CN109575321B - 一种电响应型互穿聚合物水凝胶及其制备方法 - Google Patents

一种电响应型互穿聚合物水凝胶及其制备方法 Download PDF

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CN109575321B
CN109575321B CN201811507442.XA CN201811507442A CN109575321B CN 109575321 B CN109575321 B CN 109575321B CN 201811507442 A CN201811507442 A CN 201811507442A CN 109575321 B CN109575321 B CN 109575321B
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应宗荣
李博
王奇
谢杰
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种电响应型互穿聚合物水凝胶及其制备方法。本发明电响应型互穿聚合物水凝胶为水溶性聚氨酯交联网络与丙烯酸‑co‑2‑丙烯酰胺基‑2‑甲基丙磺酸‑co‑N，N′‑亚甲基双(丙烯酰胺)交联网络构成的互穿聚合物网络水凝胶。水溶性聚氨酯交联网络是采用多异氰酸酯单体、聚乙二醇、丙三醇聚合反应所生成。制备方法依次：采用多异氰酸酯单体、聚乙二醇、丙三醇聚合反应得到水溶性聚氨酯交联网络体，然后采用丙烯酸、2‑丙烯酰胺基‑2‑甲基丙磺酸、N，N′‑亚甲基双(丙烯酰胺)和过硫酸钾的水溶液浸泡直到溶胀平衡，最后进行热引发聚合，即制得本发明电响应型互穿聚合物水凝胶。本发明电响应水凝胶可用作人工肌肉。

Description

一种电响应型互穿聚合物水凝胶及其制备方法
技术领域
本发明涉及一种智能水凝胶及其制备方法，特别涉及一种电响应型互穿聚合物水凝胶及其制备方法，属于电驱动智能水凝胶领域。
背景技术
智能材料能够对外界温度、光、电场磁场等外部信号刺激做出响应，成为当今功能材料研究的一大热门，其中，高分子水凝胶是最常见最重要的一种。聚合物水凝胶是一种具有亲水性的三维聚合物网络结构的智能高分子，在水中可吸水膨胀，这些特性使水凝胶可以广泛应用在组织工程、人工肌肉、分离膜、化学阀、传感器等前沿领域。
由于电场的可控和便于调节强度，所以在电场下发生刺激响应的电响应型水凝胶引起了人们的广泛研究兴趣。由离子单体聚合成的聚合物水凝胶能对电刺激表现出膨胀或收缩的形态变化，进而产生弯曲行为，因此这类水凝胶在人工肌肉、机器人手臂、仿生鱼和履带爬行器等领域具有广泛的应用前景。但是，目前高分子水凝胶的机械性能差，严重限制了其应用。因此，提高力学性能和保持高的电响应性成为目前高分子水凝胶领域的一大难题。
发明内容
本发明的目的在于提供一种力学性能和电响应性能都优异的电响应型互穿聚合物水凝胶及其制备方法。
实现本发明目的的技术解决方案为：一种电响应型互穿聚合物水凝胶为水溶性聚氨酯交联网络与丙烯酸-co-2-丙烯酰胺基-2-甲基丙磺酸-co-N，N′-亚甲基双(丙烯酰胺)交联网络构成的互穿聚合物网络水凝胶。
本发明电响应型互穿聚合物水凝胶中的水溶性聚氨酯交联网络是采用多异氰酸酯单体、聚乙二醇、丙三醇聚合反应所生成。
对于本发明电响应型互穿聚合物水凝胶，水溶性聚氨酯交联网络采用的多异氰酸酯单体可以是甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯之一种或一种以上；聚乙二醇分子量在800～1200范围。
本发明电响应型互穿聚合物水凝胶的制备方法，依次包括以下步骤：
第一步，将聚乙二醇、丙三醇和多异氰酸酯单体混合均匀并脱泡；
第二步，将第一步混合所得的混合物熔体倒入模具，然后升温进行聚合反应得到水溶性聚氨酯交联网络体；
第三步，将丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸、N，N′-亚甲基双(丙烯酰胺)和过硫酸钾加入水中混合均匀，配制得到聚合单体水溶液；
第四步，将第二步制得的水溶性聚氨酯交联网络体，浸泡在第三步配制的聚合单体水溶液中，直到溶胀平衡；
第五步，将浸泡有聚合单体水溶液的水溶性聚氨酯交联网络体加热升温，使聚合单体进行热引发聚合，以在水溶性聚氨酯交联网络体内部形成丙烯酸-co-2-丙烯酰胺基-2-甲基丙磺酸-co-N，N′-亚甲基双(丙烯酰胺)交联网络的第二网络，制得水溶性聚氨酯交联网络/丙烯酸-co-2-丙烯酰胺基-2-甲基丙磺酸-co-N，N′-亚甲基双(丙烯酰胺)交联网络两者构成的互穿聚合物网络水凝胶。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第一步采用的聚乙二醇、丙三醇两者的羟基与多异氰酸酯单体的异氰酸酯之间摩尔比为1∶1.1～1.3。第一步采用的多异氰酸酯单体可以是甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯之一种或一种以上；聚乙二醇分子量在800～1200范围。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第二步的聚合反应最好包括两个阶段：第1阶段为在65～80℃下聚合反应0.5～1.5小时，第2阶段为在110～130℃下聚合反应0.5～3小时。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第三步采用的丙烯酸∶2-丙烯酰胺基-2-甲基丙磺酸∶N，N′-亚甲基双(丙烯酰胺)∶过硫酸钾的摩尔比为1～0∶0～1∶0.05～0.2∶0.01～0.05。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第五步的热引发聚合条件最好为：在60～90℃下聚合反应2～12小时。
本发明电响应型互穿聚合物水凝胶具有以下显著优点：(1)采用的原料低廉，制备方法简单，产品成本低；(2)本发明电响应型互穿聚合物水凝胶的力学性能优异，具有高的拉伸强度；(3)本发明电响应型互穿聚合物水凝胶在电场中的响应速度快，在智能水凝胶人工肌肉领域有良好的应用前景。
具体实施方式
本发明电响应型互穿聚合物水凝胶为水溶性聚氨酯交联网络与丙烯酸-co-2-丙烯酰胺基-2-甲基丙磺酸-co-N，N′-亚甲基双(丙烯酰胺)交联网络构成的互穿聚合物网络水凝胶。
本发明电响应型互穿聚合物水凝胶中的水溶性聚氨酯交联网络是采用多异氰酸酯单体、聚乙二醇、丙三醇聚合反应所生成。采用的多异氰酸酯单体可以是甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯之一种或一种以上。本发明电响应型互穿聚合物水凝胶采用的聚乙二醇分子量不得低于800，否则聚合速度太快，难以获得合适形状和尺寸的水溶性聚氨酯交联网络体；也不能过高，不能高于1200，否则无法混合均匀和制得水溶性聚氨酯交联网络体。
本发明电响应型互穿聚合物水凝胶的制备方法，依次包括以下步骤：
第一步，将聚乙二醇、丙三醇和多异氰酸酯单体混合均匀并脱泡；
第二步，将第一步混合所得的混合物熔体倒入模具，然后升温进行聚合反应得到水溶性聚氨酯交联网络体；
第三步，将丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸、N，N′-亚甲基双(丙烯酰胺)和过硫酸钾加入水中混合均匀，配制得到聚合单体水溶液；
第四步，将第二步制得的水溶性聚氨酯交联网络体，浸泡在第三步配制的聚合单体水溶液中，直到溶胀平衡；
第五步，将浸泡有聚合单体水溶液的水溶性聚氨酯交联网络体加热升温，使聚合单体进行热引发聚合，以在水溶性聚氨酯交联网络体内部形成丙烯酸-co-2-丙烯酰胺基-2-甲基丙磺酸-co-N，N′-亚甲基双(丙烯酰胺)交联网络的第二网络，制得水溶性聚氨酯交联网络/丙烯酸-co-2-丙烯酰胺基-2-甲基丙磺酸-co-N，N′-亚甲基双(丙烯酰胺)交联网络两者构成的互穿聚合物网络水凝胶。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第一步采用的聚乙二醇、丙三醇两者的羟基与多异氰酸酯单体的异氰酸酯之间摩尔比为1∶1.1～1.3。聚乙二醇与丙三醇之摩尔比可以为1∶0.4～1.1。采用的多异氰酸酯单体可以是甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯之一种或一种以上；聚乙二醇分子量在800～1200范围。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第二步的聚合反应最好包括两个阶段：第1阶段为在65～80℃下聚合反应0.5～1.5小时，第2阶段为在110～130℃下聚合反应0.5～3小时。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第三步采用的丙烯酸∶2-丙烯酰胺基-2-甲基丙磺酸∶N，N′-亚甲基双(丙烯酰胺)∶过硫酸钾的摩尔比为1～0∶0～1∶0.05～0.2∶0.01～0.05。第三步配制的聚合单体水溶液的单体总质量浓度最好在30％～70％之间。
对于本发明电响应型互穿聚合物水凝胶的制备方法，第五步的热引发聚合条件最好为：在60～90℃下聚合反应2～12小时。
实施例1
采用5千克聚乙二醇1000(分子量1000)、0.3千克丙三醇和2.08千克甲苯二异氰酸酯搅拌混合均匀并充分减压脱泡。然后，将混合所得的混合物熔体倒入模具，在80℃下聚合反应1小时，接着在120℃下交联固化2小时，制得水溶性聚氨酯交联网络体。将1.242千克2-丙烯酰胺基-2-甲基丙磺酸、0.432千克丙烯酸、0.096千克N，N′-亚甲基双(丙烯酰胺)和0.032千克过硫酸钾加入6千克去离子水，混合均匀配成聚合单体水溶液。随后，将水溶性聚氨酯交联网络体浸泡在配制的聚合单体水溶液中，直到溶胀平衡。最后，将浸泡有聚合单体水溶液的水溶性聚氨酯交联网络体加热升温，使聚合单体在75℃热引发聚合10小时，即制得本发明电响应型互穿聚合物水凝胶。本发明电响应型互穿聚合物水凝胶的拉伸强度650kPa，断裂伸长率45％，在直流电电场强度为2.5V/cm的电驱动作用下电驱动弯曲角度可高达90°的极限弯曲角度，弯曲角度90°的电响应时间125s。
实施例2
采用5千克聚乙二醇1000(分子量1000)、0.3千克丙三醇和3.0千克二苯基甲烷二异氰酸酯搅拌混合均匀并充分减压脱泡。然后，将混合所得的混合物熔体倒入模具，在80℃下聚合反应1小时，接着在120℃下交联固化2小时，制得水溶性聚氨酯交联网络体。将0.2千克2-丙烯酰胺基-2-甲基丙磺酸、0.792千克丙烯酸、0.096千克N，N′-亚甲基双(丙烯酰胺)和0.032千克过硫酸钾加入6千克去离子水，混合均匀配成聚合单体水溶液。随后，将水溶性聚氨酯交联网络体浸泡在配制的聚合单体水溶液中，直到溶胀平衡。最后，将浸泡有聚合单体水溶液的水溶性聚氨酯交联网络体加热升温，使聚合单体在85℃热引发聚合8小时，即制得本发明电响应型互穿聚合物水凝胶。本发明电响应型互穿聚合物水凝胶的拉伸强度625kPa，断裂伸长率58％，在直流电电场强度为2.5V/cm的电驱动作用下电驱动弯曲角度可高达90°的极限弯曲角度，弯曲角度90°的电响应时间108s。

Claims (5)

1.一种电响应型互穿聚合物水凝胶的制备方法，其特征在于：依次包括以下步骤：
第一步，将聚乙二醇、丙三醇和多异氰酸酯单体混合均匀并脱泡；
第二步，将第一步混合所得的混合物熔体倒入模具，然后升温进行聚合反应得到水溶性聚氨酯交联网络体；
第三步，将丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸、N，N’-亚甲基双(丙烯酰胺)和过硫酸钾加入水中混合均匀，配制得到聚合单体水溶液；
第四步，将第二步制得的水溶性聚氨酯交联网络体，浸泡在第三步配制的聚合单体水溶液中，直到溶胀平衡；
第五步，将浸泡有聚合单体水溶液的水溶性聚氨酯交联网络体加热升温，使聚合单体进行热引发聚合，以在水溶性聚氨酯交联网络体内部形成丙烯酸-co-2-丙烯酰胺基-2-甲基丙磺酸co-N，N’-亚甲基双(丙烯酰胺)交联网络的第二网络，制得水溶性聚氨酯交联网络/丙烯酸co-2-丙烯酰胺基-2-甲基丙磺酸-co-N，N-亚甲基双(丙烯酰胺)交联网络两者构成的互穿聚合物网络水凝胶；
其中，聚乙二醇分子量为800～1200；聚乙二醇、丙三醇两者的羟基与多异氰酸酯单体的异氰酸酯之间摩尔比为1∶1.1～1.3。
2.根据权利要求1所述的电响应型互穿聚合物水凝胶的制备方法，其特征在于：第一步采用的多异氰酸酯单体为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯之一种或一种以上。
3.根据权利要求1所述的电响应型互穿聚合物水凝胶的制备方法，其特征在于：第二步的聚合反应包括两个阶段，第1阶段为在65～80℃下聚合反应0.5～1.5小时，第2阶段为在110～130℃下聚合反应0.5～3小时。
4.根据权利要求1所述的电响应型互穿聚合物水凝胶的制备方法，其特征在于：第三步采用的丙烯酸∶2-丙烯酰胺基-2-甲基丙磺酸∶N，N’-亚甲基双(丙烯酰胺)∶过硫酸钾的摩尔比为1～0∶0～1∶0.05-0.2∶0.01～0.05。
5.根据权利要求1所述的电响应型互穿聚合物水凝胶的制备方法，其特征在于：第五步的热引发聚合条件为，在60～90℃下聚合反应2～12小时。
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