CN108929543A - 硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料及其制备方法 - Google Patents
硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料及其制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明提供一种硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料,以重量份计,由如下组分制备而成:硅橡胶100份、载纳米银改性蒙脱土抗菌剂0.1‑1份、分散介质150‑200份、交联剂7‑8份和促进剂0.1‑0.2份。本发明还提供了该符合材料的制备方法。本发明首先对纳米蒙脱土进行有机化插层处理,不仅可以提高蒙脱土与聚合物的相容性,而且使蒙脱土片层部分剥离,使银离子更加容易进入蒙脱土的片层间距中,缩短了银离子与蒙脱土的离子交换时间,并提高蒙脱土的载银量,从而提高抗菌剂的抗菌效果。
Description
技术领域
本发明属于复合材料领域,具体涉及一种硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料及其制备方法。
背景技术
院内感染是目前临床上急需解决的突出问题。目前,临床上使用的大多数医疗器械、导管等人工生物材料如聚氨酯、硅橡胶、天然胶乳等本身不具备抗菌性,微生物极易附着在其表面生长,成为院内感染的主要根源。研究表明,无论是长期留置或短期接触人体的生物材料,都容易引起各种各样的细菌感染。美国疾控预防中心(CDC)数据显示,由内置型医疗设备引发的感染在美国住院病人死亡原因中排名第五,而约45%的院内感染与生物材料的使用相关。
聚合物/蒙脱土纳米复合材料领域的研究已成为当今科研的热点之一,由于蒙脱土所具有的层状硅酸盐结构,以及纳米分散形态下的纳米尺寸效应,使蒙脱土在聚合物基体中表现出较强的界面作用力,可以将蒙脱土的尺寸稳定性、无机刚性、热稳定性等与聚合物本身性能相结合,从而制备出具有一定特性的纳米复合材料。蒙脱土((Al2·xMgx)Si4O10(OH)2·(M·nH2O))是一种层状硅酸盐,整个片层结构片层厚约1nm,长宽约100nm,层间富含Na+、Ca+和Mg+ 等阳离子,具有强吸附及离子交换能力,是一种优异的抗菌剂载体,但是无机粉末与聚合物的相容性差,且纳米粉末由于表面能大,自身容易团聚,加入到聚合物中反而会影响制品的物理性能。
纳米银是以纳米技术为基础研制的新型生物材料。随着科学医疗技术的不断发展,纳米银被广泛应用在医疗产品中用于抗菌治疗,如纳米抗菌辅料、纳米银眼药、纳米银织物、纳米银导尿管、纳米银骨水泥、含纳米银的心脏瓣膜、纳米银隐形避孕套等。纳米银材料是优良的抗菌剂,由于其表面积大,粒径小,容易跟病原微生物发生密切接触,极少量的纳米银就可以产生很强力的杀菌作用。而且纳米银具有比同类常规无机抗菌材料更强的抗菌活性。这是因为纳米银微溶于水后能释放出浓度为70ppm的Ag+和Ago,而其他形式的银(如硝酸银和磺胺嘧啶银)只能释放出Ag+,Ago的灭菌活性比 Ag+更持久。因此纳米银是一种很好的抑菌材料。然而在实际应用中纳米银比较容易流失从而失去抑菌性能,因此常常需要利用载体将纳米银固定以起到长效抑菌的作用。化学还原法是最常见的制备稳定态纳米银的方法。常见的还原剂包括硼氢化钠、柠檬酸、抗坏血酸和氢等,然而在制备过程中添加的还原剂及稳定剂限制了纳米银颗粒在医学等领域的应用,并且还会带来环境污染。近年来,在纳米银的合成过程中,多采用可再生的材料作为纳米银的还原剂或者保护剂,并且兼具软模板的功能。例如,利用还原性的葡萄糖作为稳定剂和软模板合成了纳米银粒子。
发明内容
本发明的目的是提供一种硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料及其制备方法,提高蒙脱土与聚合物的相容性和抗菌效果。
本发明的技术方案:
硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料,以重量份计,由如下反应物制备而成:硅橡胶100份、载纳米银改性蒙脱土抗菌剂0.1-1份、分散介质150-200份、交联剂7-8份和促进剂0.1-0.2 份。
进一步的,所述载纳米银改性蒙脱土抗菌剂由如下方法制备而成:将银盐水溶液与改性蒙脱土混合均匀,加入还原剂抗坏血酸和稳定剂聚乙烯吡咯烷酮,进行还原反应,得到载纳米银改性蒙脱土抗菌剂。
具体的,配制银盐水溶液0.8M,10ml,加入改性蒙脱土2g,分散均匀;加还原剂抗坏血酸1-2g和稳定剂聚乙烯吡咯烷酮1-2g, 35℃下搅拌3小时,抽滤分离,洗涤,干燥,即得载纳米银改性蒙脱土抗菌剂。
所述改性蒙脱土的制备方法如下:将纳米蒙脱土与去离子水配制成质量分数为1.5%悬浮液,加入纳米蒙脱土重量的80%的卵磷脂,升温至70℃,充分搅拌2小时后,抽滤分离,洗涤,干燥,得到有机化插层处理的纳米蒙脱土。改性蒙脱土的制备方法采用现有文献中的技术,该文献是“Na Meng,Xiaohong Chu,Man Qing Ge, Ming Zhang,Baohong Sun,Yu-Tian Su,Ning-Lin Zhou.Preparation and characterization of Lecithin–heparinintercalated in montmorillonite nanocomposite.Applied Clay Science 162(2018)454–460.”
进一步的,所述的硅橡胶是RTV107硅橡胶。
硅橡胶(PDMS)具有独特的结构:无极性的有机甲基形成一朵“云”,盘绕着具有高度灵活性的无机硅氧烷链。这种材料在室温下为疏水液体,玻璃态转化温度(Tg)极低,对气体(包括水蒸气) 的渗透性很高。同时具有很好的光滑性、弹性、生物相容性及血液相容性,因而是被研究最广的抗凝血和抗菌医用高分子材料之一。特别用于医用导管,其平滑表面可减少与尿道的摩擦,使插入更方便、舒适,有助于避免对尿道或膀胱造成损伤。硅胶涂层还可以减少细菌感染和坏死的风险,以及因盐在端头或导管腔内沉积引起的结壳。盐结壳在抽出时会引起疼痛,或堵塞导孔。
进一步的,所述的交联剂是正硅酸乙酯。
进一步的,所述的促进剂是二月桂酸二丁基锡。
正硅酸乙酯用作硅橡胶的交联剂。二月桂酸二丁基锡用作硅橡胶催化剂。
进一步的,所述的分散介质是水、乙醇或环己烷。
本发明还提供硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的制备方法,包括顺次相接的如下步骤:将载纳米银改性蒙脱土抗菌剂分散于分散介质中,加入硅橡胶混合搅拌均匀后,加入交联剂、促进剂,涂敷于模具上,放置7天制备得到硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料。
本发明的优点在于:
本发明首先对纳米蒙脱土进行有机化插层处理,不仅可以提高蒙脱土与聚合物的相容性,而且使蒙脱土片层部分剥离,使银离子更加容易进入蒙脱土的片层间距中,缩短了银离子与蒙脱土的离子交换时间,并提高蒙脱土的载银量,从而提高抗菌剂的抗菌效果。
本发明提出将抗坏血酸作为合成纳米银的还原剂,对纳米银的大小,形貌进行修饰,制备载银/蒙脱土和硅橡胶复合的抗菌复合材料,希望通过缓控释作用将纳米银逐步释放出来,局部维持一定的作用浓度的同时减轻纳米银的团聚和迁移带来的危害。本发明通过研究改性蒙脱土在硅橡胶中的应用,为提高硅橡胶力学性能和抗菌性能提供一个新的方法。
附图说明
图1不同含量(A 0%B 0.1%C 0.5%D 1%)载纳米银改性蒙脱土抗菌剂的硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的XRD图
图2不同含量载纳米银改性蒙脱土抗菌剂的硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的热重图。
图3是菌落数对比实验;
图4是菌落圈对比实验;
具体实施方式
下面结合实施例和附图对本发明提供的具体实施方式作详细说明。以下列举部分实施例用于对本发明的进一步说明,但不限制本发明。
以下实施例所用到的原料来源如下:
蒙脱土(阿拉丁);硝酸银(上海化学试剂有限公司);抗坏血酸(阿拉丁);聚丙烯吡咯烷酮(阿拉丁);硅橡胶(硫化型 RTV-107);硅酸乙酯(阿拉丁);二月桂酸二丁基锡(阿拉丁)。
实施例1
(1)改性蒙脱土的制备:
将纳米蒙脱土与去离子水配制成质量分数为1.5%悬浮液,加入纳米蒙脱土重量的80%的卵磷脂,升温至70℃,充分搅拌2小时后,真空泵抽滤分离,去离子水洗涤多次,60℃烘箱干燥24h,得到有机化插层处理的纳米蒙脱土。
(2)载纳米银改性蒙脱土抗菌剂的制备
配制0.8M,10ml银盐水溶液,加入2g改性蒙脱土,分散均匀;加还原剂抗坏血酸1.36g和稳定剂聚乙烯吡咯烷酮1.36g,35℃下搅拌3小时,真空泵抽滤分离,去离子水洗涤多次,60℃烘箱干燥24 h。即得载纳米银改性蒙脱土抗菌剂。
(3)硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的制备
100份硅橡胶分散到环己烷中,载纳米银改性蒙脱土抗菌剂0.1 份分散到硅橡胶溶液中,混合搅拌5分钟,搅拌均匀后,加入交联剂硅酸乙酯7.2份,搅拌20分钟,在加入促进剂二月桂酸二丁基锡 0.1份,混合搅拌20分钟,涂敷于模具上,放置7天制备得到硅橡胶 /载纳米银改性蒙脱土纳米抗菌复合材料。
实施例2
步骤(1)和步骤(2)与实施例1相同。
(3)硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的制备
100份硅橡胶分散到环己烷中,载纳米银改性蒙脱土抗菌剂0.5 份分散到硅橡胶溶液中,混合搅拌5分钟,搅拌均匀后,加入交联剂硅酸乙酯7.2份,搅拌20分钟,在加入促进剂二月桂酸二丁基锡 0.1份,混合搅拌20分钟,涂敷于模具上,放置7天制备得到硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料。
实施例3
步骤(1)和步骤(2)与实施例1相同。
(3)硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的制备
100份硅橡胶分散到环己烷中,载纳米银改性蒙脱土抗菌剂1 份分散到硅橡胶溶液中,混合搅拌5分钟,搅拌均匀后,加入交联剂硅酸乙酯7.2份,搅拌20分钟,在加入促进剂二月桂酸二丁基锡 0.1份,混合搅拌20分钟,涂敷于模具上,放置7天制备得到硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料。
具体实例4
步骤(1)和步骤(2)与实施例1相同。
(3)硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的制备
100份硅橡胶分散到环己烷中,载纳米银改性蒙脱土抗菌剂1 份分散到硅橡胶溶液中,混合搅拌5分钟,搅拌均匀后,加入交联剂硅酸乙酯7.5份,搅拌20分钟,在加入促进剂二月桂酸二丁基锡 0.15份,混合搅拌20分钟,涂敷于模具上,放置7天制备得到硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料。
具体实例5
步骤(1)和步骤(2)与实施例1相同。
(3)硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的制备
100份硅橡胶分散到环己烷中,载纳米银改性蒙脱土抗菌剂1 份分散到硅橡胶溶液中,混合搅拌5分钟,搅拌均匀后,加入交联剂硅酸乙酯7.8份,搅拌20分钟,在加入促进剂二月桂酸二丁基锡 0.16份,混合搅拌20分钟,涂敷于模具上,放置7天制备得到硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料。
图1载纳米银改性蒙脱土抗菌剂的硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的XRD图,蒙脱土片层的周期性结构已被破坏,蒙脱土以无序状态分布在硅橡胶基体中,得到了剥离型的硅橡胶/改性蒙脱土纳米复合材料。
图2所示为添加不同含量的载纳米银改性蒙脱土抗菌剂的硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料的TG曲线。
图3菌落数实验所示实例三硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料(A2,B2)与不添加抗菌剂的硅橡胶材料(A1,B1)相比,对(A)大肠杆菌(ATCC 25922)和(B)金黄色葡萄球菌(ATCC 25923)的生长有显著地抑制效果。
图4抑菌圈实验所示实例三硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料(A2,A3,B2,B3)与不添加抗菌剂的硅橡胶材料(A1,B1) 相比,对(A)大肠杆菌(ATCC 25922)和(B)金黄色葡萄球菌(ATCC 25923)有明显的抑菌圈。
固定硅橡胶的量,添加不同含量的载纳米银改性蒙脱土抗菌剂 (实施例1-实施例3),其力学性能见表1(微机控制万能试验机测试,GB/528-2009)。由表1可看出,添加0.5%含量的载纳米银改性蒙脱土抗菌剂,可使硅橡胶的断裂伸长率比未加填料的空白体系提高,断裂伸长率可达到167.98%,这表明载纳米银改性蒙脱土抗菌剂对硅橡胶有较好的补强作用。
表1
以上已对本发明创造的较佳实施例进行了具体说明,但本发明创造并不限于所述实施例,熟悉本领域的技术人员在不违背本发明创造精神的前提下还可做出种种的等同的变型或替换,这些等同的变型或替换均包含在本申请权利要求所限定的范围内。
Claims (7)
1. 一种硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料,其特征在于,以重量份计,由如下组分制备而成:硅橡胶100份、载纳米银改性蒙脱土抗菌剂 0.1-1份、分散介质150-200份、交联剂7-8份和促进剂0.1-0.2份。
2.根据权利要求1所述的复合材料,其特征在于,所述载纳米银改性蒙脱土抗菌剂由如下方法制备而成:将银盐水溶液与改性蒙脱土混合均匀,加入还原剂抗坏血酸和稳定剂聚乙烯吡咯烷酮,进行还原反应,得到载纳米银改性蒙脱土抗菌剂。
3.根据权利要求1所述的复合材料,其特征在于,所述的硅橡胶是RTV107硅橡胶。
4.根据权利要求1所述的复合材料,其特征在于,所述的交联剂是正硅酸乙酯。
5.根据权利要求1所述的复合材料,其特征在于,所述的促进剂是二月桂酸二丁基锡。
6.根据权利要求1所述的复合材料,其特征在于,所述的分散介质是水、乙醇或环己烷。
7.如权利要求1-6任意一项所述的复合材料的制备方法,其特征在于,包括顺次相接的如下步骤:将载纳米银改性蒙脱土抗菌剂分散于分散介质中,加入硅橡胶混合搅拌均匀后,加入交联剂、促进剂,涂敷于模具上,放置7天制备得到硅橡胶/载纳米银改性蒙脱土纳米抗菌复合材料。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113637337A (zh) * | 2021-07-07 | 2021-11-12 | 南京师范大学 | 蓝色荧光碳量子点修饰的超疏水材料及其制备方法和应用 |
CN115109560A (zh) * | 2022-08-09 | 2022-09-27 | 东莞市金博奕印刷有限公司 | 一种具有抑菌效果的无痕硅胶贴 |
CN116162355A (zh) * | 2023-02-03 | 2023-05-26 | 昆山力普电子橡胶有限公司 | 一种抗菌硅胶及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1163288A (zh) * | 1997-04-16 | 1997-10-29 | 中国科学院化学研究所 | 硅橡胶/蒙脱土插层复合材料及其制备方法 |
CN1948394A (zh) * | 2006-11-07 | 2007-04-18 | 南京师范大学 | 聚合物/蒙脱土-大蒜素纳米抗菌复合材料及其制备方法 |
CN1970634A (zh) * | 2006-11-07 | 2007-05-30 | 南京师范大学 | 聚合物/蒙脱土-有机硅抗菌剂-磺胺嘧啶银纳米抗菌复合材料及其制备方法 |
CN1970633A (zh) * | 2006-11-07 | 2007-05-30 | 南京师范大学 | 聚合物/蒙脱土-大豆卵磷脂-磺胺嘧啶银纳米抗菌复合材料及其制备方法 |
CN106540691A (zh) * | 2016-09-30 | 2017-03-29 | 天津宝兴威科技有限公司 | 一种纳米银催化剂的制备方法 |
-
2018
- 2018-08-27 CN CN201810979856.6A patent/CN108929543A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1163288A (zh) * | 1997-04-16 | 1997-10-29 | 中国科学院化学研究所 | 硅橡胶/蒙脱土插层复合材料及其制备方法 |
CN1948394A (zh) * | 2006-11-07 | 2007-04-18 | 南京师范大学 | 聚合物/蒙脱土-大蒜素纳米抗菌复合材料及其制备方法 |
CN1970634A (zh) * | 2006-11-07 | 2007-05-30 | 南京师范大学 | 聚合物/蒙脱土-有机硅抗菌剂-磺胺嘧啶银纳米抗菌复合材料及其制备方法 |
CN1970633A (zh) * | 2006-11-07 | 2007-05-30 | 南京师范大学 | 聚合物/蒙脱土-大豆卵磷脂-磺胺嘧啶银纳米抗菌复合材料及其制备方法 |
CN106540691A (zh) * | 2016-09-30 | 2017-03-29 | 天津宝兴威科技有限公司 | 一种纳米银催化剂的制备方法 |
Non-Patent Citations (2)
Title |
---|
李新平: "高分散纳米金属/蒙脱土复合材料的制备及其催化活性研究", 《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》 * |
王静,等: "银系无机抗菌材料研究进展", 《材料导报A:综述篇》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113637337A (zh) * | 2021-07-07 | 2021-11-12 | 南京师范大学 | 蓝色荧光碳量子点修饰的超疏水材料及其制备方法和应用 |
CN115109560A (zh) * | 2022-08-09 | 2022-09-27 | 东莞市金博奕印刷有限公司 | 一种具有抑菌效果的无痕硅胶贴 |
CN116162355A (zh) * | 2023-02-03 | 2023-05-26 | 昆山力普电子橡胶有限公司 | 一种抗菌硅胶及其制备方法 |
CN116162355B (zh) * | 2023-02-03 | 2023-12-05 | 昆山力普电子橡胶有限公司 | 一种抗菌硅胶及其制备方法 |
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