CN114016002B - 一种自再生功能的抗菌复合涂层及其制备方法 - Google Patents
一种自再生功能的抗菌复合涂层及其制备方法 Download PDFInfo
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Abstract
本发明涉及抗菌技术领域,特别涉及一种自再生功能的抗菌复合涂层及其制备方法。该抗菌复合涂层附着于基材上,该抗菌复合涂层由若干层抗菌层和若干层可降解层交替复合而成;其中,抗菌层的厚度为0.2‑2µm,可降解层的厚度为0.1‑1µm。本发明的抗菌复合涂层具有良好的杀菌效果,通过采用多层交替复合的可降解层和抗菌层,使得表层的抗菌层在失去抗菌能力后,利用可降解层的降解脱落,暴露出来的新的抗菌层延续抗菌能力。
Description
技术领域
本发明涉及抗菌技术领域,特别涉及一种自再生功能的抗菌复合涂层及其制备方法。
背景技术
在医疗器械领域,对于抗菌的要求是比较高的,如留置导尿管,其抗菌性能与患者的治疗及恢复直接相关。留置导尿管作为临床医学中一种最普遍的医用器材,主要功能是用于患者的被动排尿。利用留置导尿管排尿是危重患者以及尿失禁患者所采取的一种有效的排尿手段。由于***导尿管是一种侵入人体内的操作,因此,留置导尿管一旦被细菌污染就极易导致人体***以及引起相关的并发症。如果频繁更换导尿管,不仅会给患者带来巨大的额外痛苦,同时也增加了医疗成本和患者的经济压力
经分析发现导尿管上的单个细菌可在24小时内形成生物膜,由于生物膜内部的细菌受到细胞外基质的保护,导致很难被抗生素根除。因此,只有能够抑制细菌生物膜的形成才是根除细菌解决问题的根本。而能否抑制生物膜形成的关键在于,是否能够把最初定殖在材料表面的细菌杀死,从而防止细菌的扩散增殖和转移。
人们通过制备具有杀菌功能的表面来防止生物膜的形成。这种仅具备杀菌功能的抗菌表面在短时间内具有良好的杀菌效果,但随着细菌残骸以及细菌分泌物的黏附,材料表面的杀菌功能逐渐丧失,仍会导致生物膜形成。为了改善抗菌涂层的功能人们制备出一些可以在外部光、温度、湿度等刺激下切换杀菌和排斥功能的表面。这些表面可以有效地杀死接触的细菌并随后在外部刺激下释放污染物,但是这些外部刺激很难在人体内部使用,所以留置装置表面的抗菌问题仍未得到解决。
留置医疗设备留置医疗设备的理想抗菌表面要求为在无外部刺激的生理条件下,既可以杀死接触的细菌,又能将所有细胞碎片完全脱离该表面。实现该方案的难点在于大多数具有接触杀菌作用的抗菌表面都依赖于,表面上正电荷与细菌膜上负电荷之间的静电吸引,但这也是细菌细胞和碎片被吸附的原因。这样就提高了实现该解决方案的难度。
综上,基于包括留置导尿管在内的医疗设备的表面附着细菌无法根除,带来了医疗难度增加、医疗成本的增加的问题。这就需要一种新的方案来解决该问题。
虽然目前有人提出采用丢弃表面层以及附着的物质,并再生出新的抗菌表面来提高抗菌性,但是相关的制备方法步骤繁琐,条件要求较高。
发明内容
本发明的目的为了解决上述的抗菌问题,提供了一种自再生功能的抗菌复合涂层。
同时,本发明还提供了针对这种抗菌复合涂层的具体制备方法。
具体的,本发明提供的是一种采用引发式化学气相沉积法在基材表面构建具有可再生功能的抗菌复合涂层以及相应的制备方法。通过该制备方法制备的抗菌复合涂层,能够达到较好的杀菌效果。本发明的方案是利用基材上复合涂层中的可降解层的降解特性,在可降解层降解之后使抗菌层随之一起脱落,从而将新的抗菌层完全裸露出来,这样,新的抗菌层就具有全新的抗菌效果;从而使材料再次恢复良好的杀菌抗菌能力。
本发明解决上述技术问题所采用的技术方案是:
一种具有自再生功能的抗菌复合涂层,该抗菌复合涂层附着于基材上,该抗菌复合涂层由若干层抗菌层和若干层可降解层交替复合而成;其中,抗菌层的厚度为0.2-2 µm,可降解层的厚度为0.1-1 µm。
为了解决目前的材料不能达到长期抗菌的问题,我们通过用引发式化学气相沉积法制备了复合聚合物抗菌镀层结构,该抗菌镀层采用可降解层和抗菌层交替设置;利用抗菌层进行抗菌,当上层的抗菌层失去抗菌效果后,将可降解层脱落,暴露出新的抗菌层,从而延续抗菌效果。所制备的复合涂层中,抗菌层在最初杀菌测试中具有良好的杀菌效果,可降解层脱落后,新的抗菌层完全裸露出来可以再次恢复良好的杀菌能力。
优选的,所述抗菌层为带正电的聚合物,可降解层为在生理环境下能够发生水解反应的聚合物。利用带正电的聚合物的抗菌性能进行抗菌,可降解层要求能够发生水解,从而能在水解之后脱落。
优选的,所述抗菌复合涂层采用引发式化学气相沉积法制备而成。
优选的,所述抗菌层为带季铵盐阳离子基团单体的聚合物,或
带季铵盐阳离子基团单体与带两个及以上乙烯性双键的烯烃类单体的共聚物。
优选的,所述可降解层为:含有乙烯性双键和酸酐类基团单体的聚合物、
含有乙烯性双键和酸酐类基团单体与带两个及以上乙烯性双键烯烃类单体的共聚物、
含有乙烯性双键和酸酐类基团单体与带乙烯性双键烯烃类水溶性单体的共聚物中的一种或多种。
如,抗菌层为聚(二甲基氨基苯乙烯-乙二醇双丙烯酸酯),可降解层为聚甲基丙烯酸酐。
另外,一种关于上述的抗菌复合涂层的制备方法,具体包括以下步骤:
步骤1:将待承载抗菌复合涂层的基材置于带有合金加热丝的真空反应腔内,保持基材的温度为30-50℃;
步骤2:在基材上交替采用引发式化学气相沉积法制备抗菌层和可降解层的抗菌复合涂层;其中:
抗菌层的制备过程具体为:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,将单体A、单体B和引发剂分别汽化后通入反应腔,其中,单体A和单体B的流量为0.1 sccm~10 sccm,引发剂的流量为0.5 sccm~10 sccm;反应10-60 min,使抗菌层的厚度为0.1-1 μm;
可降解层的制备采用下述方式之一进行:
方式一:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体C和引发剂分别加热汽化后混合通入反应腔内,单体C和引发剂的流量分别为0.1sccm~10 sccm和0.5 sccm~10 sccm;反应5~60 min,使可降解层的厚度为0.2-2 μm;
方式二:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体B、单体C及引发剂分别加热汽化后混合后通入反应腔内,单体B和单体C的流量均控制在0.1 sccm~10 sccm,引发剂的流量控制在0.5 sccm~10 sccm,反应5~60 min,使可降解层的厚度为0.2-2 μm;
方式三:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体C、单体D与引发剂分别加热汽化后混合通入真空反应腔,单体C和单体D的流量范围均为0.1 sccm~10 sccm,引发剂的流量范围为0.5 sccm~10 sccm;反应5~60 min,使可降解层的厚度为0.2-2 μm;
上述中,单体A为含有季铵盐阳离子的单体;
单体B为含有两个及以上乙烯性双键烯烃类单体;
单体C为含有乙烯性双键和酸酐类基团单体;
单体D为带乙烯性双键烯烃类水溶性单体。
本申请采用的是引发式化学气相沉积法,利用气相沉积优势可以实时调节可降解层成分和厚度,得到具有不同降解时间的可降解层,从而制备具有不同再生时间的可再生抗菌复合涂层。
优选的,所述单体A为二甲基氨基甲基苯乙烯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯中的一种或多种。
本发明通过引发式化学气相沉积制备可再生抗菌涂层。本发明通过更换通入的单体制备了复合涂层,实现了抗菌涂层的可再生。
优选的,单体B为二丙烯酸乙二醇酯、乙二醇二甲基丙烯酸酯、2,4,6-三乙烯基-2,4,6-三甲基环三硅氧烷、2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷和二乙烯基苯中的一种或多种。
优选的,单体C为丙烯酸酐、甲基丙烯酸酐、顺丁烯二酸酐中的一种或多种。
优选的,引发剂为二叔丁基过氧化氢、二叔戊基过氧化氢、过氧化苯甲酰、过氧化二苯甲酰、偶氮二异丁腈和全氟丁基磺酰氟中的一种或多种。
进一步的,单体A的饱和蒸汽压为0.01 mmHg~4 mmHg,单体B的饱和蒸汽压为0.01mmHg~4 mmHg,单体C的饱和蒸汽压为0.01 mmHg~4 mmHg,单体D的饱和蒸汽压为0.01mmHg~4 mmHg。
本案的发明人经过长期的研究,采用引发式化学气相沉积法,使用含有季铵盐阳离子基团的单体和含交联性乙烯性双键单体在导尿管表面沉积一层抗菌层,再使用具有不同降解动力学的酸酐类聚合物作为中间可降解层,最后在材料表面继续制备含有季铵盐阳离子基团的单体和含交联性乙烯性双键单体的抗菌层。该复合材料在细菌溶液中具有良好的杀菌功能,并且在降解过程中能释放表层的污染物,可以再次恢复杀菌能力。
本发明的有益效果是:本发明的抗菌复合涂层具有良好的杀菌效果,通过采用多层交替复合的可降解层和抗菌层,使得表层的抗菌层在失去抗菌能力后,利用可降解层的降解脱落,暴露出来的新的抗菌层延续抗菌能力。这样的结果使得负载抗菌复合涂层的材料的表面能够长期具有抗菌能力。本发明所提供的制备方法过程简单,制备过程无需使用任何溶剂,可在导尿管等医疗基材表面形成抗菌复合涂层,确保医疗基材表面的无菌环境的形成及持续保持。
附图说明
图1给出的是本发明得到的一种自再生功能的抗菌镀层的结构示意图。
图2给出的是实施例1中的样品降解前后红外和接触角的数据。
图3给出的是实施例1中的样品降解前后XPS数据。
图4给出的是实施例3样品抗菌测试过程中的SEM图。
图5给出的是对比例1的单层涂层SEM图。
图6给出的是对比例1抗菌测试过程中SEM图。
图1中:1抗菌层,2可降解层,3基材。
具体实施方式
现将进一步细化基于附图的代表性实施方案。以下描述并非旨在将实施方案限制于一个优选实施方案,而是在涵盖可被包括在由所附权利要求限定的所述实施方案的实质和范围内的替代形式、修改形式和等同形式。
本发明提供了一种自再生功能的抗菌镀层,如图1所示,该抗菌复合涂层附着于基材上,该抗菌复合涂层由若干层抗菌层和若干层可降解层交替复合而成;其中,抗菌层的厚度为0.2-2 µm,可降解层的厚度为1-1 µm。
所述抗菌层为带正电的聚合物,可降解层为在生理环境下能够发生水解反应的聚合物。抗菌层和可降解层采用引发式化学气相沉积法交替制备成所述抗菌复合涂层。
具体的,所述抗菌层为带季铵盐阳离子基团单体的聚合物,或带季铵盐阳离子基团单体与带两个及以上乙烯性双键的烯烃类单体的共聚物。
所述可降解层为:含有乙烯性双键和酸酐类基团单体的聚合物、
含有乙烯性双键和酸酐类基团单体与带两个及以上乙烯性双键烯烃类单体的共聚物、
含有乙烯性双键和酸酐类基团单体与带乙烯性双键烯烃类水溶性单体的共聚物中的一种或多种。
一种具有自再生功能的抗菌复合涂层的制备方法,具体包括以下步骤:
具体包括以下步骤:
步骤1:将待承载抗菌复合涂层的基材置于带有合金加热丝的真空反应腔内,保持基材的温度为30-50℃;
步骤2:在基材上交替采用引发式化学气相沉积法制备抗菌层和可降解层的抗菌复合涂层;其中:
抗菌层的制备过程具体为:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,将单体A、单体B和引发剂分别汽化后通入反应腔,其中,单体A和单体B的流量为0.1 sccm~10 sccm,引发剂的流量为0.5 sccm~10 sccm;反应10-60 min,使抗菌层的厚度为0.1-1 μm;
可降解层的制备采用下述方式之一进行:
方式一:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体C和引发剂分别加热汽化后混合通入反应腔内,单体C和引发剂的流量分别为0.1sccm~10 sccm和0.5 sccm~10 sccm;反应5~60 min,使可降解层的厚度为0.2-2 μm;
方式二:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体B、单体C及引发剂分别加热汽化后混合后通入反应腔内,单体B和单体C的流量均控制在0.1 sccm~10 sccm,引发剂的流量控制在0.5 sccm~10 sccm,反应5~60 min,使可降解层的厚度为0.2-2 μm;
方式三:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体C、单体D与引发剂分别加热汽化后混合通入真空反应腔,单体C和单体D的流量范围均为0.1 sccm~10 sccm,引发剂的流量范围为0.5 sccm~10 sccm;反应5~60 min,使可降解层的厚度为0.2-2 μm;
上述中,单体A为含有季铵盐阳离子的单体;
单体B为含有两个及以上乙烯性双键烯烃类单体;
单体C为含有乙烯性双键和酸酐类基团单体;
单体D为带乙烯性双键烯烃类水溶性单体。
上述中,单体A为含有季铵盐阳离子的单体;具体的,所述单体A为二甲基氨基甲基苯乙烯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯中的一种或多种。单体A的饱和蒸汽压为0.01 mmHg~4 mmHg,单体B的饱和蒸汽压为0.01 mmHg~4 mmHg。
单体B为含有乙烯性双键的烯烃类单体;更具体的,单体B为二丙烯酸乙二醇酯、乙二醇二甲基丙烯酸酯、2,4,6-三乙烯基-2,4,6-三甲基环三硅氧烷、2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷和二乙烯基苯中的一种或多种。
单体C为含有酸酐类可降解单体;具体的,单体C为为含有乙烯性双键和酸酐类基团单体。单体C的饱和蒸汽压为0.01 mmHg~4 mmHg。
单体D为带乙烯性双键烯烃类水溶性单体。单体D的饱和蒸汽压为0.01 mmHg~4mmHg。
引发剂为二叔丁基过氧化氢、二叔戊基过氧化氢、过氧化苯甲酰、过氧化二苯甲酰、偶氮二异丁腈和全氟丁基磺酰氟中的一种或多种。
实施例1:
单体A为二甲基氨基甲基苯乙烯、单体B丙烯酸乙二醇酯、单体C甲基丙烯酸酐,采用引发式化学气相沉积法来制备抗菌镀层,二叔丁基过氧化物作为引发剂。
镀膜开始,将医用导尿管放入反应腔的样品台上,样品台温度为37℃,开启机械泵,将反应腔室抽真空,至真空度为400 mtorr并保持该真空度;反应腔热丝加热到220℃;加热单体A和单体B使其气化,使其流量分别控制在0.7 sccm和0.08 sccm;引发剂二叔丁基过氧化氢温度控制在25℃,流量控制在0.5 sccm;沉积时间为45 min,镀层厚度约为800nm,该镀层为抗菌层。
然后关闭单体A和单体B所在管道的阀门,单独通入单体C和二叔丁基过氧化氢,其流量分别控制在0.8 sccm和0.45 sccm,沉积时间18 min,镀层厚度约为600 nm,为可降解层。
然后关闭单体C所在管道的阀门,重复通入单体A和单体B流量控制制备得到抗菌层,厚度为800 nm。
在如图1所示,实施例1得到的医用导尿管表面抗菌镀层为2.2 μm。
选取浓度为106(CFU/mL)的大肠杆菌和金黄色葡萄球菌对实施例1所得到的样品进行抗菌测试。
初次抗菌数据表明,该样品表面对大肠杆菌和金黄色葡萄球菌均具有优良的杀菌效果,杀菌率高达95%以上。
一次杀菌测试结束之后继续对该样品进行杀菌测试,发现杀菌率逐渐降低。
将样品放置在pH=7.4的PBS缓冲液中浸泡,中间可降解层逐渐发生降解,具体的降解过程见表3。
后续对降解后样品表面进行红外和接触角测试,发现降解后样品具备的特殊官能团峰位和表层的抗菌层相比并没有发生明显变化,接触角也没有明显差异如图2。说明降解层去除的比较彻底,能够充分地将新的抗菌层暴露出来。
XPS测试也进一步证明可降解层完全发生降解,连同表面抗菌层一起脱离材料表面如图3。新的抗菌层完全裸露出来,再次恢复杀菌功能,对大肠杆菌和金黄色葡萄球菌的杀菌率达到90%以上,具体见表1和表2。
实施例2:
将实施例1中单体A单体B单体C和引发剂不变,沉积所使、用的单体A、单体B和引发剂流量分别为0.7 sccm、0.08 sccm及0.6 sccm;反应腔热丝加热到220℃,腔体真空度为200 mtorr并保持该真空度,样品台温度为37℃,沉积时间为45 min,镀层厚度约为800 nm,为抗菌层。
然后关闭单体A所在管道的阀门,通入单体B单体C和引发剂二叔丁基过氧化氢,其流量分别控制在0.07 sccm、0.8 sccm和0.45 sccm,沉积时间8 min,镀层厚度约为600 nm,为可降解层。
然后关闭单体C所在管道的阀门,重复通入单体A和单体B流量控制和抗菌层一致厚度为800 nm,为抗菌层。
选取浓度为106(CFU/mL)的大肠杆菌和金黄色葡萄球菌对实施例2所得到的样品进行抗菌测试。
初次抗菌数据表明,该样品表面对大肠杆菌和金黄色葡萄球菌均具有优良的杀菌效果,杀菌率高达95%以上。一次杀菌测试结束之后继续对该样品进行杀菌测试,发现杀菌率逐渐降低,具体见表1和表2。
将样品放置在pH=7.4的PBS缓冲液中浸泡,可降解层逐渐发生降解,降解过程见表3。
可降解层充分降解之后,会连同表面抗菌层一起脱离材料表面。此时新的抗菌层全部裸露出来,再次恢复杀菌功能,对大肠杆菌和金黄色葡萄球菌的杀菌率达到90%以上如表1。
实施例3:
将实施例2中通入单体B更换通入单体D。其他制备条件同实施例2。
镀膜开始,将医用导尿管放入反应腔的样品台上,样品台温度为37℃,开启机械泵,将反应腔室抽真空,至真空度为400 mtorr并保持该真空度;反应腔热丝加热到220℃;加热单体A和单体B使其气化,使其流量分别控制在0.7 sccm和0.08 sccm;引发剂二叔丁基过氧化氢温度控制在25℃,流量控制在0.45 sccm;沉积时间为18 min,镀层厚度约为800nm。
然后关闭单体A所在管道的阀门,通入单体C单体D和引发剂,其流量分别控制在0.8 sccm和0.2 sccm,沉积时间18 min,镀层厚度约为600 nm,为可降解层;
采用同样方法,在可降解层上制备抗菌层,厚度为600 nm。
选取浓度为106(CFU/mL)的大肠杆菌和金黄色葡萄球菌对实施例3所得到的样品进行抗菌测试。
初次抗菌数据表明,该样品表面对大肠杆菌和金黄色葡萄球菌均具有优良的杀菌效果,杀菌率高达95%以上,具体见表1和表2。一次杀菌测试结束之后继续对该样品进行杀菌测试,发现杀菌率逐渐降低。
将样品放置在pH=7.4的PBS缓冲液中浸泡,中间可降解层逐渐发生降解,可降解层的降解过程见表3。
降解过程中对样品表面进行SEM观察如图4,发现最初材料表面细菌很少分析是由于此时材料表面具有良好的杀菌效果。随着时间的延长材料表面逐渐积累了大量的细菌,说明材料不再具备良好的杀菌功能。当材料在PBS缓冲液中浸泡24 h后,观察到材料表面分布少量细菌,说明材料表面黏附的细菌随着可降解层的降解一起脱离材料表面。对大肠杆菌和金黄色葡萄球菌的杀菌率达到90%以上,具体见表1和表2,证明新的抗菌层全部裸露出来,再次恢复杀菌功能。
对比例1:
对比例1只制备了一层抗菌层。
具体如下:镀膜开始,将医用导尿管放入反应腔的样品台上,样品台温度为37℃,开启机械泵,将反应腔室抽真空,至真空度为400 mtorr并保持该真空度;反应腔中的热丝加热到220℃;加热单体A和单体B使其气化,使其流量分别控制在0.7 sccm和0.08 sccm;引发剂二叔丁基过氧化氢温度控制在25℃,流量控制在0.45 sccm;沉积时间为45 min,镀层厚度约为800 nm。
如图5对比例1所得到的为单功能抗菌镀层。选取浓度为106(CFU/mL)的大肠杆菌和金黄色葡萄球菌对对比例1所得到的样品进行抗菌测试。
初次抗菌数据表明,该样品表面对大肠杆菌和金黄色葡萄球菌均具有优良的杀菌效果,杀菌率高达95%以上。一次杀菌测试结束之后继续对该样品进行杀菌测试,发现杀菌率逐渐降低。对抗菌测试的样品进行形貌观察如图6。
由于表面黏附了大量的死细菌以及细菌分泌物等,导致杀菌功能逐渐丧失,也无法恢复杀菌功能,说明材料不适用于长期杀菌。
表1:上述各产品对大肠杆菌的抗菌效果表。
杀菌率(%) | 第一次杀菌 | 第二次杀菌 | PBS浸泡暴露出新的抗菌层 |
对比例1 | 98.7 | 21.3 | |
实施例1 | 98.5 | 23.5 | 94.3 |
实施例2 | 96.8 | 20.1 | 95.6 |
实施例3 | 98.5 | 19.7 | 95.6 |
表2:上述各产品对金黄色葡萄球菌的抗菌效果表。
杀菌率(%) | 第一次杀菌 | 第二次杀菌 | PBS浸泡暴露出新的抗菌层 |
对比例1 | 99.2 | 17.5 | |
实施例1 | 99.3 | 21.6 | 95.0 |
实施例2 | 98.9 | 17.5 | 97.2 |
实施例3 | 97.1 | 22.0 | 96.4 |
表3:实施例1、2、3制备的复合涂层中的可降解层在不同降解时间(浸泡时间)下的降解率数据表。
降解率 | 30 min | 1 h | 3 h | 12 h | 24 h |
实施例1/PMAH | 20% | 50% | 100% | / | / |
实施例2/P(MAH-co-MAA) | 100% | / | / | / | / |
实施例3/P(MAH-co-EGDA) | 10% | 25% | 40% | 70% | 100% |
综上,采用本申请的技术方案制备了抗菌复合涂层,这种抗菌复合涂层能够利用可降解层的降解特点,在表层的抗菌层失去抗菌性能后,将可降解层进行降解处理,从而将负载其上的已经失去抗菌性能的抗菌层去除,暴露出新的抗菌层,从而使具有这种抗菌复合涂层的基材(导尿管)重新恢复抗菌效果,最终达到了长期抗菌的效果。
为了便于进行解释,上述描述中使用特定命名以提供对所述实施方案的彻底理解。对于本领域技术人员而言显而易见的是,在上述教导内容的基础,还能够进行一定的修改、组合和以及变型。
Claims (6)
1. 一种具有自再生功能的抗菌复合涂层,该抗菌复合涂层附着于基材上,其特征在于:该抗菌复合涂层由若干层抗菌层和若干层可降解层交替复合而成;其中,抗菌层的厚度为0.2-2 µm,可降解层的厚度为0.1-1 µm;
所述抗菌复合涂层采用引发式化学气相沉积法制备而成;
所述抗菌层为带季铵盐阳离子基团单体与带两个及以上乙烯性双键的烯烃类单体的共聚物;
所述可降解层为:含有乙烯性双键和酸酐类基团单体的聚合物、含有乙烯性双键和酸酐类基团单体与带两个及以上乙烯性双键烯烃类单体的共聚物、含有乙烯性双键和酸酐类基团单体与带乙烯性双键烯烃类水溶性单体的共聚物中的一种或多种。
2.根据权利要求1所述的一种具有自再生功能的抗菌复合涂层的制备方法,其特征在于:具体包括以下步骤:
步骤1:将待承载抗菌复合涂层的基材置于带有合金加热丝的真空反应腔内,保持基材的温度为30-50℃;
步骤2:在基材上交替采用引发式化学气相沉积法制备抗菌层和可降解层的抗菌复合涂层;其中:
抗菌层的制备过程具体为:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,将单体A、单体B和引发剂分别汽化后通入反应腔,其中,单体A和单体B的流量为0.1 sccm~10 sccm,引发剂的流量为0.5 sccm~10 sccm;反应10-60 min,使抗菌层的厚度为0.1-1 μm;
可降解层的制备采用下述方式之一进行:
方式一:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体C和引发剂分别加热汽化后混合通入反应腔内,单体C和引发剂的流量分别为0.1 sccm~10 sccm和0.5 sccm~10 sccm;反应5~60 min,使可降解层的厚度为0.2-2 μm;
方式二:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体B、单体C及引发剂分别加热汽化后混合后通入反应腔内,单体B和单体C的流量均控制在0.1 sccm~10 sccm,引发剂的流量控制在0.5 sccm~10 sccm,反应5~60 min,使可降解层的厚度为0.2-2 μm;
方式三:保持反应腔内真空度为100 mTorr~1000 mTorr,温度为180~300℃,然后将单体C、单体D与引发剂分别加热汽化后混合通入真空反应腔,单体C和单体D的流量范围均为0.1 sccm~10 sccm,引发剂的流量范围为0.5 sccm~10 sccm;反应5~60 min,使可降解层的厚度为0.2-2 μm;
上述中:
单体A为含有季铵盐阳离子的单体;
单体B为含有两个及以上乙烯性双键烯烃类单体;
单体C为含有乙烯性双键和酸酐类基团单体;
单体D为带乙烯性双键烯烃类水溶性单体。
3.根据权利要求2所述的制备方法,其特征在于:所述单体A为二甲基氨基甲基苯乙烯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯中的一种或多种。
4.根据权利要求2所述的制备方法,其特征在于:单体B为二丙烯酸乙二醇酯、乙二醇二甲基丙烯酸酯、2,4,6-三乙烯基-2,4,6-三甲基环三硅氧烷、2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷和二乙烯基苯中的一种或多种。
5.根据权利要求2所述的制备方法,其特征在于:单体C为丙烯酸酐、甲基丙烯酸酐、顺丁烯二酸酐中的一种或多种。
6.根据权利要求2所述的制备方法,其特征在于:引发剂为二叔丁基过氧化氢、二叔戊基过氧化氢、过氧化苯甲酰、过氧化二苯甲酰、偶氮二异丁腈和全氟丁基磺酰氟中的一种或多种。
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