CN114805894A - 一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法 - Google Patents
一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法 Download PDFInfo
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Abstract
本发明提供了一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，先以水为溶剂，草酸为催化剂，阳离子表面活性剂为分散剂，在纳米粒子的作用下，氟硅烷与硅烷偶联剂于25~40℃下水解缩合反应1~24小时，然后超声处理，制得氟硅烷聚合物乳液；再将透气膜浸泡于氟硅烷聚合物乳液中10秒~20分钟，压滤去除多余液体后在140~190℃下固化处理2~20分钟，制得超双疏防水防油透气膜。本发明通过纳米粒子与氟硅烷聚合物的协同效应，在透气膜表面构建低表面能微‑纳结构，使得超双疏防水防油透气膜具有优异的静态、动态超双疏性能和良好的透气率，极具应用前景。
Description
技术领域
本发明涉及一种防水防油透气膜的制备，尤其是涉及一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，属于功能膜材料技术领域。
背景技术
防水透气膜在电子材料、航空航天、生物医疗、密封材料和新能源领域都有着广泛的应用。虽然防水透气膜有一定的防水能力，但是其在遇到油性物质时，就会被轻易污染，丧失其防水防污的性能。因此，赋予防水透气膜防油性能是非常必要的。通过在防水透气膜表面制备超双疏涂层是赋予其防油能力的有效途径，而通过氟硅烷聚合物提供低表面能，利用微纳米颗粒提供粗糙结构，是实现超双疏功能的有效方法。例如，中国专利CN108546326B以四氢呋喃为溶剂，通过分散含氟环氧树脂来实现防水透气膜的防油性能；中国专利CN113248776A以乙醇为溶剂，通过分散氟硅烷最终实现的防水透气膜的超双疏改性。然而，有机溶剂的使用造成了巨大的安全隐患和环境污染问题，也增加了制造成本。同时，生产过程中对于操作工人也有一定程度的危害。与有机溶剂相比，水是一种绿色溶剂，但很少用于制备超双疏防水防油透气膜，这是因为低表面能的材料通常不能很好地溶解或分散在水中，导致溶液发生分层，产生沉淀或氟硅烷聚合物大量粘附在瓶壁上，从而严重影响超双疏功能的实现。为了解决这一问题，通常采用含氟表面活性剂来分散氟硅烷聚合物于水性溶液中。但是，由于含氟表面活性剂价格昂贵，分散后所得溶液的均匀性、长期放置稳定性无法保证，限制了其应用。
此外，制备超双疏防水防油透气膜与制备超双疏织物不同，这是由于透气膜与织物的固有结构差异导致的。与织物相比，透气膜更加平整光滑，这对制备超双疏防水防油透气膜提出了更高的要求，需要更加精细地调控涂层的微结构和化学组成，以使透气膜表面能形成稳定的超双疏涂层。因此在防水透气膜表面形成稳定的超双疏涂层，以提高其防水防油性能，是目前亟需解决的问题。
发明内容
本发明的目的是提供一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，以进一步提高超双疏防水防油透气膜性能。
一、超双疏防水防油透气膜的制备
本发明超双疏防水防油透气膜的制备方法，包括以下工艺步骤：
（1）氟硅烷聚合物乳液的制备：以水为溶剂，草酸为催化剂，阳离子表面活性剂为分散剂，在纳米粒子的作用下，氟硅烷与硅烷偶联剂于25~40℃下水解缩合反应1~24小时，然后超声处理，制得氟硅烷聚合物乳液。
所述氟硅烷为全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷中的一种；所述硅烷偶联剂为γ-氨丙基三甲氧基硅烷、γ-(2,3-环氧丙氧) 丙基三甲氧基硅烷中的至少一种；硅烷偶联剂与氟硅烷的质量比为0.1:1~0.5：1。
所述纳米粒子为二氧化硅、二氧化钛、纳米碳管中的一种，纳米粒子与氟硅烷的质量比为0.5:1~1.5:1。
所述草酸与氟硅烷的质量比为0.25：1~0.8:1。
所述阳离子表面活性剂为十二烷基聚氧乙烯、十二烷基三甲基溴化铵、双十二烷基二甲基溴化铵、双十六烷基二甲基溴化铵、十六烷基三甲基溴化铵、十八烷基三甲基氯化铵中的至少一种，阳离子表面活性剂与氟硅烷的质量比为0.1:1~0.3:1。
（2）超双疏防水防油透气膜的制备：将经清洗的透气膜浸泡于上述制备的氟硅烷聚合物乳液中10秒~20分钟，取出，压滤去除多余液体后在140~190℃下固化处理2~20分钟，制得超双疏防水防油透气膜。
所述透气膜为聚四氟乙烯膜、PET膜、聚乙烯膜或聚丙烯膜。
二、超双疏防水防油透气膜的结构
图1为未加入纳米粒子制备的防水防油透气膜（左）和加入纳米粒子制备的超双疏防水防油透气膜（右）的扫描电镜图。通过比较可以看出：未加入纳米粒子制备的防水防油透气膜，透气膜表面未形成低表面能微-纳粗糙结构；加入纳米粒子制备的超双疏防水防油透气膜，通过纳米粒子与氟硅烷聚合物的协同效应，在透气膜表面构建了低表面能微-纳粗糙结构，从而使得超双疏防水防油透气膜具有优异的静态和动态超双疏性能。
三、超双疏防水防油透气膜的性能
1、乳液的稳定性
将本发明制备的氟硅烷聚合物乳液在60℃烘箱中放置96小时、冻融3次或室温条件下放置10个月后，其仍然保持良好的均匀性，因此具有优异的稳定性。
2、透气膜的超双疏性能
经测试，本发明超双疏防水防油透气膜，10μL水滴的接触角>155°、滚动角≤4°，10μL正癸烷的接触角>152°、滚动角≤10°；正癸烷的耐冲击高度为≥11cm。因此，超双疏防水防油透气膜具有优异的静态超双疏性能，同时也具有较好的动态超双疏性能。
2、超双疏膜的透气性
采用织物透气性测试仪测试发现（GB/T5453-1997），本发明制备的超双疏防水防油透气膜具有较高的透气性，其透气率保持在未改性膜的90%以上。
综上所述，本发明相对于现有技术具有以下优点：
1、本发明通过纳米粒子与氟硅烷聚合物的协同效应，在透气膜表面构建低表面能微-纳结构，制备了性能优异的超双疏防水防油透气膜；
2、本发明以水为溶剂，成本低和绿色环保；
3、本发明制备工艺简单、易于规模化等优点，为其实际应用奠定了基础。
附图说明
图1为未加入纳米粒子（左）和加入纳米粒子（右）制备的超双疏防水防油透气膜的扫描电镜图。
具体实施方式
为了更好的理解本发明，下面结合实施例进一步说明本发明的内容。
实施例1
（1）氟硅烷聚合物乳液的制备：将0.6g二氧化硅加入到盛有50 mL蒸馏水的100 mL烧杯中，超声10分钟；再依次加入0.6g全氟癸基三甲氧基硅烷、0.1gγ-(2,3-环氧丙氧) 丙基三甲氧基硅烷、0.25 g草酸、0.03g十二烷基三甲基溴化铵、0.09g十六烷基三甲基溴化铵，在25℃下磁力搅拌反应4小时，超声10分钟，得到均匀的氟硅烷聚合物乳液；
（2）超双疏防水防油透气膜的制备：将清洗干净的聚丙烯膜在氟硅烷聚合物乳液中浸泡10分钟，取出，去除多余残液，在160℃下处理10分钟，构建低表面能微-纳结构，即得到具有微-纳结构的超双疏防水防油透气膜；
（3）超双疏防水防油透气膜的性能：在所得的超双疏防水防油透气膜表面，10μL水滴的接触角为155.4°、滚动角为4°，10μL正癸烷滴的接触角为152.8°、滚动角为9°、耐冲击高度为11cm，透气率为未改性膜的92%。
对比例
（1）氟硅烷聚合物乳液的制备：将0.6g全氟硅基三乙氧基硅烷、0.1gγ-(2,3-环氧丙氧) 丙基三甲氧基硅烷、0.25 g草酸、0.03g双十二烷基二甲基溴化铵，0.09g十八烷基三甲基氯化铵依次加入到盛有50 mL蒸馏水的100 mL烧杯中，在25℃下磁力搅拌反应4小时，超声5分钟，得到均匀的氟硅烷聚合物乳液；
（2）防水防油透气膜的制备：将清洗干净的PET膜在氟硅烷聚合物乳液中浸泡10分钟，取出，去除多余残液，在160℃处理10分钟，即得到表面平整的防水防油透气膜；
（3）在所得的防水防油透气膜表面，10μL水滴的接触角为142.8°、滚动角为15°，10μL正癸烷滴的接触角为122.7°、不滚动、粘附于膜表面，透气率为未改性膜的91%。
可见，纳米粒子的加入，在很大程度上提高了防水透气膜的超双疏性能。
实施例2
（1）氟硅烷聚合物乳液的制备：将0.4g二氧化钛加入到盛有50 mL蒸馏水的100 mL烧杯中，超声10分钟；再依次加入0.5g全氟硅基三乙氧基硅烷、0.1gγ-(2,3-环氧丙氧) 丙基三甲氧基硅烷、0.25 g草酸、0.03g双十二烷基二甲基溴化铵，0.09g十八烷基三甲基氯化铵，在25℃下磁力搅拌反应4小时，超声5分钟，得到均匀的氟硅烷聚合物乳液；
（2）超双疏防水防油透气膜的制备：将清洗干净的PET膜在氟硅烷聚合物乳液中浸泡8分钟，取出，去除多余残液，在180℃处理4 分钟，构建低表面能微-纳结构，即得到具有微-纳结构的超双疏防水防油透气膜；
（3）超双疏防水防油透气膜的性能：在所得的超双疏防水防油透气膜表面，10μL水滴的接触角为156.5°、滚动角为3°，10μL正癸烷滴的接触角为154.6°、滚动角为7°、耐冲击高度为15cm；透气率为未改性膜的90%。
实施例3
（1）氟硅烷聚合物乳液的制备：将0.6g二氧化钛加入到盛有50 mL蒸馏水的100 mL烧杯中，超声10分钟；再依次加入0.75g全氟癸基三甲氧基硅烷、0.15g γ-氨丙基三甲氧基硅烷、0.25 g草酸、0.03g双十六烷基二甲基溴化铵、0.09g十六烷基三甲基溴化铵，在25℃下磁力搅拌反应8小时，超声5分钟，得到均匀的氟硅烷聚合物乳液；
（2）超双疏防水防油透气膜的制备：将清洗干净的聚四氟乙烯膜于氟硅烷聚合物乳液中浸泡2分钟，取出，去除多余残液，在170℃处理6 分钟，构建低表面能微-纳结构，即得到具有微-纳结构的超双疏防水防油透气膜；
（3）超双疏防水防油透气膜的性能：在所得的超双疏防水防油透气膜表面，10μL水滴的接触角为156.8°、滚动角为3°，10μL正癸烷滴的接触角为152.6°、滚动角为10°、耐冲击高度为12cm；透气率为未改性膜的91%。
实施例4
（1）氟硅烷聚合物乳液的制备：将5g纳米碳管加入到盛有500 mL蒸馏水的1000 mL烧杯中，超声10分钟；再依次加入5g全氟癸基三乙氧基硅烷、1.5g γ-氨丙基三甲氧基硅烷、2.5 g草酸、0.3g双十六烷基二甲基溴化铵、0.9g十六烷基三甲基溴化铵，在25℃下磁力搅拌反应12小时，超声10分钟，得到均匀的氟硅烷聚合物乳液；
（2）超双疏防水防油透气膜的制备：将清洗干净的聚乙烯膜在氟硅烷聚合物乳液中浸泡3分钟，取出，去除多余残液，在180℃处理4 分钟，构建低表面能微-纳结构，即得到具有微-纳结构的超双疏防水防油透气膜；
超双疏防水防油透气膜的性能在所得超双疏防水防油透气膜表面，10μL水滴的接触角为156.1°、滚动角为5°，10μL正癸烷滴的接触角为152.5°、滚动角为10°、耐冲击高度为14cm，透气率为未改性膜的93%。
实施例5
（1）氟硅烷聚合物乳液的制备：将5g二氧化硅加入到盛有500 mL蒸馏水的100 mL烧杯中，超声10分钟；再依次加入7g全氟硅基三乙氧基硅烷、1.0g γ-氨丙基三甲氧基硅烷、1.0g γ-氨丙基三甲氧基硅烷、2.5 g草酸、0.3g双十二烷基二甲基溴化铵、0.9g十六烷基三甲基溴化铵，在25℃下磁力搅拌反应16小时，超声10分钟，得到均匀的氟硅烷聚合物乳液；
（2）超双疏防水防油透气膜的制备：将清洗干净的聚丙烯膜在氟硅烷聚合物乳液中浸泡3分钟，取出，去除多余残液，在180℃处理4 分钟，构建低表面能微-纳结构，即得到具有微-纳结构的超双疏防水防油透气膜；
（3）超双疏防水防油透气膜的性能：在所得超双疏防水防油透气膜表面，10μL水滴的接触角为155.5°、滚动角为3°，10μL正癸烷滴的接触角为153.0°、滚动角为8°，耐冲击高度为13cm，透气率为未改性膜的90%。
Claims (8)
1.一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，包括以下工艺步骤：
（1）氟硅烷聚合物乳液的制备：以水为溶剂，草酸为催化剂，阳离子表面活性剂为分散剂，在纳米粒子的作用下，氟硅烷与硅烷偶联剂于25~40℃下水解缩合反应1~24小时，然后超声处理，制得氟硅烷聚合物乳液；
（2）超双疏防水防油透气膜的制备：将经清洗的透气膜浸泡于上述制备的氟硅烷聚合物乳液中10秒~20分钟，取出，压滤去除多余液体后在140~190℃下固化处理2~20分钟，制得超双疏防水防油透气膜。
2.如权利要求1所述一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，其特征在于：所述氟硅烷为全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷中的一种。
3.如权利要求1所述一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，其特征在于：所述硅烷偶联剂为γ-氨丙基三甲氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的至少一种。
4.如权利要求1所述一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，其特征在于：所述硅烷偶联剂与氟硅烷的质量比为0.1:1~0.5:1。
5.如权利要求1所述一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，其特征在于：所述纳米粒子为二氧化硅、二氧化钛、纳米碳管中的一种，纳米粒子与氟硅烷的质量比为0.5:1~1.5:1。
6.如权利要求1所述一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，其特征在于：所述草酸与氟硅烷的质量比为0.25:1~0.8:1。
7.如权利要求1所述一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，其特征在于：所述阳离子表面活性剂为十二烷基聚氧乙烯、十二烷基三甲基溴化铵、双十二烷基二甲基溴化铵、双十六烷基二甲基溴化铵、十六烷基三甲基溴化铵、十八烷基三甲基氯化铵中的至少一种，阳离子表面活性剂与氟硅烷的质量比为0.1:1~0.3:1。
8.如权利要求1所述一种基于氟硅烷聚合物与纳米粒子协同的超双疏防水防油透气膜的制备方法，其特征在于：所述透气膜为聚四氟乙烯膜、PET膜、聚乙烯膜、聚丙烯膜中的一种。
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