CN114196031A - 一种基于噻吩类MOFs的POTS超疏水改性材料的制备方法及应用 - Google Patents
一种基于噻吩类MOFs的POTS超疏水改性材料的制备方法及应用 Download PDFInfo
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Abstract
本发明提供了一种基于噻吩类MOFs的POTS超疏水改性材料,该超疏水改性材料的主要原料为由三乙氧基‑1H,1H,2H,2H‑十三氟代正辛基硅烷(POTS),以及由铜盐、3,4‑乙撑二氧基噻吩‑2,5‑二羧酸、2,2′‑联吡啶。所述的Cu‑MOFs/POTS疏水性材料,可作为助剂,应用于环氧树脂涂层中,可以极大提高涂层的防腐性能。
Description
技术领域
本发明属于一种疏水材料制备技术领域,具体涉及基于噻吩类MOFs的 POTS超疏水改性材料的制备方法及其在环氧树脂涂层中的应用。
背景技术
涂料助剂在涂料配方用量少,但对增强涂料的性能起到关键作用。涂料助剂总共有大约40种不同功能的类型(乳化剂、分散剂、消泡剂、增稠剂、防缩孔剂、干燥促进剂、杀菌剂等)。由于助剂的价值相对较高,配方设计时应尽可能地选择最优助剂,尽可能使用最少的助剂发挥最大的效果。涂料助剂的应用和应用水平,已成为衡量涂料生产技术水平的标志之一。
由于水性防腐涂料中残留水性基团导致疏水性能、机械性能较差,针对这一特点,在水性防腐涂料所用助剂除了一些基础助剂之外,还需加入少量特殊助剂到水性防腐涂料配方中,如目前被研究人员报道的助剂有石墨烯、纳米二氧化硅、多壁碳纳米管、纳米氧化铝颗粒、稀土助剂以及MOFs助剂等,这些助剂在配方中用量虽少,但明显提高水性防腐涂料的综合性能。
MOFs材料的比表面积高、表面曲率大,更容易形成纳米复合材料涂层。将 MOFs材料作为防腐助剂加入水性防腐涂料中,可以提高涂层的机械性能、热稳定性和防腐性能。因此关于MOFs材料作为防腐助剂应用于水性防腐涂料,已成为新型防腐涂料性能改善与开发的研究重点。
Kumaraguru等人将合成出的Co-MOFs、Ni-MOFs、Cu-MOsF作为助剂加入到水性丙烯酸树脂中,然后涂刷到碳钢表面,采用电化学阻抗谱(EIS)研究涂覆了不同MOFs的低碳钢在3.5wt.%NaCl和0.1mol/LHCl溶液中上的腐蚀速率,结果发现分别涂覆有Co-MOFs、Ni-MOFs、Cu-MOFs的碳钢片的腐蚀速度均比只涂覆水性丙烯酸树脂的碳钢片慢很多。作者认为添加了MOFs的涂层能抑制低碳钢表面附近的Cl-扩散并与低碳钢存在着稳定的协同作用,进而增强涂料的防腐能力。
水性防腐涂料由于以水为溶剂,导致涂料成膜时的疏水性与机械强度等有所欠缺,这会导致腐蚀介质容易与基材表面发生接触,从而降低涂层对基材的防腐作用。在这一背景下,研究人员开始对MOFs材料进行改性,希望改性后的MOFs 材料可以提高水性涂料形成的涂层的机械性能、防腐性能、疏水性能等。对MOFs 助剂进行改性是改善水性涂料性能的重要发展方向之一。
本发明提出了一种制备疏水性MOFs复合材料的策略。通过POTS对 Cu-MOFs粒子表面进行修饰,制备Cu-MOFs/POTS疏水性材料。再将 Cu-MOFs/POTS疏水性材料作为助剂添加到环氧树脂(EP)防腐涂层中,制备出超疏水Cu-MOFs/POTS/EP复合涂层。测定了水滴在所有涂层表面的水接触角,以验证涂层的疏水性能;利用电化学测试技术,系统的研究了空白碳钢片试样和超疏水防腐涂层在3.5wt.%NaCl溶液中的电化学腐蚀的变化情况。
发明内容
发明目的:目前对碳钢进行腐蚀防护最简单有效的方法就是在碳钢的表面涂上一层有机涂层。但有机涂层存在疏水性差,易产生缩孔,对抗机械性能较弱,分散稳定性差的问题。在防腐涂层中添加一些助剂特别是疏水性助剂是解决这些问题的重要手段。本发明制备一种基于噻吩类MOFs的POTS超疏水改性材料作为助剂,添加进入环氧树脂涂层中,提高了涂层的防腐性能。
发明思路:
首先,噻吩类羧酸配体有良好的刚性结构,而且其氧和硫原子均可参与可配位,使配位模式丰富。S原子的孤对电子在噻吩环的富电子共轭体系内容易离域,可优化配合物的性能。因此,利用含噻吩羧酸配体设计并合成新型功能配合物的材料是一个重要策略。结合噻吩羧酸配体的以上特点,预先进行结构设计,完成配体连接和金属节点的空间排布,可得到预期的框架结构。因此噻吩类羧酸是一类构筑MOFs材料的理想配体。
其次,三乙氧基-1H,1H,2H,2H-十三氟代正辛基硅烷(POTS)对MOFs进行疏水改性可以进一步提高MOFs的疏水性。因为POTS中的氟原子(下式)几乎将 C-C-C键完全包围起来,水分子很难进入破坏C-C键,因此,POTS具有优异的疏水性能,可以提高MOFs材料的疏水性能。由于噻吩羧酸配体具有富电性和刚性结构特点,POTS对其进行疏水改性后不会改变其结构特点。
本发明提出的一种基于噻吩类MOFs的POTS超疏水改性材料的制备方及应用方案主要包括以下内容:
所述的基于噻吩类MOFs的POTS超疏水材料,其特征在于,其制备方法为:
(1)将0.345g3,4-乙撑二氧基噻吩-2,5-二羧酸配体和0.234g2,2′-联吡啶 (2,2′-bipy)溶于含7mLN,N-二甲基甲酰胺(DMF)的烧杯1中,0.393g二水合氯化铜溶于含7mL去离子水烧杯2中,分别磁力搅拌至完全溶解后,将烧杯1 溶液倒入烧杯2中互混,继续搅拌20min,最后移入反应釜中,在100℃下加热 96h,然后每1h降温5℃,直至降至室温,即获得Cu-MOFs沉淀;
(2)将三乙氧基-1H,1H,2H,2H-十三氟代正辛基硅烷(POTS)加入到无水乙醇中进行混合,超声处理40min,再将POTS的乙醇溶液均匀搅拌1个小时后,加入上述步骤(1)获得的Cu-MOFs中,继续搅拌24分钟,得到的悬浊液即为 Cu-MOFs/POTS疏水性材料。
所述的Cu-MOFs/POTS疏水性材料,可作为助剂,应用于环氧树脂涂层中,可以极大提高涂层的防腐性能,其涂层制备过程如下:按质量比10:1:0.05将环氧树脂(EP)、聚酰胺、Cu-MOFs/POTS疏水性材料混合后,利用电动搅拌机不断搅拌,搅拌过程中,取15mL丙酮分三次加入,每隔半个小时滴加一次,每次添加5mL,搅拌均匀,获得Cu-MOFs/POTS/EP超疏水性涂料,在打磨好后的碳钢片上均匀涂覆Cu-MOFs/POTS/EP,固化6h后,可以获得超疏水性防腐涂层。
附图说明
图1Cu-MOFs/POTS红外光谱图(M1P76)
图2Cu-MOFs/POTS的XRD图(M1P77)
图3碳钢(a)及其表面上(b)EP涂层、(c)POTS涂层、(d)Cu-MOFs涂层、 (e)Cu-MOFs/POTS涂层、(f)Cu-MOFs/POTS/EP涂层的水接触角测试结果图。 (M1P82)
图4裸碳钢和涂覆有EP、Cu-MOFs/EP、Cu-MOFs/POTS/EP防腐涂层的时间-电位曲线(M1P83)
图5裸碳钢和涂覆有EP、Cu-MOFs/EP、Cu-MOFs/POTS/EP防腐涂层的动电位极化曲线图(M1P83)
具体实施方式
以下实施例是对本发明的进一步说明,而不是对本发明的限制。
实施例1
1.Cu-MOFs的制备方法
将0.345g3,4-乙撑二氧基噻吩-2,5-二羧酸配体和0.234g2,2′-联吡啶 (2,2′-bipy)溶于含7mLN,N-二甲基甲酰胺(DMF)的烧杯1中,0.393g二水合氯化铜溶于含7mL去离子水烧杯2中,分别磁力搅拌至完全溶解后,将烧杯1 溶液倒入烧杯2中互混,继续搅拌20min,最后移入反应釜中,在100℃下加热 96h,然后每1h降温5℃,直至降至室温,即获得Cu-MOFs沉淀。
2.Cu-MOFs/POTS疏水性材料的制备方法
将三乙氧基-1H,1H,2H,2H-十三氟代正辛基硅烷(POTS)加入到无水乙醇中进行混合,超声处理40min,再将POTS的乙醇溶液均匀搅拌1个小时后,加入上述步骤(1)获得的Cu-MOFs中,继续搅拌24分钟,得到的悬浊液即为 Cu-MOFs/POTS疏水性材料。
3.Cu-MOFs/POTS疏水性材料在环氧树脂涂层中的应用 Cu-MOFs/POTS疏水性材料,可作为助剂,应用于环氧树脂涂层中,可以极大提高涂层的防腐性能,其涂层制备过程如下:按质量比10:1:0.05将环氧树脂(EP)、聚酰胺、Cu-MOFs/POTS疏水性材料混合后,利用电动搅拌机不断搅拌,搅拌过程中,取15mL丙酮分三次加入,每隔半个小时滴加一次,每次添加5mL,搅拌均匀,获得Cu-MOFs/POTS/EP超疏水性涂料,在打磨好后的碳钢片上均匀涂覆Cu-MOFs/POTS/EP,固化6h后,可以获得超疏水性防腐涂层。
4.Cu-MOFs/POTS红外光谱图测试分析
对Cu-MOFs、POTS和Cu-MOFs/POTS的化学组成进行FTIR光谱表征,结果如附图1所示。Cu-MOFs在3518、2362、1667、1603和728cm-1处有五个特征峰,分别与噻吩类羧酸配体的O-H、C-S、C=O、C-S和Cu-N的振动吸收峰相对应。而Cu-MOFs的红外吸收峰都出现在Cu-MOFs/POTS复合材料的FTIR光谱中,证明复合材料中Cu-MOFs的存在。此外,与Cu-MOFs相比,Cu-MOFs/POTS 的光谱中还出现了三个新的吸附峰,而这些峰与POTS的吸附峰均是一一对应的。 POTS分子中C-F、吸收峰位于1243cm-1,位于1095和951cm-1处的吸附峰,分别对应C-O-Si和Si-O-C2H5的吸收峰。以上FTIR光谱结果分析表明,Cu-MOFs 以及Cu-MOFs/POTS超疏水性材料成功制备。
5.Cu-MOFs/POTS的XRD图测试分析
利用XRD测试研究了Cu-MOFs粒子和Cu-MOFs/POTS复合材料的晶体结构,结果如附图2所示。从Cu-MOFsXRD图谱中可以看到2θ从5°到60°之间具有许多衍射峰,这是由于Cu-MOFs的有序多孔结构产生。而Cu-MOFs/POTS的衍射峰分别和Cu-MOFs/几乎一致,表明POTS对Cu-MOFs/修饰后,晶体结构几乎没有影响,这也进一步说明了Cu-MOFs具有较强的结构稳定性。同时,通过jade5.6软件计算Cu-MOFs/POTS复合材料的平均晶粒尺寸为76.9nm。
6.水接触角测试结果分析
附图3为碳钢(a)及其表面上(b)EP涂层、(c)POTS涂层、(d)Cu-MOFs涂层、 (e)Cu-MOFs/POTS涂层、(f)Cu-MOFs/POTS/EP涂层的水接触角测试结果图。由附图3可知,与纯碳钢片表面相比其接触角非常小,这是由于本专利用水和DMF 作为溶剂来制备MOFs纳米粒子,制备的Cu-MOFs在水中分散性较好,具有亲水性。Cu-MOFs具有多孔结构,根据Wenzel理论,亲水表面粗糙度越大,接触角会越小,因此,Cu-MOFs涂层的接触角只有38.5°。EP涂层的接触角为58.9°,为亲水界面(如图(b))。图(c)是涂覆有POTS/乙醇溶液的接触角照片,水接触角为85.3°,大于未处理之前的纯碳钢片,这是因为POTS本身具有一定的疏水性,但因碳钢片表面较为光滑,疏水性较差。图(e)是将疏水性Cu-MOFs/POTS超疏水性材料涂覆到碳钢片表面后的接触角照片,MOFs本身粗糙表面以及得到 POTS修饰后获得低表面能,使得该涂层疏水性增强,接触角高达127.7°,证实了构建超疏水表面的两个条件分别是一定的粗糙度以及低表面能。与Cu-MOFs/EP涂层相比,图(f)显示超疏水Cu-MOFs/POTS/EP复合涂层表现出更高的疏水性,接触角较Cu-MOFs//EP涂层相比有所增大,达到了154.8°,达到了超疏水级别。这是因为环氧树脂粘结层的存在,提供了微米级的粗糙结构,而 Cu-MOFs/POTS超疏水材料给涂层提供了良好的低表面能,再加上 Cu-MOFs/POTS中的Cu-MOFs及POTS分子具有平面性,因此二者能够形成稳定的超疏水材料;另外超疏水材料中MOFs羧基中的氢能与环氧树脂中的氧能形成氢键,增强了Cu-MOFs/POTS超疏水材料在环氧树脂中的相容性,因此Cu-MOFs/POTS/EP更适合形成超疏水表面。疏水性能的大小为 Cu-MOFs/POTS/EP>Cu-MOFs/EP>POTS>裸碳钢片>Cu-MOFs。
7.时间-电位曲线分析
裸碳钢和涂有EP、Cu-MOFs/EP、Cu-MOFs/POTS/EP复合涂层在 3.5wt.%NaCl溶液中的开路电位(EOCP)与浸泡时间的关系曲线如附图4所示。如附图4所示,对于包括裸碳钢在内的所有样品,开路电位均有不同程度的负移,并在约2000s后达到稳态条件。结果表明,裸碳钢的EOCP值为-0.7176V,纯环氧树脂涂层的EOCP为-0.7140V,Cu-MOFs/EP、Cu-MOFs/POTS/EP涂层的EOCP值分别为-0.5532、-0.5813V。涂覆有复合涂层的EOCP值均比空白裸碳钢和纯环氧树脂防腐涂层的高,说明复合涂层均能较好的保护碳钢不受腐蚀介质的侵蚀。
8.电位极化曲线分析
附图5为裸碳钢和涂覆有EP、Cu-MOFs/EP、Cu-MOFs/POTS/EP复合涂层的碳钢在3.5wt.%NaCl溶液中的动电位极化曲线图。
与裸碳钢相比,涂覆有EP、Cu-MOFs/EP、Cu-MOFs/POTS/EP复合涂层的极化曲线均往下移,腐蚀电流减小,腐蚀电位正向移动,表明碳钢受到保护,腐蚀速率减小。
Claims (3)
1.一种基于噻吩类MOFs的POTS超疏水改性材料,其特征在于:三乙氧基-1H,1H,2H,2H-十三氟代正辛基硅烷(POTS),以及由铜盐、3,4-乙撑二氧基噻吩-2,5-二羧酸、2,2′-联吡啶形成的Cu-MOFs组成。
2.根据权利要求1所述的基于噻吩类MOFs的POTS超疏水材料,其特征在于,其制备方法为:
(1)将0.345g 3,4-乙撑二氧基噻吩-2,5-二羧酸配体和0.234g 2,2′-联吡啶(2,2′-bipy)溶于含7mL N,N-二甲基甲酰胺(DMF)的烧杯1中,0.393g二水合氯化铜溶于含7mL去离子水的烧杯2中,分别磁力搅拌至完全溶解后,将烧杯1溶液倒入烧杯2中互混,继续搅拌20min,最后移入反应釜中,在100℃下加热96h,然后按每1小时降温5℃,直至降至室温,即获得Cu-MOFs沉淀;
(2)将三乙氧基-1H,1H,2H,2H-十三氟代正辛基硅烷(POTS)加入到无水乙醇中进行混合,超声处理40min,再将该POTS乙醇溶液均匀搅拌1个小时后,加入上述步骤(1)获得的Cu-MOFs中,继续搅拌24分钟,得到的悬浊液即为Cu-MOFs/POTS疏水性材料。
3.根据权利要求2所述的Cu-MOFs/POTS疏水性材料,可作为助剂,应用于环氧树脂涂层中,可以极大提高涂层的防腐性能,其涂层制备过程如下:按质量比10:1:0.05将环氧树脂(EP)、聚酰胺、Cu-MOFs/POTS疏水性材料混合后,利用电动搅拌机不断搅拌,搅拌过程中,取15mL丙酮分三次加入,每隔半个小时滴加一次,每次添加5mL,搅拌均匀,获得Cu-MOFs/POTS/EP超疏水性涂料,在打磨好后的碳钢片上均匀涂覆Cu-MOFs/POTS/EP,固化6h后,可以获得Cu-MOFs/POTS/EP超疏水性防腐涂层。
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