CN116376339A - 一种抗微生物纳米复合材料及其制备方法与应用 - Google Patents
一种抗微生物纳米复合材料及其制备方法与应用 Download PDFInfo
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Abstract
本案涉及一种抗微生物纳米复合材料及其制备方法与应用，是以亚微米碳酸钙隔离分散的石墨烯纳米片为载体，在其表面吸附苯胺后原位氧化聚合形成PANI/GNP纳米材料，之后加入铜盐水合物，进一步还原后得到单原子Cu负载于GNP/PANI复合纳米片微观形貌的抗微生物纳米复合材料，记为Cu@GNP/PANI。本发明的Cu@GNP/PANI添加少量至有机涂料即可达到抗微生物的效果，且不会对海洋生物形成毒性；单原子Cu的载体PANI/GNP复合纳米片不仅能够提高涂层的附着力与韧性，同时能够改善涂层的防腐性能；既适合应用于自抛光防污涂料又适合应用于低表面能防污涂料体系中；应用范围广。
Description
本发明涉及防污功能材料领域，具体涉及一种抗微生物纳米复合材料及其制备方法与应用。
背景技术
海洋生物污损是指海洋中的约4000种微生物在海洋船体以及其他用于海洋作业的设备表面进行附着和累积的过程，这种现象会带来严重的危害，比如增加船体重量，增大表面粗糙度，降低航行速度，增加燃油量；堵塞海水输送管道，加大运行费用等，是制约海洋经济发展和维护海防安全的技术瓶颈。
污损生物随着船的航行而迁移在不同海域进行生存繁殖导致生态系统的紊乱。传统的海洋防污方法比如机械清除、超声等，需要耗费大量的人力物力等资源，而解决生物污损的有效方法是涂覆高分子防污涂层，如自抛光有机锡和氧化亚铜的防污涂料，可以有效地进行毒杀微生物，达到较好的防污效果。TBT防污漆，即含有具有三丁基锡侧基的直链丙烯酸共聚物的防污涂料，在海水中，聚合物逐渐水解释放三丁基锡，而剩余含有羧酸基团残基的丙烯酸共聚物在海水中变得足够可溶或可分散，以将其从涂覆表面洗掉或腐蚀掉。这种自抛光效应提供了生物活性化合物在涂料中的受控释放，导致优异的防污效率和光滑表面，并因此降低了摩擦阻力。然而，自IMO公约颁布以来，含TBT的防污涂料被禁止使用，氧化亚铜也由于存在着严重的危害性同样已经受到了禁用。
因此，研发可替代的兼具防腐蚀和抗海洋微生物等性能的安全环保型防污材料成为亟待解决的问题。
发明内容
针对现有技术中的不足之处，本发明基于石墨烯与聚苯胺形成的复合纳米片形貌的复合材料来有效稳定单原子铜制得纳米复合材料，以期望应用于防污涂料中使其具备抗微生物性能。
为实现上述目的，本发明提供如下技术方案：
一种抗微生物纳米复合材料，是以亚微米碳酸钙隔离分散的石墨烯纳米片为载体，在其表面吸附苯胺后原位氧化聚合形成PANI/GNP纳米材料，之后加入铜盐水合物，进一步还原后得到单原子Cu负载于GNP/PANI复合纳米片微观形貌的抗微生物纳米复合材料，记为Cu@GNP/PANI。
本发明进一步提供一种如上所述的抗微生物纳米复合材料的制备方法，包括如下步骤：
S1：在酸性的苯胺盐溶液中加入亚微米CaCO3隔离分散的石墨烯纳米片粉末，磁力搅拌吸附35-40min；随后置于0-5℃冰水浴中，滴加过硫酸铵的去离子水溶液，滴加完毕进一步聚合6-12小时；
S2：称取一定量的铜盐水合物置于S1的反应体系中，搅拌过夜，加入乙醇，于一定温度条件下进行还原反应；
S3：反应完成后，抽滤，并用蒸馏水与乙醇分别洗涤三次，60℃真空干燥得到抗微生物纳米复合材料粉末，记为Cu@PANI/GNP。
进一步地，所述S1中，酸性的苯胺盐溶液是在苯胺的水溶液中加入盐酸、硫酸或有机磷酸中至少一种搅拌混合而成。
进一步地，所述铜盐水合物为五水合硫酸铜、三水合硝酸铜或二水合氯化铜。
进一步地，所述苯胺、亚微米CaCO3隔离分散的石墨烯纳米片粉末、过硫酸铵、铜盐水合物的质量比为0.1～0.4:1:0.9～1:0.04～0.05。
进一步地，所述步骤S2中的反应条件为60℃反应1-2h。
本发明第三目的提供一种如上所述的抗微生物纳米复合材料的应用，在有机涂料中添加其固体质量的0.3-0.5％的抗微生物纳米复合材料，即可达到抗微生物效果。
本发明的抗微生物纳米复合材料，是以石墨烯与聚苯胺复合纳米片为载体，利用聚苯胺分子中N上的孤对电子与单原子Cu上的空轨道形成强配位作用，从而形成单原子Cu稳定负载于GNP/PANI复合纳米片微观形貌的纳米复合材料(Cu@PANI/GNP)；利用单原子铜能有效地将周围的氧与水催化形成超氧
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自由基而呈现高效抗微生物活性；PANI/GNP载体易分散于涂料树脂中，制备出的涂层还具有智能防腐活性。
本发明的有益效果是：
(1)达到抗微生物效果需要的纳米复合材料添加量少，为有机涂料固体质量的0.3-0.5％；
(2)Cu@PANI/GNP复合材料中，单原子Cu以配位键稳定在PANI/GNP复合纳米片上，不会对海洋生物形成毒性；
(3)单原子Cu的载体PANI/GNP复合纳米片不仅能够提高涂层的附着力与韧性，同时能够改善涂层的防腐性能；
(4)既适合应用于自抛光防污涂料又适合应用于低表面能防污涂料体系中；不仅可以应用于金属基材而且可以应用于钢筋混凝土构建、塑料及其纤维基材表面。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为亚微米碳酸钙隔离分散石墨烯微片的SEM图。
图2为Cu@PANI/GNP纳米复合材料的(a)TEM图(较低放大倍数)；(b)TEM图(较高放大倍数)；(c)HrTEM图；(d)对应(c)的衍射图；(e)HAADF-STEM以及元素映射图。
图3为Cu@PANI/GNP纳米复合材料的红外光谱图。
图4为Cu@PANI/GNP纳米复合材料的拉曼光谱图。
图5为Cu@PANI/GNP纳米复合材料的小角x射线衍射图。
图6为实施例2(a)和实施例3(b)制得的复合材料的HrTEM图。
图7为添加丙烯酸聚氨酯涂料固体质量的0.5％的实施例1和对比例1制备的纳米复合涂层表面硅藻附着荧光显微镜照片图。
图8为添加不同丙烯酸聚氨酯涂料固体质量的实施例1制备的纳米复合材料制备的涂层表面硅藻附着性能测试结果统计图。
图9为添加丙烯酸聚氨酯涂料固体质量分数的0.5％的实施例1和对比例1制备的纳米复合材料制备的涂层表面藤壶幼虫附着率随培养时间的变化图。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
本案中所用原料如无特殊说明均可从市场购得，其中CaCO3隔离分散GNP粉末见发明人已公开授权专利CN107849391A，其SEM如图1所示，显示石墨烯纳米片被亚微米(250×650nm)碳酸钙所隔离，在酸性溶液中碳酸钙分解为CO2气体，其位置将被苯胺替代，并与石墨烯微片形成π-π电子相互作用，为下一步苯胺在石墨烯微片表面进行原位氧化聚合奠定基础。
实施例1：
(1)在100ml烧杯中称取0.2g苯胺，50ml水，再在苯胺溶液中加入0.2g浓硫酸，用磁力搅拌形成苯胺的硫酸盐溶液；
(2)在磁力搅拌下加入0.6g的CaCO3隔离分散GNP粉末，以80r/min转速搅拌35min使苯胺在GNP纳米片表面的吸附达到平衡，得到苯胺吸附于石墨烯(苯胺@GNP)的悬浮液；
(3)称取0.55g的过硫酸铵(APS)，并溶解于20ml水中；
(4)将步骤(2)制备的苯胺@GNP悬浮液转移至三口烧瓶中，30ml水清洗烧杯后一并转移至三口烧瓶中，将整个反应置于冰水浴中(0℃-5℃)，以200r/min的转速搅拌；
(5)将步骤(3)配制的APS溶液通过滴液漏斗滴加入上述三口烧瓶中，控制30分钟内滴完，并进一步聚合8h，得到PANI/GNP纳米复合片；
(6)往步骤(5)中加入27.3mg五水合硫酸铜，搅拌吸附过夜，进一步在反应体系中加入100ml乙醇，在60℃还原反应1小时。
(7)反应结束后，用布氏漏斗过滤，并用蒸馏水与乙醇分别洗涤三次，60℃真空干燥得到Cu@PANI/GNP粉末。
图2(a)可以看出，PANI/GNP纳米复合片中少层石墨烯微片表面被扭曲，表面不再是光滑的石墨烯形貌，而是均匀地生长出粗糙的PANI层；较高放大倍数TEM图(图2(b))，可以清楚地看到复合纳米片形貌；从图2(c)复合纳米片的HrTEM，清晰地看到指纹形貌的5-8层石墨烯组成的石墨烯微片，表面生长了无定型PANI层，厚度在3-5纳米之间，纳米复合片扭曲成纵横交错形貌；从图2(d)可以清晰地看到石墨烯纳米片的结晶衍射峰的消失，说明苯胺在石墨烯纳米片之间进行了聚合，破坏了石墨烯微片的结晶形态。图2(e)为Cu@PANI/GNP纳米复合材料的HAADF-STEM以及元素映射图像，虽然在复合纳米片的HrTEM看不到Cu的信息，而在纳米复合材料元素映射图上除有“C”与“N”元素均匀分布外可以清晰地看到“Cu”元素的均匀分布，这个结果表明“Cu”在纳米复合材料中以单原子形态存在。而“O”元素几乎没有。这个结果说明，在乙醇中进行还原反应时只是将“Cu2+”还原成“Cu1+”或“Cu0”，并没有与“O”结合，形成Cu2O形态，说明石墨烯表面的PANI分子上“N”更易于与“Cu1+”或“Cu0”形成配位。
图3是Cu@PANI/GNP纳米复合材料的红外光谱图：1188cm-1是PANI苯环面内的弯曲振动峰；1230cm-1是PANI中C-N伸缩振动吸收峰；1517cm-1是PANI中苯式伸缩振动吸收峰；1614cm-1是PANI中醌式伸缩振动的吸收峰；1994cm-1是PANI与GNP界面复合形成了新的不对称累积双键区的伸缩振动峰；2124cm-1是PANI局域在GNP纳米片上后，形成界面不对称振动。
图4是Cu@PANI/GNP纳米复合材料的拉曼光谱图，石墨烯微片的G特征峰与PANI的C＝C伸缩振动在1580cm-1处发生偶合，说明GNP与PANI界面间形成了强π-π电子相互作用。1345cm-1峰，相比石墨烯在1360cm-1处的D峰，显著增大，这是因为在石墨烯片间与表面形成了PANI纳米层，并与石墨烯纳米片形成强电子相互作用的结果。
图5是Cu@PANI/GNP纳米复合材料的小角x射线衍射图，可以看到相比石墨烯微片在26.5°处出现的特别尖锐的峰(石墨002晶面)，纳米复合材料在26.06°处呈现中等强度的衍射峰，以及在14.77°以及20.73°出现两个非常微弱的PANI的特征半结晶峰。这个结果说明苯胺在石墨烯纳米片间以及表面的聚合会破坏石墨烯的结晶，同时PANI的结晶也会受石墨烯纳米片而影响。这与图2(d)Cu@PANI/GNP纳米复合材料的衍射结果是一致的。
实施例2(GNP:ANI＝1:0.2)
同实施例1，苯胺的用量变为0.1g，浓硫酸的用量变为0.1g，APS的用量变为0.275g，其它条件不变。
实施例3(GNP:ANI＝1:0.1)
同实施例1，苯胺的用量变为0.05g，浓硫酸的用量变为0.05g，APS的用量变为0.1375g，聚合时间为12h，其它条件不变。
图6为实施例2和3制得复合材料的HRTEM图，同样可以清晰地看到指纹形貌的5-8层石墨烯组成的石墨烯微片，表面生长了无定型PANI层，证明复合材料成功制得。
对比例：
以PANI/GNP纳米复合片作为涂料助剂。
应用：
将实施例1的Cu@PANI/GNP纳米复合材料和对比例的PANI/GNP纳米复合片添加到丙烯酸聚氨酯涂料中(购自江苏华夏制漆科技有限公司，型号：PU700-J，添加量为固体质量的0.5％，Cu@PANI/GNP纳米复合材料和对比例的PANI/GNP纳米复合片都经过分散剂作用下的砂磨工艺，形成纳米浆后与PU700-J涂料均匀混合，室温干燥后形成纳米复合涂层(涂层厚度60μm)分别记为实验样和对比样，进行抗硅藻测试。
1、抗硅藻测试：选用已经培养好的硅藻在23℃恒温培养箱中对不同涂层样片进行测试，3天后取出样片用生理盐水进行轻轻冲洗，然后用荧光显微镜进行观察选取20张照片并用ImageJ软件进行统计。
图7为实验样和对照样制备的纳米复合涂层表面硅藻附着荧光显微镜照片图。图中红色部分代表硅藻的荧光作用在荧光显微镜下的球形藻，与对比样相比，实验样具有较好的硅藻防污能力，而没有单原子铜的PANI/GNP纳米材料并没有显著的抗硅藻粘附活性。
此外，通过对本案实施例1制备的纳米复合材料在聚氨酯涂料中添加量(涂料固体质量0.3％-0.5％)的对比(图8)，可知最终制得的涂层，添加有Cu@PANI/GNP纳米复合材料的涂层表现出显著的硅藻粘附抑制性能。
2、抗藤壶幼虫粘附活性测试：
将涂片样品剪成圆形，消毒后，置于无菌聚苯乙烯24孔板的每一个孔中，每个样品至少有三个平行样。加入1mL经0.22μm过滤的新鲜海水，对照孔则是1mL经0.22μm过滤的新鲜海水。向每个孔加入15个左右的藤壶幼虫，置于28℃下恒温培养。每隔24h记录每个孔中，附着幼体的数量，用于计算抗藤壶幼虫粘附活性。
图9为藤壶幼虫附着率随培养时间的变化，可以看出采用本发明制备的Cu@PANI/GNP纳米复合材料作为抗微生物助剂得到的涂层具有出色的抗藤壶幼虫附着的性能，从对比结果可以看出，本申请的制备的Cu@PANI/GNP纳米复合材料具有较好的藤壶幼虫防污能力，而没有单原子铜的PANI/GNP纳米材料并没有显著的抗藤壶幼虫粘附活性。
3、抗菌性能测试：
如表1所示，结果表明，相比不添加Cu@PANI/GNP的涂层，添加0.4％Cu@PANI/GNP的涂层，作用24h后菌浓度显著降低。而且抗菌性能R＝LgC24h，不加-LgC24h，加＞2，说明相对于不加Cu@PANI/GNP的涂层材料抗菌率＞99％；而且添加Cu@PANI/GNP的涂层材料对金黄色葡萄球菌相比大肠杆菌具有更优异的抑菌性能。
表1
综上，在涂料中添加固体质量的0.3-0.5％的本案制得的Cu@PANI/GNP纳米复合材料时，形成的涂层对大肠杆菌与金色黄葡萄球菌的抑菌率超过99％；对硅藻表现显著的抗粘附以及对藤壶幼虫的附着力明显降低的效果。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。
Claims (7)
1.一种抗微生物纳米复合材料，其特征在于，是以亚微米碳酸钙隔离分散的石墨烯纳米片为载体，在其表面吸附苯胺后原位氧化聚合形成PANI/GNP纳米材料，之后加入铜盐水合物，进一步还原后得到单原子Cu负载于GNP/PANI复合纳米片微观形貌的抗微生物纳米复合材料，记为Cu@GNP/PANI。
2.一种如权利要求1所述的抗微生物纳米复合材料的制备方法，其特征在于，包括如下步骤：
S1：在酸性的苯胺盐溶液中加入亚微米CaCO3隔离分散的石墨烯纳米片粉末，磁力搅拌吸附35-40min；随后置于0-5℃冰水浴中，滴加过硫酸铵的去离子水溶液，滴加完毕进一步聚合6-12小时；
S2：称取一定量的铜盐水合物置于S1的反应体系中，搅拌过夜，加入乙醇，于一定温度条件下进行还原反应；
S3：反应完成后，抽滤，并用蒸馏水与乙醇分别洗涤三次，60℃真空干燥得到抗微生物纳米复合材料粉末，记为Cu@PANI/GNP。
3.如权利要求2所述的抗微生物纳米复合材料的制备方法，其特征在于，所述S1中，酸性的苯胺盐溶液是在苯胺的水溶液中加入盐酸、硫酸或有机磷酸中至少一种搅拌混合而成。
4.如权利要求2所述的抗微生物纳米复合材料的制备方法，其特征在于，所述铜盐水合物为五水合硫酸铜、三水合硝酸铜或二水合氯化铜。
5.如权利要求2所述的抗微生物纳米复合材料的制备方法，其特征在于，所述苯胺、亚微米CaCO3隔离分散的石墨烯纳米片粉末、过硫酸铵、铜盐水合物的质量比为0.1～0.4:1:0.9～1:0.04～0.05。
6.如权利要求2所述的抗微生物纳米复合材料的制备方法，其特征在于，所述步骤S2中的反应条件为60℃反应1-2h。
7.如权利要求1所述的抗微生物纳米复合材料的应用，其特征在于，在有机涂料中添加其固体质量的0.3-0.5％的权利要求1所述的抗微生物纳米复合材料，形成抗微生物防污涂料。
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| 唐伟: "三维石墨烯／聚苯胺复合材料的制备及其电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 02 * |
| 姜云龙等: "石墨烯/聚苯胺复合材料的制备及防腐性能的研究", 《涂料工业》, vol. 52, no. 3, pages 0 * |
| 杨小刚;王传洁;李斌;: "石墨烯/聚苯胺纳米复合材料的制备及防腐应用研究进展", 微纳电子技术, no. 04 * |
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| CN116376339B (zh) | 2024-02-27 |
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