CN102985366A - 特别是对聚合物复合材料具有杀真菌性能的二氧化硅纳米粉末的制备方法 - Google Patents
特别是对聚合物复合材料具有杀真菌性能的二氧化硅纳米粉末的制备方法 Download PDFInfo
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Abstract
制备具有杀真菌性能的二氧化硅纳米粉末的方法，该方法在于，由含有四烷氧基硅烷和脂肪族醇的反应混合物、在铵化合物的存在下通过溶胶-凝胶法制备二氧化硅凝胶，随后加入可热分解的铜(II)盐化合物，以及来自碳官能化的烷氧基硅烷的集合的化合物，接着，在溶剂蒸发后在铜(II)盐的分解温度下加热干燥的残余物。
Description
本发明涉及一种特别是对聚合物复合材料具有杀真菌性能的二氧化硅纳米粉末的制备方法。
用于医学、药物、家用制品、纺织品和木材工业的材料的需求是必须赋予高分子化合物混合物杀微生物和杀真菌性能的原因。
在文献中可以发现关于使用铜纳米颗粒例如作为纤维素纤维的添加剂(Grace Mary，S.K.Bajpai，Navin Chand；Journal of Applied PolymerScience；vol.113 Issue 2，757-766)具有对大肠杆菌的杀微生物性能的信息。在出版物Nicola Cioffi，Luisa Torsi，Nicoletta Ditaranto，GiuseppinaTantillo，Lina Ghibelli，Luigia Sabbatini，Teresa Bleve-Zacheo，MariaD′Alessio，P.Giorgio Zambonin，Enrico Traversa；2005 American ChemicalSociety；vol.17(21)，5255-5262中记载了在聚合物复合材料中使用铜纳米颗粒形式的添加剂后，发现完全抑制或者减缓了活有机体例如病原真菌类和微生物的生长。
铜纳米颗粒比该元素的微粒具有明显更高的杀微生物活性。其实质问题在于在二氧化硅中固定了铜纳米颗粒。出版物(Optical properties ofcooper-dopes silica gels；，Journal of Alloys and Compounds 262-263(1997)438-442)的作者(T.Lutz，C.Estrournes，J.C.Merle，J.L.Guille)声称一种有用的方法是通过使用合适波长(紫外)的激光植入离子。
使用含有固定到二氧化硅中的铜纳米颗粒的纳米粉末作为纳米复合物和纳米材料的组分是可能的，条件是它们具有可再现的和确定的组成和化学结构。
从专利US6,495,257的说明书，可以知道一种通过溶胶-凝胶法制备含有金属(尤其是Ag，Zn)氧化物纳米颗粒的球形SiO2颗粒的方法，在水热分散的过程中引入二氧化硅和金属氧化物的水性悬浮液，水热分散包括在加压釜中于185-200℃的温度下搅拌几介小时。所得粉末的粒径在1-200μm的范围内。所述过程并不能解决制备粒径在200nm以下的包含金属纳米颗粒的二氧化硅纳米粉末的问题。这可能导致与它们作为纳米填料例如在聚合物复合材料中使用有关的一些限制。
与纳米填料颗粒的尺寸相关的聚合物纳米复合材料的性能与用颗粒尺寸在200nm以上的填料所得的复合材料的性能完全不同。在聚合物纳米复合材料中仅使用0.5-6％的少量纳米填料就能够提高机械、光学和阻碍性能以及更高的耐化学性和耐热性。降低线性膨胀系数和易燃性，这有利于最终的产品。使用标准量的填料(基于整个复合材料的约百分之几十)无法获得这些结果。
本发明的通过溶胶-凝胶法制备具有杀真菌性能的二氧化硅纳米粉末的方法，其特征在于，含有固定的纳米铜颗粒的二氧化硅溶胶由含有摩尔比为1∶5至1∶35的四烷氧基硅烷和乙醇或脂肪族C1-C4醇的混合物的水性反应混合物在铵化合物的存在下制备，其中烷氧基基团包含C1-C4碳原子，铵化合物的用量为每1mol四烷氧基硅烷使用0.001-0.05mol的铵化合物，在上述组分充分混合之后，以水溶液的形式、以每1mol四烷氧基硅烷0.0015-0.095mol的量引入可热分解的铜(II)盐，并且以每1mol铜(II)盐0.015-1mol的量加入来自碳官能化的烷氧基硅烷的集合的化合物，充分混合并且蒸发溶剂之后，在铜(II)盐的热分解温度下加热干燥残余物。
优选地，采用四甲基氢氧化铵或四乙基氢氧化铵作为铵化合物。
优选地，采用乙酸铜(II)盐或者甲酸铜(II)盐作为铜(II)盐。
优选地，采用γ-氨基丙基三乙氧基硅烷或者γ-(缩水甘油氧基)丙基三乙氧基硅烷作为来自碳官能化的烷氧基硅烷的集合的化合物。
通过本发明的方法在纳米粉末的表面上沉积的纳米铜颗粒的尺寸不超过50nm。本发明方法中含有颗粒尺寸为48nm的固定的铜颗粒的二氧化硅纳米粉末经过表征其堆积密度为86g/l，而类似颗粒尺寸的未改性的纳米二氧化硅的堆积密度为49.1g/l(根据PE-EN 1097-3：2000)。
通过在营养物质自由可达的条件下进行的基于在液体媒介中通过生长介质法的微生物实验，表征了含有固定的铜纳米颗粒的二氧化硅纳米粉末的杀微生物活性。发现1.2ppm剂量的含有固定的纳米铜颗粒的二氧化硅纳米粉末显示出对丝状菌的杀微生物活性。未改性的二氧化硅纳米粉末并未显示杀真菌活性。
通过本发明的方法制备的含有固定的铜纳米颗粒的二氧化硅纳米粉末是储存稳定的，并且纳米铜颗粒的尺寸不会改变。
通过本发明的方法获得的含有固定的纳米铜颗粒的二氧化硅纳米粉末的性质在使用该粉末作为在利于真菌和霉生长的条件下使用的聚合物复合材料的组分时是重要的。例如，它们可能是设计用于生产木材成型或者包装材料的含有纤维素纤维的复合材料。通过本发明的方法获得的含有固定的纳米铜颗粒二氧化硅纳米粉末可用作油漆、清漆、用于更高卫生要求的房间的油漆的添加剂。它们能够阻止霉菌在潮湿区域的生长：烟曲霉、焦曲霉、聚多曲霉、疣孢青霉菌、淡紫拟青霉以及绿脓杆菌、杆菌以及单链粪产碱杆菌，木糖葡萄球菌、绿色气球菌、琼氏不动杆菌、木糖氧化无色杆菌、囊泡短波单胞菌、嗜麦芽窄食单胞菌和溶血孪生球菌。
在下述实施例中说明了通过本发明的方法在表面上含有纳米铜颗粒的二氧化硅纳米粉末的制备。
实施例I：
将160.1g(3.47mol)的无水乙醇、1.2g 25％的四乙基氢氧化铵(0.002mol)的水溶液和55.2g蒸馏水在锥形烧瓶中通过磁力搅拌器进行搅拌。所得混合物的pH值为11.11。随后，将21.3g(0.10mol)四乙氧基硅烷加入到反应混合物中。在初期反应混合物是澄清的，但是在50min后观测到溶液的乳色。烧瓶中的内含物保持在环境温度下并搅拌2.5h；根据所得溶胶的光子相关光谱分析可以发现溶胶颗粒的尺寸为50-56nm。在24h之后将2.4g 0.1mol的乙酸铜(II)(0.00024mol)水溶液和0.00489g γ-(缩水甘油氧基)丙基三乙氧基硅烷(0.000019mol)加入到反应混合物中，将整个混合物搅拌1h。之后产物于90℃的温度下在炉中干燥1.5h并在250℃下加热2h以分解乙酸铜。
图1展现了允许实施金属含量的定性和定量分析的、具有铜的可见特征峰的X-射线分散光谱(EDS-能量分散光谱)图。
通过原子吸收光谱测定的铜的含量为0.0032wt％。
将如此获得的含有固定的铜颗粒的二氧化硅粉末以5wt％的量加入到基于聚碳酸酯的聚合物复合材料中；根据实施的微生物实验可以发现所得含有0.00016wt％(1.6ppm)的固定在二氧化硅纳米粉末上的铜纳米颗粒的聚合物复合材料对真菌烟曲霉、焦曲霉、聚多曲霉具有杀微生物活性。
实施例II：
将160.1g(3.47mol)的无水乙醇、0.47g 25％的四乙基氢氧化铵(0.002mol)的水溶液和55.2g蒸馏水在锥形烧瓶中通过磁力搅拌器进行搅拌，所得混合物的pH值为11.39。随后，将21.3g(0.10mol)四乙氧基硅烷加入到反应混合物中，在初期反应混合物是澄清的，但是在50min后观测到溶液的乳色。烧瓶中的内含物保持在环境温度下并搅拌2.5h；根据所得溶胶的光子相关光谱分析可以发现溶胶颗粒的尺寸为75-80nm。在24h之后将6.8g 0.1mol的甲酸铜(II)(0.00069mol)水溶液和0.0106g γ-氨基丙基三乙氧基硅烷(0.000048mol)加入到反应混合物中。将整个混合物搅拌1h。之后产物于90℃的温度下在炉中干燥1.5h并在280℃加热2h以分解甲酸铜。通过原子吸收光谱测定的铜的含量为0.006wt％。通过扫描电子显微镜测定所得纳米粉末由尺寸约为80nm的含有固定的铜纳米颗粒的二氧化硅颗粒组成。
将如此得到的含有固定的铜颗粒的二氧化硅粉末以3wt％的量加入到基于聚丙烯的聚合物复合材料中。根据实施的微生物实验可以发现，所得的含有固定在二氧化硅纳米粉末上的0.00025wt％(2.5ppm)的铜纳米颗粒的聚合物复合材料对疣孢青霉菌、淡紫拟青霉具有杀微生物活性。
实施例III：
将160.1g(3.47mol)的无水乙醇、1.77g 25％的四乙基氢氧化铵(0.002mol)的水溶液和55.2g蒸馏水在锥形烧瓶中通过磁力搅拌器进行搅拌，所得混合物的pH值为11.51。随后，将21.3g(0.10mol)四乙氧基硅烷加入到反应混合物中。在初期反应混合物是澄清的，但是在50min后观测到溶液的乳色。烧瓶中的内含物保持在环境温度下并搅拌2.5h；根据所得溶胶的光子相关充谱分析可以发现溶胶颗粒的尺寸为100-120nm。在24h之后加入70.0g 0.1mol的乙酸铜(II)(0.007mol)水溶液和0.1397g γ-氨基丙基三乙氧基硅烷(0.00063mol)。将整个混合物搅拌1h。之后产物于90℃的温度下在炉中干燥1.5h并在250℃加热2h以分解乙酸铜。通过原子吸收光谱测定的铜的含量为3.9wt％。
将如此获得的含有固定的铜颗粒的二氧化硅粉末以0.3wt％的量加入到基于聚乙烯的聚合物复合材料中。根据实施的微生物实验可以发现，所得的含有固定在二氧化硅纳米粉末上的0.00792wt％(79.2ppm)铜纳米颗粒的聚合物复合材料对疣孢青霉菌、淡紫拟青霉、烟曲霉、焦曲霉、聚多曲霉具有杀微生物活性。
实施例IV：
将189.23g(4.10mol)的无水乙醇、0.06g 25％的氨水溶液(0.0004mol)和48.75g蒸馏水在锥形烧瓶中通过磁力搅拌器进行搅拌，所得混合物的pH值为11.54。随后，将28.2g(0.13mol)四乙氧基硅烷加入到反应混合物中。在初期反应混合物是澄清的，但是在13min后观测到溶液的乳色。烧瓶中的内含物保持在环境温度下并搅拌2.5h。根据所得溶胶的光子相关光谱分析可以发现溶胶颗粒的尺寸为180-190nm。在24h之后加入73.0g 0.1mol的乙酸铜(II)(0.0073mol)水溶液和0.1457g γ-(缩水甘油氧基)丙基三乙氧基硅烷(0.00058mol)。将整个混合物搅拌1h。之后产物于90℃的温度下在炉中干燥1.5h并在250℃加热2h以分解乙酸铜。通过原子吸收光谱测定的铜的含量为4.5wt％。
将如此获得的含有固定的铜颗粒的二氧化硅粉末以1.5wt％的量加入到基于聚酰胺6的聚合物复合材料中。根据实施的微生物实验可以发现，所得的含有固定在二氧化硅纳米粉末上的0.07wt％(700ppm)铜纳米颗粒的聚合物复合材料对疣孢青霉菌、淡紫拟青霉、烟曲霉、焦曲霉、聚多曲霉具有微生物活性。
实施例V：
将156.2g(3.39mol)的无水乙醇、0.5g 25％的氨水溶液(0.0036mol)和36.8g蒸馏水在锥形烧瓶中通过磁力搅拌器进行搅拌。所得混合物的pH值为11.49。随后，将20.03g(0.09mol)四乙氧基硅烷加入到反应混合物中。在初期反应混合物是澄清的，但是在25min后观测到溶液的乳色。烧瓶中的内含物保持在环境温度下并搅拌2.5h。根据所得溶胶的光子相关光谱分析可以发现溶胶颗粒的尺寸为140-160nm。在24h之后加入77.0g 0.1mol的乙酸铜(II)(0.008mol)水溶液和1.597g γ-氨基丙基三乙氧基硅烷(0.0072mol)。将整个混合物搅拌1h。之后产物于90℃的温度下在炉中干燥1.5h并在250℃加热2h以分解乙酸铜。通过原子吸收光谱测定的铜的含量为3.5wt％。
将如此获得的含有固定的铜颗粒的二氧化硅粉末以0.75wt％的量加入到基于聚对苯二甲酸乙二醇酯的聚合物复合材料中。根据实施的微生物实验可以发现，所得的含有固定在二氧化硅纳米粉末上的0.09wt％(900ppm)铜纳米颗粒的聚合物复合材料对疣孢青霉菌、淡紫拟青霉、烟曲霉、焦曲霉、聚多曲霉具有杀微生物活性。
Claims (5)
1.通过溶胶-凝胶法制备具有杀真菌性能的二氧化硅纳米粉末的方法，其特征在于：含有固定的纳米铜颗粒的二氧化硅溶胶由含有摩尔比为1∶5至1∶35的四烷氧基硅烷和乙醇或脂肪族C1-C4醇的混合物的水性反应混合物在铵化合物的存在下制备，其中烷氧基基团包含C1-C4碳原子，其中铵化合物的用量为每1mol四烷氧基硅烷0.001-0.05mol的铵化合物，在上述组分充分混合之后，以水溶液的形式、以每1mol四烷氧基硅烷0.0015-0.095mol的量引入可热分解的铜(II)盐，并且以每1mol铜(II)盐0.015-1mol的量加入来自碳官能化的烷氧基硅烷的集合的化合物，充分混合并且蒸发溶剂之后，在铜(II)盐的热分解温度下加热干燥的残余物。
2.如权利要求1所述的方法，其特征在于采用四甲基氢氧化铵或四乙基氢氧化铵作为铵化合物。
3.如权利要求1所述的方法，其特征在于采用乙酸铜(II)或甲酸铜(II)作为铜(II)盐。
4.如权利要求1所述的方法，其特征在于采用γ-氨基丙基三乙氧基硅烷作为来自碳官能化的烷氧基硅烷的集合的化合物。
5.如权利要求1所述的方法，其特征在于采用γ-(缩水甘油氧基)丙基三乙氧基硅烷作为来自碳官能化的烷氧基硅烷的集合的化合物。
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| CN107848811A (zh) * | 2015-07-31 | 2018-03-27 | 福吉米株式会社 | 二氧化硅溶胶的制造方法 |
| CN109824901A (zh) * | 2019-03-06 | 2019-05-31 | 青岛科技大学 | 一种强吸水生物相容硅氧烷凝胶及其制备方法 |
| CN110668453A (zh) * | 2019-11-12 | 2020-01-10 | 东海县博汇新材料科技有限公司 | 一种利用微生物混合菌种提纯超细微硅粉的方法 |
| CN112841218A (zh) * | 2021-01-21 | 2021-05-28 | 江南大学 | 一种采用纳米硅量子点防治玉米粘虫的方法 |
| CN115536031A (zh) * | 2022-10-24 | 2022-12-30 | 中国科学院过程工程研究所 | 一种二氧化硅微球及其制备方法 |
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| CN109824901A (zh) * | 2019-03-06 | 2019-05-31 | 青岛科技大学 | 一种强吸水生物相容硅氧烷凝胶及其制备方法 |
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| CN112841218A (zh) * | 2021-01-21 | 2021-05-28 | 江南大学 | 一种采用纳米硅量子点防治玉米粘虫的方法 |
| CN112841218B (zh) * | 2021-01-21 | 2021-08-24 | 江南大学 | 一种采用纳米硅量子点防治玉米粘虫的方法 |
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| WO2011139170A1 (en) | 2011-11-10 |
| CN102985366B (zh) | 2015-01-14 |
| PL217463B1 (pl) | 2014-07-31 |
| EP2566814A1 (en) | 2013-03-13 |
| PL2566814T3 (pl) | 2018-01-31 |
| WO2011139170A8 (en) | 2013-01-17 |
| EP2566814B1 (en) | 2017-08-09 |
| US9126839B2 (en) | 2015-09-08 |
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