CN104372440B - 一种生物医用静电纺丝膜及其制备方法 - Google Patents

一种生物医用静电纺丝膜及其制备方法 Download PDF

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CN104372440B
CN104372440B CN201410623913.9A CN201410623913A CN104372440B CN 104372440 B CN104372440 B CN 104372440B CN 201410623913 A CN201410623913 A CN 201410623913A CN 104372440 B CN104372440 B CN 104372440B
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CN104372440A (zh
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赵晓
娄莉华
胡宇鹏
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Shanghai Kedai New Material Technology Co., Ltd.
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Shanghai Kedi Environmental Protection Technology Co Ltd
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Priority to CN201610336206.0A priority Critical patent/CN105970481A/zh
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Priority to CN201610336209.4A priority patent/CN105839292A/zh
Priority to CN201610336210.7A priority patent/CN105887335A/zh
Priority to CN201610336211.1A priority patent/CN106012102A/zh
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Priority to CN201610336208.XA priority patent/CN105970482A/zh
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Abstract

本发明提供了一种生物医用静电纺丝膜及其制备方法，所述静电纺丝膜原料包括聚乳酸-羟基乙酸共聚物、聚丁二酸丁二醇酯、聚氨酯、壳聚糖、对氯邻硝基苯胺、亚磷酸二乙酯、戊二醛、乙烯基三甲氧基硅烷、甲基丙烯酸丙酯、二丁基二月桂酸锡和N，N-二甲基甲酰胺。其制备方法为先将各组分加至混合搅拌机中，搅拌混合均匀，再将所得混合物料加入到反应釜中，在氮气氛围中加热搅拌反应，然后将所得纺丝液送入静电纺丝装置，制得电纺膜，最后将电纺膜恒温真空干燥后，经Co60辐射灭菌，即得。本发明的电纺膜在干态和湿态下均具有较高的力学强度，并且具有较好的柔韧性，完全可以满足手术操作过程及植入后对其力学性能方面的要求。

Description

一种生物医用静电纺丝膜及其制备方法
技术领域
本发明属于医用高分子材料技术领域，具体涉及一种生物医用静电纺丝膜及其制备方法。
背景技术
纤维通常是指任何植物的、动物的、再生的、合成的或矿物的短纤维和长丝。一般将长径比大于1000的连续的丝成为纤维。纤维一般具有柔软性，组成纤维的材料均有一定的弹性回复性。常规纤维可分为天然纤维和人造纤维。常规纤维材料的直径多为5～50μm的范围，在常用于纺织的纤维中，蚕丝是最细的，直径为4～5μm，最新开发的超细旦纤维直径可达0.4～4μm。
纳米纤维是指直径处在纳米范围(1～100nm)内的纤维，还可以将不同维数的纳米纤维复合用常规方法成型的纤维也看成是纳米纤维。当直径从微米(如10～100μm)缩小到亚微米或纳米时，聚合物纤维与相应的材料相比，表现出多种惊人的特性，如非常大的比表面积(其比表面积是微米纤维的103倍)、柔性以及超强的力学行为(如：硬度和抗张强度)，这些优异的特性使纳米纤维具有许多重要的用途。
生物医用领域，最常见的膜材料是外伤敷料、过滤阻隔材料和药物控释材料。皮肤是人体的天然屏障，对维持机体内环境的稳定和阻止微生物的入侵起着重要作用。失去皮肤的屏障作用，机体会产生一系列复杂的病理生理变化，其中包括水、电解质紊乱和酸碱失衡、感染、以及败血症等，甚至可能危及生命。裸露的创面需要用敷料覆盖加以保护，以提供有利于创面愈合、促进组织修复的环境，而创面愈合又是创伤后机体功能康复的重要前提，因此，创伤敷料成为生物医用材料领域的研究热点。
纳米生物医用膜会表现出明显不同于传统敷料的一些特性"将材料加工到纳米尺寸，就出现了诸如小尺寸效应、量子效应、表面效应等不同于常规材料的特异性能。例如：传统的银及其他一些氧化物材料具有一定的杀菌能力，而制备成纳米量级的颗粒后，杀菌活性将成倍提高。经临床应用表明，纳米银生物医用膜对金黄色葡萄球菌、大肠杆菌、绿脓杆菌、芽袍杆菌等均具有抑菌或杀菌作用，且对真菌也有很强的杀菌作用，而且应用中未见局部刺激和过敏症状，尚未出现中毒反应。静电纺丝纤维膜的孔径通常在500nm到1μm之间，足以阻挡细菌的侵入，比表面积为5～100m2/g，对于伤口渗液的吸收非常有效，同时可以控制水挥发，具有透氧性、提高液体流动能力、控制微生物的滋生的特点。
发明内容
本发明的目的是克服现有技术的不足而提供一种生物医用静电纺丝膜及其制备方法，该电纺膜在干态和湿态下均具有较高的力学强度，并且具有较好的柔韧性，完全可以满足手术操作过程及植入后对其力学性能方面的要求。
一种生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物2～9份，聚丁二酸丁二醇酯1～7份，聚氨酯2～10份，壳聚糖3～12份，对氯邻硝基苯胺1～9份，亚磷酸二乙酯3～9份，戊二醛4～10份，乙烯基三甲氧基硅烷2～7份，甲基丙烯酸丙酯1～6份，二丁基二月桂酸锡3～10份，N，N-二甲基甲酰胺2～9份。
作为上述发明的进一步改进，所述生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物3～7份，聚丁二酸丁二醇酯2～6份，聚氨酯4～9份，壳聚糖5～10份，对氯邻硝基苯胺4～8份，亚磷酸二乙酯5～8份，戊二醛6～9份，乙烯基三甲氧基硅烷3～6份，甲基丙烯酸丙酯2～5份，二丁基二月桂酸锡5～9份，N，N-二甲基甲酰胺4～7份。
作为上述发明的进一步改进，所述生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物5份，聚丁二酸丁二醇酯3份，聚氨酯7份，壳聚糖8份，对氯邻硝基苯胺6份，亚磷酸二乙酯6份，戊二醛7份，乙烯基三甲氧基硅烷5份，甲基丙烯酸丙酯3份，二丁基二月桂酸锡8份，N，N-二甲基甲酰胺5份。
上述生物医用静电纺丝膜的制备方法，包括以下步骤：
步骤1，将各组分加至混合搅拌机中，搅拌混合均匀，得到混合物料；
步骤2，将步骤1所得混合物料加入到反应釜中，在氮气氛围中加热到65～80℃，搅拌反应30～40min，得到纺丝液；
步骤3，将步骤2所得纺丝液送入静电纺丝装置，制得厚度为100μm～2mm的电纺膜；
步骤4，将步骤3所得电纺膜在20～45℃条件下恒温真空干燥后，经Co60辐射灭菌，即得。
作为上述发明的进一步改进，步骤1中搅拌混合均匀的搅拌速度为300～400rpm，搅拌时间为20～40min。
作为上述发明的进一步改进，步骤3中静电纺丝条件为：初纺电压为10～15KV，续纺电压按每消耗1毫升电纺液用量相应增加0.5～2.0KV进行调节，接收距离为5～50cm，出液速率为5～25mL/h，接收器为直径10～300cm的表面附有锡纸的旋转金属圆盘，圆盘转速为10～1000rpm。
作为上述发明的进一步改进，步骤4中真空干燥时间为24～72h。
本发明的生物医用静电纺丝膜，一方面，在干态和湿态下均具有较高的力学强度，并且具有较好的柔韧性，完全可以满足手术操作过程及植入后对其力学性能方面的要求；另一方面，所采用的静电纺丝工艺制备得到的纤维直径在纳米至亚微米级且表面光滑，大小均一的电纺纤维，所得到的电纺膜表面光洁平整且厚度均一。
具体实施方式
实施例1
一种生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物2份，聚丁二酸丁二醇酯1份，聚氨酯2份，壳聚糖3份，对氯邻硝基苯胺1份，亚磷酸二乙酯3份，戊二醛4份，乙烯基三甲氧基硅烷2份，甲基丙烯酸丙酯1份，二丁基二月桂酸锡3份，N，N-二甲基甲酰胺2份。
上述生物医用静电纺丝膜的制备方法，包括以下步骤：
步骤1，将各组分加至混合搅拌机中，搅拌混合均匀，搅拌速度为300rpm，搅拌时间为40min，得到混合物料；
步骤2，将步骤1所得混合物料加入到反应釜中，在氮气氛围中加热到65℃，搅拌反应40min，得到纺丝液；
步骤3，将步骤2所得纺丝液送入静电纺丝装置，静电纺丝条件为：初纺电压为10KV，续纺电压按每消耗1毫升电纺液用量相应增加0.5KV进行调节，接收距离为5cm，出液速率为5mL/h，接收器为直径10cm的表面附有锡纸的旋转金属圆盘，圆盘转速为10rpm，制得厚度为100μm的电纺膜；
步骤4，将步骤3所得电纺膜在20℃条件下恒温真空干燥72h后，经Co60辐射灭菌，即得。
实施例2
一种生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物3份，聚丁二酸丁二醇酯2份，聚氨酯4份，壳聚糖5份，对氯邻硝基苯胺4份，亚磷酸二乙酯5份，戊二醛6份，乙烯基三甲氧基硅烷3份，甲基丙烯酸丙酯2份，二丁基二月桂酸锡5份，N，N-二甲基甲酰胺4份。
上述生物医用静电纺丝膜的制备方法，包括以下步骤：
步骤1，将各组分加至混合搅拌机中，搅拌混合均匀，搅拌速度为350rpm，搅拌时间为30min，得到混合物料；
步骤2，将步骤1所得混合物料加入到反应釜中，在氮气氛围中加热到70℃，搅拌反应35min，得到纺丝液；
步骤3，将步骤2所得纺丝液送入静电纺丝装置，静电纺丝条件为：初纺电压为12KV，续纺电压按每消耗1毫升电纺液用量相应增加1.2KV进行调节，接收距离为30cm，出液速率为15mL/h，接收器为直径80cm的表面附有锡纸的旋转金属圆盘，圆盘转速为200rpm，制得厚度为1.2mm的电纺膜；
步骤4，将步骤3所得电纺膜在45℃条件下恒温真空干燥24h后，经Co60辐射灭菌，即得。
实施例3
一种生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物5份，聚丁二酸丁二醇酯3份，聚氨酯7份，壳聚糖8份，对氯邻硝基苯胺6份，亚磷酸二乙酯6份，戊二醛7份，乙烯基三甲氧基硅烷5份，甲基丙烯酸丙酯3份，二丁基二月桂酸锡8份，N，N-二甲基甲酰胺5份。
上述生物医用静电纺丝膜的制备方法，包括以下步骤：
步骤1，将各组分加至混合搅拌机中，搅拌混合均匀，搅拌速度为400rpm，搅拌时间为20min，得到混合物料；
步骤2，将步骤1所得混合物料加入到反应釜中，在氮气氛围中加热到80℃，搅拌反应30min，得到纺丝液；
步骤3，将步骤2所得纺丝液送入静电纺丝装置，静电纺丝条件为：初纺电压为15KV，续纺电压按每消耗1毫升电纺液用量相应增加2KV进行调节，接收距离为50cm，出液速率为25mL/h，接收器为直径300cm的表面附有锡纸的旋转金属圆盘，圆盘转速为1000rpm，制得厚度为2mm的电纺膜；
步骤4，将步骤3所得电纺膜在35℃条件下恒温真空干燥48h后，经Co60辐射灭菌，即得。
实施例4
一种生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物7份，聚丁二酸丁二醇酯6份，聚氨酯9份，壳聚糖10份，对氯邻硝基苯胺8份，亚磷酸二乙酯8份，戊二醛9份，乙烯基三甲氧基硅烷6份，甲基丙烯酸丙酯5份，二丁基二月桂酸锡9份，N，N-二甲基甲酰胺7份。
上述生物医用静电纺丝膜的制备方法，包括以下步骤：
步骤1，将各组分加至混合搅拌机中，搅拌混合均匀，搅拌速度为300rpm，搅拌时间为40min，得到混合物料；
步骤2，将步骤1所得混合物料加入到反应釜中，在氮气氛围中加热到65℃，搅拌反应40min，得到纺丝液；
步骤3，将步骤2所得纺丝液送入静电纺丝装置，静电纺丝条件为：初纺电压为10KV，续纺电压按每消耗1毫升电纺液用量相应增加1.8KV进行调节，接收距离为35cm，出液速率为20mL/h，接收器为直径240cm的表面附有锡纸的旋转金属圆盘，圆盘转速为600rpm，制得厚度为1.5mm的电纺膜；
步骤4，将步骤3所得电纺膜在35℃条件下恒温真空干燥36h后，经Co60辐射灭菌，即得。
实施例5
一种生物医用静电纺丝膜，原料以重量份计包括：聚乳酸-羟基乙酸共聚物9份，聚丁二酸丁二醇酯7份，聚氨酯10份，壳聚糖12份，对氯邻硝基苯胺9份，亚磷酸二乙酯9份，戊二醛10份，乙烯基三甲氧基硅烷7份，甲基丙烯酸丙酯6份，二丁基二月桂酸锡10份，N，N-二甲基甲酰胺9份。
上述生物医用静电纺丝膜的制备方法，包括以下步骤：
步骤1，将各组分加至混合搅拌机中，搅拌混合均匀，搅拌速度为300rpm，搅拌时间为40min，得到混合物料；
步骤2，将步骤1所得混合物料加入到反应釜中，在氮气氛围中加热到65℃，搅拌反应40min，得到纺丝液；
步骤3，将步骤2所得纺丝液送入静电纺丝装置，静电纺丝条件为：初纺电压为10KV，续纺电压按每消耗1毫升电纺液用量相应增加1.0KV进行调节，接收距离为40cm，出液速率为10mL/h，接收器为直径100cm的表面附有锡纸的旋转金属圆盘，圆盘转速为800rpm，制得厚度为500μm的电纺膜；
步骤4，将步骤3所得电纺膜在20℃条件下恒温真空干燥72h后，经Co60辐射灭菌，即得。
试验例1
参照GB/T16886.5-2003，采用标准Hela细胞系对实施例1至5所得静电纺丝膜的浸提液进行体外细胞毒性检测实验。首先通过接种浓度梯度板的预实验确定吸光度值与细胞增殖线性关系最好的接种浓度，结果表明当接种浓度为每孔3000～4000Hela细胞时，细胞增殖良好并且接种3天后细胞未见明显接触抑制。
分别制备100％、50％、10％和5％四种不同浓度的浸提液，以检测细胞毒性是否与电纺膜溶出物有关。同时设置了阴性对照组(细胞维持液+细胞组)，阳性对照组(0.64％苯酚溶液+细胞组)和空白对照组(调零组)，每组均有6个复孔作为平行对照。将各组孔板置于恒温37℃及5％CO2浓度的孵箱内培养2天后取出，加入MTT处理后于倒置显微镜下观察，结果显示不同浓度浸提液组的孔内细胞形态未呈现较明显的差异。通过测得的OD值计算各组细胞相对增殖率(RGR)。结果显示，本实验阳性对照组RGR值为0，具有明显的细胞毒性，即0.64％苯酚溶液细胞毒性为5级；实施例1至5所得电纺膜RGR值介于96～114％之间，细胞毒性为0级或1级，即无细胞毒性。
试验例2
将实施例1所得电纺膜用消毒后的手术剪刀裁成直径为7mm的试样，用75％的乙醇浸泡1h后再用pH7.4的PBS缓冲液冲洗三次。取体重180～200克的健康SD大鼠18只，用3％戊巴比妥钠按50mg/Kg浓度进行腹腔麻醉，背部剃毛后用碘伏消毒，然后切开皮肤至深筋膜，向两侧分离皮下组织，植入电纺膜，用3-0缝合线将其固定于肌层，然后将皮肤缝合，用无菌敷料覆盖包扎并定期换药。实验鼠术后单笼饲养，并于术后1周、4周及13周任选3只SD大鼠切开皮肤取出植入试样。
将在不同时间点从大鼠体内取出的试样先置于4％的中性甲醛溶液中固定24h，再用30％的蔗糖溶液浸泡12h脱水，然后用包埋剂包埋并放入液氮中速冻后在-80℃条件下冷冻10h，之后采用冷冻切片机制备厚度为7μm的冷冻切片，最后采用苏木素-伊红染色法对切片进行染色并在光学显微镜下观察。结果显示，实施例1所得电纺膜植入SD大鼠体内1周、4周及13周后均起到了较好的屏蔽纤维组织长入的作用，并且整个体内试验的过程中SD大鼠没有出现明显的炎症反应。

Claims (7)

1.一种生物医用静电纺丝膜，其特征在于：原料以重量份计包括：聚乳酸-羟基乙酸共聚物2～9份，聚丁二酸丁二醇酯1～7份，聚氨酯2～10份，壳聚糖3～12份，对氯邻硝基苯胺1～9份，亚磷酸二乙酯3～9份，戊二醛4～10份，乙烯基三甲氧基硅烷2～7份，甲基丙烯酸丙酯1～6份，二丁基二月桂酸锡3～10份，N，N-二甲基甲酰胺2～9份。
2.根据权利要求1所述的生物医用静电纺丝膜，其特征在于：原料以重量份计包括：聚乳酸-羟基乙酸共聚物3～7份，聚丁二酸丁二醇酯2～6份，聚氨酯4～9份，壳聚糖5～10份，对氯邻硝基苯胺4～8份，亚磷酸二乙酯5～8份，戊二醛6～9份，乙烯基三甲氧基硅烷3～6份，甲基丙烯酸丙酯2～5份，二丁基二月桂酸锡5～9份，N，N-二甲基甲酰胺4～7份。
3.根据权利要求1所述的生物医用静电纺丝膜，其特征在于：原料以重量份计包括：聚乳酸-羟基乙酸共聚物5份，聚丁二酸丁二醇酯3份，聚氨酯7份，壳聚糖8份，对氯邻硝基苯胺6份，亚磷酸二乙酯6份，戊二醛7份，乙烯基三甲氧基硅烷5份，甲基丙烯酸丙酯3份，二丁基二月桂酸锡8份，N，N-二甲基甲酰胺5份。
4.权利要求1至3任一项所述的生物医用静电纺丝膜的制备方法，其特征在于：包括以下步骤：
步骤1，将各组分加至混合搅拌机中，搅拌混合均匀，得到混合物料；
步骤2，将步骤1所得混合物料加入到反应釜中，在氮气氛围中加热到65～80℃，搅拌反应30～40min，得到纺丝液；
步骤3，将步骤2所得纺丝液送入静电纺丝装置，制得厚度为100μm～2mm的电纺膜；
步骤4，将步骤3所得电纺膜在20～45℃条件下恒温真空干燥后，经Co60辐射灭菌，即得。
5.根据权利要求4所述的生物医用静电纺丝膜的制备方法，其特征在于：步骤1中搅拌混合均匀的搅拌速度为300～400rpm，搅拌时间为20～40min。
6.根据权利要求4所述的生物医用静电纺丝膜的制备方法，其特征在于：步骤3中静电纺丝条件为：初纺电压为8～13kV，续纺电压按每消耗1毫升电纺液用量相应增加0.4～1.5kV进行调节，接收距离为10～30cm，出液速率为10～20mL/h，接收器为直径100～250cm的表面附有锡纸的旋转金属圆盘，圆盘转速为200～600rpm。
7.根据权利要求4所述的生物医用静电纺丝膜的制备方法，其特征在于：步骤4中真空干燥时间为24～72h。
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