CN110437727B - 一种基于n-羟乙基丙烯酰胺的抗菌/防雾涂层及其制备方法 - Google Patents
一种基于n-羟乙基丙烯酰胺的抗菌/防雾涂层及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于N‑羟乙基丙烯酰胺的抗菌/防雾涂层及其制备方法。首先通过自由基聚合合成N‑羟乙基丙烯酰胺、季铵盐和氟烷基甲基丙烯酸酯的无规共聚物，而后在二月桂酸二丁基锡催化下与六亚甲基二异氰酸酯三聚体热交联成膜。具有较强水合能力的N‑羟乙基丙烯酰胺和带正电荷的季铵盐分别赋予涂层抗细菌粘附和杀菌性能，实现协同抗菌，且二者均含有亲水性基团，可赋予涂层良好的防雾性能。氟烷基甲基丙烯酸酯的引入有利于提高涂层稳定性。所制备涂层耐水性良好、透明性高，可用于多种基材表面，且表现出良好的抗菌性能和防雾性能，在医疗器械领域具有实际应用价值。
Description
技术领域
本发明属于高分子材料涂层领域，具体涉及一种基于N-羟乙基丙烯酰胺的抗菌/防雾涂层及其制备方法。
背景技术
由于细菌在医疗器械表面粘附所引起的医源性感染已经严重威胁到人类的生命健康与安全，因此赋予材料表面抗菌性能具有重大意义。目前常见的抗菌策略主要集中在杀死表面粘附的细菌，却忽略了死细菌/碎片积累所导致的持续污染问题。构建杀菌、“脱菌”综合型抗菌表面可显著提高抗菌效果，有效解决死细菌残留问题。此外，对于内窥镜镜头等透明材料而言，雾化也是使用过程中的另一问题。传统解决方法如采用加热防雾装置、使用防雾油或酒精灯擦拭镜头表面以及大网膜擦拭法存在操作繁琐、成本高、生物相容性差、对镜头损伤较大、适用范围有限等缺点，在镜头表面涂覆防雾涂层具有操作简便、成本低、适用范围广泛等特点而被广泛关注。
N-羟乙基丙烯酰胺是一种改性的丙烯酰胺类单体，其分子上同时存在酰胺基和羟基两个基团，能够与水分子发生强烈水合作用，可赋予涂层优良的防雾性能。此外，研究表明聚N-羟乙基丙烯酰胺具有优异的抗蛋白、细胞、细菌等粘附性能，且能够保持抗粘附效果高达三天(Zhao C,Patel K,Aichinger L M,et al.Antifouling and biodegradablepoly(N-hydroxyethyl acrylamide)(polyHEAA)-based nanogels.RSC Adv.,2013,3:19991-20000)。但此类单一的防污表面一旦有少量细菌粘附，便会迅速增殖形成顽固的生物膜，因此有必要综合抗细菌粘附与杀菌策略进行协同抗菌。
季铵盐因其良好的细胞膜渗透性、环境稳定性、无刺激性、低腐蚀性和较好的生物活性，已广泛应用于抗菌领域。
相较于亲水性和疏水性涂层，两亲性防雾涂层更易实现长效防雾效果。其中，亲水性组分负责将水分子吸入并通过氢键作用将其均匀铺展在涂层内部，疏水性组分用于调控涂层亲疏水性，提高其耐水稳定性，实现长效防雾。
本发明基于N-羟乙基丙烯酰胺的水合作用及季铵盐良好的杀菌性能，以及含氟甲基丙烯酸酯的疏水性，构建一种具有抗细菌粘附、杀菌与防雾功能的综合型表面，此类表面有望用于医疗内窥镜镜头上，解决其在使用过程中的细菌感染和雾化问题，相关内容到目前为止鲜有报道。
发明内容
基于医疗器械在使用过程中的细菌感染与雾化问题，本发明的目的在于提供一种基于N-羟乙基丙烯酰胺的抗菌/防雾涂层及其制备方法。本发明通过自由基聚合合成聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)无规共聚物，在少量交联剂作用下热固化成膜。其中，N-羟乙基丙烯酰胺和季铵盐分别赋予涂层抗细菌粘附和杀菌性能，实现协同抗菌，且二者均含有亲水性基团，赋予涂层良好的防雾性能。疏水性氟烷基甲基丙烯酸酯的引入有利于提高涂层稳定性。
本发明的技术方案如下：
一种基于N-羟乙基丙烯酰胺的抗菌/防雾涂层，其特征在于，各组分及其质量百分比如下：
聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)：2～10％；
六亚甲基二异氰酸酯三聚体：0.1～1％；
二月桂酸二丁基锡：0.02～0.5％；
溶剂：余量。
上述聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)的结构式为：
其中，x:y:z＝(200～500):(100～200):(30～100)，x表示N-羟乙基丙烯酰胺的重复单元数，y表示季铵盐的重复单元数，z表示氟烷基甲基丙烯酸酯的重复单元数，r＝0～16，R为-CH2CF3、-CH2CF2CHFCF3或-CH2CF(CF3)CFHCF(CF3)2中的一种。
上述六亚甲基二异氰酸酯三聚体的结构式为：
上述二月桂酸二丁基锡的结构式为：
上述溶剂为四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜或甲苯中的一种。
上述聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)的合成方法如下：
按摩尔比(200～500):(100～200):(30～100)分别称取N-羟乙基丙烯酰胺、季铵盐和氟烷基甲基丙烯酸酯三种单体，溶于四氢呋喃中，配置成浓度为20～50％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于60～80℃油浴锅中反应6～10h，反应结束后，透析，室温下冻干。
上述一种基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备方法如下：
按比例称取聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)、六亚甲基二异氰酸酯三聚体、二月桂酸二丁基锡和溶剂，配置成溶液，通过旋涂的方式涂覆至玻璃基材表面，70～90℃下反应12～40h，获得涂层。
我们对涂层抗菌性能和防雾性能进行测试：
采用平板菌落计数法测试涂层的抗菌性能。将面积为1×1cm2的涂层与浓度为3×105CFU/mL的细菌悬液在37℃下共培养24h，将共培养后的细菌悬液稀释一定倍数，涂覆至营养琼脂板上，置于37℃摇床中培养24h，观察并记录菌落情况，计算涂层抑菌率。所制备涂层对革兰氏阴性大肠杆菌(E.coli)及革兰氏阳性金黄葡萄球菌(S.aureus)的抑菌率均在90％以上，表现出良好的抗菌性能。
将涂层样品置于-20℃环境下约30min后，取出，立即进行透光率测试。结果表明所制备涂层在雾化条件下的透光率均在85％以上，与空白玻璃片形成鲜明对比。
本发明的优点在于：(1)本发明选用N-羟乙基丙烯酰胺作为涂层中主要组分，一方面由于其自身较强的水合作用，可赋予涂层防污及防雾性能，另一方面N-羟乙基丙烯酰胺中的羟基可作为交联点，与六亚甲基二异氰酸酯三聚体中的-N＝C＝O发生反应，形成三维网状结构，赋予涂层良好的稳定性。同时向体系中引入季铵盐，与N-羟乙基丙烯酰胺进行协同抗菌，有利于提高涂层抗菌效果；(2)通过一步法合成共聚物，并采用热交联固化，涂层制备工艺简便，应用范围广泛；(3)所制备涂层耐水性良好、透明性高，可用于多种基材表面；(4)所制备涂层同时具有抗菌性能与防雾性能，有望用于解决医疗器内窥镜在使用过程中所面临的细菌感染与雾化问题。
具体实施方式
下面结合实施案例对本发明的技术方案作进一步阐述，以下实施案例是对本发明的进一步说明，并不限制本发明的适用范围。
实施例1
(1)聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基丁基溴化铵-co-甲基丙烯酸三氟乙酯)的合成：
按摩尔比300:150:50分别称取N-羟乙基丙烯酰胺、甲基丙烯酰氧乙基二甲基丁基溴化铵和甲基丙烯酸三氟乙酯三种单体，溶于四氢呋喃中，配置成浓度为30％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于65℃油浴锅中反应8h，反应结束后，透析，室温下冻干24h，得到聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基丁基溴化铵-co-甲基丙烯酸三氟乙酯)，其结构式为：
(2)基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备：
聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基丁基溴化铵-co-甲基丙烯酸三氟乙酯)：5％；
六亚甲基二异氰酸酯三聚体：0.5％；
二月桂酸二丁基锡：0.1％；
四氢呋喃：94.4％。
按上述质量百分比配置共聚物溶液，通过旋涂的方式涂覆至玻璃基材表面，80℃下反应24h，获得涂层。
所制备涂层对金黄葡萄球菌和大肠杆菌的抑菌率分别为95.3±2.8％和93.3±3.8％，防雾时在400-800nm波长范围内的透光率为85.6～89.3％，而空白玻璃片的透光率只有26.3～29.6％。
实施例2
(1)聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基三甲基溴化铵-co-甲基丙烯酸三氟乙酯)的合成：
按摩尔比200:100:30分别称取N-羟乙基丙烯酰胺、甲基丙烯酰氧乙基三甲基溴化铵和甲基丙烯酸三氟乙酯三种单体，溶于四氢呋喃中，配置成浓度为20％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于60℃油浴锅中反应10h，反应结束后，透析，室温下冻干24h，得到聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基三甲基溴化铵-co-甲基丙烯酸三氟乙酯)，其结构式为：
(2)基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备：
聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基三甲基溴化铵-co-甲基丙烯酸三氟乙酯)：10％；
六亚甲基二异氰酸酯三聚体：1％；
二月桂酸二丁基锡：0.5％；
四氢呋喃：88.5％。
按上述质量百分比配置共聚物溶液，通过旋涂的方式涂覆至玻璃基材表面，70℃下反应40h，获得涂层。
所制备涂层对金黄葡萄球菌和大肠杆菌的抑菌率分别为94.8±3.7％和92.6±3.1％，防雾时在400-800nm波长范围内的透光率为86.2～89.9％。
实施例3
(1)聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基十一烷基溴化铵-co-甲基丙烯酸六氟丁酯)的合成：
按摩尔比400:200:40分别称取N-羟乙基丙烯酰胺、甲基丙烯酰氧乙基二甲基十一烷基溴化铵和甲基丙烯酸六氟丁酯三种单体，溶于四氢呋喃中，配置成浓度为50％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于70℃油浴锅中反应9h，反应结束后，透析，室温下冻干24h，得到聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基十一烷基溴化铵-co-甲基丙烯酸六氟丁酯)，其结构式为：
(2)基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备：
聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基十一烷基溴化铵-co-甲基丙烯酸六氟丁酯)：2％；
六亚甲基二异氰酸酯三聚体：0.1％；
二月桂酸二丁基锡：0.02％；
N,N-二甲基甲酰胺：97.88％。
按上述质量百分比配置共聚物溶液，通过旋涂的方式涂覆至玻璃基材表面，90℃下反应12h，获得涂层。
所制备涂层对金黄葡萄球菌和大肠杆菌的抑菌率分别为95.8±4.2％和94.8±2.8％，防雾时在400-800nm波长范围内的透光率为85.7～89.5％。
实施例4
(1)聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基十七烷基溴化铵-co-甲基丙烯酸六氟丁酯)的合成：
按摩尔比500:200:100分别称取N-羟乙基丙烯酰胺、甲基丙烯酰氧乙基二甲基十七烷基溴化铵和甲基丙烯酸六氟丁酯三种单体，溶于四氢呋喃中，配置成浓度为30％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于80℃油浴锅中反应6h，反应结束后，透析，室温下冻干24h，得到聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基十七烷基溴化铵-co-甲基丙烯酸六氟丁酯)，其结构式为：
(2)基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备：
聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基十七烷基溴化铵-co-甲基丙烯酸六氟丁酯)：5％；
六亚甲基二异氰酸酯三聚体：0.5％；
二月桂酸二丁基锡：0.1％；
甲苯：94.4％。
按上述质量百分比配置共聚物溶液，通过旋涂的方式涂覆至玻璃基材表面，80℃下反应20h，获得涂层。
所制备涂层对金黄葡萄球菌和大肠杆菌的抑菌率分别为98.2±4.9％和96.8±4.2％，防雾时在400-800nm波长范围内的透光率为85.2～88.6％。
实施例5
(1)聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基丁基溴化铵-co-甲基丙烯酸十二氟庚酯)的合成：
按摩尔比500:180:30分别称取N-羟乙基丙烯酰胺、甲基丙烯酰氧乙基二甲基丁基溴化铵和甲基丙烯酸十二氟庚酯三种单体，溶于四氢呋喃中，配置成浓度为40％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于65℃油浴锅中反应8h，反应结束后，透析，室温下冻干24h，得到聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基丁基溴化铵-co-甲基丙烯酸十二氟庚酯)，其结构式为：
(2)基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备：
聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基二甲基丁基溴化铵-co-甲基丙烯酸十二氟庚酯)：8％；
六亚甲基二异氰酸酯三聚体：0.8％；
二月桂酸二丁基锡：0.4％；
二甲基亚砜：90.8％。
按上述质量百分比配置共聚物溶液，通过旋涂的方式涂覆至玻璃基材表面，85℃下反应18h，获得涂层。
所制备涂层对金黄葡萄球菌和大肠杆菌的抑菌率分别为95.3±3.7％和93.1±2.9％，防雾时在400-800nm波长范围内的透光率为86.1～89.8％。
实施例6
(1)聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基三甲基溴化铵-co-甲基丙烯酸十二氟庚酯)的合成：
按摩尔比350:150:50分别称取N-羟乙基丙烯酰胺、甲基丙烯酰氧乙基三甲基溴化铵和甲基丙烯酸十二氟庚酯三种单体，溶于四氢呋喃中，配置成浓度为25％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于65℃油浴锅中反应8h，反应结束后，透析，室温下冻干24h，得到聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基三甲基溴化铵-co-甲基丙烯酸十二氟庚酯)，其结构式为：
(2)基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备：
聚(N-羟乙基丙烯酰胺-co-甲基丙烯酰氧乙基三甲基溴化铵-co-甲基丙烯酸十二氟庚酯)：6％；
六亚甲基二异氰酸酯三聚体：0.5％；
二月桂酸二丁基锡：0.08％；
二甲基亚砜：93.42％。
按上述质量百分比配置共聚物溶液，通过旋涂的方式涂覆至玻璃基材表面，80℃下反应36h，获得涂层。
所制备涂层对金黄葡萄球菌和大肠杆菌的抑菌率分别为93.2±2.9％和91.9±3.7％，防雾时在400-800nm波长范围内的透光率为87.3～90.2％。
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。
Claims (5)
1.一种基于N-羟乙基丙烯酰胺的抗菌/防雾涂层，其特征在于，各组分及其质量百分比如下：
聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)：2～10％；
六亚甲基二异氰酸酯三聚体：0.1～1％；
二月桂酸二丁基锡：0.02～0.5％；
溶剂：余量。
2.如权利要求1所述的抗菌/防雾涂层，其特征是所述聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)的结构式为：
其中，x:y:z＝(200～500):(100～200):(30～100)，x表示N-羟乙基丙烯酰胺的重复单元数，y表示季铵盐的重复单元数，z表示氟烷基甲基丙烯酸酯的重复单元数，r＝0～16，R为-CH2CF3、-CH2CF2CHFCF3或-CH2CF(CF3)CFHCF(CF3)2中的一种。
3.如权利要求1所述的抗菌/防雾涂层，其特征是聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)的合成方法如下：
按摩尔比(200～500):(100～200):(30～100)分别称取N-羟乙基丙烯酰胺、季铵盐和氟烷基甲基丙烯酸酯三种单体，溶于四氢呋喃中，配置成浓度为20～50％的均一溶液，随后向其中加入单体总质量的0.5wt％的偶氮二异丁腈，置于60～80℃油浴锅中反应6～10h，反应结束后，透析，室温下冻干。
4.如权利要求1所述的抗菌/防雾涂层，其特征在于，所述溶剂为四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜或甲苯中的一种。
5.权利要求1所述的一种基于N-羟乙基丙烯酰胺的抗菌/防雾涂层的制备方法，其特征在于步骤如下：
称取聚(N-羟乙基丙烯酰胺-co-季铵盐-co-氟烷基甲基丙烯酸酯)、六亚甲基二异氰酸酯三聚体、二月桂酸二丁基锡和溶剂，配置成溶液，通过旋涂的方式涂覆至玻璃基材表面，70～90℃下反应12～40h，获得涂层。
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| CN113402971B (zh) * | 2021-05-28 | 2022-04-05 | 浙江大学衢州研究院 | 一种玻璃珠填充的硅酮凝胶抗污抑菌涂层及其制备方法和应用 |
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| JPS61133283A (ja) * | 1984-12-04 | 1986-06-20 | Achilles Corp | 耐久性に優れた防曇剤 |
| EP0339909B1 (en) * | 1988-04-28 | 1993-02-17 | Nippon Oil And Fats Company, Limited | Anti-fogging resin film-forming composition |
| CN102911309A (zh) * | 2012-11-02 | 2013-02-06 | 中国海洋大学 | 一种水性丙烯酸高分子化合物及其制备方法与它的用途 |
| CN108504150A (zh) * | 2018-03-22 | 2018-09-07 | 天津大学 | 一种基于两性离子聚电解质共聚物的防雾涂层及其制备方法 |
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| JPS61133283A (ja) * | 1984-12-04 | 1986-06-20 | Achilles Corp | 耐久性に優れた防曇剤 |
| EP0339909B1 (en) * | 1988-04-28 | 1993-02-17 | Nippon Oil And Fats Company, Limited | Anti-fogging resin film-forming composition |
| CN102911309A (zh) * | 2012-11-02 | 2013-02-06 | 中国海洋大学 | 一种水性丙烯酸高分子化合物及其制备方法与它的用途 |
| CN108504150A (zh) * | 2018-03-22 | 2018-09-07 | 天津大学 | 一种基于两性离子聚电解质共聚物的防雾涂层及其制备方法 |
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