CN111441170A - 医用抗菌敷料的制备方法 - Google Patents

医用抗菌敷料的制备方法 Download PDF

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CN111441170A
CN111441170A CN202010408583.7A CN202010408583A CN111441170A CN 111441170 A CN111441170 A CN 111441170A CN 202010408583 A CN202010408583 A CN 202010408583A CN 111441170 A CN111441170 A CN 111441170A
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medical
quaternary ammonium
medical antibacterial
ammonium salt
antibacterial dressing
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周鑫
于家傲
陈欣欣
石凯
高欣欣
洪雷
张修行
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First Hospital Jinlin University
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Abstract

本发明公开了一种医用抗菌敷料的制备方法，在乙腈溶液中加入0.01～2mol催化剂和15～30g医用羧甲基纤维素钠银敷料，接着加入0.1～2mol带有活性基团的季铵盐小分子，密封后于20～80℃接技反应1～96h；最后将医用羧甲基纤维素钠银敷料取出后用乙醇清洗，在真空下干燥至恒重，即得经季铵盐改性的医用抗菌敷料。解决了现有技术中深度创面或者是难愈性创面治疗存在的问题。

Description

医用抗菌敷料的制备方法
技术领域
本发明属于抗菌敷料技术领域，具体涉及一种以医用羧甲基纤维素钠银敷料为前体，具有高效抗菌和吸水性能的新型医用抗菌敷料的制备方法。
背景技术
作为人体最大的器官，皮肤不仅能够调节机体的代谢，同时在抵御外界伤害作用中起到重要的作用。正因如此，皮肤也极容易受到例如烧伤，撕裂伤以及各种原因引起的难愈性创面等，这些损伤经常引起创面感染，并且延迟创面愈合。众所周知，创面愈合分为几个阶段，包括炎症反应期，肉芽组织形成期以及痂皮形成期。在创面愈合期间里，经常受多种因素干扰，每个环节出现问题都会使创面愈合延迟。创面如何能够更好，更快的愈合，主要包括：1)提高创面抗菌性，2)保持创面微湿环境，3)减少创面坏死组织，4)保留局部生长因子以及其受体成分。综上所述，在创面微湿的环境下，减少创面痂皮愈合过程中活性组织的失活，增加其抗菌性是加速创面愈合的关键。
目前，羧甲基纤维素钠结合银离子敷料广泛应用在浅二度治疗中，在此类损伤中，创面残留活性物质较多，生长因子及其受体更能充分发挥作用，羧甲基纤维素钠能够吸收创面分泌物，破坏细菌成活及繁殖的有利环境，吸收渗出后，该物质会在创面表面形成凝胶状形态，同时银离子作为受到广泛认同的抑菌和杀菌物质，持续作用在创面，两种物质共同营造出微湿的抗菌环境，利于创面的修复。然而，对于损伤更为严重的创面深二度或者难愈性创面来说，活性组织残留更少，创面自身愈合能力更差，在结痂愈合过程中，活性组织会进一步失活，羧甲基纤维素钠保持微湿环境的特性便不再易于创面愈合，反而有利于创面细菌繁殖，此时银离子无法有效抑制细菌的繁殖。出于上述思考，增加原有羧甲基纤维素钠银离子敷料抗菌性能是解决此类创面的关键。
众所周知，季铵盐类抗菌剂因具有低毒性、价格低廉、广谱抗菌等优良特性倍受青睐，是目前应用最为广泛的有机抗菌剂。近年来，小分子季铵盐类抗菌剂的研究已经取得了长足的进展。例如，2003年，Shao等人(Journal of Fluorine Chemistry.124,89(2003))合成了一种含有全氟烃基季铵盐，并对此季铵盐的抗菌活性进行测定，结果表明此种季铵盐对大肠杆菌和金黄色葡萄球菌的抗菌效果十分优异，其最小抑菌浓度为7.8μg/mL。Pernak等人(European Journal of Medicinal Chemistry.38,1035(2003))合成了一种类胆碱季铵盐氯化物，表现出优异的抗菌性能和广泛的抗菌谱。Kourai等人(European Journal ofMedicinal Chemistry.41,437(2006))合成了一系列双季铵盐化合物，并用细菌、霉菌、酵母菌对此化合物的抗菌活性进行测定，结果表明此种季铵盐化合物的抗菌性能优于噻苯咪唑，对革兰氏阴性和革兰氏阳性细菌、酵母菌和一些霉菌都具有抗菌效果。相比小分子化合物，季铵盐高分子抗菌剂具有更高的电荷密度，抗菌能力更强。此外，还具有化学稳定性高、残余毒性低、容易加工等特点，成为该研究领域的热点。例如，浙江大学的Jia等人(Carbohydrate Research.333,1(2001))在不同分子量的壳聚糖上引入季铵盐，并研究其对大肠杆菌的抗菌活性，实验证实了改性接枝后的壳聚糖的抗菌活性要比未改性接枝的壳聚糖活性强。2007年，Lu等人(Reactive&Functional Polymers.67,355(2007))合成了四种新型的季铵盐单体，然后用这四种单体分别聚合得到相应的聚合物，并对此类单体和聚合物的抗菌活性进行测定。测试结果表明，随着季铵盐取代烷基链的增长，其抗菌活性增加，相应聚合物的抗菌活性大于其单体。Xu等人(Carbohydrate Research.346,2445(2011))在壳聚糖上引入季铵盐，研究其对大肠杆菌和金黄色葡萄球菌的抗菌活性，证实了改性接枝后的壳聚糖的抗菌活性随接枝度的增加而增强。Zhang等人(Reactive&FunctionalPolymers.88,39(2015))合成了一系列含有季铵盐的丙烯酰胺单体和聚合物，并对其抗细菌和病原菌活性进行测定，结果证明其均聚物和共聚物的抗菌效果远远好于单体。2015年，Liu等人(Progress in Organic Coatings.80,150(2015))合成了一系列含有氨基甲酸酯的季铵盐化合物，并将其通过交联作用加入到聚氨酯涂料中，并对此涂料的抗菌活性进行测定，结果表明此种季铵盐涂料的抗菌性能十分优异，对大肠杆菌和金黄色葡萄球菌都具有抗菌效果，而且随着季铵盐含量的增加，涂料的抗菌性能显著增强。2016年，Tang等人(Carbohydrate Polymers.139,191(2016))用季铵盐改性的壳聚糖合成了一种抗菌生物大分子染料，对大肠杆菌和金黄色葡萄球菌的抗菌效果十分优异，抑菌率均大于99％。
但是现有技术中仍然对于深度创面或者难愈性创面的治疗效果仍有待提高。
本发明将有机小分子季铵盐引入到羧甲基纤维素钠银离子结构中，不仅保持原有材料理化特性，而且增加改性后材料的抑菌杀菌性能。通过检测改性材料的理化特性/细胞毒性/以及抑菌杀菌能力，证实改性材料对于深度创面或者难愈性创面的治疗更为有效。
发明内容
为了达到上述目的，本发明提供一种医用抗菌敷料的制备方法，解决了现有技术中深度创面或者是难愈性创面治疗存在的问题。
为解决上述技术问题，本发明以医用羧甲基纤维素钠银敷料为前体，采用温和的反应体系引发接枝反应，在医用羧甲基纤维素钠银敷料上引入季铵盐抗菌链段，从而制备具有高效抗菌和吸水性能的新型医用敷料。
本发明所采用的技术方案是，一种医用抗菌敷料的制备方法，包括以下步骤：
在乙腈溶液中加入0.01～2mol催化剂和15～30g医用羧甲基纤维素钠银敷料，接着加入0.1～2mol带有活性基团的季铵盐小分子，密封后于20～80℃接技反应1～96h；最后将医用羧甲基纤维素钠银敷料取出后用乙醇清洗，在真空下干燥至恒重，即得经季铵盐改性的医用抗菌敷料。
相比于其他溶剂，乙腈作为反应介质，可充分溶解原料小分子季铵盐，且沸点适中，有利于反应向正方向进行，进而提高反应产物的接枝率与产物的抗菌能力。
医用羧甲基纤维素钠银敷料选择15g是因为使用量过少，浪费原料小分子季铵盐及催化剂，使用量过多，会导致接枝率降低，影响产物抗菌能力。
进一步的，催化剂为吡啶、氢氧化钠、碳酸钠、盐酸、硫酸中的一种。也可以酸性催化剂混合使用(吡啶、氢氧化钠、碳酸钠)与碱性催化剂混合使用(盐酸、硫酸)，混合使用是酸性催化剂与碱性催化剂质量比为1：1。
进一步的，所述活性基团为环氧基、酰氯基、酯基中的一种或任意混合。这些活性基团可以在催化剂作用下和羧甲基纤维素钠银敷料的羟基发生化学反应，使其接枝到羧甲基纤维素钠银敷料上。
进一步的，所述季铵盐小分子为酯基二甲基烷基氯化铵、酰氯基二甲基烷基氯化铵、环氧丙基二甲基烷基氯化铵中的一种或任意混合。氯化铵所含有的活性基团可以在催化剂作用下和羧甲基纤维素钠银敷料的羟基发生化学反应，使其接枝到羧甲基纤维素钠银敷料上。季铵盐小分子选择加入量为0.1～1mol的原因是：使用量过少，会导致接枝率降低，影响产物抗菌能力；使用量过多，浪费原料小分子季铵盐。
进一步的，所述乙腈溶液使用量是1500～3000mL。乙腈含量低于1500ml时，原料小分子季铵盐与催化剂溶解不完全，导致反应不完全，反应产物接枝率过低，乙腈含量高于3000ml时，虽然原料与催化剂完全溶解，但相对浓度过低，也会导致反应不完全，反应产物接枝率过低，进而影响产物抗菌效果。
进一步的，所述乙腈溶液中催化剂的加入量为0.01～1mol。催化剂含量过少，会降低反应速率，影响反应接枝率，催化剂含量高时和本文范围内催化剂含量催化效果相类似，但会造成不必要的浪费。
进一步的，所述乙腈溶液中季铵盐小分子的加入量为0.1～1mol。
进一步的，所述的接枝反应，反应时间为1～72h，反应温度为30～80℃。适宜的温度和反应时间有利于反应进行完全，影响产物的接枝率，进而影响产物的抗菌效果。温度过低或反应时间过短，反应不完全，产物接枝率低，抗菌效果差，乙腈沸点为82℃，故最高温度只能为80℃，反应时间过长，反应早已完成，不利于工作效率。
进一步的，所述烷基为C12H25、C14H29、C16H33或C18H37。烷基为C12H25、C14H29、C16H33或C18H37，烷基链过短或过长，抗菌效果差，将影响产物的抗菌效果，只有烷基链长度为12-18时，抗菌效果最好。
本发明的有益效果是：
本发明首次利用温和的催化体系在医用羧甲基纤维素钠银敷料上引入季铵盐抗菌链段。医用羧甲基纤维素钠银敷料本身所具有的羟基与反应试剂中的活性位点(酯基、酰氯基、环氧丙基)充分作用并引发接枝聚合，使接枝后的医用羧甲基纤维素钠银敷料具有更强的抗菌性能。
本发明采用温和的催化体系引发反应在医用羧甲基纤维素钠银敷料上引入了抗菌基团，所得材料具有抗菌功能的同时又能具有良好的吸水性能，相对于其他高聚物抗菌材料，本发明所制备的医用羧甲基纤维素钠银抗菌敷料具备抗菌能力强、广谱抗菌及吸水速率快等特点，同时，整个材料的制备方法具有反应条件温和，方法简便易行的特点，且制备周期短，因而易于放大制备。
本发明所制备的医用抗菌辅料，对于深度创面或者是难愈性创面，提供一个能够保持创面微湿环境的同时，减少创面疼痛，具有较强抗菌性能。更好的治疗此类型创面愈合。改性后材料通过季铵盐成分增加抗菌性，同时保持了原有的理化特点。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1a是改性后产物对金黄色葡萄球菌的抗菌效果图。
图1b是空白对照(金黄色葡萄球菌)图。
图1c是改性前产物对金黄色葡萄球菌的抗菌效果图。
图2a是空白对照(大肠杆菌)图。
图2b是改性前产物对大肠杆菌的抗菌效果图。
图2c是改性后产物对大肠杆菌的抗菌效果图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
在5000mL两口烧瓶中加入2000mL乙腈，0.1mol氢氧化钠和20g医用羧甲基纤维素钠银敷料，加入0.4mol环氧丙基二甲基十八烷基氯化铵，密封，于60℃反应24h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
实施例2
在5000mL两口烧瓶中加入2000mL乙腈，0.1mol氢氧化钠和0.5mol吡啶混合物，20g医用羧甲基纤维素钠银敷料，加入0.5mol酰氯基二甲基烷基氯化铵，密封，于30℃反应48h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
实施例3
在5000mL两口烧瓶中加入2000mL乙腈，0.1mol氢氧化钠、0.1mol吡啶、0.1mol碳酸钠、0.15mol盐酸、0.15mol硫酸的混合物，20g医用羧甲基纤维素钠银敷料，加入0.6mol酯基二甲基烷基氯化铵，密封，于80℃反应4h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
实施例4
在5000mL两口烧瓶中加入1500mL乙腈，0.01mol盐酸，15g医用羧甲基纤维素钠银敷料，加入0.1mol环氧丙基二甲基十二烷基氯化铵，密封，于80℃反应1h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
实施例5
在5000mL两口烧瓶中加入3000mL乙醇，0.5mol氢氧化钠和0.5mol碳酸钠混合物，20g医用羧甲基纤维素钠银敷料，加入1mol环氧丙基二甲基十八烷基氯化铵，密封，于30℃反应72h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
实施例6
在5000mL两口烧瓶中加入2000mL乙腈，2mol氢氧化钠，30g医用羧甲基纤维素钠银敷料，加入2mol环氧丙基二甲基十八烷基氯化铵，密封，于20℃反应96h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
实施例7
在5000mL两口烧瓶中加入2000mL乙腈，0.1mol氢氧化钠，20g医用羧甲基纤维素钠银敷料，加入0.2mol酰氯基二甲基十八烷基氯化铵，密封，于30℃反应48h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
实施例8
在5000mL两口烧瓶中加入2000mL乙腈，0.1mol氢氧化钠，20g医用羧甲基纤维素钠银敷料，加入0.2mol酯基二甲基十八烷基氯化铵，密封，于30℃反应48h，样品取出后用乙醇清洗，在真空烘箱中干燥至恒重，得到经季铵盐改性的新型医用抗菌敷料。
8组实施例均进行：
抗菌测试：准确称取一定量上述得到的新型医用抗菌敷料，剪成5mm×5mm大小，采用《纺织品抗菌性能的评价》第3部分记载的“振荡法(GB/T 20944.3)”检测其抗菌性能，检测用菌为大肠杆菌和金黄色葡萄球菌。该过程重复三次，测量的平均值作为抑菌率。
取0.75克得到的医用抗菌敷料，分别按照上面所述的方法测定其对大肠杆菌、金黄色葡萄球菌的抑菌率，8组实施例对大肠杆菌的抑菌率均为＞99％，对金黄色葡萄球菌的抑菌率均为＞99％。
对比例为改性前样品为市售的商品化产品。
图1a-1c及2a-2c说明改性前和改性后(实施例1)的样品对大肠杆菌和金黄色葡萄球菌都有抗菌效果，但改性后的产物抗菌能力远优于改性前的产品。
以上所述仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。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，均包含在本发明的保护范围内。

Claims (9)

1.一种医用抗菌敷料的制备方法，其特征在于，包括以下步骤：
在乙腈溶液中加入0.01～2mol催化剂和15～30g医用羧甲基纤维素钠银敷料，接着加入0.1～2mol带有活性基团的季铵盐小分子，密封后于20～80℃接技反应1～96h；最后将医用羧甲基纤维素钠银敷料取出后用乙醇清洗，在真空下干燥至恒重，即得经季铵盐改性的医用抗菌敷料。
2.根据权利要求1所述的医用抗菌敷料的制备方法，其特征在于，所述催化剂为吡啶、氢氧化钠、碳酸钠、盐酸、硫酸中的一种。
3.根据权利要求1所述的医用抗菌敷料的制备方法，其特征在于，所述活性基团为环氧基、酰氯基、酯基中的一种或任意混合。
4.根据权利要求1所述的医用抗菌敷料的制备方法，其特征在于，所述季铵盐小分子为酯基二甲基烷基氯化铵、酰氯基二甲基烷基氯化铵、环氧丙基二甲基烷基氯化铵中的一种或任意混合。
5.根据权利要求1-4任一项所述的医用抗菌敷料的制备方法，其特征在于，所述乙腈溶液使用量是1500～3000mL。
6.根据权利要求1-4任一项所述的医用抗菌敷料的制备方法，其特征在于，所述乙腈溶液中催化剂的加入量为0.01～1mol。
7.根据权利要求1-4任一项所述的医用抗菌敷料的制备方法，其特征在于，所述乙腈溶液中季铵盐小分子的加入量为0.1～1mol。
8.根据权利要求1-4任一项所述的医用抗菌敷料的制备方法，其特征在于，所述的接枝反应，反应时间为1～72h，反应温度为30～80℃。
9.根据权利要求4所述的医用抗菌敷料的制备方法，其特征在于，所述烷基为C12H25、C14H29、C16H33或C18H37。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116590821B (zh) * 2023-05-10 2024-02-06 潮州市苏菲亚时装有限公司 一种透气涤纶面料的合成方法及应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107722342A (zh) * 2017-10-13 2018-02-23 中国科学院长春应用化学研究所 一种多孔抗菌材料及其制备方法
CN110184814A (zh) * 2019-06-14 2019-08-30 吉林大学 一种医用抗菌敷料及其制备方法
CN110585473A (zh) * 2019-09-16 2019-12-20 董英 含有新型抗菌剂的泡沫敷料及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107722342A (zh) * 2017-10-13 2018-02-23 中国科学院长春应用化学研究所 一种多孔抗菌材料及其制备方法
CN110184814A (zh) * 2019-06-14 2019-08-30 吉林大学 一种医用抗菌敷料及其制备方法
CN110585473A (zh) * 2019-09-16 2019-12-20 董英 含有新型抗菌剂的泡沫敷料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
龚云表等: "《合成树脂与塑料手册》", 31 August 1993, 上海科学技术出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116590821B (zh) * 2023-05-10 2024-02-06 潮州市苏菲亚时装有限公司 一种透气涤纶面料的合成方法及应用

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