CN106432597B - 一种双物理交联的自修复水凝胶的制备方法 - Google Patents
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Abstract
本发明提供一种双物理交联自修复的水凝胶的制备方法。本发明将蒙脱土(MMT)、丙烯酰胺(AM)、疏水单体甲基丙烯酸十八烷基酯(SMA)和十二烷基苯磺酸钠(SDBS)位主要原料，共混后得到的前驱液经胶束原位聚合得到HPAAm/MMT复合水凝胶。本发明原料廉价易得，制备过程简单。胶束的存在及MMT和丙烯酰胺之间的物理吸附作用使水凝胶双重交联，机械强度提高到0.23MPa；凝胶在60℃下修复5h，可恢复至原有形貌与性能。本发明制备得到的自修复凝胶在医疗缝合、工业密封和自修复弹性体等领域具有广阔的应用前景。
Description
技术领域
本发明涉及一种双物理交联的自修复水凝胶及其制备方法，属于功能高分子材料领域。
背景技术
水凝胶是一种结构空隙中充满了介质水的具有空间网状结构的特殊功能材料。它与生物体软组织在结构与性能上有很多相似之处。其具有很强的保水能力，即使在受压的情况下也不易失水，在园林工艺、生理卫生、医药、人工组织、石油化工、日用品等领域有广阔的应用前景。
受生物组织在损伤后可自行修复的启发，自修复水凝胶应运而生。通过引入可逆的氢键、疏水相互作用、主客体相互作用、π-π堆集、离子键或者动态可逆化学键的方法，赋予了水凝胶自修复的功能，其大大拓宽了水凝胶的潜在应用前景。但是，由于绝大多数自修复水凝胶的力学性能差，限制了其在生产、生活中的应用。采用双重物理交联得到水凝胶，既能提高其机械强度，又不影响它的自修复性能，拓宽了自修复水凝胶的应用。
本发明利用蒙脱土的物理吸附作用及疏水作用实现双物理交联，以丙烯酰胺(AM)、疏水单体甲基丙烯酸十八烷基酯(SMA)和十二烷基苯磺酸钠(SDBS)位主要原料，共聚复合水凝胶。本发明原料廉价易得，制备过程简单；本发明制备得到的自修复凝胶在医疗缝合、工业密封和自修复弹性体等领域具有广阔的应用前景。
发明内容
本发明的目的是提供一种简单的双物理交联制备自修复凝胶的制备方法，使所得凝胶具有良好的自修复性能和机械性能。
为实现上述目的，本发明采用以下技术方案：
一种双重物理交联的自修复水凝胶，其包括以下原料：丙烯酰胺(AM)、甲基丙烯酸十八烷基酯(SMA)、钠基蒙脱土(MMT)、十二烷基苯磺酸钠(SDBS)、水、过硫酸钾。优选的各原料重量配比为：AM 155～183份，SMA 17～45份，MMT 0～36份，SDBS 26份，过硫酸钾1份，水666份。
一种双重物理交联的自修复水凝胶的制备方法，其包括以下步骤：
步骤1.将取一定份数的钠基蒙脱土分散于水溶液中，超声3h，室温下搅拌12h，再投入一定份数的丙烯酰胺(AM)室温下搅拌12h，得到蒙脱土-丙烯酰胺水溶液。
步骤2.向步骤1得到的蒙脱土-丙烯酰胺水溶液中加入一定份数的十二烷基苯磺酸钠(SDBS)和甲基丙烯酸十八烷基酯(SMA)，35℃条件下搅拌5h，得到反应的前驱液。
步骤3.向步骤(2)得到的前驱液加入一定份数的过硫酸钾并搅拌30min，随后倒入圆柱体模具，50℃条件下反应12h即可得到所述的双物理交联的自修复水凝胶。
本发明的双物理交联的自修复水凝胶的有益效果：
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双物理交联的自修复水凝胶，其机械强度提高到0.23MPa。利用物理作用的可逆性，使水凝胶网络结构被破坏后，通过疏水区重组及MMT和丙烯酰胺物理吸附重新产生使得水凝胶具有良好的自修复性能。
附图说明
图1HPAAm/MMT凝胶的自修复、拉伸及弯曲照片
图2HPAAm/MMT凝胶起始和修复后的拉伸曲线
具体实施方式
实施例一
将0.79g十二烷基苯磺酸钠、0.52g甲基丙烯酸十八烷基酯和5.48g丙烯酰胺至于20g水中，35℃条件下搅拌5h至溶解，得到反应的前驱液。向前驱液加入0.03g过硫酸钾并搅拌30min，随后倒入圆柱体模具，50℃条件下反应12h即可得到单物理交联的水凝胶。
对本实施例所得样品做自修复测试：
所制备的圆柱体凝胶在用刀切成两段，得到的两段凝胶断面接触置于圆柱体模具中，60℃下修复5h，然后用拉伸机对其修复前后的拉伸强度进行对比，计算其修复效率。
实施例二
将0.18g钠基蒙脱土分散于20g水中，超声3h，室温下搅拌12h，再投入5.48g丙烯酰胺室温下搅拌12h，得到蒙脱土-丙烯酰胺水溶液。向上述水溶液中加入0.79g十二烷基苯磺酸钠和0.52g甲基丙烯酸十八烷基酯，35℃条件下搅拌5h，得到反应的前驱液。再将0.03g过硫酸钾加入前驱液，并搅拌30min，随后倒入圆柱体模具，50℃条件下反应12h即可得到所述的双物理交联的自修复水凝胶。
对本实施例所得样品做自修复测试方法与实施例一相同。
实施例三
将0.36g钠基蒙脱土分散于20g水中，超声3h，室温下搅拌12h，再投入5.48g丙烯酰胺室温下搅拌12h，得到蒙脱土-丙烯酰胺水溶液。向上述水溶液中加入0.79g十二烷基苯磺酸钠和0.52g甲基丙烯酸十八烷基酯，35℃条件下搅拌5h，得到反应的前驱液。再将0.03g过硫酸钾加入前驱液，并搅拌30min，随后倒入圆柱体模具，50℃条件下反应12h即可得到所述的双物理交联的自修复水凝胶。
本实施例的双重物理交联自修复水凝胶的制备方法与实施例二的制备方法相同。
Claims (2)
1.一种双物理交联的自修复水凝胶的制备方法，其特征在于以丙烯酰胺和甲基丙烯酸十八烷基酯为主要原料，十二烷基苯磺酸钠为表面活性剂，钠基蒙脱土为增强剂和物理交联点，通过共聚得到双物理交联的水凝胶；其制备方法如下：
将一定量的钠基蒙脱土分散于20g水中，超声3h，室温下搅拌12h，再投入5.48g丙烯酰胺室温下搅拌12h，得到蒙脱土-丙烯酰胺水溶液；向上述水溶液中加入0.79g十二烷基苯磺酸钠和0.52g甲基丙烯酸十八烷基酯，35℃条件下搅拌5h，得到反应的前驱液；再将0.03g过硫酸钾加入前驱液，并搅拌30min，随后倒入圆柱体模具，50℃条件下反应12h即可得到所述的双物理交联的自修复水凝胶。
2.根据权利要求1所述的制备方法，其特征在于所得的水凝胶被切开后，在60℃下放置5h后，水凝胶自修复至原有形貌与性能。
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| CN108440772A (zh) * | 2018-03-06 | 2018-08-24 | 长春工业大学 | 一种自修复导电双网络结构水凝胶及其制备方法 |
| CN108341906B (zh) * | 2018-03-12 | 2020-03-17 | 福州大学 | 一种阳离子染料复合吸附材料的制备方法及应用 |
| CN109054052A (zh) * | 2018-07-24 | 2018-12-21 | 武汉工程大学 | 一种高韧性双网络物理交联自修复水凝胶的制备方法 |
| CN109943291A (zh) * | 2019-04-04 | 2019-06-28 | 江南大学 | 一种高导热自修复凝胶基相变材料及其制备方法 |
| CN110384957A (zh) * | 2019-06-12 | 2019-10-29 | 李嘉诚 | 一种高效油浆沉降剂 |
| CN110156943B (zh) * | 2019-06-24 | 2022-02-01 | 四川轻化工大学 | 一种水凝胶材料的制备方法和应用 |
| CN110343266A (zh) * | 2019-07-08 | 2019-10-18 | 南京信息工程大学 | 一种颜色自愈智能水凝胶及其制备方法 |
| CN110551296B (zh) * | 2019-08-13 | 2022-03-15 | 天津大学 | 一种果胶基双物理交联水凝胶及制备方法和应用 |
| CN116333700B (zh) * | 2023-03-24 | 2024-04-12 | 西南石油大学 | 双控相变自修复韧性凝胶堵剂及其制备方法 |
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| Light-healable hard hydrogels through photothermally induced melting–crystallization phase transition;Hongji Zhang等;《Journal of Materials Chemistry A》;20140611;第2卷;第13373-13379页 * |
| Self-Healable, Tough, and Ultrastretchable Nanocomposite Hydrogels Based on Reversible Polyacrylamide/Montmorillonite Adsorption;Guorong Gao等;《ACS Appl. Mater. Interfaces》;20150210;第7卷;第5029−5037页 * |
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