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水凝胶是一种可被水分子渗透的柔软聚合物网络。这种水合状态使得水凝胶可用于生物医学研究,以及隐形眼镜和伤口敷料等消费品。与加热或冷却时发生状态转变的聚合物相反,水凝胶因具有水合作用而通常不发生聚合相变。然而,温度变化会蒸发或冻结聚合物网络中的游离水分子,从而改变水凝胶的力学性能,这将损害水凝胶的弹性,使其更易破裂。2025年2月28日,Zhang等在《Science》发表论文,报告了一种控制聚合物网络水分子的方法,并制备了一种能在-115~143℃较大的温度范围内保持弹性的耐温水凝胶。这使得过去因操作条件限制而无法实现的应用成为可能。

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(图片来源:麻省理工学院新闻网)

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一种由2种不同聚合物网络组成的水凝胶能够有效地固定水分子,同时不会破坏其结构完整性。被锁住的水分使水凝胶在较大的温度范围内都能保持弹性。

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能“锁水”的耐温水凝胶
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Zhaohan Yu, Shaoting Lin
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出版时间: 2025-03-28
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水凝胶是一种可被水分子渗透的柔软聚合物网络。这种水合状态使得水凝胶可用于生物医学研究,以及隐形眼镜和伤口敷料等消费品。与加热或冷却时发生状态转变的聚合物相反,水凝胶因具有水合作用而通常不发生聚合相变。然而,温度变化会蒸发或冻结聚合物网络中的游离水分子,从而改变水凝胶的力学性能,这将损害水凝胶的弹性,使其更易破裂。2025年2月28日,Zhang等在《Science》发表论文,报告了一种控制聚合物网络水分子的方法,并制备了一种能在-115~143℃较大的温度范围内保持弹性的耐温水凝胶。这使得过去因操作条件限制而无法实现的应用成为可能。

, . 能“锁水”的耐温水凝胶. 科技导报, 2025 , 43 (6) : 12 -13 .
Zhaohan Yu, Shaoting Lin. Science & Technology Review, 2025 , 43 (6) : 12 -13 .
水凝胶是一种可被水分子渗透的柔软聚合物网络。这种水合状态使得水凝胶可用于生物医学研究,以及隐形眼镜和伤口敷料等消费品。与加热或冷却时发生状态转变的聚合物相反,水凝胶因具有水合作用而通常不发生聚合相变。然而,温度变化会蒸发或冻结聚合物网络中的游离水分子,从而改变水凝胶的力学性能,这将损害水凝胶的弹性,使其更易破裂。2025年2月28日,Zhang等在《Science》发表论文,报告了一种控制聚合物网络水分子的方法,并制备了一种能在-115~143℃较大的温度范围内保持弹性的耐温水凝胶。这使得过去因操作条件限制而无法实现的应用成为可能。
制备耐温弹性水凝胶的主要挑战在于如何将水分子有效固定于聚合物网络内部。策略之一是为聚合物网络设计官能团。一组具有不同化学性质的原子可与临近水分子结合,而其他水分子可在聚合物网络中自由流动。另一种方法是将吸湿盐(从周围环境吸收水分的化合物)掺入水凝胶。这种方法通过促进水分子与盐中离子的相互作用,降低水分子的整体流动性。然而,由于吸湿盐也会在水凝胶内运动,因此不能完全锁住网络中的水。
研究人员利用硫酸碳化反应制备耐温水凝胶。在该反应中,硫酸吸水并在材料上产生富碳残留物。这种方法可形成硫酸水合物,将水分子成功固定于聚合物网络。然而,这一反应会也分解聚合物,导致其碎裂,从而使水凝胶降解。为此,Zhang等设计了一种具有2个互穿聚合物链网络的水凝胶,其中一个是牺牲网络,与硫酸反应后在另一个聚合物网络上形成碳层,用于保护和固定水分子(见图)。双网络水凝胶设计具有更强的韧性,但尚未实现耐温性。
实现选择性碳化反应需要2种不同性质的聚合物。藻酸盐(一种天然多聚糖)通过离子相互作用形成网络,而聚丙烯酰胺(一种合成聚合物)则通过共价键连接。在该研究的硫酸碳化反应中,硫酸主要与藻酸盐网络反应,产生短碳链(“碳蛇”),同时保持交联聚丙烯酰胺的结构完整性。在约143℃下观察到的放热峰证实了碳化反应。碳蛇可黏附并封装聚丙烯酰胺网络的主链,并作为屏障,保护聚合物免受过度反应和降解。最终获得的水凝胶由单一的聚丙烯酰胺网络构成,其表面覆有硫酸结合的碳层,可有效固定相邻水分子。在较大的温度范围内,断裂的藻酸盐链或聚丙烯酰胺网络中均未观察到相变。这证实碳蛇能将水分子有效固定在水凝胶内部。此外,研究人员并未观察到与水分子蒸发相关的放热反应,而这种现象通常在高温下的传统水凝胶中出现。因此,耐温水凝胶在-100~140℃之间能够保持弹性。
在选择性碳化策略下,需要有一个牺牲网络,因此该方法看似不能用于单网络水凝胶。为了证明该方法的通用性,研究人员在由单一类型聚合物制成的水凝胶上进行反应实验。这种合成聚合物(聚(N-乙烯基吡咯烷酮))可在酸性条件下形成活性侧链。硫酸与这些较短的辅助链反应形成“碳蛇”,“碳蛇”将包裹构成主网络的长链。得到的水凝胶在-112~135℃表现出相似的耐温力学特性。
尽管研究人员的工作证实了固定水分子策略的普适性,但仍需进一步分析以阐明水凝胶耐温性的潜在机理。其使用差示扫描量热法,根据样品吸收或释放的热量确定热转变,以证明水凝胶在极端温度下不存在相变,并提出了一个合理假设,即固定的水分子抑制了水凝胶中聚合物和水的相变。然而,远离聚合物链的水分子行为尚不可知。通过超分辨率拉曼显微镜之类的额外表征或可提供潜在机理的更详细信息。
该研究的发现或具有深远意义。目前,高性能水凝胶研发主要聚焦于优化聚合物网络结构设计,普遍忽视水凝胶中的水分子,因为一般认为其力学性能影响可忽略不计。此方法开辟了一条设计高性能水凝胶的新途径,即策略性地安排水分子,使其固定于聚合物网络内部。精确操纵水凝胶中水分子可使人们突破以前无法掌握的先进技术,包括但不限于组织防腐剂和阻燃剂。
(译自《Science》,原文参考文献略2025,38(6737))

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  • 首发时间:2025-04-19
  • 出版时间:2025-03-28
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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