CN110406215A - 一种全降解抗菌无纺布 - Google Patents

一种全降解抗菌无纺布 Download PDF

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CN110406215A
CN110406215A CN201910689802.0A CN201910689802A CN110406215A CN 110406215 A CN110406215 A CN 110406215A CN 201910689802 A CN201910689802 A CN 201910689802A CN 110406215 A CN110406215 A CN 110406215A
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preparation
nonwoven cloth
dopamine
polycaprolactone
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CN110406215B (zh
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张正男
段书霞
周静
杨敬鹏
韩涵
崔彬彬
郝明
张鹏
王喜卫
赵燕
魏聪
韩颖
周永恒
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Tonggao textile chemical fiber (Shenzhen) Co.,Ltd.
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Henan Yadu Industrial Co Ltd
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Abstract

本发明公开了一种全降解抗菌无纺布，该无纺布为夹心层结构，包括上下两层抗细菌粘附纤维网A和中间一层杀菌抑菌纤维网B，通过将三层纤维网热轧制备得到。所述纤维网A由聚己内酯、改性聚乳酸、壳聚糖、聚乙二醇制备得到；纤维网B由聚丁二酸丁二醇酯、多巴胺、纳米银组成。本发明提供的全降解抗菌无纺布，通过将三层纤维网热轧制备得到，具有优异的力学性能，上下表层纤维网采用壳聚糖聚乙二醇修饰，具有良好的吸水保水性能和抗细菌粘附性，中间层聚丁二酸丁二醇酯静电纺丝纤维网表面通过多巴胺自组装后一步实现纳米银的还原和固定，杀菌速度快且持久抑菌，该无纺布降解周期短，分解率高，在医疗卫生领域有较好的应用前景。

Description

一种全降解抗菌无纺布
技术领域
本发明属于医疗卫生材料领域，具体涉及一种全降解抗菌无纺布。
背景技术
目前的一次性医疗卫生用品所用的无纺布均以聚烯烃树脂为基础原料，其在自然环境中的降解时间长达数百年，对环境造成严重污染。此外，现有医疗卫生用无纺布大多易粘附细菌，不具有抗菌性或抗菌能力不强，贮存或使用不当极易造成二次污染和交叉感染，对使用者的健康造成威胁。
中国发明专利申请(公开号CN104532401A)公开了一种可生物降解的超吸水无纺布。该无纺布由30-50wt％多功能超吸水海藻纤维、50-70wt％聚乳酸纤维复配而成，热粘合固网。所述无纺布具有良好的吸水性、保水性、抗菌性及生物降解性，主要用于一次性使用卫生用品。聚乳酸虽然具有较高的压缩模量和拉伸强度，但是质硬、韧性较差，亲水性也差，缺乏柔性和弹性，极易弯曲变形，而海藻纤维具有强力低、脆性大的缺点，因此二者复配的无纺布柔韧性较差，制约了其使用范围，此外由于所得无纺布的抗菌性完全取决于季铵化海藻酸钠的抗菌性，因此所得无纺布抗菌性不强，难以满足医疗卫生使用要求。
中国发明专利申请(公开号CN108532126A)公开了一种抗菌性生物可降解聚酯无纺布及制备方法。以丁二甲酸、1,4-丁二醇和具有氨基保护基的二元氨醇为原料，在相应的催化剂经缩合聚合制备改性聚丁二甲酸丁二醇酯；在一定的反应条件下经脱氨基保护基反应，得到具有功能侧基聚酯；在相应催化剂及一定的反应条件下，经化合反应，实现左氧氟沙星在聚酯上的化学固载，经熔喷法制备抗菌性生物可降解聚酯无纺布。所得无纺布不但具备PBS聚酯生物可降解、性能良好等特点，还具有高效的抗菌性能，但是存在降解周期长、吸湿性差的缺点，所用抗菌剂左氧氟沙星临床上不良反应率高，副作用多，甚至有严重副作用发生，长期使用还会导致耐药菌的产生。
因此研制出一种能完全降解、柔韧性和吸湿性好，同时具备抗细菌粘附和杀菌抑菌作用的无纺布是需要进一步研究的技术问题。
发明内容
本发明提供了一种全降解抗菌无纺布，可有效解决现有可降解医疗卫生材料存在的不能完全降解、易引发细菌粘附、抗菌抑菌性不足、强度或韧性差、吸湿性差的问题。具体技术方案如下：
一种全降解抗菌无纺布，包括上下两层抗细菌粘附纤维网A和中间一层杀菌抑菌纤维网B，通过将三层纤维网层叠热轧制备得到。所述纤维网A由聚己内酯、改性聚乳酸、壳聚糖、聚乙二醇制备得到；纤维网B由聚丁二酸丁二醇酯、多巴胺、纳米银组成。
进一步地，所述改性聚乳酸是由端羟基改性聚乳酸与乳酸共聚得到；所述端羟基改性聚乳酸是以乳酸和1,4-丁二醇为原料，以辛酸亚锡为催化剂，采用梯度升温法，在168℃、0.098MPa下直接熔融缩聚合成。
一种全降解抗菌无纺布的制备方法，包括以下步骤：
步骤一、纤维网A的制备：将聚丁二酸丁二醇酯溶解在氯仿里，制备成纺丝液，通过静电纺丝制成聚丁二酸丁二醇酯纤维网，抽真空去除残余溶剂；然后将聚丁二酸丁二醇酯纤维网浸入盐酸多巴胺Tris HCl缓冲溶液，磁力搅拌，反应结束后用超纯水冲洗，得到聚丁二酸丁二醇酯/多巴胺纤维网，再将其浸泡在硝酸银溶液中，磁力搅拌，反应结束后用超纯水冲洗，得聚丁二酸丁二醇酯/多巴胺-纳米银复合纳米纤维网，为纤维网A；
步骤二、聚己内酯/改性聚乳酸纤维网的制备：将聚己内酯与改性聚乳酸按质量配比1:1混合在开炼机中160℃下混炼10min，得到片状共混物，粉碎成颗粒；共混物颗粒由吸料机吸取，引导至加热装置中加热，得到熔融状态的纤维聚合物；将纤维聚合物通过挤压机加压喷丝，将喷丝经过拉伸器进行拉伸，形成纤维拉丝物，并引导至成网机上，得到聚己内酯/改性聚乳酸纤维网；
步骤三、纤维网B的制备：首先将壳聚糖与聚乙二醇按质量配比为1:1混合，溶于1％的稀醋酸溶液中，搅拌溶解，静置脱泡，得壳聚糖聚乙二醇溶液，在聚己内酯/改性聚乳酸纤维网浸入壳聚糖聚乙二醇溶液，浴比1:40，超声20min，冷水洗，烘干，得到壳聚糖聚乙二醇修饰的聚己内酯/改性聚乳酸纤维网，为纤维网B；
步骤四、无纺布的制备：每两层步骤三所得纤维网B和一层步骤一所得纤维网A为一组，将每组的三层纤维网其按照BAB的顺序依次层叠，并输送至热轧机中进行热轧，形成无纺布，通过将无纺布传送至卷扎机中收卷，并且质检、包装、入库。
进一步地，步骤一中所述盐酸多巴胺Tris HCl缓冲溶液中多巴胺浓度为4.0～6.0mmol/L，Tris HCl缓冲液的pH＝8.5。
进一步地，步骤一中所述硝酸银溶液的浓度为0.5～1.5mmol/L。
进一步地，步骤二中加热装置加热温度为140～180℃；挤压机喷丝加压范围为3.0～4.5MPa。
进一步地，步骤四中热轧机热轧温度为35～40℃，压力为2.5～4.5MPa。
本发明通过使用端羟基改性聚乳酸与聚己内酯共混制备纤维网，聚己内酯韧性极佳，热稳定性良好，与改性聚乳酸共混，能够发挥聚乳酸拉伸强度好、降解速率快、熔点高的优势，同时弥补其质脆、韧性和耐热性差的不足，以二者混炼后的共混颗粒为原料制备得到的纤维网，既能保证柔软性，又有足够的韧性，降解周期短。
本发明所用端羟基改性聚乳酸与聚乳酸相比，抗污性大大增强，而且与壳聚糖、聚乙二醇具有良好的相容性，能够促使壳聚糖及聚乙二醇自发在改性聚乳酸纤维表面组装，从而得到均匀的壳聚糖聚乙二醇包覆层，壳聚糖属于刚性分子比较脆，而聚乙烯醇具有很好的柔软性和水溶性，二者共同在纤维网表面组装，聚乙二醇的高亲水性能够抗细菌粘附，壳聚糖既具有一定的抗细菌粘附性能又能杀菌，进一步避免细菌在皮肤表面的粘附和增殖。
现有的纳米银抗菌纤维制备方法通常直接将纳米银颗粒直接掺入纺丝液进行纺丝，银容易聚集不能良好分散在纤维中，同时由于聚合物包裹，纳米银释放缓慢，杀菌效果持久但是杀菌强度不够，而利用还原法制备的纳米纤维只有表面为纳米银，纤维内包裹的银离子不能完全还原。本申请在聚丁二酸丁二醇酯静电纺丝纤维网表面通过多巴胺自组装后聚合包裹得到活性层，酚羟基可以结合银离子，游离氨基能将银离子还原成纳米银，一步实现纳米银的还原和固定。
本发明所用聚丁二酸丁二醇酯易被自然界的多种微生物或动植物体内的酶分解、代谢，最终分解为二氧化碳和水，是典型的可完全生物降解聚合物材料。所包覆的多巴胺具有高亲水性和良好的稳定性，能够提高纤维的生物相容性，由于仅在外层包覆，不会影响聚丁二酸丁二醇酯的力学性能。
本发明无纺布的制备方法中将抗细菌粘附纤维网A和杀菌抑菌纤维网B在成网机上层叠，中间一层为杀菌抑菌层，上下两层为抗细菌粘附层，并输送至热轧机中进行热轧，形成无纺布，纤维网间通过多巴胺的粘性在较低温度下即能结合牢固，柔韧性和吸水性良好，应用于医疗卫生领域能够抗细菌粘附、快速杀菌，并发挥长期的抗菌功效。
本发明提供的全降解抗菌无纺布，与现有技术相比具有以下有益效果：
1、本发明提供的全降解抗菌无纺布由纤维网热轧制成，质轻、柔软，具有多孔结构，透气性良好，纤维表面含有大量亲水基团，吸湿性能优异；
2、本发明提供的全降解抗菌无纺布，上下外表面修饰的壳聚糖聚乙二醇包覆层具有抗细菌粘附性和杀菌性，内层所含纳米银颗粒直径在20～50nm，而且均匀地分布在无纺布内部，能够发挥快速杀菌和长效抑菌的功效，因此在医疗卫生领域具有良好的应用前景；
3、本发明提供的全降解抗菌无纺布，通过将聚己内酯与改性聚乳酸共混后进行表面修饰得到纤维网A和聚丁二酸丁二醇酯纤维表面修饰纳米银得到纤维网B，各自成网后再热轧结合在一起，所得无纺布质轻，能够完全降解，且降解周期短，具有良好的韧性，能够满足医疗卫生使用的强度要求，同时具有良好亲水性和生物相容性，吸水性好，使用舒适度高。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例进行详细描述。
实施例1
一种全降解抗菌无纺布，包括上下两层抗细菌粘附纤维网A和中间一层杀菌抑菌纤维网B，通过将三层纤维网层叠热轧制备得到。所述纤维网A由聚己内酯、改性聚乳酸、壳聚糖、聚乙二醇制备得到；纤维网B由聚丁二酸丁二醇酯、多巴胺、纳米银组成。
进一步地，所述改性聚乳酸是由端羟基改性聚乳酸与乳酸共聚得到；所述端羟基改性聚乳酸是以乳酸和1,4-丁二醇为原料，以辛酸亚锡为催化剂，采用梯度升温法，在168℃、0.098MPa下直接熔融缩聚合成。
一种全降解抗菌无纺布的制备方法，包括以下步骤：
步骤一、纤维网A的制备：将聚丁二酸丁二醇酯溶解在氯仿里，制备成纺丝液，通过静电纺丝制成聚丁二酸丁二醇酯纤维网，抽真空去除残余溶剂；然后将聚丁二酸丁二醇酯纤维网浸入盐酸多巴胺Tris HCl缓冲溶液，磁力搅拌，反应结束后用超纯水冲洗，得到聚丁二酸丁二醇酯/多巴胺纤维网，再将其浸泡在硝酸银溶液中，磁力搅拌，反应结束后用超纯水冲洗，得聚丁二酸丁二醇酯/多巴胺-纳米银复合纳米纤维网，为纤维网A；
步骤二、聚己内酯/改性聚乳酸纤维网的制备：将聚己内酯与改性聚乳酸按质量配比1:1混合在开炼机中160℃下混炼10min，得到片状共混物，粉碎成颗粒；共混物颗粒由吸料机吸取，引导至加热装置中加热，得到熔融状态的纤维聚合物；将纤维聚合物通过挤压机加压喷丝，将喷丝经过拉伸器进行拉伸，形成纤维拉丝物，并引导至成网机上，得到聚己内酯/改性聚乳酸纤维网；
步骤三、纤维网B的制备：首先将壳聚糖与聚乙二醇按质量配比为1:1混合，溶于1％的稀醋酸溶液中，搅拌溶解，静置脱泡，得壳聚糖聚乙二醇溶液，在聚己内酯/改性聚乳酸纤维网浸入壳聚糖聚乙二醇溶液，浴比1:40，超声20min，冷水洗，烘干，得到壳聚糖聚乙二醇修饰的聚己内酯/改性聚乳酸纤维网，为纤维网B；
步骤四、无纺布的制备：每两层步骤三所得纤维网B和一层步骤一所得纤维网A为一组，将每组的三层纤维网其按照BAB的顺序依次层叠，并输送至热轧机中进行热轧，形成无纺布，通过将无纺布传送至卷扎机中收卷，并且质检、包装、入库。
进一步地，步骤一中所述盐酸多巴胺Tris HCl缓冲溶液中多巴胺浓度为4.0mmol/L，Tris HCl缓冲液的pH＝8.5。
进一步地，步骤一中所述硝酸银溶液的浓度为0.5mmol/L。
进一步地，步骤二中加热装置加热温度为140℃；挤压机喷丝加压范围为3.0MPa。
进一步地，步骤四中热轧机热轧温度为35℃，压力为2.5MPa。
实施例2
一种全降解抗菌无纺布，包括上下两层抗细菌粘附纤维网A和中间一层杀菌抑菌纤维网B，通过将三层纤维网层叠热轧制备得到。所述纤维网A由聚己内酯、改性聚乳酸、壳聚糖、聚乙二醇制备得到；纤维网B由聚丁二酸丁二醇酯、多巴胺、纳米银组成。
进一步地，所述改性聚乳酸是由端羟基改性聚乳酸与乳酸共聚得到；所述端羟基改性聚乳酸是以乳酸和1,4-丁二醇为原料，以辛酸亚锡为催化剂，采用梯度升温法，在168℃、0.098MPa下直接熔融缩聚合成。
一种全降解抗菌无纺布的制备方法，包括以下步骤：
步骤一、纤维网A的制备：将聚丁二酸丁二醇酯溶解在氯仿里，制备成纺丝液，通过静电纺丝制成聚丁二酸丁二醇酯纤维网，抽真空去除残余溶剂；然后将聚丁二酸丁二醇酯纤维网浸入盐酸多巴胺Tris HCl缓冲溶液，磁力搅拌，反应结束后用超纯水冲洗，得到聚丁二酸丁二醇酯/多巴胺纤维网，再将其浸泡在硝酸银溶液中，磁力搅拌，反应结束后用超纯水冲洗，得聚丁二酸丁二醇酯/多巴胺-纳米银复合纳米纤维网，为纤维网A；
步骤二、聚己内酯/改性聚乳酸纤维网的制备：将聚己内酯与改性聚乳酸按质量配比1:1混合在开炼机中160℃下混炼10min，得到片状共混物，粉碎成颗粒；共混物颗粒由吸料机吸取，引导至加热装置中加热，得到熔融状态的纤维聚合物；将纤维聚合物通过挤压机加压喷丝，将喷丝经过拉伸器进行拉伸，形成纤维拉丝物，并引导至成网机上，得到聚己内酯/改性聚乳酸纤维网；
步骤三、纤维网B的制备：首先将壳聚糖与聚乙二醇按质量配比为1:1混合，溶于1％的稀醋酸溶液中，搅拌溶解，静置脱泡，得壳聚糖聚乙二醇溶液，在聚己内酯/改性聚乳酸纤维网浸入壳聚糖聚乙二醇溶液，浴比1:40，超声20min，冷水洗，烘干，得到壳聚糖聚乙二醇修饰的聚己内酯/改性聚乳酸纤维网，为纤维网B；
步骤四、无纺布的制备：每两层步骤三所得纤维网B和一层步骤一所得纤维网A为一组，将每组的三层纤维网其按照BAB的顺序依次层叠，并输送至热轧机中进行热轧，形成无纺布，通过将无纺布传送至卷扎机中收卷，并且质检、包装、入库。
进一步地，步骤一中所述盐酸多巴胺Tris HCl缓冲溶液中多巴胺浓度为4.5mmol/L，Tris HCl缓冲液的pH＝8.5。
进一步地，步骤一中所述硝酸银溶液的浓度为1.0mmol/L。
进一步地，步骤二中加热装置加热温度为150℃；挤压机喷丝加压范围为3.5MPa。
进一步地，步骤四中热轧机热轧温度为36℃，压力为3.0MPa。
实施例3
一种全降解抗菌无纺布，包括上下两层抗细菌粘附纤维网A和中间一层杀菌抑菌纤维网B，通过将三层纤维网层叠热轧制备得到。所述纤维网A由聚己内酯、改性聚乳酸、壳聚糖、聚乙二醇制备得到；纤维网B由聚丁二酸丁二醇酯、多巴胺、纳米银组成。
进一步地，所述改性聚乳酸是由端羟基改性聚乳酸与乳酸共聚得到；所述端羟基改性聚乳酸是以乳酸和1,4-丁二醇为原料，以辛酸亚锡为催化剂，采用梯度升温法，在168℃、0.098MPa下直接熔融缩聚合成。
一种全降解抗菌无纺布的制备方法，包括以下步骤：
步骤一、纤维网A的制备：将聚丁二酸丁二醇酯溶解在氯仿里，制备成纺丝液，通过静电纺丝制成聚丁二酸丁二醇酯纤维网，抽真空去除残余溶剂；然后将聚丁二酸丁二醇酯纤维网浸入盐酸多巴胺Tris HCl缓冲溶液，磁力搅拌，反应结束后用超纯水冲洗，得到聚丁二酸丁二醇酯/多巴胺纤维网，再将其浸泡在硝酸银溶液中，磁力搅拌，反应结束后用超纯水冲洗，得聚丁二酸丁二醇酯/多巴胺-纳米银复合纳米纤维网，为纤维网A；
步骤二、聚己内酯/改性聚乳酸纤维网的制备：将聚己内酯与改性聚乳酸按质量配比1:1混合在开炼机中160℃下混炼10min，得到片状共混物，粉碎成颗粒；共混物颗粒由吸料机吸取，引导至加热装置中加热，得到熔融状态的纤维聚合物；将纤维聚合物通过挤压机加压喷丝，将喷丝经过拉伸器进行拉伸，形成纤维拉丝物，并引导至成网机上，得到聚己内酯/改性聚乳酸纤维网；
步骤三、纤维网B的制备：首先将壳聚糖与聚乙二醇按质量配比为1:1混合，溶于1％的稀醋酸溶液中，搅拌溶解，静置脱泡，得壳聚糖聚乙二醇溶液，在聚己内酯/改性聚乳酸纤维网浸入壳聚糖聚乙二醇溶液，浴比1:40，超声20min，冷水洗，烘干，得到壳聚糖聚乙二醇修饰的聚己内酯/改性聚乳酸纤维网，为纤维网B；
步骤四、无纺布的制备：每两层步骤三所得纤维网B和一层步骤一所得纤维网A为一组，将每组的三层纤维网其按照BAB的顺序依次层叠，并输送至热轧机中进行热轧，形成无纺布，通过将无纺布传送至卷扎机中收卷，并且质检、包装、入库。
进一步地，步骤一中所述盐酸多巴胺Tris HCl缓冲溶液中多巴胺浓度为5.0mmol/L，Tris HCl缓冲液的pH＝8.5。
进一步地，步骤一中所述硝酸银溶液的浓度为1.2mmol/L。
进一步地，步骤二中加热装置加热温度为160℃；挤压机喷丝加压范围为4.0MPa。
进一步地，步骤四中热轧机热轧温度为38℃，压力为3.5MPa。
实施例4
一种全降解抗菌无纺布，包括上下两层抗细菌粘附纤维网A和中间一层杀菌抑菌纤维网B，通过将三层纤维网层叠热轧制备得到。所述纤维网A由聚己内酯、改性聚乳酸、壳聚糖、聚乙二醇制备得到；纤维网B由聚丁二酸丁二醇酯、多巴胺、纳米银组成。
进一步地，所述改性聚乳酸是由端羟基改性聚乳酸与乳酸共聚得到；所述端羟基改性聚乳酸是以乳酸和1,4-丁二醇为原料，以辛酸亚锡为催化剂，采用梯度升温法，在168℃、0.098MPa下直接熔融缩聚合成。
一种全降解抗菌无纺布的制备方法，包括以下步骤：
步骤一、纤维网A的制备：将聚丁二酸丁二醇酯溶解在氯仿里，制备成纺丝液，通过静电纺丝制成聚丁二酸丁二醇酯纤维网，抽真空去除残余溶剂；然后将聚丁二酸丁二醇酯纤维网浸入盐酸多巴胺Tris HCl缓冲溶液，磁力搅拌，反应结束后用超纯水冲洗，得到聚丁二酸丁二醇酯/多巴胺纤维网，再将其浸泡在硝酸银溶液中，磁力搅拌，反应结束后用超纯水冲洗，得聚丁二酸丁二醇酯/多巴胺-纳米银复合纳米纤维网，为纤维网A；
步骤二、聚己内酯/改性聚乳酸纤维网的制备：将聚己内酯与改性聚乳酸按质量配比1:1混合在开炼机中160℃下混炼10min，得到片状共混物，粉碎成颗粒；共混物颗粒由吸料机吸取，引导至加热装置中加热，得到熔融状态的纤维聚合物；将纤维聚合物通过挤压机加压喷丝，将喷丝经过拉伸器进行拉伸，形成纤维拉丝物，并引导至成网机上，得到聚己内酯/改性聚乳酸纤维网；
步骤三、纤维网B的制备：首先将壳聚糖与聚乙二醇按质量配比为1:1混合，溶于1％的稀醋酸溶液中，搅拌溶解，静置脱泡，得壳聚糖聚乙二醇溶液，在聚己内酯/改性聚乳酸纤维网浸入壳聚糖聚乙二醇溶液，浴比1:40，超声20min，冷水洗，烘干，得到壳聚糖聚乙二醇修饰的聚己内酯/改性聚乳酸纤维网，为纤维网B；
步骤四、无纺布的制备：每两层步骤三所得纤维网B和一层步骤一所得纤维网A为一组，将每组的三层纤维网其按照BAB的顺序依次层叠，并输送至热轧机中进行热轧，形成无纺布，通过将无纺布传送至卷扎机中收卷，并且质检、包装、入库。
进一步地，步骤一中所述盐酸多巴胺Tris HCl缓冲溶液中多巴胺浓度为6.0mmol/L，Tris HCl缓冲液的pH＝8.5。
进一步地，步骤一中所述硝酸银溶液的浓度为1.5mmol/L。
进一步地，步骤二中加热装置加热温度为180℃；挤压机喷丝加压范围为4.5MPa。
进一步地，步骤四中热轧机热轧温度为40℃，压力为4.5MPa。
对比例1
除未对聚己内酯/改性聚乳酸纤维网进行表面修饰即不含步骤三外，其余同实施例3。
性能测试
力学性能测试
对实施例1～4制得的无纺布进行力学性能测试，测试结果见表1：
表1实施例1～4制得的无纺布力学性能测试结果
由表1中的数据可知，本发明制得的全降解抗菌无纺布质轻，透气性好，韧性足，具有优异的力学性能。
吸水率测试
对实施例1～4制得的全降解抗菌无纺布进行生理盐水测试，测试结果见表2：
表2实施例1～4制得的全降解抗菌无纺布吸水率测试结果
由表2中的数据可知，本发明制得的全降解抗菌无纺布具有良好的吸水保水性能。
抗细菌粘附性测试
采用3H-TDR标记的表皮葡萄球菌悬液进行粘附试验，以普通聚乳酸无纺布作为对照，对实施例3和对比例1制得的无纺布样品进行测试，结果见表3。
表3样品表皮葡萄球菌粘附情况
由表3中可以看出，与普通聚乳酸无纺布相比，本发明实施例3和对比例1制得的全降解抗菌无纺布具有明显的抗细菌粘附和杀菌效果，且实施例3的抗细菌粘附效果明显优于对比例1。
抗菌/抑菌性测试
选取金黄色葡萄球菌、白色念珠菌、大肠杆菌、铜绿假单胞菌对本发明实施例1～4提供的全降解抗菌无纺布的抗菌/抑菌性进行测试，结果见表4。
表4实施例1～4提供的全降解抗菌无纺布样本杀菌测试结果
根据表4所示的杀菌试验结果，本发明实施例1～4制得的全降解抗菌无纺布对金黄色葡萄球菌、白色念珠菌、大肠杆菌、铜绿假单胞菌均有杀灭作用，5分钟内即能杀灭80％以上，杀菌速度快，24h杀菌率大于99.9％，抑菌时间长，且杀菌抑菌效果与无纺布的厚度无关。
降解性测试
按照ISO 14855:1999《受控堆肥条件下材料最终需氧生物分解和崩解能力的测定--采用测定释放的二氧化碳的方法》测试，12周测试结果如表5所示。
表5实施例1～4提供的全降解抗菌无纺布样本12周降解测试结果
从表5中12周降解测试的试验结果可以看到，本发明提供的全降解抗菌无纺布CO2分解率大于99％，分解残留成分小于5％，具有很好的降解效果。
由以上测试结果可知，本发明提供的全降解抗菌无纺布具有良好的韧性，透气性好，吸水率和保水率高，不仅能抗细菌粘附、快速杀菌，还能持久抑菌，降解周期短且分解率高，在医疗卫生领域有良好的应用前景。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，本领域普通技术人员对本发明的技术方案所做的其他修改或者等同替换，只要不脱离本发明技术方案的精神和范围，均应涵盖在本发明的权利要求范围当中。

Claims (8)

1.一种全降解抗菌无纺布，其特征在于，包括上下两层抗细菌粘附纤维网A和中间一层杀菌抑菌纤维网B，通过将三层纤维网热轧制备得到；所述纤维网A由聚己内酯、改性聚乳酸、壳聚糖、聚乙二醇制备得到；纤维网B由聚丁二酸丁二醇酯、多巴胺、纳米银组成。
2.根据权利要求1所述的全降解抗菌无纺布，其特征在于，所述改性聚乳酸是由端羟基改性聚乳酸与乳酸共聚得到；所述端羟基改性聚乳酸是以乳酸和1,4-丁二醇为原料，以辛酸亚锡为催化剂，采用梯度升温法，在168 ℃、0.098 MPa下直接熔融缩聚合成。
3.一种根据权利要求1~2任一项所述全降解抗菌无纺布的制备方法，其特征在于，包括以下步骤：
步骤一、纤维网A的制备：将聚丁二酸丁二醇酯溶解在氯仿里，制备成纺丝液，通过静电纺丝制成聚丁二酸丁二醇酯纤维网，抽真空去除残余溶剂；然后将聚丁二酸丁二醇酯纤维网浸入盐酸多巴胺Tris HCl缓冲溶液，磁力搅拌，反应结束后用超纯水冲洗，得到聚丁二酸丁二醇酯/多巴胺纤维网，再将其浸泡在硝酸银溶液中，磁力搅拌，反应结束后用超纯水冲洗，得聚丁二酸丁二醇酯/多巴胺-纳米银复合纳米纤维网，为纤维网A；
步骤二、聚己内酯/改性聚乳酸纤维网的制备：将聚己内酯与改性聚乳酸按质量配比1:1混合在开炼机中160 ℃下混炼10 min，得到片状共混物，粉碎成颗粒；共混物颗粒由吸料机吸取，引导至加热装置中加热，得到熔融状态的纤维聚合物；将纤维聚合物通过挤压机加压喷丝，将喷丝经过拉伸器进行拉伸，形成纤维拉丝物，并引导至成网机上，得到聚己内酯/改性聚乳酸纤维网；
步骤三、纤维网B的制备：首先将壳聚糖与聚乙二醇按质量配比为1:1混合，溶于1%的稀醋酸溶液中，搅拌溶解，静置脱泡，得壳聚糖聚乙二醇溶液，在聚己内酯/改性聚乳酸纤维网浸入壳聚糖聚乙二醇溶液，浴比1:40，超声20 min，冷水洗，烘干，得到壳聚糖聚乙二醇修饰的聚己内酯/改性聚乳酸纤维网，为纤维网B；
步骤四、无纺布的制备：每两层步骤三所得纤维网B和一层步骤一所得纤维网A为一组，将每组的三层纤维网其按照BAB的顺序依次层叠，并输送至热轧机中进行热轧，形成无纺布，通过将无纺布传送至卷扎机中收卷，并且质检、包装、入库。
4.根据权利要求3所述的全降解抗菌无纺布的制备方法，其特征在于，步骤一中所述盐酸多巴胺Tris HCl缓冲溶液中多巴胺浓度为4.0~6.0 mmol/L，Tris HCl缓冲液的pH=8.5。
5.根据权利要求3所述的全降解抗菌无纺布的制备方法，其特征在于，步骤一中所述硝酸银溶液的浓度为0.5~1.5 mmol/L。
6.根据权利要求3所述的全降解抗菌无纺布的制备方法，其特征在于，步骤二中加热装置加热温度为140~180 ℃；挤压机喷丝加压范围为3.0~4.5 MPa。
7.根据权利要求3所述的全降解抗菌无纺布的制备方法，其特征在于，步骤四中热轧机热轧温度为35~40 ℃，压力为2.5~4.5 MPa。
8.权利要求1~7任一项所述的全降解抗菌无纺布在医疗卫生领域的应用。
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