Page 91 - 摩擦学学报2025年第5期

第 5 期 秦晨曦, 等: 基于主客体相互作用的水下自适应仿生胶黏剂的设计及性能研究 725

We prepared hyperbranched polymers P1 containing adhesion groups dihydroxyphenylalanine (DOPA) and AD, as well
as PDMS polymers P2 capped with β-CD. Through a one-step Michael addition reaction, the adhesion functional group
DOPA, the rigid hydrophobic group benzylamine hydrochloride (BENA), and the guest functional unit AD were
successfully integrated into the hyperbranched polymers P1. The (β-CD)-capped PDMS host polymers P2 was obtained
by reacting the host functional unit β-CD with poly(dimethylsiloxane), diglycidyl ether terminated (PDMS-DGE). The
host-guest underwater adhesive was obtained by mixing P1 and P2 polymer solutions and forming a stable inclusion P3
complex of AD with β-CD in water. Strong underwater adhesion was mainly realized through three points: 1. AD and β-
CD were adaptively underwater assembled through the host-guest interaction, which squeezed out the water from the
inner cavity of the β-CD, realizing the hydrophobic repulsion of molecular chains and increasing the cohesive energy;
2. the catechol group of DOPA formed a large number of hydrogen bonds with the surface of the substrate, resulting in
strong interfacial adhesion; 3. hydrophobic PDMS resisted water erosion and protected the internal polymer chain, thus
achieving the strength of the underwater adhesion stable for a long period of time. Experimental tests had shown that this
rational design endowed the underwater adhesive with exceptional performance. The stabilized inclusion P3 formed
through adaptive assembly exhibited strong underwater adhesion strength (brass substrate in pure water 12 h reaches
940.8 kPa), which was a significant improvement over the adhesion strength of existing underwater adhesives (200~
600 kPa). Significantly, P3 required only one hours to initially cure and adhere the substrate tightly, and reached peak
adhesion strength after 12h of curing. Contact angle tests had confirmed the good wettability of P3 adhesives on
different substrate surfaces (organic and inorganic). This allowed the adhesive to tend to displace interfacial water when
applied to the substrate in an underwater environment, thereby gaining sufficient contact area on the substrate to achieve
strong adhesion to a wide range of substrates. In addition to its strong adhesive properties, our underwater adhesive
remained stable in a wide range of aquatic environments (ultrapure water, acidic and alkaline solutions, seawater). Even
after 15 days of immersion in water, it maintained high adhesion strength. The host-guest adhesive P3 maintained strong
adhesion properties after several adhesion-detachment cycles underwater, which proved its reusability. Economically
and environmentally, this not only helped to reduce costs, but was also in line with the concept of green chemistry,
which protected the environment and helped to reduce the burden on marine. This in-situ underwater adaptive curing
strategy greatly improved the ease of application of underwater adhesives in complex environments and provides
abundant possibilities for the subsequent design of a new generation of green underwater adhesives that combined high
adhesion strength, long-term durability and stability in harsh environments.
Key words: underwater adhesion; host-guest interaction; self-adaptive; bioinspired adhesive; mussel

胶黏剂是日常生活、工业及生物医学领域不可或 泉，在过去的几十年中，研究人员揭示了贻贝优异的黏
缺的材料 [1-3] . 工作于干燥空气环境的胶黏剂已得到了 附性能与蛋白质内部含有邻苯二酚氨基酸(3，4-二羟
[4]
广泛的研究 . 然而，在水下环境中这些胶黏剂黏附能力 基苯基-L-丙氨酸，DOPA)以及蛋白质内部的多种非
往往会严重减弱甚至丧失 [5-7] ，因为水分子的存在会导致 共价/共价相互作用相关 [9, 12-13] . 相互作用主要包括疏
胶黏剂本体溶胀松散并同时造成黏附界面的脱落. 具 水相互作用、静电相互作用、氢键、π-π相互作用以及
体来说，一方面水的存在会使胶黏剂分子溶胀，机械强 阳离子-π相互作用等 [14-16] ，利用这些相互作用，研究人
度减弱甚至丧失，从而破坏胶黏剂的内聚力，出现黏附 员通过合成带有DOPA基团的聚合物发展出了一系列
[20]
失效；另一方面由于水分子会吸附在胶黏剂界面上形成 的水下胶黏剂 [17-19] . Zhou等 报导了1种由DOPA和双
1层薄薄的水化膜，大大阻碍胶黏剂与黏附基底的紧密 酚A二缩水甘油醚组成的共聚物，这种共聚物在FeCl 3
接触，从而破坏界面结合力，导致黏附胶脱落. 因此，开 氧化剂的作用下，在水下显示了高黏附强度. Joy等 [21]
发水下具有高黏附强度的通用胶黏剂是1个巨大的挑战. 制备了1种由长链脂肪烃、DOPA和香豆素聚合而成的
在自然界中，许多海洋生物，如贻贝、藤壶和沙堡 胶黏剂，在紫外光照下引发交联固化，水下黏附强度
[22]
蠕虫为了适应复杂多变的海洋生活环境，它们在长期 最大达到0.65 MPa. Kamperman等 将含有阳离子的
进化过程中获得了分泌黏液的能力. 这种黏液是由多 聚合物和阴离子的聚合物分别接枝到聚(N-异丙基丙
种氨基酸组成的黏性蛋白，其固化后展现出强大的本 烯酰胺)上，在温度的触发下，实现胶黏剂固化. 类似地，
体黏附和高界面黏附 [8-11] ，可以牢固而快速地黏附在 相关研究 [23-24] 通过温度的变化触发实现水下黏附，然
岩石上. 向自然界学习是人类不断创新发展进步的源 而这些胶黏剂的凝聚固化需要外界的能量引发，比如