CN108047860A - 一种具有防污自净功能的表面涂层产品的制备方法 - Google Patents

一种具有防污自净功能的表面涂层产品的制备方法 Download PDF

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CN108047860A
CN108047860A CN201711295842.4A CN201711295842A CN108047860A CN 108047860 A CN108047860 A CN 108047860A CN 201711295842 A CN201711295842 A CN 201711295842A CN 108047860 A CN108047860 A CN 108047860A
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purification function
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唐新德
董福营
王传栋
韩念凤
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Shandong Sen Pipeline Technology Co ltd
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Abstract

本发明公开了一种具有防污自净功能的表面涂层产品的制备方法,是在室温下,将盐酸多巴胺、两性离子单体、交联剂和氧化剂依次溶于Tris缓冲溶液中,搅拌均匀,形成混合溶液,然后将基材表面浸渍其中,超声分散10‑60min取出,用去离子水清洗、室温干燥后获得。本发明方法简便快速且不受基材类型的限制,涂层稳定性好,适用性广,应用前景广阔。

Description

一种具有防污自净功能的表面涂层产品的制备方法
技术领域
本发明涉及一种具有防污自净功能的表面涂层产品的制备方法,属于有机无机复合功能材料技术领域。
背景技术
通过表面改性能够赋予基质材料表面新的功能和性质,常用的表面改性方法有化学接枝、物理复合以及物理化学接枝法等。化学接枝法通过改性剂与基质材料主体的化学反应而实现复合,在一定程度上降低了基质材料的本征性能,影响基材的机械强度和化学稳定性;物理复合法以基质材料和表面改性层之间的非共价键结合力为前提,二者之间的结合力较弱,改性产品的功能化表层易被破坏,稳定性较差,使用寿命短。
聚多巴胺改性是近年来受贻贝类粘附启发而发展起来的新型高效表面修饰技术,通过小分子多巴胺及其衍生物在惰性材料表面的氧化自聚,为制备高性能复合材料提供新途径。自2007年首次报道以来,聚多巴胺表面改性已经在生物、医药、催化、水处理等领域受到广泛关注。多巴胺能依靠自身的氧化实现聚合,不会破坏基质材料的结构,且能更好地结合多种材料的优点;多巴胺作为改性单体,能浸润大多数惰性材料,具有良好的适应性。此外,聚多巴胺改性涂层含有大量活性基团,可进行二次表面改性。但聚多巴胺表面改性也存在局限性,例如聚多巴胺改性反应时间长、在有机溶剂或酸碱性环境中的稳定性较差,限制了聚多巴胺涂层的使用范围。
两性离子聚合物同时含有阴离子、阳离子基团,可以结合大量自由水分子,形成水化层,可有效抑制细菌和蛋白质的黏附。将两性离子聚合物引入材料表面,可提高材料表面的防污染和自净功能,在医疗器件、传感器、水处理、油水分离等领域都具有广阔的应用前景,尽管如此,两性离子聚合物表面涂层的制备仍然受限于制备方法的复杂性及适用基材的局限性。两性离子聚合物表面涂层的制备通常采用表面接枝或表面固定的方法。表面接枝两性离子聚合物刷通过化学共价键作用得到的涂层表面具有良好的稳定性和均匀性,但对基材的要求严格,需要对基材表面进行活化改性,还须严格控制反应条件,且化学修饰过程繁琐、制备周期较长。表面固定法则通过范德华力、氢键作用或电荷作用将聚合物以物理非共价键的作用固定在基材表面,较化学接枝法简单、快速,但需要提前聚合物和基材进行电荷或活性基团的修饰,使基材的适用范围受限,且聚合物与基材的结合力弱、表面涂层稳定性差,不利于长期使用。因此,将化学作用的稳定性与物理作用的简易性有机结合起来,开发出一种简便、快速、稳定且不受基材限制的制备方法,对两性离子聚合物表面涂层的推广应用具有重要意义。
目前已报道的公开号为CN105498291A的中国专利公开了一种具有自净功能的油水分离网膜及其制备方法,以不锈钢网、铝合金网或铜网为基底,在网表面及网孔的表面化学接枝含两性基团的丙烯酸酯类聚合物制得。公开号为CN106422421A的中国专利公开了一种滤纸改性制备油水分离膜的方法与应用,以普通定性滤纸为基材,通过聚多巴胺的黏附作用,在滤纸表面构建PDA介导层,然后将带有活性酯基团的聚乙二醇或两性离子聚合物与PDA介导层表面的氨基通过酰胺化作用共价接枝固定在表面。公开号为CN103394295A的中国专利公开了一种亲水性PVDF复合滤膜及其制备方法,由PVDF、多巴类助剂与端环氧PEO的反应产物共混制备而成。但以上制备方法仍存在工艺复杂、步骤繁琐等问题,有待进一步改进和优化。
发明内容
针对现有技术的不足,本发明要解决的问题是提供一种具有防污自净功能的表面涂层产品的制备方法。
本发明所述的具有防污自净功能的表面涂层产品的制备方法,步骤是:
(1)室温下,将盐酸多巴胺、两性离子单体、交联剂和氧化剂按摩尔比为1:10~100:1~10:1~10的比例,依次溶于pH=8.5的Tris缓冲溶液中,搅拌均匀,形成混合溶液;
(2)将基材表面浸渍于步骤(1)制得的混合溶液中,超声分散10~60min取出,用去离子水清洗、室温干燥,即得到具有防污自净功能的表面涂层产品。
上述具有防污自净功能的表面涂层产品的制备方法中,所述盐酸多巴胺、两性离子单体、交联剂和氧化剂的摩尔比优选为1:15~70:1~7:1~7。
其中,所述盐酸多巴胺、两性离子单体、交联剂和氧化剂的摩尔比最优选1:15~30:2~5:2~5。
上述具有防污自净功能的表面涂层产品的制备方法中,所述的两性离子单体优选2-甲基丙烯酰氧乙基磷酸胆碱、2-甲基丙烯酰氧乙基磺酸甜菜碱或2-甲基丙烯酰氧乙基羧基甜菜碱。
上述具有防污自净功能的表面涂层产品的制备方法中,所述的交联剂优选二胺、多元胺或戊二醛,或其几种任意摩尔比组合。
其中,所述的交联剂最优选二胺或戊二醛。
上述具有防污自净功能的表面涂层产品的制备方法中,所述的氧化剂优选过硫酸盐、高氯酸盐、高碘酸盐或双氧水。
其中,所述的氧化剂最优选过硫酸钾或过硫酸铵。
上述具有防污自净功能的表面涂层产品的制备方法中,所述的基材为滤纸、海绵、棉布、聚偏氟乙烯膜、玻璃或金属筛网。
与现有技术相比,本发明具有以下有益效果:
(1)方法操作简单,只需要一步溶液浸渍即可实现聚多巴胺和两性离子聚合物在基材表面的固定,并且不受基材类型的限制,有效克服了现有方法操作复杂、表面稳定性差等问题,为具有防污自净功能的表面涂层提供了高效、快速的制备方法。
(2)多巴胺在氧化自聚合的同时,其活性功能基团可以引发两性离子单体的聚合,氧化剂的存在加快了二者的聚合速度。通过交联剂与聚多巴胺中的活性功能团反应,将可溶性小分子低聚多巴胺交联成三维立体网络结构,提高聚多巴胺、两性离子聚合物分子之间以及聚多巴胺、两性离子聚合物分子与基质材料之间的结合强度。
(3)制备工艺条件温和,在常温下即可进行,易于产业化。
具体实施方式
下面通过给出的具体实施例进一步阐述本发明,但下述实施例只用于理解本发明并不是对本发明保护范围的限定。
实施例1:
(1)室温下,将盐酸多巴胺(38mg,0.2mmol)、2-甲基丙烯酰氧乙基磷酸胆碱(0.885g,3mmol)、乙二胺(0.06g,1mmol)和过硫酸铵(0.27g,1mmol)依次溶于Tris缓冲溶液(20mL,50mM,pH=8.5)中,搅拌均匀,形成混合溶液;
(2)将普通滤纸浸渍于步骤(1)得到的混合溶液中,超声分散45min取出,用去离子水清洗、室温干燥,即得到具有防污自净功能的表面改性滤纸。
实施例2:
本实施例按照实施例1相同的方式制备表面涂层,区别仅在于步骤(2)中以薄层海绵替代普通滤纸,得到具有防污自净功能的表面改性海绵。
实施例3:
本实施例按照实施例1相同的方式制备表面涂层,区别仅在于步骤(2)中以玻璃片替代普通滤纸,得到具有防污自净功能的表面改性玻璃片。
实施例4:
本实施例按照实施例1相同的方式制备表面涂层,区别仅在于步骤(2)中以不锈钢筛网替代普通滤纸,得到具有防污自净功能的表面改性不锈钢筛网。
实施例5:
(1)室温下,将盐酸多巴胺(38mg,0.2mmol)、2-甲基丙烯酰氧乙基磺酸甜菜碱(0.837g,3mmol)、戊二醛(0.10g,1mmol)和过硫酸钾(0.27g,1mmol)依次溶于Tris缓冲溶液(20mL,50mM,pH=8.5)中,搅拌均匀,形成混合溶液;
(2)将普通滤纸浸渍于步骤(1)得到的混合溶液中,超声分散30min取出,用去离子水清洗、室温干燥,即得到具有防污自净功能的表面改性滤纸。
实施例6:
本实施例按照实施例5相同的方式制备表面涂层,区别仅在于步骤(2)中以薄层海绵替代普通滤纸,得到具有防污自净功能的表面改性海绵。
实施例7:
本实施例按照实施例5相同的方式制备表面涂层,区别仅在于步骤(2)中以玻璃片替代普通滤纸,得到具有防污自净功能的表面改性玻璃片。
实施例8:
本实施例按照实施例5相同的方式制备表面涂层,区别仅在于步骤(2)中以不锈钢筛网替代普通滤纸,得到具有防污自净功能的表面改性不锈钢筛网。
实施例9:
(1)室温下,将盐酸多巴胺(57mg,0.3mmol)、2-甲基丙烯酰氧乙基羧基甜菜碱(0.972g,4mmol)、戊二醛(0.15g,1.5mmol)和过硫酸钾(0.81g,3mmol)依次溶于Tris缓冲溶液(20mL,50mM,pH=8.5)中,搅拌均匀,形成混合溶液;
(2)将普通滤纸浸渍于步骤(1)得到的混合溶液中,超声分散15min取出,用去离子水清洗、室温干燥,即得到具有防污自净功能的表面改性滤纸。
实施例10:
本实施例按照实施例9相同的方式制备表面涂层,区别仅在于步骤(2)中以薄层海绵替代普通滤纸,得到具有防污自净功能的表面改性海绵。
实施例11:
本实施例按照实施例9相同的方式制备温敏性表面涂层,区别仅在于步骤(2)中以玻璃片替代普通滤纸,得到具有防污自净功能的表面改性玻璃片。
实施例12:
本实施例按照实施例9相同的方式制备温敏性表面涂层,区别仅在于步骤(2)中以不锈钢筛网替代普通滤纸,得到具有防污自净功能的表面改性不锈钢筛网。

Claims (9)

1.一种具有防污自净功能的表面涂层产品的制备方法,步骤是:
(1)室温下,将盐酸多巴胺、两性离子单体、交联剂和氧化剂按摩尔比为1:10~100:1~10:1~10的比例,依次溶于pH=8.5的Tris缓冲溶液中,搅拌均匀,形成混合溶液;
(2)将基材表面浸渍于步骤(1)制得的混合溶液中,超声分散10~60min取出,用去离子水清洗、室温干燥,即得到具有防污自净功能的表面涂层产品。
2.根据权利要求1所述具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述盐酸多巴胺、两性离子单体、交联剂和氧化剂的摩尔比为1:15~70:1~7:1~7。
3.根据权利要求2所述基于具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述盐酸多巴胺、两性离子单体、交联剂和氧化剂的摩尔比为1:15~30:2~5:2~5。
4.根据权利要求1所述具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述的两性离子单体为2-甲基丙烯酰氧乙基磷酸胆碱、2-甲基丙烯酰氧乙基磺酸甜菜碱或2-甲基丙烯酰氧乙基羧基甜菜碱。
5.根据权利要求1所述具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述的交联剂为二胺、多元胺或戊二醛,或其几种任意摩尔比组合。
6.根据权利要求5所述具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述的交联剂为二胺或戊二醛。
7.根据权利要求1所述具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述的氧化剂为过硫酸盐、高氯酸盐、高碘酸盐或双氧水。
8.根据权利要求7所述具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述的氧化剂为过硫酸钾或过硫酸铵。
9.根据权利要求1所述具有防污自净功能的表面涂层产品的制备方法,其特征在于,所述的基材为滤纸、海绵、棉布、聚偏氟乙烯膜、玻璃或金属筛网。
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