CN106432593B - 一种基于氢键作用的热响应形状记忆水凝胶及其制备方法 - Google Patents

一种基于氢键作用的热响应形状记忆水凝胶及其制备方法 Download PDF

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CN106432593B
CN106432593B CN201610816463.4A CN201610816463A CN106432593B CN 106432593 B CN106432593 B CN 106432593B CN 201610816463 A CN201610816463 A CN 201610816463A CN 106432593 B CN106432593 B CN 106432593B
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张洪吉
陈然
陈益鸣
陈明清
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Abstract

本发明公开了一种基于氢键作用的热响应形状记忆水凝胶及其制备方法，所述水凝胶为：N,N’‑二甲基丙烯酰胺(DMA)、N,N’‑亚甲基双丙烯酰胺(MBA)、2‑脲‑4[1H]‑甲基嘧啶酮甲基丙烯酸酯(UPyMA)的共聚物。本发明的形状记忆水凝胶利用聚合物侧链上的UPy(2‑脲‑4[1H]‑甲基嘧啶酮)单元间形成的动态氢键，兼具共价键的强度和物理交联的可逆性。本发明原料易得，制备过程简单。本发明制得的基于四重氢键的水凝胶具有较强的机械性能和良好的形状记忆性能。在药物输送等方面有广阔的应用前景。

Description

一种基于氢键作用的热响应形状记忆水凝胶及其制备方法
技术领域
本发明涉及一种基于氢键作用的热响应形状记忆水凝胶及其制备方法，属于功能高分子材料领域。
背景技术
水凝胶是一种在水中溶胀，但是并不能溶解的物质。过去几十年间，水凝胶广泛应用于生物医学方面，比如药物载体、创伤敷料、软骨替换、人工肾脏膜等医学器件。但是水凝胶弱的机械性能大大限制了其应用。作为医用材料，出了一定的生物相容性和无毒性之外，还必须具有一定的机械强度和形变回复性能。传统的水凝胶主要依靠化学交联，而在新型水凝胶的研究中，将化学交联和物理交联结合在一起已经越来越受到人们的关注。
在作为植入材料时，便捷性是人们最为关注的问题，形状记忆聚合物刚好满足了这方面的需求。在进行植入手术时，可以将具有初始形状的器件加工成适合手术的临时形状，在植入完成后再通过一定刺激回复其原始形状，如此既提高了手术的效率又减少了病人的痛苦。
发明内容
本发明的目的是提供一种较为简单的制备方法，合成基于氢键作用的热响应形状记忆水凝胶，具有良好的形状记忆性能和机械性能。
为实现上述目的，本发明采用以下技术方案：
一种基于氢键的形状记忆水凝胶，其包括以下原料：N,N’-二甲基丙烯酰胺(DMA)、N,N’-亚甲基双丙烯酰胺(MBA)、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯(UPyMA)，水，过硫酸铵，二亚甲砜(DMASO)。
优选的各原料重量配比为：DMA10-50份，UPyMA 10-50份，MBA 5-20份，DMSO 20份，水100份，过硫酸铵1-2份。其中UPyMA和DMA的总量为100份。
一种基于氢键的形状记忆水凝胶的制备方法，其包括以下步骤：
1)将N,N’-二甲基丙烯酰胺(DMA)、N,N’-亚甲基双丙烯酰胺(MBA)、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯(UPyMA)，过硫酸铵，二亚甲砜(DMASO)按比例投入容器内，先在40-50℃预热使原料溶解混合均匀，然后升温到65-80℃，反应3小时；
2)将所制得的DMSO凝胶于室温下浸泡在去离子水中一定时间，使DMSO完全被水置换；
3)将步骤2所得干凝胶放入去离子水中溶胀7天，即得到所述基于硼酸酯键的形状记忆水凝胶。
本发明的基于氢键的形状记忆水凝胶的有益效果：
本发明提出的制备方法简单易行，反应条件温和，原料成本低。本发明使用提出的方法成功合成了基于氢键作用的热响应形状记忆水凝胶。利用氢键的可逆性，具有初始形状的水凝胶在一定温度变形后，在室温下冷却固定形状，再将具有临时形状的水凝胶放在一定温度下能回到初始形状，具有良好的形状记忆性能。
附图说明
图1形状记忆水凝胶的形状记忆原理以及水凝胶的变形、固定及回复的照片。
具体实施方式
为了使发明的内容更容易被清楚的理解，下面根据本发明的具体实施例对本发明作进一步详细的说明。
实施例一
一种基于氢键作用的热响应形状记忆水凝胶，其包括以下重量的原料：N,N’-二甲基丙烯酰胺(DMA)1.7g、N,N’-亚甲基双丙烯酰胺(MBA)0.05g、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯(UPyMA)1.6g，过硫酸铵0.03g，二亚甲砜(DMASO)10mL。
上述各原料按照以下步骤制备：
1)将N,N’-二甲基丙烯酰胺(DMA)、N,N’-亚甲基双丙烯酰胺(MBA)、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯(UPyMA)，过硫酸铵，二亚甲砜(DMASO)按比例投入容器内，先在40-50℃预热使原料溶解混合均匀，然后升温到65-80℃，反应3小时；
2)将所制得的DMSO凝胶于室温下浸泡去离子水中一定时间，使DMSO完全被水置换；
3)将步骤2所得的水凝胶继续去离子水中溶胀7天达到溶胀平衡，即得到所述基于氢键作用的形状记忆水凝胶。
对本实施例所得样品做形状记忆测试：
将长条形水凝胶在80℃的热水中加热5min，3N的外力下将其弯成‘U’形，保持外力不变在室温下冷却10h，撤去外力后水凝胶形状固定，再将‘U’形水凝胶放入80℃的热水中，水凝胶回到直线形。
实施例二
本实施例的形状记忆水凝胶，包括以下重量的原料：N,N’-二甲基丙烯酰胺(DMA)2.1g、N,N’-亚甲基双丙烯酰胺(MBA)0.06g、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯(UPyMA)1.3g，过硫酸铵0.05g，二亚甲砜(DMASO)10mL。
本实施例的基于氢键的形状记忆水凝胶的制备方法与实施例一的制备方法相同。
本实施例的基于氢键的形状记忆水凝胶具有与实施例一基本相同的机械性能和形状记忆性能。
实施例三
本实施例的形状记忆水凝胶，包括以下重量的原料：N,N’-二甲基丙烯酰胺(DMA)2.8g、N,N’-亚甲基双丙烯酰胺(MBA)0.06g、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯(UPyMA)1.2g，过硫酸铵0.04g，二亚甲砜(DMSO)10mL。
本实施例的基于氢键键的形状记忆水凝胶的制备方法与实施例一的制备方法相同。
本实施例的基于氢键键的形状记忆水凝胶具有与实施例一基本相同的机械性能和形状记忆性能。
上述具体实施方式只是对本发明的技术方案进行详细解释，本发明并不只仅仅局限于上述实施例，本领域技术人员应该明白，凡是依据上述原理及精神在本发明基础上的改进、替代，都应在本发明的保护范围之内。

Claims (5)

1.一种基于氢键作用的热响应形状记忆水凝胶，其特征在于：原料包括N,N’-二甲基丙烯酰胺、N,N’-亚甲基双丙烯酰胺、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯、二甲基亚砜、水、过硫酸铵；其中2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯的质量占2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯和N,N’-二甲基丙烯酰胺总质量的30-50％。
2.根据权利要求1所述的基于氢键作用的热响应形状记忆水凝胶，其特征在于，所述水凝胶实现形状记忆功能的应用条件如下：
a)将制得的共聚物置于模具中溶胀，脱模后得到具有初始形状的水凝胶；
b)在50℃-100℃的任一温度、外力作用下，将水凝胶的初始形状改变为临时形状，冷却至室温即得具有固定临时形状的水凝胶；
c)将具有步骤b)临时形状的水凝胶加热到b)中对应的所用温度，即得具有初始形状的水凝胶。
3.根据权利要求1所述的基于氢键作用的热响应形状记忆水凝胶，其特征在于：所述形状记忆水凝胶的原料包括按质量配比的2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯10-50份，N,N’-二甲基丙烯酰胺10-50份，N,N’-亚甲基双丙烯酰胺5-10份，二甲基亚砜20份，过硫酸铵1-2份，水100份。
4.根据权利要求1或2所述的形状记忆水凝胶，其特征是采用物理交联和化学交联的方式，利用2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯中的UPy单元形成四重氢键以及N,N’-二甲基丙烯酰胺形成的化学交联，制备基于氢键作用的形状记忆水凝胶。
5.一种制备具有形状记忆的生物医学材料的方法，其特征在于，所述方法以包括N,N’-二甲基丙烯酰胺、N,N’-亚甲基双丙烯酰胺、2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯、二甲基亚砜、水、过硫酸铵的原料制备具有形状记忆的水凝胶，将该水凝胶用于生物医学材料的制备；其中，2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯的质量占2-脲-4[1H]-甲基嘧啶酮甲基丙烯酸酯和N,N’-二甲基丙烯酰胺总质量的30-50％。
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