CN113754794B - 抗菌性好耐高温可加工的羧甲基壳聚糖流体及其制备方法 - Google Patents
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Abstract
本发明涉及一种抗菌性好耐高温可加工的羧甲基壳聚糖流体及其制备方法，本发明通过羧甲基壳聚糖(N‑CMC)溶液与聚乙二醇(PEG)取代的十八叔胺(PEG‑STA)溶液共混，通过扩散‑静电自组装法将反应后的混合溶液透析之后烘干，制备得到自流动羧甲基壳聚糖材料。通过本发明制备方法得到的壳聚糖材料其粒径分布均一，具有耐高温，抗菌性，可加工性，在温度为26℃无溶剂的状态下具有类似液体的流动，热降解温度达到250℃以上。本发明制备过程简单且环保不使用任何有机溶剂，低成本，可大规模生产。
Description
技术领域
本发明属于高聚物材料的制备方法领域，特别涉及一种抗菌性好耐高温可加工的羧甲基壳聚糖流体及其制备方法。
背景技术
多糖聚合物具有良好的生物相容性，低毒性，生物可降解性和抗菌活性，这些独特的性能使其在生物医药领域，食物包装领域以及染料吸附等领域得到很好的发展。但是，多糖聚合物分子链呈现半刚性，分子量高，分子链之间具有强的氢键相互作用，分子链段之间很难运动，宏观显示固体状态。对于多糖聚合物，通常熔融温度高于分解温度，导致其不能用于高温熔融加工，严重限制其应用。目前文献所报道合成的多糖高分子衍生物均为固态，如表面接枝共聚，离子液体改性从而改善多糖高分子的加工性能，但存在着化学改性复杂，消耗溶剂，与其它聚合物共混时加工温度受限、容易二次团聚，发生相分离等问题。因此开发出一种无溶剂条件下具有加工性，热稳定性，溶解性能好的多糖聚合显得尤为必要。受无溶剂纳米类流体概念启发，突破常规制备方法，将无机纳米粒子类液化的工作原理应用于构筑液化多糖高分子类流体。基于这一独特思路，以降低多糖高分子本体粘度为目标，通过调节多糖分子链的电荷分布，利用扩散-静电组装策略，引入带有相反电荷的有机长链低聚物组装到多糖分子链上，利用脱水过程中有机长链低聚物阻止氢键重建和分子链聚集。而且有机长链低聚物作为润滑剂，实现无溶剂下多糖高分子呈现液体流动性，降低了多糖高分子加工粘度，提高了耐热性，解决了多糖高分子低浓度高粘度、难以高温加工的关键问题。同传统方法相比，新方法具有以下优势：1)工艺简单，能在不同溶剂中溶解分散；2)降低聚合物直接共混粘度或者获得高浓度低粘度静电纺丝原液；3)拓展多糖高分子材料功能，能实现抗菌性，流动性，耐高温性。因此，以液化多糖类流体黏度调控为主要手段，发展环保型高浓度下降黏度的制备工艺，对建立多糖高分子调控生物基复合材料高效成型加工新方法具有重要意义。
发明内容
本发明的所要解决的技术问题是提供一种抗菌性好耐高温可加工的羧甲基壳聚糖流体及其制备方法。
本发明解决上述技术问题的技术方案如下：
抗菌性好耐高温可加工的羧甲基壳聚糖流体制备方法，包括以下步骤：
步骤1、配制质量分数为10wt％-30wt％的羧甲基壳聚糖溶液，配置质量分数为10wt％-30wt％的PEG取代的十八叔胺溶液；
步骤2、将PEG取代的十八叔胺溶液逐滴加到羧甲基壳聚糖溶液中，并在超声条件下搅拌；
步骤3、将上一步反应完的溶液在60-70℃下浸泡20-30h，得到反应液；
步骤4、将上一步的反应液置于透析袋中透析；
步骤5、将透析后的剩余产物在真空干燥箱中50-70℃条件下干燥2-4天，得到抗菌性好耐高温可加工的羧甲基壳聚糖流体。
进一步的，所述PEG取代的十八叔胺的分子式为[C18H37N(CH2CH2O)nH(CH2CH2O)mH(m+n＝10)]。
进一步的，所述PEG取代的十八叔胺的用量为羧甲基壳聚糖摩尔质量的1-3倍。
进一步的，所述羧甲基壳聚糖分子量为10kDa-30kDa,脱乙酰度为90％，取代度≥80％。
进一步的，配制质量分数为10wt％-30wt％的羧甲基壳聚糖溶液的方法具体为：将去离子水的pH调至5-7，将羧甲基壳聚糖溶解在去离子水中配置成质量分数为10wt％-30wt％的溶液。
抗菌性好耐高温可加工的羧甲基壳聚糖流体，由上述的制备方法制备得到。
本发明的有益效果为：由于多糖聚合物分子内和分子间链之间有许多氢键，使其溶解性和加工性能差。本发明采用一步接枝的方法，直接将PEG取代的十八叔胺溶液逐滴加到羧甲基壳聚糖溶液中，通过扩散-静电组装将带相反电荷的有机长链低聚物组装到多糖分子链上，整个过程不使用有机溶剂，反应温度温和而且接枝的有机低聚物在调节流体的流变行为和改善其在各种溶剂中的分散性方面起着重要作用；并对采用不同m+n值的PEG取代的十八叔胺进行了试验发现，只有使用分子式为[C18H37N(CH2CH2O)nH(CH2CH2O)mH(m+n＝10)]的PEG取代的十八叔胺最终才能得到流体，采用m+n等于其他数值的PEG取代的十八叔胺得到的最终产品均为固体。
由于有机低聚物的存在使多糖聚合物流体具有较高的热稳定性和抗菌能力。这些优异的性能将使本发明的壳聚糖流体成为一些基材上的抗菌涂层以及能够作为3D打印、喷涂和刮涂相关的候选材料。
附图介绍
图1为N-CMCFs的制备流程图；
图2为N-CMC和N-CMCFs-1810的热重分析图；
图3为纯棉织物i和N-CMCFs-1810ii涂层棉织物经金黄色葡萄球菌处理后的扫描电镜图；
图4为纯棉织物和N-CMC涂层棉织物对金黄色葡萄球菌和大肠杆菌的抗菌活性；
图5为纯棉织物和N-CMCFs-1810涂层棉织物对金黄色葡萄球菌和大肠杆菌的抗菌活性。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
将羧甲基壳聚糖溶解在pH为5-7的去离子水中配置成质量分数为10wt％-30wt％的溶液；将质量分数为10wt％-30wt％的PEG取代的叔胺C18H37N(CH2CH2O)nH(CH2CH2O)mH(m+n＝10)(物质的量为N-CMC的1～3倍)溶液逐步滴到羧甲基壳聚糖溶液中并超声，搅拌；并将反应完的溶液在65℃下浸泡24h。后反应液置于透析袋中透析5～7天。透析结束后将透析后产物在真空干燥箱中60℃干燥3天，得到一种具有耐高温，抗菌性，可加工的羧甲基壳聚糖流体。
实施例2
将羧甲基壳聚糖溶解在pH为5-7的去离子水中配置成质量分数为10wt％-30wt％的溶液；将质量分数为10wt％-30wt％的PEG取代的叔胺C18H37N(CH2CH2O)nH(CH2CH2O)mH(m+n＝10)(物质的量为N-CMC的1～3倍)溶液逐步滴到羧甲基壳聚糖溶液中并超声，搅拌；并将反应完的溶液在65℃下浸泡24h。后反应液置于透析袋中透析5～7天。透析结束后将透析后产物在真空干燥箱中60℃干燥3天，得到一种具有耐高温，抗菌性，可加工的羧甲基壳聚糖流体
实施例3
将羧甲基壳聚糖溶解在pH为5-7的去离子水中配置成质量分数为10wt％-30wt％的溶液；将质量分数为10wt％-30wt％的PEG取代的叔胺C18H37N(CH2CH2O)nH(CH2CH2O)mH(m+n＝10)(物质的量为N-CMC的1～3倍)溶液逐步滴到羧甲基壳聚糖溶液中并超声，搅拌；并将反应完的溶液在65C下浸泡24h。后反应液置于透析袋中透析5～7天。透析结束后将透析后产物在真空干燥箱中60℃干燥3天，得到一种具有耐高温，抗菌性，可加工的羧甲基壳聚糖流体。
通过三种实施例表明，N-CMCFs-1810(m+n＝10)在26℃下表现出凝胶状行为，而原始N-CMC、N-CMCFs-1815(m+n＝15)和N-CMCFs-1820(m+n＝20)在196℃下仍然表现为固体状。出现一方面，随着接枝的PEG-STA分子量的增加，N-CMCFs的分子链长度(CH2CH2O)随之增加，其熔融温度也会依次增加，因此，N-CMCFs-1810的流动温度比N-CMCFs-1815和N-CMCFs-1820低。另一方面，随着温度的升高，热能的增加使分子链能够克服能垒。所接枝的PEG-STA的分子链越长，分子链缠绕的可能性就越大。因此，对于分子链相对较短的PEG-STA-1810来说，侧链运动所需要的能量降低了，同时，当其受到外部的作用力或加热产生变形时，PEG-CMC主链中的PEG-STA-1810链的长程滑移和电荷排斥力导致PEG-STA-1810链之间有序组装，从而导致相邻的N-CMC之间容易重排，使得整体N-CMC材料具有的流动性。
如图1所示，为本发明的N-CMCFs的制备流程图。将N-CMC溶液调节pH至5-7，然后聚乙二醇取代的叔胺(根据(CH2CH2O)m+n重复单元的数量(m+n＝10、15、20)命名为PEG-STA-1810,PEG-STA-1815和PEG-STA-1820)通过羧酸和叔胺基团之间的离子键连接到N-CMC的骨架上。之后透析除去残留的未反应的PEG-STA，最终获得不同的N-CMCFs(根据PEG-STA结构上的(CH2CH2O)m+n重复单元(m+n＝10、15、20)的数量不同表示为N-CMCFs-1810、N-CMCFs-1815和N-CMCFs-1820)。
如图2所示，N-CMC和N-CMCFs-1810耐热性能。其中N-CMCFs-1810在250℃以上仍保持热稳定性。
如图3所示，通过扫描电镜观察纯棉织物表面细菌的粘附性，并与N-CMCFs-1810涂层棉织物进行了比较，观察发现细菌很容易附着在纯棉织物表面，相反，在N-CMCFs-1810涂层棉织物表面细菌数量明显减少。这些结果表明N-CMCFs-1810涂层棉织物具有一定的抗细菌粘附能力。
如图4所示，采用琼脂培养皿扩散法，培养24小时后，将N-CMC和纯棉织物con对金黄色葡萄球菌(S.aureus)和大肠杆菌(E.coli)的抗菌活性进行了定性评价。对于纯棉织物con和N-CMC涂层棉织物，没有观察到抑制区(ZOI)，结果表明纯棉织物con和N-CMC抑制细菌生长的能力差。
如图5所示，N-CMCFs-1810涂层棉织物对金黄色葡萄球菌的ZOI值为20/10毫米，对大肠杆菌的值为16/10毫米(图5a和5b),并且N-CMCFs-1810使金黄色葡萄球菌和大肠杆菌的菌落数也显著减少，结果表明N-CMCFs-1810对金黄色葡萄球菌和大肠杆菌的抗菌活性分别高达91.6％和95.3％(图5c-5f)。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (5)
1.抗菌性好耐高温可加工的羧甲基壳聚糖流体制备方法，其特征在于，包括以下步骤：
步骤1、配制质量分数为10wt％-30wt％的羧甲基壳聚糖溶液，配置质量分数为10wt％-30wt％的PEG取代的十八叔胺溶液；
步骤2、将PEG取代的十八叔胺溶液逐滴加到羧甲基壳聚糖溶液中，并在超声条件下搅拌；所述PEG取代的十八叔胺的分子式为[C 18 H 37 N(CH 2 CH 2 O) n H(CH 2 CH 2 O)m H(m+n＝10)]；
步骤3、将上一步反应完的溶液在60-70℃下浸泡20-30h，得到反应液；
步骤4、将上一步的反应液置于透析袋中透析；
步骤5、将透析后的剩余产物在真空干燥箱中50-70℃条件下干燥2-4天，可得到具有抗菌性好耐高温可加工的羧甲基壳聚糖流体。
2.根据权利要求1所述的抗菌性好耐高温可加工的羧甲基壳聚糖流体制备方法，其特征在于，所述PEG取代的十八叔胺的用量为羧甲基壳聚糖摩尔质量的1-3倍。
3.根据权利要求1所述的抗菌性好耐高温可加工的羧甲基壳聚糖流体制备方法，其特征在于，所述羧甲基壳聚糖分子量为10kDa-30kDa,脱乙酰度为90％，取代度≥80％。
4.根据权利要求1所述的抗菌性好耐高温可加工的羧甲基壳聚糖流体制备方法，其特征在于，配制质量分数为10wt％-30wt％的羧甲基壳聚糖溶液的方法具体为：将去离子水的pH调至5-7，将羧甲基壳聚糖溶解在去离子水中配置成质量分数为10wt％-30wt％的溶液。
5.抗菌性好耐高温可加工的羧甲基壳聚糖流体，其特征在于，由权利要求1-4中任一项所述的制备方法制备得到。
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| Title |
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| Carboxymethyl cellulose-chitosan composite hydrogel: Modelling and experimental study of the effect of composition on microstructure and swelling response;Kindness A Uyanga等;《International journal of biological macromolecules》;20210630;第181卷;全文 * |
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