见芯材有亚麻籽油、BTA、MBT和硅油。而近5年来，更多的研究者重点开展内在型WPU自修复研究，尝试了在分子链中设计引入各种功能团，利用光、热、等因素刺激引发自修复，考察材料的腐蚀行为。且以德国拜尔材料为例，已经开发出数种自修复涂料产品。
国内WPU自修复研究方法类似，早期多集中在外在型自修复，之后转向内在型。近五年来，国内研究者巧妙设计制备了多种外在型WPU和内在型WPU。虽然材料设计构思巧妙，但是未将两种自修复机制结合起来。因此，设计水性聚氨酯室温可见光下自修复复合涂层体系，将会实现材料的耐腐蚀性能的突破。
发明内容
本发明的目的是针对以上不足，提供一种利用尝试将这两种机制的修复结合起来，将为材料自修复防腐提供新的途径。与此同时，将自修复、耐腐蚀和WPU三者相结合，设计对不同尺度的裂痕损伤都能够进行自修复的水性聚氨酯涂层，并通过研究其自修复协同作用机制和耐腐蚀性能，进一步研究其如何应用于各种基材，并提出产业化路线是该课题的研究思路。其特点是：1、将外在型和内在型两种自修复机制结合起来，实现水性聚氨酯涂料在多尺度范围自修复功能。2、将水性聚氨酯复合涂料的自修复功能与耐腐蚀功能结合起来，实现自修复材料的功能化。
本发明的目的采用以下技术措施实现，其中所述原料份数除特殊说明外，均为重量份数。
一种自修复聚氨酯防腐涂料，由以下原料按照质量份数制成：
该自修复聚氨酯防腐涂料的制备方法，包括如下步骤：
(1)由聚丙二醇(PPG)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)为主要原料，合成水性聚氨酯；
(2)利用包封技术，以正硅酸四乙氧基硅(TEOS)为壁材，亚麻籽油为芯材，聚多巴胺为纳米阀，设计合成纳米硅微球；
(3)将纳米硅微球添加到步骤(1)得到的水性聚氨酯中，制备一级修复涂层；
(4)由聚丙二醇(PPG)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)、双-(1-羟基亚乙基)二硒化物(Di-Se)、氧化石墨烯(GO)为主要原料，合成双硒型水性聚氨酯/GO二级修复涂层。
本发明具有如下优点：
本发明聚氨酯涂料自修复性能优异，防腐效果良好，对人体无伤害并且对环境无污染；并且制备工艺简单，成本较低。
具体实施方式
结合实施例说明本发明的具体技术方案。
聚丙二醇(PPG)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)在110±2℃下真空干燥12h。有干燥氮气保护下在三口烧瓶中用100份PPG，0.5份IPDI和5份DMPA在催化剂作用下，55℃环境中制备预聚体；经扩链和乳化工艺合成水性聚氨酯一级涂层。经测试乳液呈乳白色稳定乳液，其热性能参数优异。以正硅酸四乙氧基硅(TEOS)10份为壁材，亚麻籽油4份为芯材，聚多巴胺18份为纳米阀，合成纳米硅微球。
经通过扫描电镜分析，微球表面光滑且分布均匀。
制备一级涂覆层，经测试该涂层低温成膜性能优异，其硬度和附着力均较一般水性聚氨酯涂层性能优异。
用100份PPG，0.6份IPDI、0.2份二硒化物(Di-Se)、2份氧化石墨烯(GO)6份DMPA为主要原料，在催化剂作用下合成双硒型水性聚氨酯/GO二级修复涂层。
经观察和测试，该涂层乳液外观均匀，成膜性能良好。
将二级修复涂层涂覆在一级涂层上。
经测试，自修复能力在一定外界环境刺激下24小时修复90％以上，同时经质量分数为10％的硫酸溶液和质量分数为10％的氢氧化钠溶液浸泡48h以后，经观察，外观涂层无失光、起泡、脱落、变黄等现象，其防腐性能优于一般涂料。
Claims (2)
1.一种自修复聚氨酯防腐涂料的制备方法，其特征在于，包括如下步骤：
(1)由PPG、IPDI、DMPA为主要原料，合成水性聚氨酯；
(2)利用包封技术，以TEOS为壁材，亚麻籽油为芯材，聚多巴胺为纳米阀，设计合成纳米硅微球；
(3)将纳米硅微球添加到步骤(1)得到的水性聚氨酯中，制备一级修复涂层；
(4)由PPG、IPDI、DMPA、双-(1-羟基亚乙基)二硒化物、GO为主要原料，合成双硒型水性聚氨酯/GO二级修复涂层；将二级修复涂层涂覆在一级涂层上；
原料按照质量份数制成：
2.一种自修复聚氨酯防腐涂料，其特征在于，由权利要求1所述的制备方法所得。
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