CN113802364A - 一种自修复、耐酸碱、抗菌多层膜涂层的制备方法 - Google Patents
一种自修复、耐酸碱、抗菌多层膜涂层的制备方法 Download PDFInfo
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Abstract
本发明公开一种自修复、耐酸碱、抗菌多层膜涂层的制备方法,属于高分子薄膜制备领域;该方法首先将预处理过的基底置于壳聚糖溶液中浸泡,取出后用去离子水漂洗,然后置于多巴胺接枝改性的羧甲基纤维素溶液中浸泡,取出后用去离子水漂洗,重复上述过程,得到CS/DA‑g‑CMC多层膜改性的基底,最后采用高碘酸钠对多层膜改性的基底进行氧化交联,制得自修复、耐酸碱、抗菌的多层膜;本发明制备成本低廉、操作简便、设备简单、条件温和,多层膜结构和性能可控,并兼具自修复、耐酸碱和抗菌三种功能,在生物医用材料、食品包装材料等领域具有广泛的应用前景。
Description
技术领域
本发明涉及一种可自修复、耐酸碱、抗菌多层膜涂层的制备方法,属于高分子薄膜制备领域。
背景技术
材料在使用过程中受到外界机械、化学等作用力的影响,不可避免地会产生局部损伤和细微裂纹,如果这些损伤部位不能得到及时的修复,不但影响了材料的正常使用性能,缩短了材料的使用寿命,而且会由此引发宏观裂缝甚至发生断裂,导致更大的安全隐患。自修复材料能够在材料受损是进行自我修复,起到延长使用寿命、降低更换成本、增加安全性的作用。此外,材料在使用过程中表面微生物的污染以及随之生成的生物膜污染会对材料的使用寿命、甚至使用安全性产生巨大的威胁,如生物医用材料、食品包装材料对材料的抗菌性能具有较高的要求。因此,具有自修复和抗菌的涂层在生物医用和食品包装材料领域具有潜在的应用价值。
中国专利CN20210132441.8公开了一种自修复透明抗菌涂层的制备方法,即首先采用层层自组装技术将阴阳离子聚电解质交替沉积在基底表面制备具有自修复多层膜涂层的基底,随后将其浸泡在抗菌剂溶液中一段时间,可得到自修复透明抗菌涂层。然而,该专利中所采用的层层自组装技术的驱动力为弱的静电相互作用力,导致所制备的自修复多层膜涂层的稳定性不足,不能抵御较为苛刻的外部环境(如酸碱侵蚀)而被破坏。迄今,还没有关于同时具有自修复、耐酸碱和抗菌功能层层自组装多层膜涂层的研发工作报道。
发明内容
为了克服上述现有技术存在的缺陷,本发明提供了一种可自修复、耐酸碱、抗菌多层膜涂层的制备方法,具体包括以下步骤:
(1)将基底(纸张、棉织物)放入高碘酸钠溶液中,在一定的温度条件下避光处理,得到预处理的基底;
所述高碘酸钠的浓度为1~3g/L,在30℃~50℃下避光处理时间为1~3h;
(2)将预处理的基底浸泡在壳聚糖(CS)溶液中10~30min,然后用去离子水漂洗3~5次,得到CS层改性的基底,将CS层改性的基底浸泡在接枝多巴胺的羧甲基纤维素(DA-g-CMC)溶液中10~30min,然后用去离子水漂洗3~5次,得到CS/DA-g-CMC双层膜改性的基底,重复上述改性过程5~15次,得到(CS/DA-g-CMC)n多层膜改性的基底,然后置于40℃~60℃下干燥;
所述DA-g-CMC的制备方法如下:在pH为3~5的磷酸氢二钠-柠檬酸缓冲溶液100mL中加入1~2g 的CMC,37℃条件下搅拌4~6h,然后再分别加入0.4~0.6g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.2~0.4g N-羟基琥珀酰亚胺,继续搅拌20-40min后加入pH为2~4、170~230mg/mL的盐酸多巴胺(DA)溶液2~4mL,放入摇床,在37℃、100~180r/min、氮气条件下避光反应24~36h,将反应所得溶液用透析袋在去蒸馏水中透析1~2天,将透析后的溶液冻干即得到DA-g-CMC;
CS溶液浓度为1~3g/L,pH为5~5.6;DA-g-CMC溶液浓度为1~3g/L,pH为6.5~7.5;
(3)将干燥后的多层膜改性的基底置于的高碘酸钠溶液中常温避光处理,然后在一定温度条件下干燥,完成多层膜涂层的制备;
步骤(3)中高碘酸钠溶液浓度为0.1-0.3g/L,处理时间为2~6h,干燥温度为35~45℃。
本发明的有益效果:
(1)本发明使用的壳聚糖、羧甲基纤维素属于天然多糖及衍生物,无毒,可再生;
(2)本发明操作简单、工艺条件温和,适合工业化生产;
(3)本发明所制备的多层膜涂层,兼具自修复、耐酸碱、抗菌三种功能,在生物医用材料、食品包装材料领域具有很好的应用前景。
附图说明
图1是实施例1中(CS/DA-g-CMC)5多层膜涂层在去离子水作用下自修复过程的显微镜照片,其中左图为修复前,右图为修复后;
图2是本发明制备的DA-g-CMC的FTIR(A)和HNMR(B)谱图。
具体实施方式
下面结合附图和实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1
(1)接枝多巴胺的羧甲基纤维素是在pH 3的磷酸氢二钠-柠檬酸缓冲溶液100mL中加入1g的羧甲基纤维素,37℃下搅拌4h,然后再加入0.6g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.2g N-羟基琥珀酰亚胺,继续搅拌20min后加入pH 2、浓度175mg/mL的盐酸多巴胺溶液4mL,放入摇床,在37℃、150r/min、氮气条件下避光反应24h,将反应所得溶液用透析袋在去蒸馏水中透析1天,透析后的溶液冻干制得,接枝多巴胺的羧甲基纤维素的和HNMR谱图见图2,从图2中(A)图中的FTIR谱图可以看出,与原始的羧甲基纤维素对比,多巴胺修饰后,在1735和1080 cm-1处出现了两个新的特征吸收峰,这是由于-COOH基团和C-N的拉伸震动引起的,表明羧甲基纤维素上成功接枝了多巴胺;从图2中(B)图中的HNMR谱图可以观察到,原始羧甲基纤维素在7.0ppm左右没有特征吸收峰,而与多巴胺发生反应的羧甲基纤维素则在7.0ppm左右处出现了特征吸收峰,这进一步表明多巴胺成功的接枝到了羧甲基纤维素上;
(2)将普通纸张放入1g/L的高碘酸钠溶液中,在35℃下避光处理3h,得到预处理的基底;将预处理的基底浸泡在pH=5、1g/L的壳聚糖(CS)溶液中10min,然后用去离子水漂洗3次,得到CS层改性的基底,将CS层改性的基底浸泡在pH=6.5、1g/L的接枝多巴胺的羧甲基纤维素(DA-g-CMC)溶液中10min,然后用去离子水漂洗3次,得到CS/DA-g-CMC双层膜改性的基底,重复上述改性过程5次,得到(CS/DA-g-CMC)5多层膜改性的基底,然后在40℃条件下干燥处理;将干燥的多层膜改性的基底置于0.1g/L的高碘酸钠溶液中常温避光处理2h,然后在35℃条件下干燥,即完成自修复、耐酸碱、抗菌多层膜涂层的制备;
将本实施例制得的带有多层膜涂层的纸张放在载玻片上,然后用尖锐的刀片在纸张表面制造出一道划痕,室温条件下,在划痕上滴加去离子水,通过显微镜观察纸张被划伤处的愈合情况;多层膜涂层具有一定的润胀性,加水使得划痕两边的多层膜涂层润胀并相互接触,该过程伴随着共价与非共价相互作用,5min之后,随着水分的蒸发干燥,多层膜涂层表面的平整度基本恢复到原状,结果见图1,结果显示本发明多层膜涂层具有良好的自修复性能。
采用摇瓶法检测纸张抑菌性,将大小为1×1.5cm的纸样浸入到5mL浓度为106 CFU/mL的菌悬液中,在37℃下以180r/min的速度摇4h;随后进行10倍梯度稀释,取10-3稀释后的菌悬液0.1mL涂布在无菌琼脂培养皿上,将涂布好的培养皿倒置,37℃下培养24h,记录菌落数目;通过与空白组做比较计算纸样的抑菌率,测得带有多层膜涂层的纸张对金黄色葡萄球菌的抑菌率为93.2%,对大肠杆菌的抑菌率为91.3%;
将本实施例制得的带有多层膜涂层的纸张分别置于pH=3的HCl溶液和pH=12的NaOH溶液中刻蚀处理9h,再通过摇瓶法检测纸张的抑菌性,带有多层膜涂层的纸张对金黄色葡萄球菌和大肠杆菌的抑菌率仍能达90.6%以上。
实施例2
(1)接枝多巴胺的羧甲基纤维素是在pH 4的磷酸氢二钠-柠檬酸缓冲溶液100mL中加入2g的羧甲基纤维素,37℃下搅拌6h,然后再加入0.5g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.3g N-羟基琥珀酰亚胺,继续搅拌30min后加入pH 3、浓度200mg/mL的盐酸多巴胺溶液3mL,放入摇床,在37℃、120r/min、氮气条件下避光反应30h,将反应所得溶液用透析袋在去蒸馏水中透析2天,透析后的溶液冻干制得;
(2)将纸张放入2g/L的高碘酸钠溶液中,在45℃下避光处理2h,得到预处理的基底;将预处理的基底浸泡在pH=5.3、2g/L的壳聚糖(CS)溶液中20min,然后用去离子水漂洗4次,得到CS层改性的基底,将CS层改性的基底浸泡在pH=7、2g/L的接枝多巴胺的羧甲基纤维素(DA-g-CMC)溶液中20min,然后用去离子水漂洗4次,得到CS/DA-g-CMC双层膜改性的基底,重复上述改性过程10次,得到(CS/DA-g-CMC)10多层膜改性的基底,然后在50℃下干燥;将干燥多层膜改性的基底置于0.2g/L的高碘酸钠溶液中常温避光处理4h,然后置于40℃条件下干燥,即完成自修复、耐酸碱、抗菌多层膜涂层的制备;
检测本实施例带有多层膜涂层的纸张的自修复性能,方法同实施例1,本实施例制得的带有多层膜涂层的纸张在7.5min后能自修复划伤,多层膜涂层表面的平整度基本恢复到原状;
抑菌率检测方法同实施例1,对金黄色葡萄球菌的抑菌率为95.7%,对大肠杆菌的抑菌率为93.6%。同时,经过pH=3和pH=12的酸性和碱性溶液刻蚀处理9h以后,多层膜涂层对金黄色葡萄球菌和大肠杆菌的抑菌率仍能达到92.5%以上。
实施例3
(1)接枝多巴胺的羧甲基纤维素是在pH 5的磷酸氢二钠-柠檬酸缓冲溶液100mL中加入1.5g的羧甲基纤维素,37℃下搅拌5h,然后再加入0.4g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.3g N-羟基琥珀酰亚胺,继续搅拌40min后加入pH 4、浓度225mg/mL的盐酸多巴胺溶液2mL,放入摇床,在37℃、150r/min、氮气条件下避光反应35h,将反应所得溶液用透析袋在去蒸馏水中透析2天,透析后的溶液冻干制得;
(2)将棉织物放入3g/L的高碘酸溶液中,在50℃下避光处理1h,得到预处理的基底;将预处理的基底浸泡在壳聚糖pH=5.6、3g/L的(CS)溶液中30min,然后用去离子水漂洗5次,得到CS层改性的基底,将CS层改性的基底浸泡在pH=7.5、3g/L的接枝多巴胺的羧甲基纤维素(DA-g-CMC)溶液中20min,然后用去离子水漂洗5次,得到CS/DA-g-CMC双层膜改性的基底,重复上述改性过程15次,得到(CS/DA-g-CMC)15多层膜改性的基底,然后置于60℃条件下干燥;将干燥的多层膜改性的基底置于0.3g/L的高碘酸钠溶液中常温避光处理6h,然后置于45℃下干燥,完成自修复、耐酸碱、抗菌多层膜涂层的制备;
检测本实施例带有多层膜涂层的棉织物的自修复性能,方法同实施例1,本实施例制得的带有多层膜涂层的棉织物在9min后能自修复划伤,多层膜涂层表面的平整度基本恢复到原状;
抑菌率检测方法同实施例1,对金黄色葡萄球菌的抑菌率为100%,对大肠杆菌的抑菌率为100%;同时,经过pH=3和pH=12的酸性和碱性溶液刻蚀处理9h以后,多层膜涂层对金黄色葡萄球菌和大肠杆菌的抑菌率仍能达到95.1%以上。
Claims (6)
1.一种自修复、耐酸碱、抗菌多层膜涂层的制备方法,其特征在于,包括以下步骤:
(1)将基底放入高碘酸钠溶液中,在30℃~50℃下避光处理,得到预处理的基底;
(2)将预处理的基底浸泡在壳聚糖溶液中10~30min,然后用去离子水漂洗3~5次,得到壳聚糖层改性的基底,将壳聚糖层改性的基底浸泡在接枝多巴胺的羧甲基纤维素溶液中10~30min,然后用去离子水漂洗3~5次,得到双层膜改性的基底,重复上述改性过程5~15次,得到多层膜改性的基底,然后置于40℃~60℃下干燥;
(3)将干燥后的多层膜改性的基底置于高碘酸钠溶液中常温避光处理,干燥后完成多层膜涂层的制备。
2.根据权利要求1所述的自修复、耐酸碱、抗菌多层膜涂层的制备方法,其特征在于:步骤(1)中高碘酸钠的浓度为1~3g/L,避光处理时间为1~3h。
3.根据权利要求1所述的自修复、耐酸碱、抗菌多层膜涂层的制备方法,其特征在于:步骤(2)中接枝多巴胺的羧甲基纤维素是在pH3~5的磷酸氢二钠-柠檬酸缓冲溶液100mL中加入1~2g的羧甲基纤维素,37℃下搅拌4~6h,然后再加入0.4~0.6g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.2~0.4g N-羟基琥珀酰亚胺,继续搅拌20~40min后加入pH2~4、170~230mg/mL的盐酸多巴胺溶液2~4mL,放入摇床,在37℃、100~180r/min、氮气条件下避光反应24~36h,将反应所得溶液用透析袋在去蒸馏水中透析1~2天,透析后的溶液冻干制得。
4.根据权利要求1所述的自修复、耐酸碱、抗菌多层膜涂层的制备方法,其特征在于:步骤(2)中壳聚糖溶液浓度为1~3g/L,pH为5~5.6;接枝多巴胺的羧甲基纤维素溶液浓度为1~3g/L,pH为6.5~7.5。
5.根据权利要求1所述的自修复、耐酸碱、抗菌多层膜涂层的制备方法,其特征在于:步骤(3)中高碘酸钠溶液浓度为0.1-0.3g/L,处理时间为2~6h,干燥温度为35~45℃。
6.根据权利要求1所述的自修复、耐酸碱、抗菌多层膜涂层的制备方法,其特征在于:基底为纸张或棉织物。
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