CN113350578A - 一种基于静电纺丝技术对真皮损伤修补的方法 - Google Patents
一种基于静电纺丝技术对真皮损伤修补的方法 Download PDFInfo
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Abstract
本发明提供一种基于静电纺丝技术对真皮损伤修补的方法，包括制备水性聚氨酯乳液、制备水性聚氨酯纳米纤维、真皮修补。本发明借助静电纺丝技术制备的水性聚氨酯纳米纤维纤度细、成纤较为光滑、规整度高，以此来对真皮的损伤部位进行修补，不仅可以提高真皮修补的完成率、均匀修复损伤表面、有更好的修补效果，更好地模拟纤维对真皮损伤部位的修补，使修复创面外观光滑平整，极大地提高了修复性能，而且借助水性聚氨酯相比较于其他以有机溶剂为载体的聚合物具有对环境污染小、毒害低、安全可靠、易于改性等优点。该发明适于为各种创伤类型的真皮缺损创面的修复提供更好地方法。
Description
技术领域
本发明涉及材料合成领域，特别涉及一种利用水性聚氨酯为原料通过静电纺丝对真皮损伤修补的方法。
背景技术
静电纺丝技术是将聚合物熔体或溶液置于高压静电环境中，从而在注射器和接地的接收装置间产生一个强大的电场力。当电场力超过一个临界值后，排斥的电场力将克服液滴的表面张力形成射流，而在静电纺丝过程中，液滴通常具有一定的静电压并处于一个电场中。因此，当射流从毛细管末端向接收装置运动的时候，都会出现加速现象，这也导致了射流在电场中的拉伸，最终在接收装置上形成纺丝膜。而通过静电纺丝法制成的膜具有直径小、均匀性好、比表面积高、规整度高等优点，可应用于高效过滤、组织工程、创伤敷料等领域。
水性聚氨酯连续相为水相，具有无污染、安全可靠、相容性好、易于改性的优点。但静电纺丝中常用的高分子聚合物多采用有机溶剂，虽然具有溶解性好、挥发性好等优点，但是有机溶液的毒性会对实验人员和环境造成危害。目前水性聚氨酯应用于静电纺丝技术的主要通过混合其他可纺聚合物来实现，其并非单一组分水性聚氨酯纳米纤维。本发明通过控制调整水性聚氨酯的分子量，实现其静电纺丝过程中泰勒锥和射流的形成，从而制备单一组分的水性聚氨酯纳米纤维。
真皮具有良好的耐热性和耐寒性、较高的机械强度、良好的透气性和透湿性，因此，我们日常生活中应用广泛。但当皮饰用品一旦出现划伤、掉皮、裂纹等受损情况，产品的外观和使用性能都会大大折扣。现在对于真皮损伤修复只有一些修补膏等固体产品，修补效果较差，且维持时间短。
发明内容
针对现有技术存在的不足，本发明提供一种使用水性聚氨酯乳液基于静电纺丝技术来对真皮损伤修补的一种方法，实现以下发明目的：
提高修补效果，维持时间长。
为解决上述技术问题，本发明采取以下技术方案:
步骤1、制备水性聚氨酯乳液
（1）恒温反应
首先将多元醇、异氰酸酯按照一定比例加入三口烧瓶中，然后往反应液中滴加催化剂，在80-90℃的油浴锅中反应0.8-1.2h；
所述催化剂为有机铋；
所述多元醇、异氰酸酯、有机铋的质量比为40-60：10-30：0.02-0.04；
（2）扩链反应
往反应体系中加入亲水性扩链剂，继续反应2.8-3.1h。
所述多元醇与亲水性扩链剂的质量比为40-60：1-10。
（3）制备预聚体
反应完成后，在上述反应的基础上，关闭加热装置，将三口烧瓶降温至45-60℃，加入丙酮进行降黏、加入中和剂三乙胺进行中和成盐，反应10-20min后得到预聚体。
所述多元醇与丙酮、中和剂的质量比为40-60：4-6:2-3。
（4）制得水性聚氨酯乳液
称取一定量的后扩链剂加入去离子水中，在分散机的作用下将预聚体反应液缓慢倒入加有后扩链剂的去离子水中分散，同时缓慢将分散机的转速调至1000-1800r/min,待分散稳定后将分散机转速降至800r/min，继续进行分散；分散时间大约25-30min，将分散好的水性聚氨酯乳液静置、消沫、负压脱除丙酮、装瓶、标号、保存。
所述多元醇与后扩链剂的质量比为40-60：3-5；
所述后扩链剂与去离子水的质量比为3-5：275-285。
步骤2、制备水性聚氨酯纳米纤维
将制得的水性聚氨酯乳液熟化三天后放置于10mL医用注射器中，搁置半小时消泡后制成纺丝原液。将制得的纺丝原液加入到带有平针头的注射器中，针头连接10-20KV的高压电源，针头距离接收器15-30cm，注射器由精密泵推进，液速为1ml/h，制备水性聚氨酯纳米纤维。
步骤3、真皮修补
接收器滚筒表面铺有一层铝箔，并将受损需修补真皮固定在滚筒铝箔纸上，滚筒可以通过自转均匀的接收纺出的丝，接收器要接地。按照上述步骤2的静电纺丝设置条件进行纺丝，使制备的水性聚氨酯纳米纤维均匀的覆盖在受损真皮的表面。
上述步骤1中的多元醇为聚丙二醇，分子量为2000，异氰酸酯为IPDI异佛尔酮二异氰酸酯、亲水性扩链剂为2，2-二羟甲基丙酸（DMPA）、后扩链剂为磺酸盐扩链剂（A50）。
上述步骤2中的注射器为10mL一次性注射器，针头标号为21G；
步骤3中接收滚筒直径17cm,高20cm，可实现轴向往复运动和自转。
与现有技术相比，本发明具有以下有益效果：
（1）相比较于大多数可纺聚合物，水性聚氨酯以水代替有机溶剂作为分散剂，无污染、安全性高、易于改性；
（2）用此方法纺出的丝纤度细、规整度和均一性高，能够更好地模拟纤维对真皮损伤部位的修补，使修复创面得到一定的掩盖，极大地提高了修复性能，修复效果好，可以实现永久性的修复。
附图说明
图1为本发明静电纺丝装置示意图；
图2为实施例2制备的水性聚氨酯纳米纤维的扫描电镜图；
纤维直径为400-600nm；
图3为受损真皮实物修补前后照片对比图；
其中3a为受损真皮实物修补前的图片；
3b为受损真皮实物修补后的图片；
图4为受损真皮修复前的扫描电镜图；
图5为受损真皮修复后的扫描电镜图。
具体实施方式
下面结合实例对本发明作进一步的说明：
实施例1 制备水性聚氨酯乳液
包括以下步骤:
(1)恒温反应
将分子量为2000的聚丙二醇在83℃下脱水2.5h，调节反应温度为88℃，以重量份计，往三口烧瓶中加入50份聚丙二醇、15份异佛尔酮二异氰酸酯，反应开始后往反应液中滴加0.03份有机铋催化剂；在热油浴中搅拌恒温反应1h。
(2)扩链反应
在上述反应基础上，往反应体系中加入5份亲水性扩链剂2,2-二羟甲基丙酸，继续反应3h。
(3)制备预聚体
关闭加热装置，将三口烧瓶降温至55℃，加入5份丙酮进行降黏、加入3份中和剂三乙胺进行中和成盐，中和12min后得到预聚体。
(4)制得水性聚氨酯乳液
称取4份后扩链剂A50加入280份去离子水中，在分散机的作用下将预聚体反应液全部缓慢倒入混有后扩链剂的去离子水中分散，同时缓慢将分散机的转速缓慢提到1800r/min，待分散稳定后将分散机的转速降至800r/min，继续进行分散。分散时间大约25min左右，将制成的水性聚氨酯乳液静置、消沫、负压脱除丙酮、装瓶、标号、保存。
实施例2 制备水性聚氨酯纳米纤维
将实施例1制得的水性聚氨酯乳液熟化三天吸取于10mL医用注射器中，静置消泡30min后得到纺丝原液。将纺丝原液加入到带有平针头的注射器中，安置于静电纺丝机上，针头连接12kV的高压电源，针头距离接收器20cm，注射器由精密泵推进，注射泵流速设为1mL/h，制备水性聚氨酯纳米纤维。设备示意图如图1，该方法所制备的纳米纤维扫描电镜图如图2。
实施例3 真皮修补
在接收器上铺一层铝箔纸，将受损需修补真皮固定于滚筒上，滚筒可以通过自转均匀地接收纺出的丝，接收器要接地。按照实施例2中静电纺丝设置条件进行纺丝，使制备的水性聚氨酯纳米纤维均匀的覆盖在受损真皮的表面。其修补前后真皮实物图如图3，通过扫描电镜观察发现修补效果良好，如图4和图5。
Claims (10)
1.一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：包括制备水性聚氨酯乳液、制备水性聚氨酯纳米纤维、真皮修补。
2.根据权利要求1所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述制备水性聚氨酯纳米纤维，将水性聚氨酯乳液熟化后放置于带有平针头的医用注射器中，静置消泡后制成纺丝原液，针头连接10-20KV的高压电源，针头距离接收器15-30cm，接收器接地，注射器由精密泵推进，液速为0.9-1.2ml/h，制备水性聚氨酯纳米纤维。
3.根据权利要求1所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述水性聚氨酯纳米纤维的直径为400-600nm。
4.根据权利要求2所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述真皮修补，接收器滚筒表面铺有一层铝箔，并将受损需修补真皮固定在铝箔纸上，滚筒可以通过自转均匀的接收纺出的水性聚氨酯纳米纤维，使制备的水性聚氨酯纳米纤维均匀的覆盖在受损真皮的表面。
5.根据权利要求4所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述注射器的针头标号为21G；所述滚筒的直径为16-18cm。
6.根据权利要求1所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述制备水性聚氨酯乳液，包括恒温反应、扩链反应、制备预聚体、制得水性聚氨酯乳液。
7.根据权利要求1所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述恒温反应，将多元醇、异氰酸酯加入反应容器中，滴加催化剂，在80-90℃下反应0.8-1.2h；所述催化剂为有机铋；
所述多元醇、异氰酸酯、有机铋的质量比为40-60：10-30：0.02-0.04。
8.根据权利要求7所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述扩链反应，加入亲水性扩链剂，继续反应2.8-3.1h，所述多元醇与亲水性扩链剂的质量比为40-60：1-10。
9.根据权利要求8所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述制备预聚体，降温至45-60℃，加入丙酮进行降黏、加入中和剂三乙胺进行中和成盐，反应10-20min后得到预聚体。
10.根据权利要求9所述的一种基于静电纺丝技术对真皮损伤修补的方法，其特征在于：所述制得水性聚氨酯乳液，将预聚体缓慢倒入加有后扩链剂的去离子水中分散，制得水性聚氨酯乳液；
所述多元醇与后扩链剂的质量比为40-60：3-5；
所述后扩链剂与去离子水的质量比为3-5：275-285；
所述多元醇为聚丙二醇，分子量为2000；所述异氰酸酯为异佛尔酮二异氰酸酯；所述亲水性扩链剂为2，2-二羟甲基丙酸；所述后扩链剂为磺酸盐扩链剂A50。
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