CN111471202A - 一种抗菌硅橡胶材料及其制备方法和应用 - Google Patents
一种抗菌硅橡胶材料及其制备方法和应用 Download PDFInfo
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- CN111471202A CN111471202A CN202010425122.0A CN202010425122A CN111471202A CN 111471202 A CN111471202 A CN 111471202A CN 202010425122 A CN202010425122 A CN 202010425122A CN 111471202 A CN111471202 A CN 111471202A
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- active ester
- silicone rubber
- antibacterial
- rubber material
- coating
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Abstract
本发明公开了一种抗菌硅橡胶材料及其制备方法和应用,该抗菌硅橡胶材料表面具有抗菌涂层,所述抗菌涂层为通过活性酯聚合物接枝于硅橡胶表面的伯胺抗菌剂,抗菌剂结合牢固、不易流失,抗菌涂层分布均匀、覆盖率高,抗菌硅橡胶材料抗菌效果迅速、显著、稳定。该硅橡胶材料的制备方法为先将活性酯聚合物接枝于硅橡胶表面,然后将伯胺抗菌剂接枝于活性酯聚合物表面,制备方法高效、简便、可控,使硅橡胶表面的抗菌涂层分布均匀、覆盖率高。该抗菌硅橡胶材料作为医用材料,可减少细菌感染,降低耐药性。
Description
技术领域
本发明涉及一种抗菌硅橡胶材料及其制备方法和应用,尤其涉及一种抗菌效果显著、稳定的抗菌硅橡胶材料及其制备方法和应用。
背景技术
硅橡胶自20世纪40年代问世以来,以其低毒、良好的血液相容性和生理稳定性而被广泛应用于生物医学领域,例如人造皮肤、泌尿和静脉导管、隐形眼镜、充氧器等医疗器械中。然而在植、介入医疗的过程中,一旦有致病菌侵入人体,由于硅橡胶材料本身固有的疏水性,细菌易在硅橡胶表面定植并生长繁殖甚至形成生物膜而导致严重的细菌感染,对机体的正常生理功能造成不良影响,威胁患者的健康和生命安全。例如,长时间保留导尿管、静脉等血管内留置导管、人工辅助呼吸时插管等使细菌易于侵入,增大了细菌感染的几率,造成尿路感染、血流感染、败血症等严重问题。其中,每年至少有25%的住院病人在住院期间会使用导管,因此导管相关性尿路感染(CAUTI)是最常见的医院获得性感染之一,占所有医院感染的40%左右。因此,提高硅橡胶医疗设备的抗菌性是硅橡胶医用材料在临床应用中亟待解决的一个问题。
发明内容
发明目的:本发明的第一目的是提供一种抗菌效果迅速、显著、稳定的抗菌硅橡胶材料,第二目的是提供一种使抗菌涂层分布均匀、覆盖率高的抗菌硅橡胶材料的制备方法,第三目的是提供一种抗菌硅橡胶材料在医用材料中的应用。
技术方案:本发明的抗菌硅橡胶材料表面具有抗菌涂层,所述抗菌涂层为通过活性酯聚合物接枝于硅橡胶表面的抗菌剂,其中,所述活性酯聚合物为琥珀酰亚胺活性酯、8-羟基喹啉活性酯、苯骈三氮唑活性酯、对硝基苯氧酰活性酯、五氟苯酚活性酯或以上任一活性酯衍生物的聚合物。
优选,所述活性酯或其衍生物为以下任一结构:
本发明选择的活性酯及其衍生物,其聚合物反应活性高,并且具有丰富的反应位点,有利于接枝于硅橡胶表面,同时也有利于伯胺抗菌剂接枝于活性酯聚合物表面,在硅橡胶表面形成较高密度且分布均匀,发挥迅速、显著、稳定的抗菌效果。
优选,所述伯胺抗菌剂为聚六亚甲基双胍、聚六亚甲基胍、万古霉素、去甲万古霉素、达帕霉素、杆菌肽或短杆菌肽。
本发明首先通过在硅橡胶表面涂覆氨基硅烷偶联剂实现硅橡胶表面氨基化,然后基于氨基与活性酯聚合物之间的酰胺化反应,将活性酯聚合物键合在硅橡胶表面,最后再通过活性酯聚合物将伯胺抗菌剂与表面氨基化的硅橡胶连接起来,以实现硅橡胶表面涂覆抗菌涂层达到杀菌目的。
本发明选择的伯胺抗菌剂可使细菌不易产生耐药性,同时其通过化学键合方式接枝于硅橡胶表面,结合牢固、不易流失,从而使硅橡胶材料可以发挥稳定的抗菌效果。
本发明的抗菌硅橡胶材料的制备方法,其特征在于,包含以下步骤:
(1)在硅橡胶表面接枝偶联剂涂层;
(2)在步骤(1)制备的偶联剂涂层上接枝活性酯聚合物涂层;
(3)在步骤(2)制备的活性酯聚合物涂层上接枝抗菌涂层。
本发明通过化学键将伯胺抗菌剂键合在硅橡胶表面,在硅橡胶材料使用过程中,抗菌剂不易流失,可以发挥稳定的抗菌作用;此外,通过活性酯聚合物进行接枝,有效提高了伯胺抗菌剂的接枝密度,从而有效提高了硅橡胶材料的抗菌效果。
本发明硅橡胶材料表面涂层的接枝方式为逐层接枝,偶联剂涂层、活性酯聚合物涂层和抗菌涂层依次接枝在上一涂层表面,每层键合方式可控、作用牢固、覆盖率高且均匀,并且可以有效利用活性酯聚合物的反应位点,在硅橡胶表面形成牢固的高密度涂层,有效减少覆盖不均匀、表面裸露的现象。
步骤(1)中所述偶联剂为KH-540、KH-550、KH-792、SI-602氨基硅烷偶联剂中的一种,偶联剂溶液中含有甲醇或乙醇、水、乙酸和偶联剂,体积比为0~10:0~10:0~1:0~1;将经过清洗的硅橡胶浸入偶联剂溶液中1min~48h,取出后干燥固化至干透,即可使硅橡胶表面覆盖有偶联剂涂层。
优选,步骤(2)中所述活性酯聚合物的制备方法为,所述活性酯或其衍生物在引发剂催化下进行聚合反应,所述引发剂与所述活性酯或其衍生物的摩尔比为0.005~0.05。
优选,步骤(2)中所述活性酯聚合物的制备方法为,所述活性酯或其衍生物在引发剂和链转移剂共同催化下进行聚合反应,所述活性酯或其衍生物与链转移剂的摩尔比为120:1~6:1;进一步优选,所述链转移剂与引发剂的摩尔比为2:1~5:1。
所述活性酯或其衍生物的聚合反应均在惰性气体氛围中进行,例如氮气、氩气,引发剂为偶氮二异丁腈,链转移剂为2-氰基-2-丙基苯并二硫或甲基-2-(十二烷基三硫代碳酸酯)-2-甲基丙酸酯,反应溶剂为三氟乙醇、二甲亚砜或N,N-二甲基甲酰胺,反应温度为40~90℃,反应时间为1~48h。
本发明的活性酯聚合物涂层采用不同方式可制备为不同结构形态的聚合物,均可以达到有效接枝伯胺抗菌剂的效果,不同聚合物形态的选择可依据活性酯单体结构或制备硅橡胶材料的应用场景需求。
优选,步骤(2)中在所述偶联剂涂层上接枝活性酯聚合物涂层的方法为,将步骤(1)制备的硅橡胶材料浸入0.5~200mg/mL的活性酯聚合物溶液中,反应1~72h。
优选,步骤(3)中在所述活性酯聚合物涂层上接枝抗菌涂层的方法为,将步骤(2)制备的硅橡胶材料浸入0.5~200mg/mL的伯胺抗菌剂溶液中,反应1~72h。
接枝参数可根据涂层的种类、反应活性或制备硅橡胶材料的应用场景需求进行选择。
本发明的抗菌硅橡胶材料在医用材料中的应用。
有益效果:与现有技术相比,本发明具有如下显著优点:
(1)该抗菌硅橡胶材料的抗菌涂层分布均匀、覆盖率高,抗菌硅橡胶材料抗菌效果迅速、显著,抗菌谱广,对以大肠杆菌为代表的革兰氏阴性菌和以金黄葡萄球菌为代表的革兰氏阳性菌均具有抑制和杀灭作用,杀菌率可达85%以上,甚至高达100.0%;接触0.79×104CFU/cm2的金黄葡萄球菌0.5h后杀菌率可达89.2%,1h后杀菌率可达100.0%;接触小于105CFU/cm2的金黄色葡萄球菌1h后杀菌率可达100.0%,接触1~5.47×105CFU/cm2范围内的金黄色葡萄球菌1h后杀菌率可达96.8%;
(2)抗菌剂通过共价键合的方式构建在硅橡胶表面,结合牢固,不易流失,抗菌效果稳定,不污染环境;
(3)该抗菌硅橡胶材料的制备方法高效、简便、可控,使硅橡胶表面的抗菌涂层分布均匀且覆盖率高;
(4)该抗菌硅橡胶材料作为医用材料,降低了使用过程中细菌感染的风险,尤其适用于长期接入人体的硅橡胶医疗器械;同时,有利于减少抗生素的使用量,降低细菌产生耐药性的几率。
附图说明
图1为不同硅橡胶材料与5μL的大肠杆菌菌液(106CFU/mL)接触2h后的平板计数图,其中,图1(A)~图1(C)为普通硅橡胶材料与5μL的大肠杆菌菌液(106CFU/mL)接触2h后的平板计数图,图1(D)~图1(F)为本发明的抗菌硅橡胶材料与5μL的大肠杆菌菌液(106CFU/mL)接触2h后的平板计数图;
图2为不同硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触2h后的平板计数图,其中,图2(A)~图2(C)为普通硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触2h后的平板计数图,图2(D)~图2(F)为本发明的抗菌硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触2h后的平板计数图;
图3为不同硅橡胶材料与5μL的金黄色葡萄球菌和大肠杆菌菌液(106CFU/mL)接触2h后细菌形貌的SEM图,其中,图3(A)为普通硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触2h后细菌形貌的SEM图,图3(B)为本发明的抗菌硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触2h后细菌形貌的SEM图,图3(C)为普通硅橡胶材料与5μL的大肠杆菌菌液(106CFU/mL)接触2h后细菌形貌的SEM图,图3(D)为本发明的抗菌硅橡胶材料与5μL的大肠杆菌菌液(106CFU/mL)接触2h后细菌形貌的SEM图;
图4为不同硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触不同时间后的平板计数图,其中,图4(A)~图4(C)分别为普通硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触0.5h、1h、1.5h后的平板计数图,图4(D)~图4(F)分别为抗菌硅橡胶材料与5μL的金黄色葡萄球菌菌液(106CFU/mL)接触0.5h、1h、1.5h后的平板计数图;
图5为不同硅橡胶材料与不同浓度的5μL的金黄色葡萄球菌菌液接触1h后的平板计数图,其中,图5(A)为普通硅橡胶材料与5×106CFU/mL的金黄色葡萄球菌菌液接触1h后的平板计数图,图5(B)为本发明的抗菌硅橡胶材料与5×106CFU/mL的金黄色葡萄球菌菌液接触1h后的平板计数图,图5(C)为普通硅橡胶材料与2.5×107CFU/mL的金黄色葡萄球菌菌液接触1h后的平板计数图,图5(D)为本发明的抗菌硅橡胶材料与2.5×107CFU/mL的金黄色葡萄球菌菌液接触1h后的平板计数图。
具体实施方式
下面结合实施例及附图对本发明的技术方案作进一步说明。
实验材料:普通硅橡胶材料购于济南晨生医用硅橡胶制品有限公司,活性酯单体、偶联剂、引发剂、伯胺抗菌剂购于上海阿拉丁科技有限公司,链转移剂购于江苏欣诺科催化剂有限公司,菌株由江苏省疾病预防控制中心提供。
实验设备:紫外可见分光光度计(MC-721,上海菁华科技仪器有限公司)、超净工作台(SW-CJ-1FD,苏州净化设备有限公司)、高压灭菌锅(BMX-30R,上海博讯实业有限公司)、恒温恒湿培养箱(HWS-250B,天津泰斯特仪器有限公司)、高分辨扫描电子显微镜(JSM-7600F,日本电子株式会社)。
实施例1
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R1为甲基丙烯酸型,n为1。
在氩气保护下,将以上活性酯单体以及引发剂偶氮二异丁腈(AIBN)溶解于适量N,N-二甲基甲酰胺中,引发剂与活性酯单体的摩尔比为0.01,均匀混合后于65℃下反应24h,反应液经甲醇沉降后得到白色聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂的溶液(甲醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-540(v%)=10:0:0.15:0.05)中浸涂2h,取出硅橡胶材料后于110℃下真空干燥固化1h至干透。将经过真空干燥的硅橡胶在甲醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成10mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将聚六亚甲基双胍盐酸盐配成浓度为10mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的聚六亚甲基双胍盐酸盐溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例2
与实施例1的区别在于,活性酯单体的结构中,R1为乙烯基苯甲酸酯型,n为1,引发剂AIBN与活性酯单体的摩尔比为0.05。
实施例3
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R1为丙烯酸型,n为0。
在氩气保护下,将上述活性酯单体与2-氰基-2-丙基苯并二硫以及AIBN溶解于适量三氟乙醇中,活性酯单体与链转移剂的摩尔比为120:1,链转移剂与引发剂的摩尔比为2:1,均匀混合后于40℃下反应48h,反应液经丙酮沉降后得到聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的偶联剂溶液(乙醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-540(v%)=9:1:1:0.15)中浸涂1min,取出硅橡胶材料后于40℃下真空干燥固化12h至干透。将经过真空干燥的硅橡胶在乙醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成1mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂72h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将聚六亚甲基胍盐酸盐配成浓度为20mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的聚六亚甲基胍盐酸盐溶液中浸涂12h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例4
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为甲基丙烯酸型,n为10。
在氩气保护下,将上述活性酯单体以及AIBN溶解于适量二甲亚砜中,AIBN与活性酯单体的摩尔比为0.005,搅拌溶解后于90℃下反应1h,反应液经甲醇沉降后得到白色聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(乙醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-792(v%)=9:1:0.15:0.15)中浸涂3h,取出硅橡胶材料后于80℃下真空干燥固化3h至干透。将经过真空干燥的硅橡胶在乙醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成200mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂1h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将万古霉素配成浓度为20mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的万古霉素溶液中反应12h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例5
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为乙烯基型,n为1。
在氮气保护下,将上述活性酯单体与链转移剂甲基-2-(十二烷基三硫代碳酸酯)-2-甲基丙酸酯以及AIBN溶解于适量三氟乙醇中,活性酯单体与链转移剂的摩尔比为6:1,链转移剂与引发剂的摩尔比为5:1,均匀混合后于70℃下反应16h,反应液经丙酮沉降后得到聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(乙醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-792(v%)=9:1:0.15:0.15)中浸涂2h,取出硅橡胶材料后于110℃下真空干燥固化2h至干透。将经过真空干燥的硅橡胶在乙醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成5mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂36h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将杆菌肽配成浓度为10mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的杆菌肽溶液中浸涂16h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例6
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为丙烯酸型,n为10。
在氮气保护下,将上述活性酯单体与AIBN溶解于适量三氟乙醇中,引发剂与活性酯单体的摩尔比为0.02,均匀混合后于50℃下反应36h,反应液经甲醇沉降后得到白色聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(甲醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-550(v%)=0:10:0:1)中浸涂1h,取出硅橡胶材料后于100℃下真空干燥固化6h至干透。将经过真空干燥的硅橡胶在甲醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成0.5mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将短杆菌肽配成浓度为0.5mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的短杆菌肽溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例7
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为丙烯酰胺型,n为1。
在氮气保护下,将上述活性酯单体与链转移剂甲基-2-(十二烷基三硫代碳酸酯)-2-甲基丙酸酯以及AIBN溶解于适量二甲亚砜中,活性酯单体与链转移剂的摩尔比为60:1,链转移剂与引发剂的摩尔比为3:1,均匀混合后于80℃下反应12h,反应液经丙酮沉降后得到聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(乙醇(v%):水(v%):乙酸(v%):硅烷偶联剂SI-602(v%)=9:1:0.15:0.15)中浸涂2h,取出硅橡胶材料后于90℃下真空干燥固化1h。将经过真空干燥的硅橡胶在乙醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成100mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将聚六亚甲基胍盐酸盐配成浓度为1mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的聚六亚甲基胍盐酸盐溶液中浸涂72h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例8
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为甲基丙烯酰胺型,n为10。
在氮气保护下,将上述活性酯单体与AIBN溶解于适量N,N-二甲基甲酰胺中,引发剂与活性酯单体的摩尔比为0.006,均匀混合后于80℃下反应10h,反应液经甲醇沉降后得到白色聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(甲醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-550(v%)=8:2:0.15:0.10)中浸涂3h,取出硅橡胶材料后于60℃下真空干燥固化5h至干透。将经过真空干燥的硅橡胶在甲醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成50mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂16h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将去甲万古霉素配成浓度为15mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的去甲万古霉素溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例9
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为苯乙烯型,n为1。
在氮气保护下,将上述活性酯单体与链转移剂2-氰基-2-丙基苯并二硫以及AIBN溶解于适量N,N-二甲基甲酰胺中,活性酯单体与链转移剂的摩尔比为10:1,链转移剂与引发剂的摩尔比为5:1,均匀混合后于75℃下反应12h,反应液经丙酮沉降后得到聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(甲醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-540(v%)=9:1:0.15:0.3)中浸涂24h,取出硅橡胶材料后于75℃下真空干燥固化12h至干透。将经过真空干燥的硅橡胶在甲醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成10mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将杆菌肽配成浓度为15mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的杆菌肽溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例10
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为甲基丙烯酸型,n为5。
在氮气保护下,将上述活性酯单体与链转移剂2-氰基-2-丙基苯并二硫以及AIBN溶解于适量三氟乙醇中,活性酯单体与链转移剂的摩尔比为20:1,链转移剂与引发剂的摩尔比为2:1,均匀混合后于70℃下反应16h,反应液经甲醇沉降后得到聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(甲醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-540(v%)=9:1:0.15:0.15)中浸涂2h,取出硅橡胶材料后于100℃下真空干燥固化1h至干透。将经过真空干燥的硅橡胶在甲醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成10mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中反应36h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将达帕霉素配成浓度为15mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的达帕霉素溶液中反应36h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
实施例11
(1)活性酯聚合物的制备
活性酯单体的结构如下:
其中,R2为丙烯酸型,n为2。
在氩气保护下,将上述活性酯单体与AIBN溶解于适量三氟乙醇中,引发剂与活性酯单体的摩尔比为0.008,均匀混合后于65℃下反应16h,反应液经甲醇沉降后得到白色聚合物,并将聚合物于室温下真空干燥,即得到活性酯聚合物。
(2)抗菌硅橡胶材料的制备
将经过等离子处理后的硅橡胶在配制的氨基硅烷偶联剂溶液(乙醇(v%):水(v%):乙酸(v%):硅烷偶联剂KH-550(v%)=8.5:1.5:0.15:0.10)中浸涂30min,取出硅橡胶材料后于110℃下真空干燥固化1h至干透。将经过真空干燥的硅橡胶在乙醇中超声,并真空干燥,即得表面涂覆有偶联剂涂层的硅橡胶材料。
将步骤(1)制得的活性酯聚合物溶于三氟乙醇溶液中配制成10mg/mL的聚合物溶液,并加入三乙胺调节pH为8~9,再将涂覆有偶联剂涂层的硅橡胶于新配制的聚合物三氟乙醇溶液中反应24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声,并真空干燥,即得表面涂覆有活性酯聚合物的硅橡胶材料。
将杆菌肽配成浓度为10mg/mL的三氟乙醇溶液,并加入三乙胺调节pH为8~9,将涂层过活性酯聚合物的硅橡胶置于配置好的杆菌肽溶液中浸涂24h,从聚合物溶液中取出硅橡胶材料,干透后于三氟乙醇中超声清洗,并真空干燥,即得表面具有抗菌涂层的硅橡胶材料。
对比例1
与实施例1的区别在于,引发剂与活性酯单体的摩尔比为0.001,活性酯聚合物溶液的浓度为250mg/mL,浸涂时间为0.5h;抗菌剂溶液的浓度为250mg/mL,浸涂时间为0.5h。
对比例2
与实施例4的区别在于,引发剂与活性酯单体的摩尔比为0.1,活性酯聚合物溶液的浓度为0.25mg/mL,涂层时间为96h;抗菌剂溶液的浓度为0.25mg/mL,涂层时间为96h。
对比例3
与实施例5的区别在于,活性酯单体与链转移剂的摩尔比为200:1,链转移剂与引发剂的摩尔比为1:1。
对比例4
与实施例7的区别在于,活性酯单体与链转移剂的摩尔比为2:1,链转移剂与引发剂的摩尔比为10:1。
对比例5
与实施例1的区别是,未使用偶联剂和活性酯聚合物对普通硅橡胶材料进行处理,而直接将普通硅橡胶材料浸没于抗菌剂溶液中进行涂覆。
实施例12:抗菌效果测试
1、菌液制备
称取3g胰蛋白胨大豆肉汤,溶解于100mL超纯水中以配制细菌液体培养基(TSB)。吸取4mL液体培养基,加入40μL冻存的细菌液,然后置于37℃恒温震荡箱中培养24h,得到活化后的菌液。活化后的菌液于3000r/min下离心10min,弃去上层液体,另加入4mL灭菌的TSB,使菌液混合均匀。通过紫外可见分光光度计定量菌液浓度,并以TSB作为溶剂,稀释菌液至菌液浓度为106CFU/mL。
2、菌液涂覆在硅橡胶表面、培养
硅橡胶材料的前处理:普通硅橡胶材料经乙醇清洗,干燥,备用;实施例1~11和对比例1~5制备的抗菌硅橡胶材料经干燥后,备用。将各备用的硅橡胶材料剪裁成直径为9mm的圆片(每组三个平行样品),置于75%酒精中灭菌30min后,于灭菌PBS中洗去材料表面的酒精,然后吸取5μL的106CFU/mL的菌液均匀分布于各硅橡胶材料表面,并立即置于恒温(37℃)恒湿(75%)培养箱中培养2h。
2h后,将材料置于1mL的灭菌PBS中并超声处理5min以将材料表面的细菌洗脱到PBS中,混合均匀后,以10倍的浓度梯度逐级稀释至合适浓度,吸取200μL的液体均匀涂抹到琼脂培养板表面,然后将接种细菌的琼脂培养板置于恒温恒湿培养箱中培养16-24h以使琼脂板上的细菌增殖为肉眼可见的菌落,并对菌落数进行统计。
3、结果统计
观察并拍照记录琼脂培养板上生长的菌落情况,并对代表普通硅橡胶材料表面细菌的琼脂培养板中的菌落数(A1,A2,A3)、实施例1~11和对比例1~5制备的抗菌硅橡胶材料表面细菌的琼脂培养板中的菌落数(B1,B2,B3)进行统计,计算杀菌率,杀菌率结果见表1~3、图1~2和图4~5。
杀菌率(%)=1-(B1+B2+B3)/(A1+A2+A3)×100%
4、细菌形貌观察
观察并拍照记录琼脂培养板上生长的细菌形貌,结果见图3。
表1不同硅橡胶材料的杀菌率(%)
表2抗菌硅橡胶材料在不同时间的杀菌率(%)
表3抗菌硅橡胶材料对不同浓度菌液的杀菌率(%)
由图1、图2和表1可见,与普通硅橡胶材料相比,本发明的抗菌硅橡胶材料对以大肠杆菌为代表的革兰氏阴性菌和以金黄葡萄球菌为代表的革兰氏阳性菌均具有抑制和杀灭作用,杀菌率可达85%以上,甚至高达100.0%,说明本发明的抗菌硅橡胶材料具有广谱抗菌效果且抗菌效果显著;对比例制备的抗菌硅橡胶材料相比,本发明的抗菌硅橡胶材料对以大肠杆菌为代表的革兰氏阴性菌和以金黄葡萄球菌为代表的革兰氏阳性菌均具有更优异的抑制和杀灭作用,说明本发明的抗菌硅橡胶材料的制备工艺是经过筛选优化得到的,制得的抗菌硅橡胶材料抗菌效果更显著。
由图3可见,与普通硅橡胶材料相比,细菌附着于本发明的抗菌硅橡胶材料表面后,其生理结构被破坏,呈现死亡迹象,说明本发明的抗菌硅橡胶材料对细菌的正常生长具有干扰和抑制作用。
由图4和表2可见,与普通硅橡胶材料相比,本发明的抗菌硅橡胶材料在0.5h时杀菌率即可达到89.2%(接触0.79×104CFU/cm2的金黄葡萄球菌),在1h时杀菌率可达100.0%,说明本发明的抗菌硅橡胶材料杀菌具有高效性,在较短的时间内即可杀死绝大多数的细菌。
由图5和表3可见,与普通硅橡胶材料相比,本发明的抗菌硅橡胶材料在1h时,对5×106CFU/mL的菌液杀菌率可达100.0%(接触小于105CFU/cm2的金黄色葡萄球菌),对2.5×107CFU/mL的菌液杀菌率可达96.8%(接触1~5.47×105CFU/cm2范围内的金黄色葡萄球菌),说明本发明的抗菌硅橡胶材料对在其表面的附着密度较大的细菌也具有很好地杀菌效果。
Claims (10)
1.一种抗菌硅橡胶材料,其特征在于,所述抗菌硅橡胶材料表面具有抗菌涂层,所述抗菌涂层为通过活性酯聚合物接枝于硅橡胶表面的伯胺抗菌剂,其中,所述活性酯聚合物为琥珀酰亚胺活性酯、8-羟基喹啉活性酯、苯骈三氮唑活性酯、对硝基苯氧酰活性酯、五氟苯酚活性酯或以上任一活性酯衍生物的聚合物。
3.根据权利要求1所述的抗菌硅橡胶材料,其特征在于,所述伯胺抗菌剂为聚六亚甲基双胍、聚六亚甲基胍、万古霉素、去甲万古霉素、达帕霉素、杆菌肽或短杆菌肽。
4.一种权利要求1~3任一所述的抗菌硅橡胶材料的制备方法,其特征在于,包含以下步骤:
(1)在硅橡胶表面接枝偶联剂涂层;
(2)在步骤(1)制备的偶联剂涂层上接枝活性酯聚合物涂层;
(3)在步骤(2)制备的活性酯聚合物涂层上接枝抗菌涂层。
5.根据权利要求4所述的抗菌硅橡胶材料的制备方法,其特征在于,步骤(2)中所述活性酯聚合物的制备方法为,所述活性酯或其衍生物在引发剂催化下进行聚合反应,所述引发剂与所述活性酯或其衍生物的摩尔比为0.005~0.05。
6.根据权利要求4所述的抗菌硅橡胶材料的制备方法,其特征在于,步骤(2)中所述活性酯聚合物的制备方法为,所述活性酯或其衍生物在引发剂和链转移剂共同催化下进行聚合反应,所述活性酯或其衍生物与链转移剂的摩尔比为120:1~6:1。
7.根据权利要求6所述的抗菌硅橡胶材料的制备方法,其特征在于,所述链转移剂与引发剂的摩尔比为2:1~5:1。
8.根据权利要求4所述的抗菌硅橡胶材料的制备方法,其特征在于,步骤(2)中在所述偶联剂涂层上接枝活性酯聚合物涂层的方法为,将步骤(1)制备的硅橡胶材料浸入0.5~200mg/mL的活性酯聚合物溶液中,反应1~72h。
9.根据权利要求4所述的抗菌硅橡胶材料的制备方法,其特征在于,步骤(3)中在所述活性酯聚合物涂层上接枝抗菌涂层的方法为,将步骤(2)制备的硅橡胶材料浸入0.5~200mg/mL的伯胺抗菌剂溶液中,反应1~72h。
10.一种权利要求1~9任一所述的抗菌硅橡胶材料在医用材料中的应用。
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