CN102071468B - 一种独立的聚合物纳米管及其制备方法和应用 - Google Patents
一种独立的聚合物纳米管及其制备方法和应用 Download PDFInfo
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Abstract
本发明的目的在于提供一种独立的聚合物纳米管及其制备方法和应用。所说的独立的聚合物纳米管以氧化铝模板法和紫外线光照法联合制备：首先利用多孔氧化铝模板制备聚合物纳米管薄膜，然后将聚合物纳米管薄膜放置于紫外光照体系下处理，就可将聚合物纳米管从所附着的聚合物薄膜上脱落下来，从而得到独立的聚合物纳米管。本发明操作工艺路线简单，耗能少，无污染，为具有分散独立性高分子纳米管的制备提供了新思路。
Description
技术领域
本发明涉及以氧化铝模板法和紫外线光照法联合制备独立的聚合物纳米管的制备方法，以及其在电子器件、催化、生物物质分离、纳米材料模板和功能性复合材料领域的应用。
技术背景
近年来纳米管的概念往往仅集中于碳纳米管系列：单壁碳纳米管、双壁碳纳米管、多壁碳纳米管、功能化多壁碳纳米管、短多壁碳纳米管、工业化多壁碳纳米管、石墨化多壁碳纳米管、大内径薄壁碳纳米管、镀镍碳纳米管。由于碳纳米管具有优异的物理化学和机械性能，其巨大的潜在应用价值得到了广泛的关注。除此之外，科学家们还努力开发了硅系纳米管（二氧化硅纳米管、碳化硅纳米管等）和硼纳米管以及金属类的纳米管系列。
纳米管所提供的纳米通道具有极高的科研价值和实际应用，比如纳米金属线由于化学上非常活泼，易于因大气中的湿气、氧气和腐蚀性气体作用而破坏，从而使其使用寿命大为缩短。采用纳米管包装金属纳米线-同心电缆式复合结构，就可以很好的解决金属纳米线阵列的防护问题；纳米通道应用在化学生物物质的分离分析方面也表现出广阔前景，引起了科研工作者越来越多的关注．纳米通道技术涉及到的学科包括分子生物学、生物化学、电子学、材料科学和信息学等多个学科，相信在不久的将来，纳米通道技术会在多个领域展现出更加美好的应用前景；利用纳米通道负载纳米形态的催化剂来构建催化体系的研究已经被报道很多，并正式被工业生产所利用；利用纳米管储存气体（氢气、甲烷等）来制作轻便的可携带式的储气容器也是近年来的研究热点。
正是基于纳米管材料的重要性以及目前纳米管种类的有限性，本发明提出一种利用氧化铝模板法和紫外线光照法联合制备独立的聚合物纳米管的途径，利用我们所述的方法可以快速高效地制备独立的聚合物纳米管，从而拓宽了传统纳米管材料的种类以及应用范围，同时我们利用独立的聚合物纳米管的自身结构，研究其在纳米电缆、纳米催化剂载体体系、生物物质分离体系、纳米材料模板、纳米管聚合物复合材料体系等方面应用。
发明内容
针对上述技术背景中所提及的独立的聚合物纳米管制备和应用的必要和重要性，本发明目的在于提供一种简单高效的独立的聚合物纳米管的制备，并将其应用到电子器件、催化、生物医药等领域之中。本发明的技术方案如下：
一种独立的聚合物纳米管，它是由氧化铝模板法和紫外线光照法联合制备：首先用多孔氧化铝模板制备聚合物纳米管薄膜，然后将粘连氧化铝模板的聚合物纳米管薄膜放置于紫外光下照射处理，再取出粘连氧化铝模板的聚合物纳米管薄膜，在氢氧化钠溶液充分浸泡后，移走氢氧化钠溶液后晾干，便可得到独立的聚合物纳米管。
以氧化铝模板法合成聚合物纳米管薄膜（聚合物纳米管生长在聚合物薄膜上，见图示），将其浸泡在蒸馏水中，然后利用紫外光照射一定时间，随后用氢氧化钠溶液处理，干燥后得到聚合物纳米管。
具体工艺途径为：将聚合物溶于有机溶剂配成聚合物溶液，然后将此溶液滴涂到一个洁净的玻璃片上，随即用氧化铝模板（孔径20-300纳米）覆盖，4-24小时后，将粘连氧化铝模板的聚合物薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为1000μw/cm2 -8000μw/cm2 （距离紫外灯38厘米处测量)的紫外光照射2-10小时，使得聚合物纳米管脆化断裂，然后取出粘连氧化铝模板的聚合物薄膜，用氢氧化钠溶液充分浸泡，待氧化铝模板充分溶解后，移走氢氧化钠溶液，晾干样品，即可得到独立的聚合物纳米管。
本发明所述的聚合物包括聚烯烃、聚苯乙烯、聚氯乙烯等。
本发明所述的有机溶液包括苯、甲苯、二甲苯、环己酮、四氯化碳、三氯化碳、乙酸乙酯、四氢呋喃、丙酮，二甲基甲酰胺等。
本发明所述的独立的聚合物纳米管可以应用于纳米电缆、纳米催化剂载体体系、生物物质分离体系、纳米材料模板、纳米管聚合物复合材料体系。
本发明所述的独立的聚合物纳米管制备工艺路线简单，耗能少，无污染，为具有分散独立性高分子纳米管的制备提供了新思路。
附图说明
图1为氧化铝模板扫描电镜图。
图2为聚合物纳米管薄膜正面的扫描电镜图。
图3为聚合物纳米管薄膜侧面的扫描电镜图。
图4为独立的聚合物纳米管扫描电镜图。
图5为银纳米粒子在聚合物纳米管表面自组装。
图6为银纳米线透射电镜图片。
具体实施方法
以下实施例用以说明本发明，而非限定其范围。
实施例1、独立的聚合物纳米管的制备
将聚苯乙烯溶于有机溶剂甲苯配成聚苯乙烯溶液，然后将此溶液滴涂到一个洁净的玻璃片上，随即用氧化铝模板（孔径200纳米，如图1所示）覆盖，12小时后，将粘连氧化铝模板的聚苯乙烯薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为6000μw/cm2 (38厘米距离处测量)的紫外光照射10小时，取出粘连氧化铝模板的聚苯乙烯薄膜，用氢氧化钠溶液充分浸泡，移走氢氧化钠溶液，晾干样品，即可得到独立的聚苯乙烯纳米管。接受紫外灯照射前的非独立的聚苯乙烯纳米管形貌如图2和图3所示；而接受紫外灯照射后，得到的独立的聚苯乙烯纳米管其形貌由扫描电镜观察如图4所示。
实施例2、独立的聚合物纳米管应用于纳米银电缆的制备
将聚氯乙烯溶于有机溶剂四氢呋喃配成聚氯乙烯溶液，然后将此溶液滴涂到一个洁净的玻璃片上，随即用氧化铝模板（孔径300纳米）覆盖，4小时后，将粘连氧化铝模板的聚氯乙烯薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为1000μw/cm2 (38厘米距离处测量)的紫外光照射10小时，取出粘连氧化铝模板的聚氯乙烯薄膜，用氢氧化钠溶液充分浸泡，移走氢氧化钠溶液，晾干样品，即可得到独立的聚氯乙烯纳米管。将独立的聚氯乙烯纳米管置于浓度为1%的硝酸银聚乙烯醇溶液中12小时，然后在紫外光下辐射5小时，即可得到包裹银纳米线的聚氯乙烯纳米同心电缆。
实施例3、独立的聚合物纳米管应用于纳米金电缆的制备
将聚丙烯溶于有机溶剂乙酸乙酯配成聚丙烯溶液，然后将此溶液滴涂到一个洁净的玻璃片上，随即用氧化铝模板（孔径300纳米）覆盖，24小时后，将粘连氧化铝模板的聚丙烯薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为8000μw/cm2 (38厘米距离处测量)的紫外光照射2小时，取出粘连氧化铝模板的聚丙烯薄膜，用氢氧化钠溶液充分浸泡，移走氢氧化钠溶液，晾干样品，即可得到独立的聚丙烯纳米管。将独立的聚丙烯纳米管置于浓度为1%的硝酸银聚乙烯醇溶液中12小时，然后在紫外光下辐射5小时，即可得到包裹银纳米线的聚丙烯纳米同心电缆。将独立的聚丙烯纳米管置于浓度为1%的氯金酸聚乙烯醇溶液中12小时，然后在紫外光下辐射5小时，即可得到包裹金纳米线的聚合物纳米同心电缆。
实施例4、独立的聚合物纳米管应用于纳米催化剂载体体系制备
将聚氯乙烯溶于有机溶剂二甲基甲酰胺配成聚氯乙烯溶液，然后将此溶液滴涂到一个洁净的玻璃片上，随即用氧化铝模板（孔径300纳米）覆盖，8小时后，将粘连氧化铝模板的聚氯乙烯薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为1000μw/cm2 (38厘米距离处测量)的紫外光照射5小时，取出粘连氧化铝模板的聚氯乙烯薄膜，用氢氧化钠溶液充分浸泡，移走氢氧化钠溶液，晾干样品，即可得到独立的聚氯乙烯纳米管。将聚氯乙烯纳米管进行表面活化后，使其表面形成有机官能团，然后采用自组装的方法将银纳米粒子在聚合物纳米管表面自组装，从而制备聚合物纳米管/银纳米粒子复合催化剂，如图5所示，该体系对碱性条件下的氧气电化学还原反应有很强的催化活性和选择性。
实施例5、独立的聚合物纳米管应用于制备生物物质分离体系
在独立的聚丙烯纳米管管内修饰十八烷基三甲基磺酸，使通道膜呈疏水性，水分子及电解质离子不能进入通道。考察疏水性药物乙胺碘呋酮和柴胡醇在疏水性通道膜内的迁移特性。
实施例6、以独立的聚合物纳米管为模板的纳米线制备
将聚苯乙烯溶于有机溶剂环己酮配成聚苯乙烯溶液，然后将此溶液滴涂到一个洁净的玻璃片上，随即用氧化铝模板（孔径300纳米）覆盖，12小时后，将粘连氧化铝模板的聚苯乙烯薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为6000μw/cm2 (38厘米距离处测量)的紫外光照射5小时，取出粘连氧化铝模板的聚苯乙烯薄膜，用氢氧化钠溶液充分浸泡，移走氢氧化钠溶液，晾干样品，即可得到独立的聚苯乙烯纳米管。将独立的聚苯乙烯纳米管置于浓度为1%的硝酸银聚乙烯醇溶液中12小时，然后在紫外光下辐射5小时，即可得到包裹银纳米线的聚合物纳米同心电缆，再利用有机溶剂将聚合物纳米管溶解去除，则可得到银纳米线，如透射电镜图6所示。
实施例7、独立的聚合物纳米管应用于制备纳米管-聚合物复合材料体系
将独立的聚苯乙烯纳米管分散在聚乙烯醇或者壳聚糖溶液中，形成纳米管-聚合物复合材料。
Claims (3)
1.一种独立的聚合物纳米管，其特征在于它是由氧化铝模板法和紫外线光照法联合制备：首先用多孔氧化铝模板制备聚合物纳米管薄膜，然后将粘连氧化铝模板的聚合物薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为1000μw/cm2 -8000μw/cm2的紫外光照射2-10小时，再取出粘连氧化铝模板的聚合物纳米管薄膜，在氢氧化钠溶液充分浸泡后，移走氢氧化钠溶液后晾干，便可得到独立的聚合物纳米管；所述的聚合物是聚丙烯、聚苯乙烯或聚氯乙烯。
2.根据权利要求1所述的独立的聚合物纳米管的制备方法，它包括用多孔氧化铝模板制备聚合物纳米管薄膜，其特征在于将粘连氧化铝模板的聚合物薄膜置于一个带有循环冷却水系统的蒸馏水浅池中，接受紫外灯强度为1000μw/cm2 -8000μw/cm2的紫外光照射2-10小时，然后取出粘连氧化铝模板的聚合物纳米管薄膜，在氢氧化钠溶液充分浸泡后，移走氢氧化钠溶液后晾干，便可得到独立的聚合物纳米管；所述的聚合物是聚丙烯、聚苯乙烯或聚氯乙烯。
3.根据权利要求1所述的独立的聚合物纳米管的用途，其特征在于可以应用在纳米电缆、纳米催化剂载体体系、生物物质分离体系、纳米材料模板、纳米管聚合物复合材料体系。
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