CN105344132B - 一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法 - Google Patents
一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法 Download PDFInfo
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Abstract
本发明公开了一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，属于功能材料技术领域。本发明要解决传统油水分离材料制备过程繁琐，不耐水流冲刷等缺陷。本发明的方法是先将网布材料浸入到一定浓度的单组份聚氨酯/N‑甲基吡咯烷酮混合溶液中，随后将网布取出放入含一定浓度丙三醇的水溶液中，再经过疏水改性剂改性获得超疏水超亲油网布材料。本发明的方法简单，不需要任何复杂的设备，原料易得，生产周期短，适于大规模的生产。本发明与的水接触角大于150°，滚动角小于10°，与油品的接触角为0，从而使其可应用于油水分离领域。本发明的方法处理后的网布具有良好的抵抗水流冲击能力，具有良好的应用前景。
Description
技术领域
本发明属于功能材料技术领域，具体涉及一种超疏水超亲油网布材料的制备方法。
背景技术
随着工业的发展，油品的使用量越来越大，而由于技术落后和管理不善引起的油品水污染情况也频频发生。目前油品的泄露对于生态环境的破坏最为严重，因此如何处理泄露的油品是人们目前关注的焦点。大量的超疏水超亲油过滤型材料被创造出来以过滤含油污水，常以铜网，棉布，玻璃纤维，不锈钢网等材料作为基材，再通过表面物理或化学改性制备出超疏水超亲油网布材料，但这些制得的材料或多或少要面临以下问题：1.成本昂贵、工艺复杂，不利于工业生产；2.强度太差，材料的寿命和重复使用率低；3.对环境不友好，对人的健康存在潜在威胁等。不仅如此，许多制备超疏水超亲油油水分离材料的方法因基材不同而异，因此在实际应用中也受到诸多限制。制备出牢固、稳定的超疏水超亲油表面，且价格低廉，工艺简单，并且可用于不同基材是解决目前产业化困难的关键。
发明内容
本发明要解决传统油水分离材料制备过程繁琐，不耐水流冲刷等缺陷，而提出一种具有实际应用价值的超疏水超亲油油水分离网布材料的制备方法。
本发明一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法是按下述步骤进行的：
步骤一、将网布材料浸入到单组份聚氨酯/N-甲基吡咯烷酮混合溶液中反应1～24小时，单组份聚氨酯/N-甲基吡咯烷酮混合溶液是由聚氨酯和N-甲基吡咯烷酮按(1～40):100的质量比配制而成的；
步骤二、将经步骤一处理后的网布材料取出后浸泡在丙三醇的水溶液中，静置反应1～12小时后取出，用大量去离子水清洗后烘干；
步骤三、将步骤二处理后的网布材料用疏水改性剂/甲苯混合溶液浸泡1分钟～1小时，然后取出用甲苯洗涤3次，再真空干燥，即得到超疏水超亲油网布材料；
其中，步骤为所述的丙三醇水溶液是由丙三醇和水按(1/9～9.5):1体积比配制的，
步骤三中所述的疏水改性剂/甲苯混合溶液是疏水改性剂与甲苯按(0.01～2)：100的体积比配制的。
另外，步骤一所述网布材料不仅适用于玻璃纤维布，天然纤维布，人造纤维布或者其他与异氰酸酯基(－N＝C＝O)形成化学键合的基材。
步骤二中烘干温度控制在100℃，或是在常温下烘干，烘干温度超过100℃会导致聚氨酯胶层被破坏。
疏水改性剂包括硅氧烷、氯硅烷、硬脂酸、聚硅氧烷或者其他能与聚氨酯涂层表面极性基团发生反应的疏水改性剂；具体是十八烷基三氯硅烷(OTS)、甲基三氯硅烷或氟代氯硅烷等。
步骤三中真空干燥在真空度为0MPa～0.095MPa、温度为20～100℃的条件下进行的。
本发明是先使玻璃纤维布表面吸附一定量的单组份聚氨酯胶黏剂/有机溶剂混合物，再将其浸泡在丙三醇的水溶液中固化，发生固化过程中聚氨酯胶由液态变为固态并自发形成粗糙结构，然后再用采用低表面能物质改性从而获得超疏水超亲油网布材料。
本发明的优点在于：
1、本发明的方法简单，只需要几步简单的浸泡便可以完成，不需要任何复杂的设备，原料易得，生产周期短，适于大规模的生产。
2、本发明的方法处理后的网布具有超疏水超亲油性。其与的水接触角大于150°，滚动角小于10°，与油品的接触角为0，从而使其可应用于油水分离领域。
3、本发明的方法处理后的网布具有良好抵抗水流冲击能力。
4、本发明无需昂贵的专用设备。
附图说明
图1为原始玻璃纤维布表面的低倍电镜照片(SEM)；图2是原始玻璃纤维布表面的高倍电镜照片(SEM)；图3是按照具体实施方式一制得的超疏水超亲油玻璃纤维布表面的低倍电镜照片(SEM)；图4是按照具体实施方式一制得的超疏水超亲油玻璃纤维布表面的高倍电镜照片(SEM)；图5是氯仿在具体实施方式一制得的超疏水超亲油玻璃纤维布表面的接触角照片；图6是水在原始玻璃纤维布表面的接触角照片；图7是具体实施方式一制备的超疏水超亲油玻璃纤维布表面经过25kPa水流循环冲击20次后的500倍SEM图。
具体实施方式
具体实施方式一：本实施方式中一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法是按下述步骤进行的：
步骤一、将玻璃纤维布浸入到单组份聚氨酯/N-甲基吡咯烷酮混合溶液中反应6小时，单组份聚氨酯/N-甲基吡咯烷酮混合溶液是由聚氨酯和N-甲基吡咯烷酮按20:100的质量比配制而成的；
步骤二、将经步骤一处理后的玻璃纤维布取出后浸泡在丙三醇的水溶液(丙三醇和水的体积比为3:7(v/v))中，静置反应6小时后取出，用大量去离子水清洗后在常温下烘干；
步骤三、将步骤二处理后的玻璃纤维布用十八烷基三氯硅烷(OTS)/甲苯混合溶液浸泡30分钟，然后取出用甲苯洗涤3次，再在真空度为0.05MPa、温度为70℃的条件下真空干燥，即得到超疏水超亲油玻璃纤维布；
其中，步骤三中所述的十八烷基三氯硅烷(OTS)/甲苯混合溶液是十八烷基三氯硅烷(OTS)与甲苯按0.1：100的体积比配制的。
玻璃纤维布表面在混合溶液中与单组分聚氨酯胶黏剂发生化学键合反应，主要是玻璃纤维布表面的羟基-OH与单组分聚氨酯胶黏剂中异氰酸酯基-N＝C＝O发生反应，并在表面吸附一定量的聚氨酯胶黏剂和N-甲基吡咯烷酮的混合物；聚氨酯和N-甲基吡咯烷酮比例过低会导致玻璃纤维布表面粘附的胶黏剂不足；过高会导致玻璃纤维布的网孔被胶黏剂堵死。
由图1和2可以看出，未经处理的玻璃纤维布表面均是光滑的；而制备获得的网材表面均呈现球状或半球状粗糙结构(3和4)，通过进一步的疏水改性，与水的接触角均大于150°，与油的接触角均为0°(图5)，显示出良好的疏水性。
本实施方式制备的超疏水超亲油玻璃纤维布表面经过25kPa水流循环冲击20次后表面如图7所示，由图7可知，本实施方式制备的玻璃纤维布表面即使在经过多次水流冲刷后表面结构依旧完整，微纳结构没有被破坏，说明具有良好的抵抗水流冲击能力。
具体实施方式二：本实施方式与具体实施方式一不同的是：用甲基三氯硅烷替换步骤三中的十八烷基三氯硅烷。其它步骤和参数与具体实施方式一相同。
具体实施方式三：本实施方式与具体实施方式一不同的是：用氟代氯硅烷替换步骤三中的十八烷基三氯硅烷。其它步骤和参数与具体实施方式一相同。
Claims (7)
1.一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，其特征在于该制备方法是按下述步骤进行的：
步骤一、将网布材料浸入到单组份聚氨酯/N-甲基吡咯烷酮混合溶液中反应1～24小时，单组份聚氨酯/N-甲基吡咯烷酮混合溶液是由聚氨酯和N-甲基吡咯烷酮按(1～40):100的质量比配制而成的；
步骤二、将经步骤一处理后的网布材料取出后浸泡在丙三醇的水溶液中，静置反应1～12小时后取出，用大量去离子水清洗后烘干；
步骤三、将步骤二处理后的网布材料用疏水改性剂/甲苯混合溶液浸泡1分钟～1小时，然后取出用甲苯洗涤3次，再真空干燥，即得到超疏水超亲油网布材料；
其中，步骤二所述的丙三醇水溶液是由丙三醇和水按(1/9～9.5):1体积比配制的，
步骤三中所述的疏水改性剂/甲苯混合溶液是疏水改性剂与甲苯按(0.01～2)：100的体积比配制的，所述疏水改性剂为十八烷基三氯硅烷、甲基三氯硅烷或氟代氯硅烷。
2.根据权利要求1所述的一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，其特征在于步骤一中单组份聚氨酯/N-甲基吡咯烷酮混合溶液是由聚氨酯和N-甲基吡咯烷酮按20:100的质量比配制而成的。
3.根据权利要求1所述的一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，其特征在于步骤一的反应时间为6小时。
4.根据权利要求1所述的一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，其特征在于步骤一所述网布材料为天然纤维布、人造纤维布或者其他与异氰酸酯基形成化学键合的基材。
5.根据权利要求1所述的一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，其特征在于步骤二中在常温或者控制在100℃以下进行烘干。
6.根据权利要求1所述的一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，其特征在于步骤三中所述疏水改性剂/甲苯混合溶液是十八烷基三氯硅烷与甲苯按0.1：100的体积比配制的。
7.根据权利要求1所述的一种基于单组份聚氨酯制备超疏水超亲油网布材料的方法，其特征在于步骤三中真空干燥在真空度为0MPa～0.095MPa、温度为20～100℃的条件下进行的。
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