CN104911675B - 一种镁基抗菌耐蚀纳米涂层的制备方法 - Google Patents
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Abstract
本发明提供了一种镁基抗菌耐蚀纳米涂层的制备方法。该制备方法包括以下步骤：首先通过普通自由基溶液聚合制备离子型无规共聚物，将上述离子型无规共聚物溶于醇类溶剂形成溶液；在搅拌条件下，向上述溶液中滴加含单宁酸抗菌分子的醇溶液，促使离子型无规共聚物与单宁酸抗菌分子发生复合自组装，形成复合纳米粒子溶液；最后以复合纳米粒子溶液为电解液，采用电泳沉积技术，在镁合金表面制备抗菌耐蚀纳米涂层。该法操作简便，适用范围广，制备的涂层提高了镁基材在模拟人体环境下的耐腐蚀性，且涂层对大肠杆菌和金黄色葡萄球菌有良好的抑制作用，有望应用于生物医学等领域。
Description
技术领域
本发明涉及一种镁基抗菌耐蚀纳米涂层的制备方法，属于抗菌涂层与纳米材料技术相结合领域。
技术背景
镁及镁合金作为新型可降解金属材料，逐渐成为生物材料领域的研究热点,并越来越受到生物、材料和医学界的关注与重视，其相比于传统医用金属合金，如钛合金、316L不锈钢、钴基合金等具有更好的生物相容性、生物可降解性、及适宜的机械性能，可有效避免应力遮蔽效应和二次手术取出(Acta Biomaterialia,2012,8,2442-2455.)。但是目前大量研究表明，阻碍镁及镁合金成为可供临床使用的医学植入材料的因素主要有两点。一是镁及镁合金性质活泼，在人体体液环境中会发生快速降解，导致植入部位产生大量气泡、聚集过多的金属离子，从而引发宿主的不良反应并导致植入失效。另一关键因素是植入部位的细菌感染问题。因此镁及镁合金需要同时满足耐腐蚀性和植入初期抗菌性的要求，才能作为医学植入材料应用于人体的相关组织修复(Surface&Coatings Technology,2011,212,1-11.)。
表面涂层技术是一种改善材料性能的有效方法，可在不改变基体性质的基础上赋予其表面额外的性能。因此可通过使用合适的表面涂层工艺，在保留镁合金本身优良性能的基础上，来提高镁合金的耐腐蚀性和抗菌性能。如Paul等利用等离子氧化技术在镁合金表面制备ZrO2涂层材料，提高了镁合金在模拟人体环境下的耐腐蚀性和抗菌性(ActaBiomaterialia,2014,10,544-556.)。Hyun等在镁合金表面制备含银的MAO涂层，赋予镁合金抗菌耐蚀特性(Journal ofThe Electrochemical Society,2010,157,C131-C136.)。然而，上述涂层中的抗菌组分多为重金属元素(如Zr、Ag等)，毒性较大，易对人体产生损害，不适用于生物医学领域。
发明内容
针对现有技术存在的上述问题，本发明提供了一种镁基抗菌耐蚀纳米涂层的制备方法，该法以离子型无规共聚物和天然抗菌剂单宁酸的复合纳米粒子为基本基元，利用工业上普遍使用的电泳沉积技术，在镁合金表面制备抗菌耐蚀纳米涂层，该涂层制备方法操作简便，适用范围广，所制备的涂层提高了镁基材的耐腐蚀性和抗菌性，且涂层具有良好的细胞相容性，应用前景广泛。
本发明的技术方案如下：
一种镁基抗菌耐蚀纳米涂层的制备方法，其步骤如下：
(1)离子型无规共聚物的制备：按配比称取离子型单体、手性单体及引发剂，依次加入圆底烧瓶内，向烧瓶内加入适量体积的二氧六环作为溶剂，通氮气30min，控制反应温度及时间进行反应，反应完成后将最终反应液在去离子水中透析，除去未反应单体、引发剂、有机溶剂，透析液经冷冻干燥得到离子型无规共聚物；
所用离子型单体选自：(甲基)丙烯酸二甲基胺基乙酯、对乙烯基苯磺酸、(甲基)丙烯酸酐，手性单体选用(甲基)丙烯酸异冰片酯，引发剂为2,2-偶氮二异丁腈或2,2-偶氮二异庚腈；所述的离子型单体与手性单体的反应摩尔比为1:1～1:2，引发剂的加入量为上述反应单体总摩尔数的1％～2％，溶剂二氧六环的体积为10mL～20mL，反应温度65℃～70℃，反应时间12h～24h。
(2)复合纳米粒子溶液的制备：将步骤(1)所制备的离子型无规共聚物溶解在醇类溶剂中，接着向上述溶液中滴加含单宁酸抗菌分子的醇溶液，促使离子型无规共聚物与单宁酸抗菌分子发生复合自组装，形成复合纳米粒子溶液。
所用的醇类溶剂选自甲醇、乙醇、正丁醇中的一种，溶液中离子型无规共聚物的浓度为1mg/mL～5mg/mL，含单宁酸抗菌分子的醇溶液浓度为1mg/mL～5mg/mL；离子型无规共聚物与单宁酸抗菌分子发生复合自组装时二者的溶液体积比为1:0.2～1:0.6，所形成的复合纳米粒子尺寸在50nm～300nm，粒子呈荷负电或荷正电。
(3)抗菌耐蚀纳米涂层的制备：以步骤(2)中所制备的复合纳米粒子溶液为电解液，镁及镁合金为工作电极，铂片电极为对电极，通过电泳沉积技术制备镁基抗菌耐蚀纳米涂层。
所用电解液体积为10mL～50mL，电泳沉积电压为10V～100V，沉积时间为1min～60min；所制备的涂层提高了镁基材的耐腐蚀性，且对大肠杆菌和金黄色葡萄球菌具有良好的抑制作用，并具有优异的细胞相容性。
本发明的有益技术效果在于：所用的离子型无规共聚物合成简单，单体来源广泛；所用的单宁酸是一种天然植物多酚，具有优异的生物学性能，成本低廉；涂层制备方法采用电泳沉积技术，操作方便，设备简单，投资少，涂层形成过程可控，沉积液为复合纳米粒子溶液，增加了电泳沉积效率；所制备的涂层兼具耐腐蚀、抗菌、细胞相容性，为镁基抗菌耐蚀纳米涂层的制备提供了一种新思路。
附图说明
图1为实施例1中离子型无规共聚物的1H-NMR谱图；
图2为实施例2中复合纳米粒子溶液样品的SEM图片；
图3为实施例3中镁基抗菌耐蚀纳米涂层的SEM形貌图；
图4为实施例4中镁基抗菌耐蚀纳米涂层样品的抑菌圈测试结果。
具体实施方式
实施例1
一种镁基抗菌耐蚀纳米涂层的制备方法，具体制备步骤如下：
(1)离子型无规共聚物的制备：称量3.144g(20mmol)甲基丙烯酸二甲基胺基乙酯、4.166g(20mmol)丙烯酸异冰片酯及0.129g(2％)2,2-偶氮二异丁腈，依次加入圆底烧瓶内，向烧瓶内加入15mL二氧六环作为溶剂，通氮气30min，体系65℃下反应24h，反应完成后将最终反应液在去离子水中透析，除去未反应单体、引发剂、有机溶剂，透析液经冷冻干燥得到离子型无规共聚物，1H-NMR谱图如附图中图1所示；
(2)复合纳米粒子溶液的制备：将步骤(1)所制备的离子型无规共聚物溶解在乙醇中形成5mg/mL溶液，接着向上述溶液中滴加含3mg/mL单宁酸抗菌分子的乙醇溶液，两者的体积比为1:0.6，促使离子型无规共聚物与单宁酸抗菌分子发生复合自组装，形成复合纳米粒子溶液；
(3)抗菌耐蚀纳米涂层的制备：以30mL步骤(2)中所制备的复合纳米粒子溶液为电解液，镁为工作电极，铂片电极为对电极，在30V电压下沉积20min，制备镁基抗菌耐蚀纳米涂层。
实施例2
一种镁基抗菌耐蚀纳米涂层的制备方法，具体制备步骤如下：
(1)离子型无规共聚物的制备：称量1.842g(10mmol)对乙烯基苯磺酸、4.446g(20mmol)甲基丙烯酸异冰片酯及0.098g(2％)2,2-偶氮二异丁腈，依次加入圆底烧瓶内，向烧瓶内加入20mL二氧六环作为溶剂，通氮气30min，体系70℃下反应18h，反应完成后将最终反应液在去离子水中透析，除去未反应单体、引发剂、有机溶剂，透析液经冷冻干燥得到离子型无规共聚物；
(2)复合纳米粒子溶液的制备：将步骤(1)所制备的离子型无规共聚物溶解在甲醇中形成2mg/mL溶液，接着向上述溶液中滴加含3mg/mL单宁酸抗菌分子的甲醇溶液，两者的体积比为1:0.4，促使离子型无规共聚物与单宁酸抗菌分子发生复合自组装，形成复合纳米粒子溶液，样品的SEM图如附图2所示；
(3)抗菌耐蚀纳米涂层的制备：以50mL步骤(2)中所制备的复合纳米粒子溶液为电解液，镁为工作电极，铂片电极为对电极，在80V电压下沉积5min，制备镁基抗菌耐蚀纳米涂层。
实施例3
一种镁基抗菌耐蚀纳米涂层的制备方法，具体制备步骤如下：
(1)离子型无规共聚物的制备：称量1.541g(10mmol)甲基丙烯酸酐、2.083g(10mol)丙烯酸异冰片酯及0.049g(1％)2,2-偶氮二异庚腈，依次加入圆底烧瓶内，向烧瓶内加入10mL二氧六环作为溶剂，通氮气30min，体系67℃下反应12h，反应完成后将最终反应液在去离子水中透析，除去未反应单体、引发剂、有机溶剂，透析液经冷冻干燥得到离子型无规共聚物；
(2)复合纳米粒子溶液的制备：将步骤(1)所制备的离子型无规共聚物溶解在正丁醇中形成3mg/mL溶液，接着向上述溶液中滴加含1mg/mL单宁酸抗菌分子的正丁醇溶液，两者的体积比为1:0.2，促使离子型无规共聚物与单宁酸抗菌分子发生复合自组装，形成复合纳米粒子溶液；
(3)抗菌耐蚀纳米涂层的制备：以15mL步骤(2)中所制备的复合纳米粒子溶液为电解液，镁为工作电极，铂片电极为对电极，在10V电压下沉积60min，制备镁基抗菌耐蚀纳米涂层，涂层的SEM形貌图如附图3所示。
实施例4
一种镁基抗菌耐蚀纳米涂层的制备方法，具体制备步骤如下：
(1)离子型无规共聚物的制备：称量1.431g(10mol)丙烯酸二甲基胺基乙酯、4.166g(20mol)丙烯酸异冰片酯及0.149g(2％)2,2-偶氮二异庚腈，依次加入圆底烧瓶内，向烧瓶内加入20mL二氧六环作为溶剂，通氮气30min，体系65℃下反应24h，反应完成后将最终反应液在去离子水中透析，除去未反应单体、引发剂、有机溶剂，透析液经冷冻干燥得到离子型无规共聚物；
(2)复合纳米粒子溶液的制备：将步骤(1)所制备的离子型无规共聚物溶解在乙醇中形成5mg/mL溶液，接着向上述溶液中滴加含5mg/mL单宁酸抗菌分子的乙醇溶液，两者的体积比为1:0.6，促使离子型无规共聚物与单宁酸抗菌分子发生复合自组装，形成复合纳米粒子溶液；
(3)抗菌耐蚀纳米涂层的制备：以30mL步骤(2)中所制备的复合纳米粒子溶液为电解液，镁为工作电极，铂片电极为对电极，在20V电压下沉积40min，制备镁基抗菌耐蚀纳米涂层，涂层对大肠杆菌的抑菌效果如附图4所示。
上述实施例用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都落入本发明的保护范围。
Claims (6)
1.一种镁基抗菌耐蚀纳米涂层的制备方法，其步骤如下：
(1)离子型无规共聚物的制备：按配比称取离子型单体、手性单体及引发剂，依次加入圆底烧瓶内，向烧瓶内加入适量体积的二氧六环作为溶剂，通氮气30min，控制反应温度及时间进行反应，反应完成后将最终反应液在去离子水中透析，除去未反应单体、引发剂、有机溶剂，透析液经冷冻干燥得到离子型无规共聚物；
所用离子型单体选自：(甲基)丙烯酸二甲基氨基乙酯、对乙烯基苯磺酸、(甲基)丙烯酸酐，手性单体选用(甲基)丙烯酸异冰片酯，引发剂为2,2-偶氮二异丁腈或2,2-偶氮二异庚腈；
(2)复合纳米粒子溶液的制备：将步骤(1)所制备的离子型无规共聚物溶解在醇类溶剂中，接着向上述溶液中滴加含单宁酸抗菌分子的醇溶液，促使离子型无规共聚物与单宁酸抗菌分子发生复合自组装，形成复合纳米粒子溶液；
(3)抗菌耐蚀纳米涂层的制备：以步骤(2)中所制备的复合纳米粒子溶液为电解液，镁及镁合金为工作电极，铂片电极为对电极，通过电泳沉积技术制备镁基抗菌耐蚀纳米涂层。
2.根据权利要求1所述的一种镁基抗菌耐蚀纳米涂层的制备方法，其特征在于步骤(1)中，离子型单体与手性单体的反应摩尔比为1:1～1:2，引发剂的加入量为上述反应单体总摩尔数的1％～2％，溶剂二氧六环的体积为10mL～20mL，反应温度65℃～70℃，反应时间12h～24h。
3.根据权利要求1所述的一种镁基抗菌耐蚀纳米涂层的制备方法，其特征在于步骤(2)中，所用的醇类溶剂选自甲醇、乙醇、正丁醇中的一种，溶液中离子型无规共聚物的浓度为1mg/mL～5mg/mL，含单宁酸抗菌分子的醇溶液浓度为1mg/mL～5mg/mL。
4.根据权利要求1所述的一种镁基抗菌耐蚀纳米涂层的制备方法，其特征在于步骤(2)中，离子型无规共聚物与单宁酸抗菌分子发生复合自组装时二者的溶液体积比为1:0.2～1:0.6，所形成的复合纳米粒子尺寸在50nm～300nm，粒子呈荷负电或荷正电。
5.根据权利要求1所述的一种镁基抗菌耐蚀纳米涂层的制备方法，其特征在于步骤(3)中，电解液体积为10mL～50mL，电泳沉积电压为10V～100V，沉积时间为1min～60min。
6.根据权利要求1所述的一种镁基抗菌耐蚀纳米涂层的制备方法，其特征在于步骤(3)中，所制备的涂层具有耐腐蚀性、抗菌性、及细胞相容性。
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