CN111676597B - 一种基于胶原蛋白/聚氨酯静电纺材料的摩擦纳米发电机 - Google Patents

一种基于胶原蛋白/聚氨酯静电纺材料的摩擦纳米发电机 Download PDF

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CN111676597B
CN111676597B CN202010413739.0A CN202010413739A CN111676597B CN 111676597 B CN111676597 B CN 111676597B CN 202010413739 A CN202010413739 A CN 202010413739A CN 111676597 B CN111676597 B CN 111676597B
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collagen
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俞昊
吕莎莎
黄涛
张欣
朱美芳
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Donghua University
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Abstract

本发明涉及一种基于胶原蛋白/聚氨酯静电纺材料的摩擦纳米发电机，包括胶原蛋白/聚氨酯静电纺材料。本发明通过胶原蛋白和聚氨酯静电纺得到聚合物基摩擦纳米发电机的输出电压得到显著提高。

Description

一种基于胶原蛋白/聚氨酯静电纺材料的摩擦纳米发电机
技术领域
本发明属于摩擦纳米发电机领域，特别涉及一种基于胶原蛋白/聚氨酯静电纺材料的摩擦纳米发电机。
背景技术
聚氨酯具有耐磨性，耐水解性，耐微生物能力等优异性能，利用静电纺丝技术制得的聚氨酯纳米纤维膜除具有耐磨性还具有一定的弹性，此外还具有良好的组织相容性和血液相容性；胶原蛋白以牛跟腱、鱼皮等为原料经提取其中的胶原蛋白而制成，可来源于水产生物和陆生动物，来源广泛，其是具有三条肽链形成的三螺旋的特殊蛋白，有许多特殊功能，在其等位点以上带负电，可与带正电的聚氨酯形成聚两性电解质，实现性能互补。
静电纺聚合物基纳米纤维质量轻，超强的柔顺性，使得其成为制备纳米发电机非常好的一门技术。
发明内容
本发明所要解决的技术问题是提供一种基于胶原蛋白/聚氨酯静电纺材料的摩擦纳米发电机，为摩擦纳米发电机提供了新的优选摩擦材料。
本发明的一种摩擦纳米发电机，胶原蛋白/聚氨酯静电纺膜作为摩擦材料，铝既作为摩擦材料又作电极材料。
所述摩擦纳米发电机包括第一摩擦材料、第二摩擦材料、电极材料，其中电极材料设于第二摩擦材料的下表面，第一摩擦材料和第二摩擦材料相对设置，其中在外力作用下第一摩擦材料与第二摩擦材料能够发生接触和分离。
所述第一摩擦材料为铝材料；第二摩擦材料为胶原蛋白/聚氨酯静电纺膜。
所述胶原蛋白/聚氨酯静电纺材料为：多层胶原蛋白/聚氨酯复合静电纺丝纳米纤维叠加膜、皮芯结构胶原蛋白/聚氨酯复合静电纺丝纤维膜、胶原蛋白/聚氨酯静电纺丝膜中的一种。
所述多层胶原蛋白/聚氨酯复合静电纺丝纳米纤维叠加膜由下列方法制备：将胶原蛋白纺丝液、聚氨酯纺丝液分别转移至不同注射器中，在推进泵上放置两只注射器，在纺丝电压为5～25KV，推进速率为0.1ml/h～5ml/h，接收距离为5～30cm，湿度为20％～70％，使用双针头喷射进行静电纺丝，所得到的胶原蛋白/聚氨酯复合静电纺丝膜记为A；当两只注射器的溶液均为胶原蛋白进行静电纺丝得到的膜记为B；将两只注射器的溶液均为聚氨酯进行静电纺丝得到的膜记为C；静电纺丝收集时，纺丝顺序可为ABC，ACB、BAC、BCA、CAB、CBA中的一种收集顺序，也可收集多种厚度的膜，例如ABCABCABC……等，得到多层胶原蛋白/聚氨酯复合静电纺丝纳米纤维叠加膜。
进一步，上述胶原蛋白/聚氨酯复合静电纺丝膜记为A具体为：将两种溶液分别置于不同的注射器中，使用同一台推进泵，但使用不同的针头，施加电压，接地铝箔在喷丝头针尖处接收纤维丝，得到无序纳米纤维膜A。
所述皮芯结构胶原蛋白/聚氨酯复合静电纺丝纤维膜由下列方法制备：将胶原蛋白纺丝液、聚氨酯纺丝液分别转移至不同注射器中，在推进泵上放置两只注射器，在纺丝电压为5～25KV，接收距离为5～30cm，湿度为20％～70％，使用同轴针头，聚氨酯溶液作为芯层，推进速率为1ml/h，胶原蛋白溶液作为皮层，推进速率为0.1～0.5ml/h，进行静电纺丝，即得皮芯结构胶原蛋白/聚氨酯复合静电纺丝纤维膜。
所述胶原蛋白纺丝液的溶剂均为冰醋酸或六氟异丙醇；聚氨酯纺丝液的溶剂均为N，N-二甲基甲酰胺DMF、六氟异丙醇，三氟乙醇TFE、三氯甲烷TCM中的一种或几种。
所述的聚氨酯材料为含有氨酯键的聚合物材料。
进一步，所述聚氨酯包括但不限于聚醚型聚氨酯、聚酯型聚氨酯或热塑性聚氨酯。
进一步，所述聚氨酯纺丝液的溶剂为N，N-二甲基甲酰胺DMF、六氟异丙醇，三氟乙醇TFE与三氯甲烷TCM的混合溶液中的一种。
所述胶原蛋白纺丝液的浓度为8％～15％(wt％)；聚氨酯纺丝液的浓度为18％～25％。
进一步，所述胶原蛋白纺丝液具体为胶原蛋白溶于溶剂中，微热搅拌至完全溶解，制备纺丝胶原蛋白纺丝溶液；聚氨酯纺丝液具体为：聚氨酯溶于溶剂中，80℃加热至完全溶解，制备聚氨酯纺丝溶液。
所述双针头静电纺丝和同轴针头静电纺丝所接收纳米纤维膜的纤维装置为滚筒或者平板。
所述针头型静电纺丝不限于双针头，多针头亦可适用。
本发明提供一种所述摩擦纳米发电机的应用。
有益效果
(1)本发明通过胶原蛋白和聚氨酯静电纺得到聚合物基摩擦纳米发电机与纯的聚氨酯基摩擦纳米发电机和纯的胶原蛋白基摩擦纳米发电机相比，输出电压得到显著提高。
(2)该方法工艺简单，易操作。
(3)本发明中使用双针头进行静电纺丝，其优点在于可将两种不同的聚合物使用不同的溶剂进行溶解而互不干涉，收集时可将双组份膜和单一组份膜进行叠加；还可使用同轴针头进行静电纺丝，所纺出的纤维为皮芯结构，两种不同的纺丝技术，除改变纤维的形貌外，将纤维膜制成摩擦纳米发电机可提高输出性能。
(4)胶原蛋白/聚氨酯复合纳米纤维膜，所得的复合薄膜有一定的弹性和生物相容性，并具有优质肤感。
附图说明
图1为双针头静电纺丝装置图；
图2为同轴静电纺丝装置图；
图3为摩擦纳米发电机示意图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
其中聚氨酯粒料型号为1195A10004 CNF3 310528，购于上海巴斯夫有限公司；胶原蛋白为牛跟腱胶原蛋白。
摩擦纳米发电机的结构如图3所示。
实施例1
称取胶原蛋白0.4g，将其溶解于5ml冰醋酸中，在磁力搅拌器上搅拌约30min,然后在70～80℃条件下加热约10分钟，使其完全溶解均匀，无气泡；然后称取聚氨酯粒料2g，将其溶解于18g N，N-二甲基甲酰胺(DMF)中，并在80℃下进行加热直至溶解均匀无气泡。然后将得到的两种纺丝溶液置于不同的注射器中进行双针头静电纺丝，纺丝电压为15kV，接收距离15cm，推进速率1ml/h，相对湿度为20％，得到胶原蛋白/聚氨酯复合静电纺纳米纤维；然后收集装置上的复合膜保留，将胶原蛋白溶液置于两只注射器中，相同条件下继续进行静电纺丝；纺丝完毕，收集装置上的静电纺丝膜仍然保留，将聚氨酯溶液置于两只注射器中继续在相同条件下进行静电纺丝，最后纺丝完毕，将得到的初生纤维膜在空气中暴露24小时，使溶剂充分挥发，得到三层胶原蛋白/聚氨酯复合静电纺纳米纤维叠加膜。将纯的聚氨酯静电纺纤维膜与铝电极组合制成摩擦纳米发电机#1，将纯的胶原蛋白纤维膜与铝电极组合制成摩擦纳米发电机#2，将三层胶原蛋白/聚氨酯纤维膜与铝电极组合，制成摩擦纳米发电机#3，测试它们的输出电压，#3的输出电压为最高，分别比#1的输出电压提高了约200V,比#2的输出电压提高了约100V。
实施例2
称取胶原蛋白0.4g，将其溶解于5ml冰醋酸中，在磁力搅拌器上搅拌约30min,然后在70～80℃条件下加热约10分钟，使其完全溶解均匀，无气泡；然后称取聚氨酯粒料2g，将其溶解于18gN，N-二甲基甲酰胺(DMF)中，并在80℃下进行加热直至溶解均匀无气泡。然后将得到的两种纺丝溶液置于不同的注射器中进行同轴静电纺丝，聚氨酯溶液为芯层，推进速率为1ml/h,胶原蛋白纺丝溶液为皮层，推进速率为0.5ml/h,纺丝电压为15kV，接收距离15cm，推进速率1ml/h，相对湿度为20％。将得到的初生纤维膜在空气中暴露24小时，使溶剂充分挥发，得到胶原蛋白/聚氨酯皮芯静电纺纳米纤维。将纯的聚氨酯静电纺纤维膜与铝电极组合制成摩擦纳米发电机#1，将纯的胶原蛋白纤维膜与铝电极组合制成摩擦纳米发电机#2，将胶原蛋白/聚氨酯皮芯静电纺纳米纤维铝电极组合，制成摩擦纳米发电机#3，测试它们的输出电压，#3的输出电压为最高，分别比#1的输出电压提高了约350V，比#2的输出电压提高了约200V。

Claims (5)

1.一种摩擦纳米发电机，其特征在于，所述摩擦纳米发电机包括第一摩擦材料、第二摩擦材料、电极材料，其中电极材料设于第二摩擦材料的下表面，第一摩擦材料和第二摩擦材料相对设置，其中在外力作用下第一摩擦材料与第二摩擦材料能够发生接触和分离；
其中所述第一摩擦材料为铝材料；第二摩擦材料为多层结构的胶原蛋白/聚氨酯复合静电纺丝纳米纤维叠加膜；
其中所述多层胶原蛋白/聚氨酯复合静电纺丝纳米纤维叠加膜由下列方法制备：将胶原蛋白纺丝液、聚氨酯纺丝液分别转移至注射器中，在推进泵上放置两只注射器，在纺丝电压为5~25KV，推进速率为0.1 ml/h~5 ml/h，接收距离为5~30cm，湿度为20%~70%，使用双针头喷射进行静电纺丝，所得到的胶原蛋白/聚氨酯复合静电纺丝膜记为A；当两只注射器的溶液均为胶原蛋白进行静电纺丝得到的膜记为B；将两只注射器的溶液均为聚氨酯进行静电纺丝得到的膜记为C；静电纺丝收集时，纺丝顺序可为ABC，ACB、BAC、BCA、CAB、CBA中的一种收集顺序，得到多层胶原蛋白/聚氨酯复合静电纺丝纳米纤维叠加膜。
2.根据权利要求1所述摩擦纳米发电机，其特征在于，所述胶原蛋白纺丝液的溶剂均为冰醋酸或六氟异丙醇；聚氨酯纺丝液的溶剂均为N，N-二甲基甲酰胺DMF、六氟异丙醇，三氟乙醇TFE、三氯甲烷TCM中的一种或几种；所述聚氨酯为聚醚型聚氨酯、聚酯型聚氨酯或热塑性聚氨酯。
3.根据权利要求1所述摩擦纳米发电机，其特征在于，所述胶原蛋白纺丝液的浓度为8%~15%（wt%）；聚氨酯纺丝液的浓度为18%~25%（wt%）。
4.根据权利要求1所述摩擦纳米发电机，其特征在于，所述静电纺丝接收装置为滚筒或者平板。
5.一种权利要求1所述摩擦纳米发电机的应用。
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