CN114133859A - 一种纳米银改性高分子涂材及其制备方法 - Google Patents
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Abstract
一种纳米银改性高分子涂材及其制备方法,以改性负载银的碳纳米管作为改性剂,水性高分子涂料作为基体物质;通过将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在‑40℃氮气保护下,球磨后再升温球磨,于制得的含改性负载银的碳纳米管的混合物中混入有机溶剂,搅拌后再混入水性高分子涂料后,制得纳米银改性高分子涂材。其具有优异的初始抗菌效果、耐磨性及抗菌的耐久性,且兼具优良的扛静电性能,纳米银固结度高,损失少,对革兰氏阳性菌、大肠杆菌的初次灭菌率超过99.99%,并且能够经受20kPa力情况下的300次反复擦拭,具有很强的实用性和广泛的适用性。
Description
技术领域
本发明涉及一种纳米银改性高分子涂材,具体涉及一种纳米银改性高分子涂材及其制备方法。
背景技术
现代研究发现,银的化学结构决定了银具有较高的催化能力,可以使其周围空间产生原子氧。原子氧具有强氧化性可以灭菌,银离子可以吸引细菌体中蛋白酶上的琉基(-SH),迅速与其结合在—起,使蛋白酶丧失活性,导致细菌死亡。
当细菌被银离子杀灭后,银离子又由细菌尸体中游离出来,再与其它菌落接触,周而复始地进行上述过程,持久杀菌。
在生活中,到处都会有各种各样的微生物繁殖,如病菌、细菌、霉菌、真菌等,平时我们肉眼看不到它们,但是它们对我们的健康造成影响,这些微生物,可以引发感染、环境过敏和其他诱发性呼吸系统和皮肤疾病等。
而涂料在使用过程中长会出现被刮擦、局部霉变等现象,因此,有必要在涂料涂材领域深入的研究,将银和高分子涂材相结合,运用银离子的先进技术,发挥长效抑菌、杀菌效果,从源头解决问题。
发明内容
为解决现有技术的不足,本发明的目的在于提供一种纳米银改性高分子涂材及其制备方法。
为了实现上述目标,本发明采用如下的技术方案:
一种纳米银改性高分子涂材的制备方法,以改性负载银的碳纳米管作为改性剂,水性高分子涂料作为基体物质;
所述改性负载银的碳纳米管的制备:将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨1-20h后,升温至20-40℃球磨1-5h,制得含改性负载银的碳纳米管的混合物;
按质量比,于混合物中混入有机溶剂,搅拌后再混入水性高分子涂料,搅拌均匀后,制得纳米银改性高分子涂材。
上述水性高分子涂料包括水性丙烯酸聚氨酯涂料、水性丙烯酸涂料、水性聚氨酯涂料、水性醇酸涂料或水性聚酯涂料中任一种。
上述步骤S1中活化后的碳纳米管和硅烷偶联剂的质量比为1:(1-1.5);碳纳米管和纳米银的质量比为1:(0.1-0.5)。
上述硅烷偶联剂为γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷和N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷中的一种或几种。
上述球磨机的磨球直径为0.5-20mm,原料与磨球的质量比为1:(10-1000)。
上述步骤有机溶剂为四氢呋喃、脂肪和芳香烃、氯代烃、甲醇、乙醇或丙酮。
上述混合物与有机溶剂的质量比为:1:(2-5),混合物和水性高分子涂料的质量比为1:(50-100)。
上述活化的碳纳米管的制备步骤为:将碳纳米管浸泡在1-2mol/L的强氧化性酸中,在室温下超声分散1-1.5h后,浸泡12-48h,冷却至室温后过滤,水洗至中性后烘干。
上述强氧化性酸为浓硝酸、浓硫酸或其混合物。
一种纳米银改性高分子涂材,由上述的制备方法制得。
本发明的有益之处在于:
一种纳米银改性高分子涂材及其制备方法,通过在低温下球磨混合改性碳纳米管、纳米银和硅烷偶联剂,保持硅烷偶联剂的固化态,降低其粒度,使得硅烷偶联剂以纳米粒的方式与改性碳纳米管,进而使得纳米银与碳纳米管结合,进一步通过相互摩擦的方式,降低颗粒相互间的互异性,增强碳纳米管的表面改性效果和增强纳米银与碳纳米管结合度与结合量。以碳纳米管作为骨架,混入水性高分子涂料中,提高涂料的耐磨性,降低因磨损而损失的纳米银,提高持久的抗菌抑菌效果。
本发明的纳米银改性高分子涂材,具有优异的初始抗菌效果、耐磨性及抗菌的耐久性,且兼具优良的扛静电性能,纳米银固结度高,损失少,对革兰氏阳性菌、大肠杆菌的初次灭菌率超过99.99%,并且能够经受20kPa力情况下的300次反复擦拭,具有很强的实用性和广泛的适用性。
具体实施方式
以下结合具体实施例对本发明作具体的介绍。
一种纳米银改性高分子涂材,以改性负载银的碳纳米管作为改性剂,水性高分子涂料作为基体物质;制备方法包括以下步骤:
S1、制备改性负载银的碳纳米管:
A1、活化碳纳米管:将碳纳米管浸泡在1-2mol/L的强氧化性酸中,在室温下超声分散1-1.5h后,浸泡12-48h,冷却至室温后过滤,水洗至中性后烘干。
强氧化性酸选用浓硝酸、浓硫酸或其混合物。
A2、按1:(0.1-0.5):(1-1.5)的质量比,将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨1-20h;球磨机的磨球直径为0.5-20mm,原料与磨球的质量比为1:(10-1000)。
硅烷偶联剂选用γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷和N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷中的一种或几种。
A3、再升温至20-40℃球磨1-5h,制得含改性负载银的碳纳米管的混合物。
S2、按1:(2-5)的质量比,于混合物中混入有机溶剂,搅拌;有机溶剂选用四氢呋喃、脂肪和芳香烃、氯代烃、甲醇、乙醇或丙酮。
S3、再混入水性高分子涂料,水性高分子涂料和混合物的质量比为(50-100):1,搅拌均匀后,制得纳米银改性高分子涂材;
水性高分子涂料包括水性丙烯酸聚氨酯涂料、水性丙烯酸涂料、水性聚氨酯涂料、水性醇酸涂料或水性聚酯涂料中任一种。
实施例1
S1、制备改性负载银的碳纳米管:
按1:0.1:1的质量比,将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨20h。
硅烷偶联剂选用γ-(甲基丙烯酰氧)丙基三甲氧基硅烷。
A3、再升温至20℃球磨5h,制得含改性负载银的碳纳米管的混合物。
S2、按1:2的质量比,于混合物中混入乙醇。
S3、再混入水性丙烯酸聚氨酯涂料,水性丙烯酸聚氨酯涂料和混合物的质量比为50:1,搅拌均匀后,制得纳米银改性高分子涂材。
实施例2
S1、制备改性负载银的碳纳米管:
按1:0.5:1.5的质量比,将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨20h。
硅烷偶联剂选用N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷。
A3、再升温至30℃球磨5h,制得含改性负载银的碳纳米管的混合物。
S2、按1:5的质量比,于混合物中混入乙醇,搅拌。
S3、再混入水性丙烯酸涂料,水性丙烯酸涂料和混合物的质量比为100:1,搅拌均匀后,制得纳米银改性高分子涂材。
实施例3
S1、制备改性负载银的碳纳米管:
按1:0.3:1.2的质量比,将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨20h。
硅烷偶联剂选用N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷。
A3、再升温至40℃球磨5h,制得含改性负载银的碳纳米管的混合物。
S2、按1:3的质量比,于混合物中混入四氢呋喃。
S3、再混入水性聚氨酯涂料,水水性聚氨酯涂料和混合物的质量比为80:1,搅拌均匀后,制得纳米银改性高分子涂材。
实施例4
S1、制备改性负载银的碳纳米管:
按1:0.2:1.4的质量比,将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨20h。
硅烷偶联剂选用γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷。
A3、再升温至20℃球磨5h,制得含改性负载银的碳纳米管的混合物。
S2、按1:4的质量比,于混合物中混入甲醇。
S3、再混入水性聚酯涂料,水性聚酯涂料和混合物的质量比为70:1,搅拌均匀后,制得纳米银改性高分子涂材。
实施例5
S1、制备改性负载银的碳纳米管:
按1:0.4:1.1的质量比,将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨20h。
硅烷偶联剂选用N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷和N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷。
A3、再升温至40℃球磨5h,制得含改性负载银的碳纳米管的混合物。
S2、按1:3的质量比,于混合物中混入丙酮。
S3、再混入水性醇酸涂料,水性醇酸涂料和混合物的质量比为60:1,搅拌均匀后,制得纳米银改性高分子涂材。
性能测试:
将实施例1-5制得的涂材分别涂刷于面积为10cm*10cm的木质板上,板厚2cm,涂层膜厚为45~55μm,膜厚测量采用膜厚仪。
抗菌性能测试:采用了ASTM E2180-07测试标准,测试菌株采用大肠杆菌ATCC25922。每次测试抗菌性均用分光光度计测定600nm下的吸光度,保证初始细菌浓度一致。
耐久性测定:进行了连续水洗过程,每次水洗如下:使用20mL水润湿表面,然后加入0.5g洗洁剂,使用擦拭海绵以10~20kPa的压强反复擦拭表面60次,最后用50mL水将表面清洗干净。
初始抗菌效果,以抑制大肠杆菌数量/106CFU达0.001的时间表示,如下表1所示,
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
4.5h | 3.5h | 3h | 4h | 3h |
表1
经过连续水洗后抗菌效果,以抑制大大肠杆菌数量/106CFU达0.001的时间表示,如下表2所示:
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
水洗1次 | 4.5h | 3.5h | 3h | 4h | 3h |
水洗2次 | 4.5h | 3.5h | 3h | 4h | 3h |
水洗3次 | 4.5h | 3.5h | 3h | 4h | 3h |
水洗4次 | 4.5h | 3.5h | 3h | 4h | 3h |
水洗5次 | 4.5h | 3.7h | 3.1h | 4.2h | 3.1h |
表2
由上表可得:本发明的纳米银改性高分子涂材,
(1)、具有优异的初始抗菌效果,5.5h内表面无细菌;
(2)、具有优异的抗菌耐久性,水洗到第5次抗菌效果才出现减弱;
(3)、具有优异的扛耐磨性,经摩擦后纳米银损失较少,纳米银的固结度较高;
(4)、随着纳米银添加量的增加,抗菌效果也增加。
结果表明,该涂材具有优异的抗菌性能和耐久性,对革兰氏阳性菌、大肠杆菌的初次灭菌率超过99.99%,并且能够经受20kPa力情况下的300次反复擦拭。
以上显示和描述了本发明的基本原理、主要特征和优点。本行业的技术人员应该了解,上述实施例不以任何形式限制本发明,凡采用等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。
Claims (10)
1.一种纳米银改性高分子涂材的制备方法,其特征在于,以改性负载银的碳纳米管作为改性剂,水性高分子涂料作为基体物质;
所述改性负载银的碳纳米管的制备:将活化后的碳纳米管、纳米银和硅烷偶联剂投入,投入球磨机中,抽真空,在-40℃氮气保护下,球磨1-20h后,升温至20-40℃球磨1-5h,制得含改性负载银的碳纳米管的混合物;
按质量比,于混合物中混入有机溶剂,搅拌后再混入水性高分子涂料,搅拌均匀后,制得纳米银改性高分子涂材。
2.根据权利要求1所述的制备方法,其特征在于,所述水性高分子涂料包括水性丙烯酸聚氨酯涂料、水性丙烯酸涂料、水性聚氨酯涂料、水性醇酸涂料或水性聚酯涂料中任一种。
3.根据权利要求1所述的制备方法,其特征在于,所述步骤S1中活化后的碳纳米管和硅烷偶联剂的质量比为1:(1-1.5);碳纳米管和纳米银的质量比为1:(0.1-0.5)。
4.根据权利要求1所述的制备方法,其特征在于,所述硅烷偶联剂为γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷和N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷中的一种或几种。
5.根据权利要求1所述的制备方法,其特征在于,所述球磨机的磨球直径为0.5-20mm,原料与磨球的质量比为1:(10-1000)。
6.根据权利要求1所述的制备方法,其特征在于,所述步骤有机溶剂为四氢呋喃、脂肪和芳香烃、氯代烃、甲醇、乙醇或丙酮。
7.根据权利要求1所述的制备方法,其特征在于,所述混合物与有机溶剂的质量比为:1:(2-5),混合物和水性高分子涂料的质量比为1:(50-100)。
8.根据权利要求1所述的制备方法,其特征在于,所述活化的碳纳米管的制备步骤为:
将碳纳米管浸泡在1-2mol/L的强氧化性酸中,在室温下超声分散1-1.5h后,浸泡12-48h,冷却至室温后过滤,水洗至中性后烘干。
9.根据权利要求1所述的制备方法,其特征在于,所述强氧化性酸为浓硝酸、浓硫酸或其混合物。
10.一种纳米银改性高分子涂材,其特征在于,由权利要求1-9任一项所述的制备方法制得。
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