中山大学余丁山团队报道了刚柔耦合树枝状分子掺杂——将商业聚合物活化为耐恶劣条件、可多次重复使用的强超分子粘合剂的通用方法。相关研究成果发表在2024年7月20日出版的《德国应用化学》。

开发兼具强粘附性、良好可回收性和多种恶劣条件适应性的功能性胶粘剂，是一项艰巨的挑战。

该文中，研究人员介绍了一种通用的树枝状分子掺杂策略，将商业聚合物激活成一种新的超分子粘合剂家族，该家族集成了高粘附强度、超低温、防水和多可重复使用的特性。该方法涉及合理设计一种新的刚柔耦合树枝状分子-M4C8OH作为多功能掺杂剂，而简单的M4C8OH掺杂到商业聚合物中可以调节内部和外部的非共价相互作用，从而实现氢键增强的链间交联，以实现坚韧的内聚力和增强的界面相互作用。

这使得20wt%的M4C8OH掺杂的聚己内酯（PCL）粘合剂（PCL-M4C8OH）在各种基材上的粘合强度得到提高，最大提高幅度可达PCL的2.87倍。特别是，PCL-M4C8OH在25°C和-196°C下对聚甲基丙烯酸甲酯的粘附强度分别达到4.67和3.58 MPa，是PCL的1.9和2.3倍，优于各种商业粘合剂和大多数报道的粘合剂。PCL-M4C8OH还显示出显著提高的多功能性，和对超低温和各种潮湿环境的耐受性。机制研究揭示了M4C8OH分子结构对卓越粘附的关键作用。

该方法可以扩展到其他聚合物基质，产生各种新的超分子粘合剂。

附：英文原文

Title: Rigid-Flexible Coupled Dendritic Molecule Doping: General Approach to Activate Commercial Polymers into Harsh Condition- Tolerant Multi-Reusable Strong Supramolecular Adhesives

Author: Jie Feng, Ziwei Lin, Yang Zhang, Long Fang, Qikai Zhu, Dingshan Yu

Issue&Volume: 2024-07-20

Abstract: Developing functional adhesives combining strong adhesion, good recyclability and diverse harsh-condition adaptability is a grand challenge. Here, we introduce a general dendritic molecule doping strategy to activate commercial polymers into a new family of supramolecular adhesives integrating high adhesion strength, ultralow temperature, water resistant and multi-reusable properties. Our method involves rational design of a new rigid-flexible coupled dendritic molecule - M4C8OH as a versatile dopant, while simple M4C8OH doping into commercial polymers can modulate internal and external non-covalent interaction to enable H-bonding enhanced interchain cross-linking for tough cohesion along with enhanced interphase interaction. This endows 20 wt% M4C8OH-doped polycaprolactone (PCL) adhesives (PCL-M4C8OH) with improved adhesion strength on various substrates with the maximum increase up to 2.87 times that of PCL. In particular, the adhesion strengths of PCL-M4C8OH on polymethyl methacrylate at 25 °C and -196 °C reach 4.67 and 3.58 MPa - 1.9 and 2.3 times those of PCL and superior to diverse commercial adhesives and most reported adhesives. PCL-M4C8OH also displays markedly-improved multi-usability and tolerance against ultralow temperature and diverse wet environments. Mechanism studies reveal the crucial role of  M4C8OH molecular structures toward superior adhesion. Our method can be expanded to other polymer matrices, yielding diverse new supramolecular adhesives.

DOI: 10.1002/anie.202411815

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202411815