CN104507313B - 使用可见光活化的聚合物表面上的光催化TiO2涂层及其制备方法和用途 - Google Patents

使用可见光活化的聚合物表面上的光催化TiO2涂层及其制备方法和用途 Download PDF

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CN104507313B
CN104507313B CN201380039330.5A CN201380039330A CN104507313B CN 104507313 B CN104507313 B CN 104507313B CN 201380039330 A CN201380039330 A CN 201380039330A CN 104507313 B CN104507313 B CN 104507313B
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沃伊切赫·马克奇
拉法尔·萨多斯基
普热梅斯劳·拉布斯
玛尔塔·布哈尔斯卡
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Abstract

本发明涉及聚合物表面上的氧化钛(IV)的可见光活性光催化涂层，其特征在于所述涂层涂覆于基板，所述基板为用于药物、食品和药品包装的有机聚合物材料，并且所述涂层为纳米晶体氧化钛(IV)或使用有机化合物表面改性的纳米晶体氧化钛(IV)。本发明还包括制备本发明的氧化钛(IV)的光催化涂层的方法，其包括如下步骤：使用低温等离子技术活化聚合物材料的表面，然后合成纳米晶体氧化钛(IV)涂层和使用有机化合物改性表面层。本发明还涉及本发明的氧化钛(IV)的光催化涂层在消毒用于药物、食品和药品包装的塑料元件中的应用以及在制造选自光消毒材料、光杀菌、光杀真菌、光催化材料的产品中的应用。

Description

使用可见光活化的聚合物表面上的光催化TiO2涂层及其制备 方法和用途
技术领域
本发明的主题是使用可见光活化的聚合物表面上的光催化氧化钛 (IV)涂层，它们的制备方法和它们的用途。聚合物表面选自用于药品和食品包装的聚合物，特别是聚氨基甲酸酯(PU)、聚碳酸酯(PC)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)。
现有技术
近年来，在人类活动的几乎每一个领域中塑料的使用均显著增加。低价格和改变材料以适应发展中社会的需要的简单特别有助于此。因为一次性医疗设备由这些聚合物材料制成，因此这些材料在医学上也发挥越来越重要的作用。将塑料表面暴露于生物膜的形成，其对健康有害并且是促成医源性感染的最重要的病因之一。根据世界卫生组织，医源性感染的最小化将对患者的健康以及医疗设施的经济状况产生积极影响。医源性感染问题的解决是设计具有潜在抗菌作用的新材料。病原体对通常可使用的抗菌剂的抵抗力的增加产生了对于其他创新性解决方案的需要。
问题的解决是使用光催化材料，特别是半导体，例如氧化钛(IV)，用于细菌的光灭活。目前的现有技术公开了这种应用，然而，氧化钛 (IV)通常在诸如玻璃或金属的矿物表面处以粉末、溶液或胶体层的形式存在(Chen,X.，Mao,S.S，2007，Chemical Reviews(化学综述),107, 2891-2959)，这显著降低其应用的可能性。
通过低温等离子体技术活化聚合物表面的方法是熟知的并且由 Hegemann(D.Hegemann等，Nuclear Instruments and Methods in Physics Research B(物理学研究B中的核仪器和方法)2003,208,281 -286)、Kasanen(J.Kasanen等，2009,J.Appl.Polym.Sci.,111,2597-2606) 和Vandencasteele(N.Vandencasteele等，2010,Journal of Electron Spectroscopy and Related Phenomena(电子能谱和相关现象期刊), 178-179,394-408)在文献中描述。聚合物表面的活化改变它们的物理和化学性质。由于活化方法，在氧的存在下，在聚合物材料的表面处产生许多含氧官能团，例如羟基(-OH)、羧基(-COOH)、羰基(-C＝O)。
通过应用等离子体处理改变材料性质而不改变体积的方法也是已知的。例如，在专利申请GB 2481891 A中公开了用于改性光纤电缆的等离子体处理。通过移动它通过等离子体炉使光学纤维的全长进行等离子体处理，在其上等离子体处理的光学纤维的表面被改性，变得更易于使它与靶标基板结合。所述方法允许形成与光纤电缆的表面粘附的靶标基板的层。用于粘附层形成的上述实例的材料为环氧树脂、聚酰胺和聚氨基甲酸酯。
在现有技术中观察到的不方便涉及在聚合物表面上获得持续的氧化钛(IV)涂层的困难和它们对可见光范围的敏化的困难。氧化钛(IV) 在聚合物表面上的永久固定提供了在TiO2处应用光催化方法的新机会，例如对于各种由塑料制成的医用材料的光消毒。
本发明的目的是在使用可见光或紫外光活化的聚合物表面上提供持久的氧化钛(IV)的光催化涂层并表现出高光催化性和高光消毒活性，以及它们的制备方法。本发明还提供了应用本发明涂层的新途径，即消毒诸如医用导管或食品包装的各种材料的一系列特征。
发明详细描述
本发明涉及使用可见光活化的聚合物表面上的氧化钛(IV)的光催化涂层，其特征在于：
a)它们涂覆于有机基板上，所述基板为用于医疗、食品和药品包装的聚合物材料，特别地选自：聚氨基甲酸酯(PU)、聚碳酸酯(PC)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)。
b)纳米晶体氧化钛(IV)或使用有机化合物表面改性的纳米晶体氧化钛(IV)的涂层。
优选地，使用选自以下的有机化合物对纳米晶体氧化钛(IV)进行表面改性：
a)具有式1的化合物：
其中：R1-R4为-H、饱和或不饱和取代基、-NH2、-NH3 +或-SO3M，其中M为：H+、K+、Na+、Li+、NH4 +且R5和R6为-OH或-COOH，
b)抗坏血酸，
c)具有式2的化合物(芸香苷)：
优选地，有机化合物选自：邻苯二甲酸、4-磺基邻苯二甲酸、4- 氨基-2-羟基苯甲酸、3-羟基-2-萘酸、水杨酸、6-羟基水杨酸、5-羟基水杨酸、5-磺基水杨酸、3,5-二硝基水杨酸、1,4-二羟基-1,3-苯二磺酸二钠盐、没食子酸、连苯三酚、2,3-萘二酚、4-甲基邻苯二酚、3,5-二叔丁基邻苯二酚、对硝基邻苯二酚、3,4-二羟基-L-苯基丙氨酸 (DOPA)、邻苯二酚、芸香苷和抗坏血酸。
本发明还涉及在用于医疗、食品和药品包装的聚合物表面上制备使用可见光活化的氧化钛(IV)光催化涂层的方法，所述聚合物特别地选自：聚氨基甲酸酯(PU)、聚碳酸酯(PC)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)，并且其特征在于其包括三个阶段：
a)使用低温等离子体技术对聚合物材料进行表面活化，
b)使用纳米晶体氧化钛(IV)悬浮液合成氧化钛(IV)的纳米晶体涂层，
c)通过在溶液中应用改性剂使用有机化合物改性涂层表面。
优选地，活化在氧等离子体或氮等离子体的影响下进行。优选地，活化在0.1-1mbar的等离子体压力下、在5-500s的等离子体操作时间内进行。还优选地，将使用等离子体活化的聚合物材料留在空气中以形成含氧官能团。
还优选地，如果胶体水溶液形式的具有粒度达100nm的纳米晶体氧化钛(IV)用于合成。优选地，通过浸渍技术(例如浸涂技术)、喷涂或涂装技术进行合成方法。优选地，所述方法在室温下进行。
优选地，使用有机化合物对涂层的表面改性在最低浓度为10-4 mol/dm3的改性剂的水溶液或醇溶液中进行，随后干燥。
优选地，有机化合物选自：邻苯二甲酸、4-磺基邻苯二甲酸、4- 氨基-2-羟基苯甲酸、3-羟基-2-萘酸、水杨酸、6-羟基水杨酸、5-羟基水杨酸、5-磺基水杨酸、3,5-二硝基水杨酸(表1)、1,4-二羟基-1,3-苯二磺酸二钠盐、没食子酸、连苯三酚、2,3-萘二酚、4-甲基邻苯二酚、3,5- 二叔丁基邻苯二酚、对硝基邻苯二酚、3,4-二羟基-L-苯基丙氨酸 (DOPA)、邻苯二酚(表2)、芸香苷和抗坏血酸。
表1.邻苯二甲酸和水杨酸衍生物。
表2.邻苯二酚衍生物。
还在图1中图示说明方法的特殊步骤。
本发明的另一主题是在聚合物表面上如上述定义使用可见光活化的和/或可在本发明的方法中获得的氧化钛(IV)的光催化涂层用于消毒在医疗、食品和药品包装中所使用的塑料成分的用途，所述塑料成分特别地选自：聚氨基甲酸酯(PU)、聚碳酸酯(PC)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)。
本发明的特殊主题是本发明的涂层和/或可通过本发明的方法获得的涂层用于制备选自以下的产品的用途：光消毒材料、光杀菌材料、光杀真菌材料、光催化材料和其他材料，特别是透明材料，例如医用导管、医用塑料管、用于食品和药品的箔片和包装。
本发明的特殊主题是本发明的涂层和/或可通过本发明的方法获得的涂层在医学(例如在皮肤病学、眼科学、耳鼻喉科学、泌尿学、妇科学、风湿病学、肿瘤学、手术、急救学(hospitality)、兽医学和牙科学)和在美容学中的用途，优选地，用于消毒医用导管、塑料管和其他表面的用途，所述消毒是有利的和/或需要的。
发明概述
当使用可见光(I>400nm；光催化是通过钛的表面复合吸收可见光的结果，电荷转移型)和紫外光(I<400nm；光催化是通过钛的表面复合吸收紫外光的结果，电荷转移型或直接通过氧化钛(IV)辐射)时，本发明的材料表现出光催化活性。由于光暴露，形成反应性氧种类 (ΟΗ·、O2 -、H2O2、1O2)，其负责有机化合物的氧化和微生物的腐化。
在图1-6中以不限制其应用范围的实施方案的形式提供本发明，其中：
图1表示在聚合物表面上制备使用可见光活化的氧化钛(IV)的光催化涂层的方法的通用图表，
图2表示涂覆TiO2并使用各种改性剂改性的PTFE的UV-vis漫反射光谱，
图3表示涂覆TiO2并使用各种改性剂改性的PTFE的UV-vis漫反射光谱转化为UV-vis吸收光谱，
图4表示天青B“干燥方式”的光降解，具有吸附模型污染物(天青 B)的TiO2@PTFE的漫反射光谱，辐射：XBO-150，滤水器，I>320nm，
图5表示天青B“干燥方式”的光降解，具有通过Kubleka-Munk功能转换的吸附模型污染物(天青B)的TiO2@PTFE的漫反射光谱，辐射：XBO-150，滤水器，I>320nm，
图6表示使用邻苯二酚和水杨酸的表面改性，与由未改性的ΤiΟ2制成的层(a)相比，其导致层对可见光K-9@TiO2(b)、S-2@TiO2(c)、 K-4@TiO2(d)的活性范围的充分定义的延伸。
实施例1.
获得可见光活性、纳米晶体光催化剂作为聚合物表面上的涂层
用于合成所描述的材料的起始基板为：
a)商购塑料材料，特别是聚氨基甲酸酯(PU)、聚碳酸酯(PC)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)，
b)具有小于100nm的粒度和有机表面改性剂的胶体、水溶液形式的未改性的、纳米晶体氧化钛(IV)。
变体1
从商购聚四氟乙烯(PTFE)膜切割3cm边长的正方形并使用清洁剂净化。在p＝0.3mbar、t＝120s、v＝2cm3/min、功率100W的条件下使用氧等离子体活化表面。在活化过程后，使聚合物材料留在空气中2分钟。使用浸渍技术(浸涂)从纳米晶体氧化钛(IV)(15％wt)的胶体溶液中进行涂层的合成。在室温下将聚合物材料从溶液中的拉拔速度建立在1cm/min。结果，在箔片的表面处形成TiO2均匀、耐久的涂层。通过将样品浸入来自组S(S-2、S-3；表1)或组K(K-1、K-4、K-9；表2)或浓度为10-4mol/dm3的水溶液形式的抗坏血酸或芸香苷的改性剂的溶液中2min、使用浸渍来改性所产生的涂层，然后在空气中干燥。
变体2
从商购聚氨基甲酸酯(PU)膜切割3cm边长的正方形并使用清洁剂净化。在p＝0.4mbar、t＝60s、v＝2cm3/min、功率100W的条件下使用氧等离子体活化表面。在活化过程后，使聚合物材料留在空气中2分钟。使用浸渍技术(浸涂)从纳米晶体氧化钛(IV)(4％wt)的胶体溶液中进行涂层的合成。在室温下将聚合物材料从溶液中的拉拔速度建立在1cm/min。结果，在箔片的表面处形成TiO2均匀、耐久的涂层。通过将样品浸入来自组S(S-2、S-3；表1)或组K(K-1、K-4、K-9；表 2)或浓度为10-4mol/dm3的水溶液形式的抗坏血酸或芸香苷的改性剂的溶液中2min使用浸渍来改性所产生的涂层，然后在空气中干燥。
变体3
从商购聚碳酸酯(PC)膜切割3cm边长的正方形并使用清洁剂净化。在p＝0.4mbar、t＝120s、v＝2cm3/min、功率100W的条件下使用氧等离子体活化表面。在活化过程后，使聚合物材料留在空气中 2分钟。使用浸渍技术(浸涂)从纳米晶体氧化钛(IV)(15％wt)的胶体溶液中进行涂层的合成。在室温下将聚合物材料从溶液中的拉拔速度建立在1cm/min。结果，在箔片的表面处形成TiO2均匀、耐久的涂层。通过将样品浸入来自组S(S-2、S-3；表1)或组K(K-1、K-4、K-9；表 2)或浓度为10-4mol/dm3的水溶液形式的抗坏血酸或芸香苷的改性剂的溶液中2min使用浸渍来改性所产生的涂层，然后在空气中干燥。
实施例2
所获得材料的特征
将根据实施例1合成的涂层永久地与基板粘附并且其不能够被擦掉。在图2和图3中提供使用来自组K的化合物改性的涂层的UV-vis 光谱。存在可见光的明显吸收，优选地在约500nm的波长范围中。
使用“干燥方式”规定获得的涂层的活性。天青B的水溶液用作光催化活性试验的模型污染物。将具有合成的TiO2涂层的塑料样品浸渍在浓度为2.5-10-4mol/dm3的颜料的溶液中1h。此后，将样品辐射3h 并监测在实验期间产生的变化。检测系统由氙气灯XBO-150组成。在灯的正后面放置具有硫酸铜(II)溶液的滤水器(其切断来自近红外范围，I>700nm的辐射)和高通滤波器，其传播I>320nm范围中的辐射。将样品放置在距离光源40cm的位置。通过分光光度计评价辐射期间染料颜色强度的变化。在图4和图5中示出辐射期间天青B降解的漫反射光谱和吸收光谱。观察到染料在3h时几乎完全降解。
实施例3
获得的涂层的光活性的研究
测试根据实施例1合成的涂层以检测它们的活性的光谱范围。对于光电化学检测，使用包括具有功率150W和电源适配器 LPS-250(Photon Technology International)的氙气灯XBO-150(Osram)、具有快门和电化学分析器BAS-50W(Bioanalytical systems)的单色器的装置。快门和单色器的控制系统允许自动控制入射光的波长和工作电极暴露于辐射的时间。在三电极电池中，在填充电解质(浓度为0.1mol dm-3的KNO3溶液)的具有体积为25cm3的石英比色皿中进行光电化学检测。铂电极用作辅助电极且氯化银电极(Ag/AgCl)用作参比电极。工作电极为根据实施例1中描述的方法涂覆使用有机化合物改性的纳米晶体TiO2层的ITO膜(透明导电材料，氧化铟-锡的混合物)。光电化学实验意图检测在应用于工作电极的恒定电势下，随在短闪光(10s)形式的光电极处入射的光波长(I＝f(l))而变的产生的光电流的强度。在随各个固定间隔(9.5nm)的闪光变化的330-700nm的波长范围下使用单色光辐射涂层。当关闭快门时发生波长变化。在电势范围600÷-200mV 下记录的绘图I＝f(l)(未考虑光的绝对强度的共享光谱)用于测定随波长和应用于工作电极的电势而变(所谓的光电流图，I＝f(E,l))的光响应 (photoreply)图。与由未改性的TiO2制成的涂层相比(图6a)，使用邻苯二酚衍生物和水杨酸的表面改性产生活性范围对可见光(图6： K-9@TiO2(b)、S-2@TiO2(c)、K-4@TiO2(d))的明确定义的延伸。

Claims (10)

1.在用于医疗、食品和药品包装的并且选自聚氨基甲酸酯(PU)、聚碳酸酯(PC)、聚氯乙烯(PVC)和聚四氟乙烯(PTFE)的聚合物材料的表面上制备氧化钛(IV)光催化涂层的方法，其特征在于其包括三个阶段：
a)使用低温等离子技术对聚合物材料进行表面活化，
b)使用纳米晶体氧化钛(IV)的悬浮液合成氧化钛(IV)的纳米晶体涂层，
c)通过在溶液中应用改性剂使用有机化合物改性所述涂层表面；
其中用于表面改性的所述有机化合物选自邻苯二甲酸、4-磺基邻苯二甲酸、4-氨基-2-羟基苯甲酸、3-羟基-2-萘酸、水杨酸、6-羟基水杨酸、5-羟基水杨酸、5-磺基水杨酸、3,5-二硝基水杨酸、1,4-二羟基-1,3-苯二磺酸二钠盐、没食子酸、连苯三酚、2,3-萘二酚、4-甲基邻苯二酚、3,5-二叔丁基邻苯二酚、对硝基邻苯二酚、3,4-二羟基-L-苯基丙氨酸(DOPA)、邻苯二酚、芸香苷和抗坏血酸。
2.如权利要求1所述的方法，其特征在于所述活化在氧等离子体或氮等离子体的影响下进行。
3.如权利要求1或2所述的方法，其特征在于所述活化在0.1-1mbar的等离子体压力下并且在5-500s的等离子体操作时间内进行。
4.如权利要求1所述的方法，其特征在于将所述等离子体聚合物材料留在空气中以形成含氧官能团。
5.如权利要求1所述的方法，其特征在于使用胶体水溶液形式的粒度高达100nm的纳米晶体氧化钛(IV)用于合成。
6.如权利要求1所述的方法，其特征在于通过浸渍技术、喷涂或涂装技术进行所述合成方法。
7.如权利要求6所述的方法，其特征在于所述浸渍技术为浸涂技术。
8.如权利要求1所述的方法，其特征在于所述方法在室温下进行。
9.如权利要求1所述的方法，其特征在于使用有机化合物对涂层的所述表面改性在最低浓度为10-4mol/dm3的改性剂的水溶液或醇溶液中进行，随后干燥。
10.权利要求1-9中任一项所述的方法制备的聚合物表面上的氧化钛(IV)光催化涂层，其特征在于：
a)所述涂层涂覆于基板，所述基板为用于医疗、食品和药品包装的并且选自聚氨基甲酸酯(PU)、聚碳酸酯(PC)、聚氯乙烯(PVC)和聚四氟乙烯(PTFE)的有机聚合物材料，
b)所述涂层包含使用有机化合物表面改性的纳米晶体氧化钛(IV)；
其中所述纳米晶体氧化钛(IV)是使用选自以下的有机化合物进行表面改性的：邻苯二甲酸、4-磺基邻苯二甲酸、4-氨基-2-羟基苯甲酸、3-羟基-2-萘酸、水杨酸、6-羟基水杨酸、5-羟基水杨酸、5-磺基水杨酸、3,5-二硝基水杨酸、1,4-二羟基-1,3-苯二磺酸二钠盐、没食子酸、连苯三酚、2,3-萘二酚、4-甲基邻苯二酚、3,5-二叔丁基邻苯二酚、对硝基邻苯二酚、3,4-二羟基-L-苯基丙氨酸(DOPA)、邻苯二酚、芸香苷和抗坏血酸。
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