CN114451423B - 一种边缘有机修饰的磷酸锆载铜抗菌剂 - Google Patents
一种边缘有机修饰的磷酸锆载铜抗菌剂 Download PDFInfo
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Abstract
本发明提供了一种边缘有机修饰的磷酸锆载铜抗菌剂,其制备方法为α‑磷酸锆冰浴下层离后进行边缘有机修饰,得到边缘有机修饰的磷酸锆絮凝后,室温下再层离,最后用铜离子絮凝自组装形成了具有较大比表面积的边缘有机修饰后不易水解的磷酸锆载铜抗菌剂。
Description
技术领域
本发明涉及抗菌剂和新材料领域,涉及了一种无机抗菌剂,尤其是一种边缘有机修饰的磷酸锆载铜抗菌剂。
背景技术
无机抗菌剂因具有抗菌能力强、时间长、稳定性高、不易产生抗菌性突变等优点近年来发展迅速,一般常使用银、铜、锌离子作为金属离子抗菌组分。相对于银的成本高、锌的抗菌强度低,铜离子成本居中,可对各类细菌进行高效广谱的杀灭,尤其是针对卫生保健领域相关感染细菌,如耐甲氧西林金黄色葡萄球菌、甲氧西林敏感金黄色葡萄球菌和大肠埃希氏菌等。
α-磷酸锆是一类离子交换容量可达600mmol/100g的层状化合物,具有尺寸可控、表面可官能化以及容易插层和絮凝、化学稳定性高等优点而备受青睐。磷酸锆载银、载铜离子的抗菌剂也被加到纤维、树脂、陶瓷和玻璃制品中用作抗菌功能添加材料,也可以高温煅烧而生成氧化物抗菌剂,应用在抗菌内衣、手术服、敷料、鞋垫和化妆品等各类商品中。专利(申请号200410000824.5)报道了用氨水、银离子、磷酸锆粉末直接浸渍制备载银磷酸锆的方法,专利(申请号201510866550.6)报道了浸渍法制备添加了氧化铜-介孔磷酸锆的抗菌性聚丙烯纤维,专利(申请号202010384379.6)报道了一种立方体磷酸锆载铜载银抗菌剂的制备方法。这些方法用磷酸锆直接负载抗菌组分,因磷酸锆自身比表面积较小(≤10m2/g),边缘磷酸根碱性环境下易水解,而限制了其应用。
鉴于此,本发明利用α-磷酸锆层离-絮凝堆积性质和边缘磷酸根易水解性质,构建了具有较大比表面积的边缘有机修饰后不易水解的磷酸锆载铜抗菌剂。
发明内容
本发明的目的是克服现有技术中的不足,提供一种边缘有机修饰的磷酸锆载铜抗菌剂,包括如下步骤:
第一步、α-磷酸锆层离:将一定量的α-磷酸锆分散到一定体积的去离子水中,超声搅拌后,加入一定量的层离剂四丁基氢氧化铵进行层离,冰水浴下搅拌一定时间,最后高速离心,取上层胶状悬浊液,得到α-磷酸锆纳米胶体,胶体中纳米磷酸锆的浓度通过测定1ml胶体完全干燥后质量得到;
第二步、边缘有机修饰:向上述一定浓度的纳米磷酸锆胶体中加入一定量的有机萘膦酸,在一定温度下搅拌一定时间后,加入过量的0.1mol/L HCl絮凝,离心取下层固体,洗涤至中性,80℃温度真空干燥,得到边缘有机修饰的磷酸锆粉体;
第三步、边缘有机修饰的磷酸锆粉体再层离:将一定量的边缘有机修饰的磷酸锆粉体分散到一定体积的去离子水中,超声搅拌后,加入一定量的四丁基氢氧化铵,室温下搅拌一定时间,然后高速离心,取上层胶状悬浊液,得到边缘有机修饰的磷酸锆胶体;
第四步、载铜抗菌剂制备:将一定量的铜盐分散到去离子水中,然后逐滴滴加到一定量的边缘有机修饰的磷酸锆胶体中,搅拌一定时间,高速离心,取下层固体,80℃真空干燥即得到蓝色边缘有机修饰的磷酸锆载铜抗菌剂。
作为优选,第一步所述层状α-磷酸锆片状单元长宽平均尺寸≥1μm,α-磷酸锆与去离子水分散固液比为1g:100ml,α-磷酸锆与四丁基氢氧化铵物质的量之比1:2,冰水浴搅拌时间2天,离心转速11000rpm,胶体中磷酸锆纳米片浓度2mg/ml。
作为优选,第二步所述胶体中磷酸锆与萘膦酸物质的量之比为1:1,搅拌温度40℃,搅拌时间6小时,HCl絮凝后离心转速11000rpm。
作为优选,第三步所述边缘有机修饰的磷酸锆粉体与去离子水的分散比为1g:100ml,与四丁基氢氧化铵物质的量之比为1:0.75,搅拌时间2天,离心转速11000rpm,胶体中边缘有机修饰的磷酸锆纳米片浓度1.7mg/ml。
作为优选,第四步所述铜盐为硝酸铜,有机修饰的磷酸锆纳米片中锆与铜物质的量之比1:3,搅拌时间3天,离心转速11000rpm。
本发明的有益效果是:第一次层离采用过量的层离剂,用冰浴阻止磷酸根水解,得到规整片状磷酸锆,再用一定温度促使磷酸锆边缘的磷酸根水解和有机膦酸根修饰,得到边缘有机修饰的磷酸锆不会继续水解,拓展了抗菌剂应用范围;第二次层离采用适量的层离剂减缓铜离子水解,层离后与铜离子絮凝,磷酸锆纳米片重新堆积形成比表面积显著增大的磷酸锆载铜抗菌剂。
附图说明
图1为α-磷酸锆的电子扫描图片;
图2为磷酸锆层离形成胶状纳米片的电子扫描图片;
图3为边缘有机修饰的磷酸锆的电子扫描图片;
图4为实施例1,边缘有机修饰的磷酸锆载铜抗菌剂的电子扫描图片。
具体实施方式
下面结合实施例对本发明做进一步描述。下述实施例的说明只是用于帮助理解本发明。应当指出,对于本技术领域的普通人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
本发明所述一种边缘有机修饰的磷酸锆载铜抗菌剂,其制备方法为α-磷酸锆冰浴下层离后进行边缘有机修饰,得到边缘有机修饰的磷酸锆室温下再层离,最后用铜离子絮凝自组装形成边缘不易水解的磷酸锆载铜抗菌剂。
在边缘有机修饰的磷酸锆载铜抗菌剂制备过程中,离心转速不同,得到的磷酸锆纳米片、边缘有机修饰的磷酸锆纳米片浓度不同:转速低,纳米片浓度高,转速高,纳米片浓度低。因此,层离后的纳米磷酸锆胶体的浓度测定是关键,对后续有机修饰、修饰后二次层离所需物质的量的确定至关重要。
实施例1
将10.000gα-磷酸锆(33mmol,比表面积3.5m2/g,)分散到1000ml的去离子水中,超声搅拌后,加入25%wt的四丁基氢氧化铵68.5g(66mmol),冰水浴搅拌2天后,11000rpm转速下离心分离,取上层胶状液。用移液枪移取1ml胶状液,120℃干燥24h称重,测得层离液中磷酸锆纳米片浓度为2mg/ml;
量取上述500ml磷酸锆纳米胶体(磷酸锆3.3mmol),加入0.872g萘膦酸(3.3mmol),40℃下搅拌时间6小时,然后滴加过量的0.1mol/L HCl至pH=2-3,11000rpm转速下离心分离,取下层固体,洗涤至中性,80℃温度真空干燥,得到边缘有机修饰的磷酸锆粉体,元素分析检测出C和H元素,没有检测到N元素;
将1.0g边缘有机修饰的磷酸锆粉体(3.3mmol),加入到100ml去离子水中,超声搅拌后,加入25%wt的四丁基氢氧化铵2.6g(2.475mmol),室温下搅拌时间2天,11000rpm转速下离心分离,取上层胶状悬浊液,得到边缘有机修饰的磷酸锆胶体,纳米片浓度为1.7mg/ml。
取90ml上述边缘有机修饰的磷酸锆胶体(0.153g,0.51mmol),逐滴滴加硝酸铜溶液(含铜1.53mmol),室温搅拌3天,11000rpm转速下离心分离,取下层固体,充分洗涤,80℃真空干燥即得到蓝色边缘有机修饰的磷酸锆载铜抗菌剂,比表面积64.1m2/g,原子比Zr:P:Cu=3.26:6.953:1.12。
实施例2
增加层离剂的量和层离时间,降低离心转速,可以增加磷酸锆纳米片浓度。
将10gα-磷酸锆(33mmol,比表面积3.5m2/g,)分散到1000ml的去离子水中,超声搅拌后,加入25%wt的四丁基氢氧化铵85.6g(82.5mmol),冰水浴搅拌3天后,9000rpm转速下离心分离,取上层胶状液。用移液枪移取1ml胶状液,120℃干燥24h称重,测得层离液中磷酸锆纳米片浓度为4mg/ml;
量取上述500ml磷酸锆纳米胶体(磷酸锆6.6mmol),加入3.488萘膦酸(13.2mmol),40℃下搅拌时间6小时,然后滴加过量的0.1mol/L HCl至pH=2-3,11000rpm转速下离心分离,取下层固体,洗涤至中性,80℃温度真空干燥,得到边缘有机修饰的磷酸锆粉体;
将1.0g边缘有机修饰的磷酸锆粉体(3.3mmol),加入到100ml去离子水中,超声搅拌后,加入25%wt的四丁基氢氧化铵2.6g(2.475mmol),室温下搅拌时间3天,9000rpm转速下离心分离,取上层胶状悬浊液,得到边缘有机修饰的磷酸锆胶体,纳米片浓度为1.9mg/ml。
取90ml上述边缘有机修饰的磷酸锆胶体(0.171g,0.57mmol),逐滴滴加硝酸铜溶液(含铜1.14mmol),室温搅拌3天,11000rpm转速下离心分离,取下层固体,充分洗涤,80℃真空干燥即得到蓝色边缘有机修饰的磷酸锆载铜抗菌剂。
Claims (7)
1.一种边缘有机修饰的磷酸锆载铜抗菌剂,其特征在于,包括以下步骤:
第一步、α-磷酸锆层离:将α-磷酸锆分散到去离子水中,固液比为1g:100ml,超声搅拌后,加入层离剂四丁基氢氧化铵进行层离,α-磷酸锆与四丁基氢氧化铵物质的量之比范围1:1~1:2.5,冰水浴下搅拌1-3天,最后高速离心,取上层胶状悬浊液,得到α-磷酸锆纳米胶体,胶体中纳米磷酸锆的浓度通过测定1ml胶体完全干燥后质量得到;
第二步、边缘有机修饰:向上述纳米磷酸锆胶体中加入有机萘膦酸,磷酸锆与萘膦酸物质的量之比范围1:1~1:2,在40-60℃下搅拌1-6小时后,加入过量的0.1mol/L HCl絮凝,离心取下层固体,洗涤至中性,80℃温度真空干燥,得到边缘有机修饰的磷酸锆粉体;
第三步、边缘有机修饰的磷酸锆粉体再层离:将边缘有机修饰的磷酸锆粉体分散到去离子水中,固液比为1g:100ml,超声搅拌后,加入四丁基氢氧化铵,磷酸锆粉体与四丁基氢氧化铵物质的量之比范围1:0.5~1:0.75;室温下搅拌1-3天,然后高速离心,取上层胶状悬浊液,得到边缘有机修饰的磷酸锆胶体;
第四步、载铜抗菌剂制备:将铜盐分散到去离子水中,然后逐滴滴加到边缘有机修饰的磷酸锆胶体中,有机修饰的磷酸锆纳米片中锆与铜物质的量之比1:1~1:3,搅拌1-3天,待铜离子和磷酸锆纳米片自组装完成,高速离心,取下层固体,80℃真空干燥即得到蓝色边缘有机修饰的磷酸锆载铜抗菌剂。
2.根据权利要求1所述的边缘有机修饰的磷酸锆载铜抗菌剂,其特征在于,第一步所述层状α-磷酸锆片状单元长宽平均尺寸≥1μm,离心转速9000-12000rpm,胶体中磷酸锆纳米片浓度1~4mg/ml。
3.根据权利要求1所述的边缘有机修饰的磷酸锆载铜抗菌剂,其特征在于,第二步所述HCl絮凝后离心转速9000-12000rpm。
4.根据权利要求1所述的边缘有机修饰的磷酸锆载铜抗菌剂,其特征在于,第三步所述离心转速9000-12000rpm,胶体中边缘有机修饰的磷酸锆纳米片浓度1~2mg/ml。
5.根据权利要求1所述的边缘有机修饰的磷酸锆载铜抗菌剂,其特征在于,第四步所述铜盐为硝酸铜、醋酸铜、氯化铜、硫酸铜的一种或几种,离心转速9000-12000rpm。
6.根据权利要求1所述的边缘有机修饰的磷酸锆载铜抗菌剂,其特征在于,磷酸锆经过两次层离,第一次层离采用过量的层离剂,用冰浴阻止磷酸根水解,得到规整片状磷酸锆,再用40-60℃水浴促使磷酸锆边缘的磷酸根水解和有机膦酸根修饰,得到边缘有机修饰的磷酸锆不会继续水解,第二次层离采用适量层离剂减缓铜离子水解,层离后与铜离子絮凝,重新堆积成磷酸锆载铜抗菌剂。
7.根据权利要求1所述的边缘有机修饰的磷酸锆载铜抗菌剂,其特征在于,两次层离后,溶液中纳米磷酸锆胶体的浓度需要测定,根据测定的纳米片浓度确定后续边缘有机膦酸修饰、自组装载铜过程中的物质的量。
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US4059679A (en) * | 1971-04-08 | 1977-11-22 | Ohio University | Modified zirconium phosphates |
JPH04149011A (ja) * | 1990-10-08 | 1992-05-22 | Rasa Kogyo Kk | 銀イオン修飾型リン酸塩層間化合物の製造方法 |
WO2009137592A2 (en) * | 2008-05-08 | 2009-11-12 | 3M Innovative Properties Company | Surface-modified nanoparticles |
WO2010059812A1 (en) * | 2008-11-24 | 2010-05-27 | 3M Innovative Properties Company | Surface-modified metal phosphate nanoparticles |
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US4059679A (en) * | 1971-04-08 | 1977-11-22 | Ohio University | Modified zirconium phosphates |
JPH04149011A (ja) * | 1990-10-08 | 1992-05-22 | Rasa Kogyo Kk | 銀イオン修飾型リン酸塩層間化合物の製造方法 |
WO2009137592A2 (en) * | 2008-05-08 | 2009-11-12 | 3M Innovative Properties Company | Surface-modified nanoparticles |
WO2010059812A1 (en) * | 2008-11-24 | 2010-05-27 | 3M Innovative Properties Company | Surface-modified metal phosphate nanoparticles |
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