CN115466448B - 一种纳米银透明抗菌母粒的制备方法及其产品和应用 - Google Patents
一种纳米银透明抗菌母粒的制备方法及其产品和应用 Download PDFInfo
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- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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Abstract
本发明公开了一种纳米银透明抗菌母粒的制备方法及其产品和应用,将乙酸硅溶于溶剂中,依次添加分散剂、硝酸银溶液、阳离子表面活性剂和还原剂搅拌均匀,通过一锅法低温快速水热合成载银硅球,得到透明二氧化硅抗菌剂,再将透明二氧化硅抗菌剂、增韧剂、无水乙醇和聚合物母粒混合搅拌,真空烘干,再熔融混合后添加偶联剂改性,挤出造粒得到纳米银透明抗菌母粒。本发明制备的纳米银透明抗菌母粒的透光率>91.7%,对大肠杆菌的抗菌率>95.2%,对金黄色葡萄球菌的抗菌率>96.7%,对白色念珠菌的抗菌率>93.8%。采用一锅法和熔融挤出造粒法,工艺简单,成本低廉,设备要求较低,适用于大规模工业化生产。
Description
技术领域
本发明涉及一种纳米银透明抗菌母粒的制备方法及其产品和应用,属于抗菌技术领域。
背景技术
近年来,人们对于卫生健康状况越来越关注,导致抗菌产品的需求量急速增长,从而促进了抗菌剂和抗菌材料领域的发展。抗菌剂通常分为三大类:天然抗菌剂、有机抗菌剂和无机抗菌剂。其中无机抗菌剂,尤其是银系抗菌剂因其稳定性好、安全性高、抗菌范围广等优点得到了广泛的关注。
目前关于透明银系抗菌剂和抗菌母粒研究的主要报道如下:
CN 114052041公开了一种硅基载银透明抗菌剂的制备方法,该方法通过对硅类前驱体的三次改性,使得硅基在溶液环境下,可以高效地吸附银粒子,并且银粒子高度分散,但是所需材料与试剂种类较多,制备步骤较为复杂,难以大规模应用生产。
CN 103601959公开了一种塑料用纳米银抗菌母粒的制备方法,该方法将银盐溶解在易挥发溶剂中,然后将其连同分散还原剂、助分散剂、聚烯烃载体树脂一起放入高速混合机中搅拌均匀后蒸除90%溶剂,最后采用双螺杆挤出机将混合物料在150~240℃下熔融挤出造粒,得到所述抗菌母粒。所述抗菌母粒抗菌性能优异,透明性好,安全性能突出且生产成本低,但由该产品制成的塑料片透光率仅在90%左右,透明度不佳。
CN 111662480公开了一种适用于透明树脂基材的玻璃抗菌剂的制备方法,该方法将氧化银、氧化硼、二氧化硅等组分混匀后高温熔融,冷却后球磨得到玻璃抗菌剂粉末。所述玻璃抗菌剂的抗菌性、耐水性、透光度和雾度均较佳,但其制备过程中的熔融温度高达1200℃,对设备和工艺要求较高,且球磨后得到的抗菌剂粉末粒径较大,分散性较差。
然而银系无机抗菌剂还存在分散性较差、抗菌延迟高、易变色等问题,无法满足制备透明抗菌产品的要求。
发明内容
发明目的:本发明的第一目的是提供一种抗菌延迟低、分散性好且透明度高的纳米银透明抗菌母粒的制备方法;本发明的第二目的是提供该制备方法得到的纳米银透明抗菌母粒;本发明的第三目的是提供一种该纳米银透明抗菌母粒在制备塑料制品中的应用。
技术方案:本发明所述一种纳米银透明抗菌母粒的制备方法,包括以下步骤:
(1)将乙酸硅溶于溶剂中,依次添加分散剂、硝酸银溶液、阳离子表面活性剂和还原剂,搅拌均匀,通过一锅法低温快速水热合成载银硅球,煅烧除去模板,得到透明二氧化硅抗菌剂;
(2)将透明二氧化硅抗菌剂、增韧剂、无水乙醇和聚合物母粒加入高混机中混合搅拌,真空烘干,转移至双螺杆挤出机,添加偶联剂熔融混合,挤出造粒,得到纳米银透明抗菌母粒。
其中,步骤(1)中,按照重量份计:乙酸硅:溶剂:分散剂:硝酸银:阳离子表面活性剂:还原剂为(100~500):(1000~4000):(100~1000):(1~5):(100~500):(1~20)。
其中,步骤(1)中,所述溶剂为环己烷、乙醚、戊醇、乙醇中的一种或多种。
其中,步骤(1)中,所述分散剂为聚乙烯吡咯烷酮、聚乙二醇、聚丙烯酰胺、氧化聚乙烯蜡、乙烯基双硬脂酰胺中的一种或多种。
其中,步骤(1)中,所述阳离子表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十六烷基溴化吡啶、十二烷基二甲基苄基氯化铵、十二烷基三甲基氯化铵中的一种或多种。
其中,步骤(1)中,所述还原剂为硼氢化钠、硼氢化钾、一水合肼、亚磷酸、亚硫酸中的一种或多种。
其中,步骤(1)中,硝酸银和还原剂配置为0.01mol/L的水溶液。
其中,步骤(1)中,混合拌均匀的搅拌速度为500~1000rpm,搅拌时间为1~3h。
其中,步骤(1)中,一锅法低温快速水热合成的反应温度为100~150℃,反应时间为6~12h。
其中,步骤(1)中,煅烧的温度为400~600℃,煅烧的时间为6~10h。
其中,步骤(1)中,所述二氧化硅抗菌剂为蒲公英状单分散透明二氧化硅抗菌剂,所述透明二氧化硅抗菌剂的粒径为200~260nm。
其中,步骤(2)中,所述增韧剂为羧基液体丁腈橡胶、苯乙烯-丁二烯热塑性弹性体、丙烯腈-丁二烯-苯乙烯共聚物、聚乙烯醇、聚醚砜中的一种或多种。
其中,步骤(2)中,所述的聚合物母粒为聚乙烯、聚丙烯、聚氯乙烯、聚甲基丙烯酸酯、聚对苯二甲酸乙二醇酯、聚苯乙烯中的一种或多种。
其中,步骤(2)中,所述偶联剂为氨基硅烷、环氧基硅烷、脲基硅烷、异氰酸酯基硅烷、乙烯基硅烷中的一种或多种。
其中,步骤(2)中,按照重量份计:透明二氧化硅抗菌剂:增韧剂:无水乙醇:聚合物母粒:偶联剂为(1~5):(1~10):(20~60):(100~150):(10~20)。
其中,步骤(2)中,混合搅拌时高混机的转速为60~120rpm,混合时间为30~60min。
其中,步骤(2)中,熔融混合时控制双螺杆挤出机的温度为150~250℃,螺杆挤出机的转速为150-300rpm,熔融混合的时间为45~90min。
本发明所述制备方法得到的纳米银透明抗菌母粒。
本发明还包括所述纳米银透明抗菌母粒在制备塑料制品中的应用。
有益效果:与现有技术相比,本发明具有以下显著优势:
(1)本发明包含的二氧化硅抗菌剂结构呈蒲公英状,比表面积大,可以为单质银颗粒提供大量的活性位点,提高了银的负载量且有助于银的缓释,使抗菌母粒具有良好的抗菌能力和较高的抗菌效率。
(2)本发明在制备介孔二氧化硅抗菌剂时使用分散剂,且前驱体粒径为200~260nm,使抗菌剂颗粒能在抗菌母粒中稳定分散,保证了抗菌母粒的透明度和抗菌性能。
(3)本发明制备的纳米银透明抗菌母粒的透光率>91.7%,对大肠杆菌的抗菌率>95.2%,对金黄色葡萄球菌的抗菌率>96.7%,对白色念珠菌的抗菌率>93.8%。
(4)本发明采用一锅法和熔融挤出造粒法,工艺简单、成本低廉、设备要求较低,适用于大规模工业化生产。
附图说明
图1为实施例1~4中制得的纳米银透明抗菌母粒中的透射电镜图。
具体实施方式
下面结合附图对本发明的技术方案作进一步的说明。
实施例1
(1)将100重量份乙酸硅溶于1000重量份环己烷,依次添加100重量份聚乙烯吡咯烷酮、1重量份硝酸银、100重量份十六烷基三甲基溴化铵和1重量份硼氢化钠,将混合溶液以 500rpm搅拌1h,移至聚四氟乙烯反应釜中,在100℃下通过一锅法水热6h合成载银硅球,400℃煅烧6h除去模板,得到蒲公英状单分散透明二氧化硅抗菌剂。
(2)将1重量份透明二氧化硅抗菌剂、1重量份羧基液体丁腈橡胶、20重量份无水乙醇和100重量份聚乙烯母粒加入高混机中以60rpm的转速混合搅拌30min,真空烘干,转移至双螺杆挤出机,添加10重量份氨基硅烷,控制加工温度为150℃,以150rpm的螺杆转速熔融混合45min,挤出造粒,得到纳米银透明抗菌母粒。
实施例2
(1)将200重量份乙酸硅溶于2000重量份乙醚,依次添加300重量份聚乙二醇、2重量份硝酸银、200重量份十六烷基三甲基氯化铵和8重量份硼氢化钾,将混合溶液以700rpm搅拌1.5h,移至聚四氟乙烯反应釜中,在110℃下通过一锅法水热8h合成载银硅球,480℃煅烧7h除去模板,得到蒲公英状单分散透明二氧化硅抗菌剂。
(2)将2重量份透明二氧化硅抗菌剂、2重量份丙烯腈-丁二烯-苯乙烯共聚物、30重量份无水乙醇和120重量份聚氯乙烯母粒加入高混机中以80rpm的转速混合搅拌40min,真空烘干,转移至双螺杆挤出机,添加14重量份环氧基硅烷,控制加工温度为180℃,以200rpm的螺杆转速熔融混合60min,挤出造粒,得到纳米银透明抗菌母粒。
实施例3
(1)将300重量份乙酸硅溶于3000重量份戊醇,依次添加500重量份聚丙烯酰胺、3重量份硝酸银、300重量份十六烷基溴化吡啶和14重量份一水合肼,将混合溶液以800rpm搅拌2h,移至聚四氟乙烯反应釜中,在120℃下通过一锅法水热10h合成载银硅球,550℃煅烧8h除去模板,得到蒲公英状单分散透明二氧化硅抗菌剂。
(2)将3重量份透明二氧化硅抗菌剂、5重量份聚乙烯醇、40重量份无水乙醇和130重量份聚对苯二甲酸乙二醇酯母粒加入高混机中以100rpm的转速混合搅拌50min,真空烘干,转移至双螺杆挤出机,添加18重量份脲基硅烷,控制加工温度为220℃,以250rpm的螺杆转速熔融混合75min,挤出造粒,得到纳米银透明抗菌母粒。
实施例4
(1)将500重量份乙酸硅溶于4000重量份乙醇,依次添加1000重量份乙烯基双硬脂酰胺、5重量份硝酸银、500重量份十二烷基三甲基氯化铵和20重量份亚磷酸,将混合溶液以1000rpm搅拌3h,移至聚四氟乙烯反应釜中,在150℃下通过一锅法水热12h合成载银硅球,600℃煅烧10h除去模板,得到蒲公英状单分散透明二氧化硅抗菌剂。
(2)将5重量份透明二氧化硅抗菌剂、10重量份聚醚砜、60重量份无水乙醇和150重量份聚苯乙烯母粒加入高混机中以120rpm的转速混合搅拌60min,真空烘干,转移至双螺杆挤出机,添加20重量份乙烯基硅烷,控制加工温度为250℃,以300rpm的螺杆转速熔融混合90min,挤出造粒,得到纳米银透明抗菌母粒。
对实施例1~4制得的纳米银透明抗菌母粒进行紫外-可见光(UV-vis)测试和平板计数法抗菌测试,结果如表1所示。
表1实施例1~4制得的纳米银透明抗菌母粒的透光率及抗菌率
实施例 | 1 | 2 | 3 | 4 |
透光率% | 92.3 | 91.7 | 94.5 | 95.3 |
大肠杆菌抗菌率% | 95.2 | 96.3 | 96.6 | 97.1 |
金黄色葡萄球菌抗菌率% | 96.7 | 97.5 | 98.2 | 98.6 |
白色念珠菌抗菌率% | 93.8 | 94.3 | 95.0 | 95.4 |
由表1可见,实施例1-4制得的纳米银透明抗菌母粒的透光率均>91.7%,对大肠杆菌的抗菌率均>95.2%,对金黄色葡萄球菌的抗菌率均>96.7%,对白色念珠菌的抗菌率均>93.8%,显示出了良好的透明度和抗菌性能。
对实施例1~4中制得的纳米银透明抗菌母粒中的抗菌剂进行透射电子显微镜测试,结果如图1所示。图1为实施例1~4中制得的纳米银透明抗菌母粒中的透射电镜图,其中,a为实施例1,b为实施例2,c为实施例3,d为实施例4。由图1可以看出,抗菌剂分散性良好,粒径为200~260nm,呈纤维球状,比表面积较大,能为单质银提供更多活性位点和释放通道,保证了抗菌母粒的透明度和抗菌性。
Claims (7)
1.一种纳米银透明抗菌母粒的制备方法,其特征在于,包括以下步骤:
(1)将乙酸硅溶于溶剂中,依次添加分散剂、硝酸银溶液、阳离子表面活性剂和还原剂,搅拌均匀,通过一锅法低温快速水热合成载银硅球,煅烧除去模板,得到透明二氧化硅抗菌剂;所述透明二氧化硅抗菌剂为蒲公英状单分散透明二氧化硅抗菌剂,所述透明二氧化硅抗菌剂的粒径为200~260 nm;所述分散剂为聚乙烯吡咯烷酮、聚乙二醇、聚丙烯酰胺、氧化聚乙烯蜡、乙烯基双硬脂酰胺中的一种或多种;所述阳离子表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十六烷基溴化吡啶、十二烷基二甲基苄基氯化铵、十二烷基三甲基氯化铵中的一种或多种;按照重量份计:乙酸硅:溶剂:分散剂:硝酸银:阳离子表面活性剂:还原剂为100~500:1000~4000:100~1000:1~5:100~500:1~20,一锅法低温快速水热合成的反应温度为100~150℃,反应时间为6~12h,煅烧的温度为400~600℃,煅烧的时间为6~10h;
(2)将透明二氧化硅抗菌剂、增韧剂、无水乙醇和聚合物母粒加入高混机中混合搅拌,真空烘干,转移至双螺杆挤出机,添加偶联剂熔融混合,挤出造粒,得到纳米银透明抗菌母粒。
2.根据权利要求1所述纳米银透明抗菌母粒的制备方法,其特征在于,步骤(1)中,所述溶剂为环己烷、乙醚、戊醇、乙醇中的一种或多种,所述还原剂为硼氢化钠、硼氢化钾、一水合肼、亚磷酸、亚硫酸中的一种或多种。
3.根据权利要求1所述纳米银透明抗菌母粒的制备方法,其特征在于,步骤(1)中,硝酸银和还原剂配置为0.01mol/L的水溶液,混合拌均匀的搅拌速度为500~1000rpm,搅拌时间为1~3h。
4.根据权利要求1所述纳米银透明抗菌母粒的制备方法,其特征在于,步骤(2)中,所述增韧剂为羧基液体丁腈橡胶、苯乙烯-丁二烯热塑性弹性体、丙烯腈-丁二烯-苯乙烯共聚物、聚乙烯醇、聚醚砜中的一种或多种,所述的聚合物母粒为聚乙烯、聚丙烯、聚氯乙烯、聚甲基丙烯酸酯、聚对苯二甲酸乙二醇酯、聚苯乙烯中的一种或多种,所述偶联剂为氨基硅烷、环氧基硅烷、脲基硅烷、异氰酸酯基硅烷、乙烯基硅烷中的一种或多种。
5.根据权利要求1所述纳米银透明抗菌母粒的制备方法,其特征在于,步骤(2)中,按照重量份计:透明二氧化硅抗菌剂:增韧剂:无水乙醇:聚合物母粒:偶联剂为1~5:1~10:20~60:100~150:10~20,混合搅拌时高混机的转速为60~120rpm,混合时间为30~60min;熔融混合时控制双螺杆挤出机的温度为150~250℃,螺杆挤出机的转速为150~300rpm,熔融混合的时间为45~90min。
6.权利要求1-5任一项所述制备方法得到的纳米银透明抗菌母粒。
7.权利要求6所述纳米银透明抗菌母粒在制备塑料制品中的应用。
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