CN102822260A - 尤其用于聚合物复合物中的具有生物杀灭性能的二氧化硅纳米粉末的生产方法 - Google Patents
尤其用于聚合物复合物中的具有生物杀灭性能的二氧化硅纳米粉末的生产方法 Download PDFInfo
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Abstract
通过溶胶-凝胶方法制备尤其是用于聚合物复合物中的,具有生物杀灭性能的二氧化硅纳米粉末。该二氧化硅溶胶由含有四烷氧基硅烷、C1-C4醇或C1-C4脂肪醇混合物的水性混合物,在铵化合物的存在下,随着在彻底混合组分之后引入银盐和随后的碱金属氢氧化物水溶液而制备,其中四烷氧基硅烷中的烷氧基包含C1-C4个碳原子,四烷氧基硅烷与C1-C4醇或C1-C4脂肪醇混合物的摩尔比为1∶5-1∶35,铵化合物的用量为每1摩尔四烷氧基硅烷0.001-0.05摩尔,银盐为水溶液的形式且用量为每1摩尔四烷氧基硅烷0.02-1摩尔,碱金属氢氧化物的用量为每1摩尔四烷氧基硅烷0.02-1摩尔氢氧化物。颗粒尺寸为200nm以下的二氧化硅纳米粉末包含固定在二氧化硅上的银纳米颗粒,具有稳定的物理化学和生物杀灭性能。
Description
本发明涉及尤其是用于聚合物复合物中的具有生物杀灭性能的二氧化硅纳米粉末的生产方法。
加强研究获得具有生物杀灭和/或杀真菌性能的高分子量混合物的原因,是用于如医疗(设备、室内设备、防护服、假肢)、纺织和制鞋工业、日用品、塑料、油漆、涂料领域的材料的高要求。
从科学文献中可以知道胶体银溶液作为生物杀灭添加剂用于不同材料,如塑料、涂层织物等。已发现胶体银溶液的生物杀灭性能在1ppm的浓度时就可以实现(Gaisford S.,Blezer A.E.,Bishop A.H.,Walter M.,Parsons D.International Journal of Pharmaceutics 2009,366,11-116)。在一些出版物中,作者强调使用胶体银时产生的问题为银颗粒和它们的凝结物的凝聚,在很大程度上阻碍获得所要求的生物杀灭活性(Halbig P.,Grau H.,Nickel U.Photochem.Photobiol.1994,60,605;Schirtcliff N.,Nickel U.,SchneiderS.,J.Colloid Interface Sci.1999,211,122;Rivas I.,Sanchez-CortesS.,Garcia-Ramos J.V.,Morcillo G.,Langmuir 2001,17,574;Nickel U.,Castell AZ.,Poppl K.,Schneider S.,Langmuir 2000,16,9087)。银纳米颗粒比银微米颗粒具有显著更高的生物杀灭活性。在银微米颗粒的情况下达到生物杀灭活性要求时使用的浓度比在银纳米颗粒的情况下获得可接受的生物杀灭活性时的浓度高103(Damm C.,Munstedt H.,Rosch A.,Materials Chemistryand Physics 2008,108,61-66)。
Sharma V.K.,Yngard R.A.,Lin Y.,Advances in Colloidal and InterfaceSci 2009,145,83描述了在通过使用保护胶体或固定在聚合物中的胶体银颗粒的稳定化方法方面的研究。由于在获得的材料的性能方面稳定剂有不利影响,这种稳定的银胶体的使用受到限制。
从US 6,482,444,US 6,495,257和US 2006/0246149中的专利说明书中可以知道包含金属化合物的微米颗粒即包含氧化锌、氧化银的粉末,包括颗粒例如SiO2。这些粉末以更高的粒度(与纳米颗粒相比)为特征,和金属化合物微米颗粒在颗粒的内部。
已知,通过溶胶-凝胶方法生产包含纳米银颗粒内含物的球形SiO2颗粒的工艺,描述在波兰专利申请P-360190中。二氧化硅粉末颗粒的尺寸在200-800nm的范围内。然而用该方法不能获得尺寸在200nm以下的包含金属银纳米颗粒的二氧化硅纳米粉末。在它们作为聚合物复合物的纳米填料的应用中有显著的局限性。
聚合的纳米复合物的独特性能与纳米填料颗粒的小尺寸相联系,它们明显区别于获得自200nm以上颗粒的复合物的性能。获得自仅某些百分比含量(0.5-5%)的纳米填料的纳米复合物显示出特别优选的性能,例如改进的隔离性能和非常高的机械和光学性能,更好的热和化学耐受性,减少的可燃性和线性膨胀系数。使用传统填料需要使用很大的量(从10%至几十%)才能获得相似的效果。
从PL198188的专利说明书中可以知道通过溶胶-凝胶方法生产具有小的颗粒尺寸多分散性的二氧化硅纳米粉末的工艺。用上述工艺获得的二氧化硅纳米粉末的尺寸取决于所用的催化剂的量和反应混合物的组成。用这种纳米粉末获得的聚合的纳米复合物显示出非常好的物理机械性能,尤其是使用功能化的纳米粉末,持久地固定在聚合物基体中。
本发明要解决生产具有生物杀灭性能的二氧化硅纳米粉末的问题,该粉末包含固定化的纳米尺寸银颗粒,且通过“原位”方法获得。并入二氧化硅结构中的银纳米颗粒是稳定的并且在储存期间不凝聚,保证生物杀灭性能的稳定性并解决了由于银颗粒的团聚而引起的这种性能衰退的问题。通过本发明的方法获得的具有固定化银纳米颗粒的二氧化硅纳米粉末的特征在于良好的物理化学性能再现性,小的颗粒尺寸分布,在二氧化硅纳米颗粒中银纳米颗粒的均一分布,这通过扫描电镜来确认。
依据本发明的通过溶胶-凝胶方法生产尤其是用于聚合物复合物的具有生物杀灭性能的二氧化硅纳米粉末的方法,其特征在于,该二氧化硅溶胶获得自包含四烷氧基硅烷、C1-C4醇或C1-C4脂肪醇的混合物的水性混合物,在铵化合物的存在下,随着在彻底混合组分之后引入银盐和随后的碱金属氢氧化物水溶液而制备,其中四烷氧基硅烷中的烷氧基包含C1-C4个碳原子,四烷氧基硅烷与C1-C4醇或C1-C4脂肪醇混合物的摩尔比各自为1∶5-1∶35,铵化合物的用量为每1摩尔四烷氧基硅烷0.001-0.05摩尔,银盐为水溶液的形式且用量为每1摩尔四烷氧基硅烷0.02-1摩尔,碱金属氢氧化物的用量为每1摩尔四烷氧基硅烷0.02-1摩尔氢氧化物。
优选地,将氢氧化四甲基铵或氢氧化四乙基铵用作铵化合物。
优选地,将硝酸银用作银盐。
优选地,将氢氧化钠用作碱金属氢氧化物。
通过本发明的方法获得的包含固定化银纳米颗粒的二氧化硅纳米粉末,通过溶剂蒸发来分离并且干燥残留物。干燥时间由温度决定,温度通常不超过250℃。
通过本发明的方法获得的包含固定化银纳米颗粒的二氧化硅纳米粉末,在储存期间稳定,并且纳米银颗粒的尺寸在长期储存期间不发生变化。
通过本发明的方法获得的包含固定化纳米尺寸银纳米颗粒的二氧化硅纳米粉末的性能在这种粉末作为聚合物复合物的组分使用时非常重要,该聚合物复合物用于家庭用品(冰箱,洗衣机等)中的具有生物杀灭性能的模制品零件的生产中,和用于具有更高卫生要求的医疗和公共设施的设备中。聚合物复合物以及含有无纺织物(例如纤维素)的混合物能够用于包装材料的生产中。进而,包含固定化纳米尺寸银纳米颗粒的二氧化硅纳米粉末可以用作指定用于具有更高卫生要求的室内油漆的组分。
下列实施例描述了依据本发明的方法生产二氧化硅纳米粉末。
实施例I
在锥形烧瓶中使用磁力搅拌器混合89.0g(1.93mol)无水乙醇,0.09g(0.001mol)20%氢氧化四甲基铵的水溶液和34.2g(1.9mol)蒸馏水。获得的混合物的pH值为11.53。随后,将17.2g(0.08mol)的四乙氧基硅烷加入反应混合物中。反应混合物在初期是澄清的,但是15分钟后观察到乳白色的溶液。烧瓶中的物质保持在环境温度下并且搅拌2.5小时。然后,将18ml的0.1M硝酸银水溶液(0.0018mol,0.31g)和18ml的0.1M氢氧化钠水溶液(0.0018mol,0.07g)加入反应混合物中。由于银盐的减少,反应混合物的颜色为浅灰色。烧瓶中的物质搅拌1小时。通过光子相关波谱法分析获得的溶胶,显示出溶胶的颗粒尺寸为120-132nm。然后,将溶胶样品在90℃下在烘箱中干燥1.5小时并且在250℃下干燥2小时。得到浅灰色可流动的二氧化硅纳米粉末。获得的纳米粉末的颗粒尺寸通过扫描电镜分析,并且发现其为118-132nm。固定化银颗粒的尺寸为28-57nm。样品中银的含量通过EDS X-射线分光光度法和原子吸收分光光度法分析,并且发现其为0.004wt%。
所获得的包含固定化纳米尺寸银颗粒的二氧化硅纳米粉末以4.5wt%的量加入到基于聚酰胺66的聚合物复合物中。根据实施的微生物学的检测,发现所获得的包含0.00018wt%(1.8ppm)的固定在二氧化硅纳米粉末上的银纳米颗粒的聚合物复合物对细菌大肠杆菌具有生物杀灭活性。
实施例II
在锥形烧瓶中使用磁力搅拌器混合179.86g(3.91mol)无水乙醇,0.5g(0.005mol)20%氢氧化四甲基铵的水溶液和54.18g(3.01mol)蒸馏水。获得的混合物的pH值为11.59。随后,将29.17g(0.14mol)的四乙氧基硅烷加入反应混合物中。反应混合物在初期是澄清的,但是10分钟后观察到乳白色的溶液。然后,将0.83g(0.005mol)的0.1M醋酸银水溶液和0.28g(0.005mol)的0.1M氢氧化钾水溶液加入反应混合物中。由于氢氧化钾的减少,反应混合物的颜色为灰色。烧瓶中的物质保持在环境温度下搅拌3.5小时。通过光子相关波谱法分析获得的溶胶,显示出溶胶的颗粒尺寸为178-180nm。然后,将溶胶样品在90℃下在烘箱中干燥1.5小时并且在250℃下干燥2小时。得到棕色可流动的二氧化硅纳米粉末。获得的纳米粉末的颗粒尺寸通过扫描电镜分析,并且发现其为180-182nm。固定化银颗粒的尺寸为36-54nm。样品中银的含量通过原子吸收分光光度法分析,并且发现其为0.007wt%。
所获得的包含固定化纳米尺寸银颗粒的二氧化硅纳米粉末以3wt%的量加入到基于聚丙烯的聚合物复合物中。根据实施的微生物学的检测,发现所获得的包含0.00021wt%(2.1ppm)的固定在二氧化硅纳米粉末上的银纳米颗粒的聚合物复合物对细菌金黄色葡萄球菌具有生物杀灭活性。
实施例III
在锥形烧瓶中使用磁力搅拌器混合156.0g(3.39mol)无水乙醇,1.0g(0.06mol)25%氨水和55.2g(3.07mol)蒸馏水。获得的混合物的pH值为11.4。随后,将20.0g(0.1mol)的四乙氧基硅烷加入反应混合物中。反应混合物在初期是澄清的,但是20分钟后观察到乳白色的溶液。烧瓶中的物质保持在环境温度下搅拌2.5小时。通过光子相关波谱法分析获得的溶胶,显示出溶胶的颗粒尺寸为82-85nm。然后,将350ml的0.1M硝酸银水溶液(0.04mol,6.8g)和350ml的0.1M氢氧化钠水溶液(0.04mol,1.4g)加入反应混合物中。由于银盐的减少,反应混合物的颜色为棕色。整个混合物搅拌1小时。然后,样品在90℃下在烘箱中干燥1.5小时并且在250℃下干燥2小时。样品中银的含量通过原子吸收分光光度法分析,并且发现其为3.5%。
所获得的包含固定化纳米尺寸银颗粒的二氧化硅纳米粉末以0.25wt%的量加入到基于聚乙烯的聚合物复合物中。根据实施的微生物学的检测,发现所获得的包含0.00875wt%(87.5ppm)的固定在二氧化硅纳米粉末上的银纳米颗粒的聚合物复合物对细菌金黄色葡萄球菌和大肠杆菌具有生物杀灭活性。
实施例IV
在锥形烧瓶中使用磁力搅拌器混合99.0g(2.15mol)无水乙醇,1.20g(0.07mol)25%氨水和36.8g(2.04mol)蒸馏水。获得的混合物的pH值为11.5。随后,将19.3g(0.09mol)的四乙氧基硅烷加入反应混合物中。反应混合物在初期是澄清的,但是8分钟后观察到乳白色的溶液。烧瓶中的物质保持在环境温度下搅拌2.5小时。通过光子相关波谱法分析获得的溶胶,显示出溶胶的颗粒尺寸为120-132nm。然后,将375ml的0.1M硝酸银水溶液(0.04mol,6.4g)和375ml的0.1M氢氧化钠水溶液(0.04mol,1.5g)加入反应混合物中。由于银盐的减少,反应混合物的颜色为棕色。整个混合物搅拌1小时。然后,样品在90℃下在烘箱中干燥1.5小时。获得的纳米粉末的颗粒尺寸通过扫描电镜分析,并且发现其为118-135nm。固定化银颗粒的尺寸为38-69nm。样品中银的含量通过EDS X射线分光光度法分析,并且发现其为3.2%。
所获得的包含固定化纳米尺寸银颗粒的二氧化硅纳米粉末以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物中。根据实施的微生物学的检测,发现所获得的包含0.024wt%(240ppm)的固定在二氧化硅纳米粉末上的银纳米颗粒的聚合物复合物对细菌金黄色葡萄球菌和大肠杆菌具有生物杀灭活性。
实施例V
在锥形烧瓶中使用磁力搅拌器混合107.0g(2.33mol)无水乙醇,0.5g(0.03mol)25%氨水和38.2g(2.12mol)蒸馏水。获得的混合物的pH值为11.38。随后,将23.5g(0.11mol)的四乙氧基硅烷加入反应混合物中。反应混合物在初期是澄清的,但是20分钟后观察到乳白色的溶液。烧瓶中的物质保持在环境温度下搅拌2.5小时。通过光子相关波谱法分析获得的溶胶,显示出溶胶的颗粒尺寸为49-53nm。然后,将400ml的0.1M硝酸银水溶液(0.04mol,6.8g)和400ml的0.1M氢氧化钠水溶液(0.04mol,1.6g)加入反应混合物中。由于银盐的减少,反应混合物的颜色为棕色。整个混合物搅拌1小时。由于氢氧化钠的减少,反应混合物的颜色为棕色。然后,样品在90℃下在烘箱中干燥1.5小时。样品中银的含量通过原子吸收分光光度法分析,并且发现其为4.0%。
所获得的包含固定化纳米尺寸银颗粒的二氧化硅纳米粉末以1.5wt%的量加入到基于聚酰胺6的聚合物复合物中。根据实施的微生物学的检测,发现所获得的包含0.06wt%(600ppm)的固定在二氧化硅纳米粉末上的银纳米颗粒的聚合物复合物对细菌金黄色葡萄球菌和大肠杆菌具有生物杀灭活性。
Claims (4)
1.一种通过溶胶-凝胶方法生产具有生物杀灭性能的二氧化硅纳米粉末的方法,该二氧化硅纳米粉末尤其用于聚合物复合物中,其特征在于,二氧化硅溶胶获得自含有四烷氧基硅烷、C1-C4醇或C1-C4脂肪醇混合物的水性混合物,在铵化合物的存在下,随着在彻底混合组分之后引入银盐和随后的碱金属氢氧化物水溶液而制备,其中四烷氧基硅烷中的烷氧基包含C1-C4个碳原子,四烷氧基硅烷与C1-C4醇或C1-C4脂肪醇混合物的摩尔比各自为1∶5-1∶35,铵化合物的用量为每1摩尔四烷氧基硅烷0.001-0.05摩尔,银盐为水溶液的形式且用量为每1摩尔四烷氧基硅烷0.02-1摩尔,碱金属氢氧化物的用量为每1摩尔四烷氧基硅烷0.02-1摩尔氢氧化物。
2.权利要求1的方法,其特征在于,将氢氧化四甲基铵或氢氧化四乙基铵用作铵化合物。
3.权利要求1的方法,其特征在于,将硝酸银用作银盐。
4.权利要求1的方法,其特征在于,将氢氧化钠用作碱金属氢氧化物。
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CN106689201A (zh) * | 2016-12-28 | 2017-05-24 | 营口盼盼环保硅藻材料有限公司 | 纳米银抗菌剂及其制备方法 |
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IT201700001597A1 (it) | 2017-01-10 | 2018-07-10 | Viganò Carlo Maria Stefano | preparazione semplice ed economica di compositi di poliolefine antibatterici con nano particelle di argento puro |
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