CN111345315A - 静电自组装缓释二氧化氯空气净化凝胶及制备方法和应用 - Google Patents
静电自组装缓释二氧化氯空气净化凝胶及制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种静电自组装缓释二氧化氯空气净化凝胶及制备方法和应用，其中，静电自组装缓释二氧化氯空气净化凝胶，包括表面带正电基团的改性带电多孔纳米颗粒和带有负电基团的凝胶剂。本发明所述的静电自组装缓释二氧化氯空气净化凝胶，该凝胶易于储存、运输，且缓释效果好。
Description
技术领域
本发明属于环保消毒技术领域，尤其是涉及一种静电自组装缓释二氧化氯空气净化凝胶及制备方法和应用。
背景技术
二氧化氯以其强氧化性和反应活性被世界卫生组织认定为A1级高效抑菌剂，因此不断地被开发使用，应用领域越来越广泛。目前，国内外已将其用于饮用水、工业废水、生活污水、食品防腐保鲜及室内空气净化等领域消毒。二氧化氯的应用已经逐渐渗透到我们生活的方方面面。虽然二氧化氯在很多行业具有广泛的应用前景，但ClO2受自身理化性质影响，在实际应用中存在着一定的局限性。液态ClO2极不稳定，不易长期贮存。而气态ClO2不易贮存和运输，并存在爆炸危险。所以为了满足市场需要，人们尝试制作稳定性二氧化氯产品，对这类产品的研究主要集中在稳定性二氧化氯溶液和二氧化氯固体制剂两大类上。稳定性二氧化氯溶液具有无色透明，性质稳定，二氧化氯含量高等优点，但使用之前需要进行活化处理，并且在室内空气净化和果蔬运输中，使用液体多有不便，于是固态和类固态二氧化氯制剂应运而生。目前报道的二氧化氯固体制剂种类繁多，形状各异，如粉末状、块状、片状等。同时，根据气体释放周期又可将其分为快速、中速及长效缓释三种类型。一般的固体二氧化氯能在一定时间内缓慢释放出二氧化氯气体，但反应稳定性不够，持续时间不长，采用类固态凝胶的方式实现二氧化氯长期稳定缓释，在应对各行各业的杀菌、消毒、除醛、除味等方面必将具有巨大的市场潜力。
发明内容
有鉴于此，本发明旨在提出一种静电自组装缓释二氧化氯空气净化凝胶，以克服现有技术的缺陷，该凝胶与传统消毒剂不同，固化状态更易于储存、运输，且缓释效果好。
为达到上述目的，本发明的技术方案是这样实现的：
静电自组装缓释二氧化氯空气净化凝胶，包括表面带正电基团的改性带电多孔纳米颗粒和带有负电基团的凝胶剂。
优选的，所述改性带电多孔纳米颗粒和凝胶剂的重量比为(0.1-2):(3-10)。
优选的，改性带电多孔纳米颗粒和凝胶剂可通过静电自组装形成复合多孔通道。
优选的，所述静电自组装缓释二氧化氯空气净化凝胶，还包括亚氯酸盐、固体酸、保水剂和水，且以重量份计，各组分含量为：
优选的，改性带电多孔纳米颗粒基材为沸石、凹凸棒、硅藻土、海泡石、气凝胶、石墨烯、碳纳米管、分子筛中的一种或几种。
优选的，凝胶剂为聚丙烯酸钠、淀粉、羧甲基纤维素、高吸水树脂中的一种或几种组成。
优选的，所述固体酸为固体硫酸、固体盐酸、固体柠檬酸、固体草酸中的一种或几种。
优选的，亚氯酸盐为亚氯酸钠、亚氯酸钾、亚氯酸镁、亚氯酸钡中的一种或两种以上。
优选的，所述保水剂为聚乙二醇、魔芋胶、瓜尔豆胶、结冷胶、石蜡中的一种或两种。
优选的，所述水为去离子水或纯水。
本发明的另一目的在于提出一种制备如上所述的静电自组装缓释二氧化氯空气净化凝胶的方法，以制备上述静电自组装缓释二氧化氯空气净化凝胶。
为达到上述目的，本发明的技术方案是这样实现的：
一种静电自组装缓释二氧化氯空气净化凝胶的制备方法，包括以下步骤：
(1)称取配方量的各组分，将配方量的亚氯酸盐溶于水中，得A溶液；
(2)将改性带电纳米颗粒与凝胶剂进行预混，随后将该混合物与固体酸、保水剂混合，得B粉体；
(3)将B粉体导入A溶液中，搅拌至凝固即得本发明所述静电自组装缓释二氧化氯空气净化凝胶。
本发明还涉及如上所述的静电自组装缓释二氧化氯空气净化凝胶在空气净化及食品防腐保鲜领域的应用。
本发明所述的静电自组装缓释二氧化氯空气净化凝胶之所以可以延缓二氧化氯的生成和释放速度，其原理如下：
带电多孔纳米颗粒通过改性肢接正电荷基团表面带正电，带有正电基团的纳米颗粒在带有负电基团的凝胶剂表面通过静电自组装方式有效结合，从而形成复合多孔通道，达到延缓二氧化氯的生成和释放速度的目的。需要说明的是，本发明中，表面带正电基团的改性带电多孔纳米颗粒和带有负电基团的凝胶剂均为市售产品，表面带正电基团是改性带电多孔纳米颗粒的固有属性，表面带负电基团也是凝胶剂的固有属性。
上述自组装技术是指基本结构单元在一定条件下自发地形成有序机结构的过程。分子自发地通过无数非共价键的弱相互作用力的协同作用是发生自组装的关键。这里的“弱相互作用力”指的是氢键、范德华力、静电力、疏水作用力、π-π堆积作用、阳离子-π吸附作用等。本发明是采用了其中的静电力作用。
相对于现有技术，本发明所述的静电自组装缓释二氧化氯空气净化凝胶具有以下优势：
(1)本发明所述的静电自组装缓释二氧化氯空气净化凝胶，所述改性带电多孔纳米颗粒通过改性肢接正电荷基团表面带正电，带有正电基团的纳米颗粒在带有负电基团的凝胶剂表面通过静电自组装方式有效结合，从而形成复合多孔通道，达到延缓二氧化氯的生成和释放速度的目的。
(2)本发明在微观层面凝胶剂表面的吸附水层中，自组装了一层改性带电纳米颗粒，构造了一个水层中的多孔复合通道，水层内含有反应离子，复合结构的通道一方面作为反应离子的载体，减缓了反应物的结合反应速度，另一方面二氧化氯气体分子通过多孔通道，降低了释放速度。
所述静电自组装缓释二氧化氯空气净化凝胶的制备方法与上述静电自组装缓释二氧化氯空气净化凝胶相对于现有技术所具有的优势相同，在此不再赘述。
附图说明
图1为本发明所述静电自组装缓释二氧化氯空气净化凝胶延缓二氧化氯生成及释放速度的原理图；
图2为实施例7-9与对比例3中空气净化凝胶二氧化氯释放对比图。
具体实施方式
除有定义外，以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂，如无特殊说明，均为常规生化试剂；所述实验方法，如无特殊说明，均为常规方法。
下面结合实施例及附图来详细说明本发明。
本发明所述的静电自组装缓释二氧化氯空气净化凝胶，在微观层面凝胶剂表面的吸附水层中，自组装了一层改性带电纳米颗粒，构造了一个水层中的多孔复合通道，水层内含有反应离子，复合结构的通道一方面作为反应离子的载体，减缓了反应物的结合反应速度，另一方面二氧化氯气体分子通过多孔通道，降低了释放速度，具体原理如图1所示。
本发明下述各实施例中的改性带电纳米颗粒均为市售产品。
一、制备方法
本发明所述静电自组装缓释二氧化氯空气净化凝胶的制备方法，该方法先称取配方量的各组分，将配方量的亚氯酸盐溶于水中，得A溶液；再将改性带电纳米颗粒与凝胶剂进行预混，随后将该混合物与固体酸、保水剂混合，得B粉体；最后将B粉体导入A溶液中，搅拌至凝固即得所述静电自组装缓释二氧化氯空气净化凝胶。
二、实施例和对比例空气净化凝胶
按上述制备方法，以表1中的配方制备实施例1-6及对比例1和对比例2的空气净化凝胶。
表1实施例1-6静电自组装缓释二氧化氯空气净化凝胶及对比例凝胶配方表质量比：(％)
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 对比例1 | 对比例2 | |
| 亚氯酸钾 | - | - | - | 7 | 3 | 5 | - | 6 |
| 亚氯酸钠 | 4 | 5 | 2 | - | - | - | 4 | - |
| 固体酸 | 5 | 3 | 6 | 11 | 7 | 13 | 10 | 8 |
| 凝胶剂 | 6 | 4 | 3 | 3 | 7 | 5 | 6 | 10 |
| 保水剂 | 2 | 1 | 0.5 | 3 | 1 | 0.5 | 2 | 4 |
| 沸石 | 0.5 | - | - | 2 | - | - | - | - |
| 海泡石 | - | 1 | - | - | 0.7 | - | - | - |
| 碳纳米管 | - | - | 0.2 | - | - | 1 | - | - |
| 去离子水 | 82.5 | 86 | 88.3 | 74 | 81.3 | 75.5 | 78 | 72 |
表1中，实施例1-6及对比例1和对比例2中固体酸、凝胶剂和保水剂的具体物质选择见表1-1。
表1-1实施例1-6及对比例1和对比例2中固体酸、凝胶剂和保水剂的具体物质选择
二、实施例及对比例空气凝胶的性能检测
称取制得的静电自组装缓释二氧化氯空气净化凝胶实施例1-6和对比例1-2各100g,测试白葡萄球菌杀灭率，测试依据和方法为《消毒技术规范》2002年版-2.1.3，结果见表2；测试甲醛去除率，在密闭空间(0.1m3)放置凝胶，采用Interscan 4160检测仪进行测试；测试氨气去除率，在密闭空间(0.1m3)放置凝胶，采用氨气检测仪测试结果见表3。
表2白色葡萄球菌测试表单位：ppm
表3甲醛与氨气测试表单位：ppm
三、二氧化氯释放性能
按照前述方法制备实施例7-9及对比例3的空气净化凝胶，实施例7-9及对比例3的空气净化凝胶的组分配比见表4。
表4实施例7-9静电自组装缓释二氧化氯空气净化凝胶及对比例凝胶配方表质量比：(％)
| 亚氯酸钾 | 固体草酸 | 淀粉 | 聚乙二醇 | 沸石 | 海泡石 | 碳纳米管 | 去离子水 | |
| 实施例7 | 4 | 5 | 5 | 3 | 1 | - | - | 82 |
| 实施例8 | 4 | 5 | 5 | 3 | - | 1 | - | 82 |
| 实施例9 | 4 | 5 | 5 | 3 | - | - | 1 | 82 |
| 对比例3 | 4 | 5 | 5 | 3 | - | - | - | 83 |
对实施例7-9及对比例3中空气净化凝胶的二氧化氯释放性能进行测试，实验测试采用二氧化氯检测仪检测的为释放浓度，用c表示，单位为ppm。二氧化氯释放速率按下式计算：
V＝c·S/t
式中，V-释放速率,单位mg/s；
c-释放浓度，单位ppm(ClO2，1ppm＝3mg/m3)；
S-释放体积，单位m3；
t-释放时间，单位s。
实验测试结果见图2，由图2可以看出，同等情况下，本发明实施例7-9由于添加了改性带电纳米颗粒，相比于未添加改性带电纳米颗粒的对比例3，添加纳米颗粒以后，有效成分的负载量得到提高，即二氧化氯总体生成提高，而且由于静电自组装纳米颗粒后，气体释放通道由单一微结构，变为复合微纳结构，延缓了气体释放并且保持平稳释放。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.静电自组装缓释二氧化氯空气净化凝胶，其特征在于：包括表面带正电基团的改性带电多孔纳米颗粒和带有负电基团的凝胶剂。
2.根据权利要求1所述的静电自组装缓释二氧化氯空气净化凝胶，其特征在于：所述改性带电多孔纳米颗粒和凝胶剂的重量比为(0.1-2):(3-10)。
3.根据权利要求1或2所述的静电自组装缓释二氧化氯空气净化凝胶，其特征在于：改性带电多孔纳米颗粒和凝胶剂可通过静电自组装形成复合多孔通道。
4.根据权利要求1至3任意一项所述的静电自组装缓释二氧化氯空气净化凝胶，其特征在于：还包括亚氯酸盐、固体酸、保水剂和水，且以重量份计，各组分含量为：
5.根据权利要求1至4任意一项所述的静电自组装缓释二氧化氯空气净化凝胶，其特征在于：改性带电多孔纳米颗粒基材为沸石、凹凸棒、硅藻土、海泡石、气凝胶、石墨烯、碳纳米管、分子筛中的一种或几种。
6.根据权利要求1至5任意一项所述的静电自组装缓释二氧化氯空气净化凝胶，其特征在于：凝胶剂为聚丙烯酸钠、淀粉、羧甲基纤维素、高吸水树脂中的一种或几种组成。
7.根据权利要求4至6任意一项所述的静电自组装缓释二氧化氯空气净化凝胶，其特征在于：所述固体酸为固体硫酸、固体盐酸、固体柠檬酸、固体草酸中的一种或几种；
和/或，亚氯酸盐为亚氯酸钠、亚氯酸钾、亚氯酸镁、亚氯酸钡中的一种或两种以上。
8.根据权利要求4至7任意一项所述的静电自组装缓释二氧化氯空气净化凝胶，其特征在于：所述保水剂为聚乙二醇、魔芋胶、瓜尔豆胶、结冷胶、石蜡中的一种或两种；
和/或，所述水为去离子水或纯水。
9.一种制备如权利要求1至8任意一项所述的静电自组装缓释二氧化氯空气净化凝胶的方法，其特征在于：包括以下步骤：
(1)称取配方量的各组分，将配方量的亚氯酸盐溶于水中，得A溶液；
(2)将改性带电纳米颗粒与凝胶剂进行预混，随后将该混合物与固体酸、保水剂混合，得B粉体；
(3)将B粉体导入A溶液中，搅拌至凝固即得本发明所述静电自组装缓释二氧化氯空气净化凝胶。
10.一种如权利要求1至8任意一项所述的静电自组装缓释二氧化氯空气净化凝胶在空气净化及食品防腐保鲜的应用。
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