氢键和硼酯键双动态交联丁苯橡胶的设计及自修复和粘附性能研究

Preparation of hydrogen and boron ester bonded double crosslinking styrene butadiene rubbers and self-healing, adhesive capability

  • 摘要: 开发优异力学性能、自修复、自焊接、粘附和导电等多功能集成的丁苯橡胶具有重要意义,但仍面临巨大挑战。本文以羟基化丁苯橡胶 (HSBR) 为主链,2-脲基-4-嘧啶酮 (UPy-NCO) 和4,4'4''-(1,3,5,2,4,6-三氧杂三硼杂环己烷-2,4,6-三基)三苯甲酰氯(芳基-硼氧烷) (BE) 分别为氢键和硼酸酯键交联剂,成功制备了一种兼具优异力学性能、自修复、自焊接和粘附的氢键和硼酯键双动态交联丁苯橡胶 (HSBR-UPy-BE)。动态氢键和硼酸酯键交联的协同作用赋予HSBR-UPy15%-BE5%优异的力学性能,其拉伸强度为5.3 MPa,断裂伸长率为281.0%,杨氏模量和韧性分别高达25.9 MPa和13.3 MJ/m3。此外,动态硼酸酯键和氢键赋予材料优异的自修复和焊接性能。HSBR-UPy5%-BE5%、HSBR-UPy10%-BE5%和HSBR-UPy15%-BE2%在60℃自修复及室温、60 ℃下自焊接24 h效率均高达100%。此外,HSBR-UPy-BE与基材间丰富的氢键、配位键、疏水等相互作用赋予其对金属、玻璃和PE基材间优异的粘附性能。进一步基于HSBR-UPy10%-BE5%,以石墨粉为导电介质,通过超声分散-热压制备了导电双交联丁苯橡胶复合材料 (GP/HSBR-UPy-BE),可作为应变传感器使用,且成功实现了心率、肌电信号的实时监测。

     

    Abstract: Developing styrene-butadiene rubber (SBR) with integrated functionality of mechanical robust, self-healing, self-welding, adhesive, and conductive properties is of great significance, but it still remains huge challenges. This work successfully prepared a double dynamically crosslinked styrene-butadiene rubber (HSBR-UPy-BE) that integrates excellent mechanical performance and self-healing, self-welding, and adhesion properties with hydroxylated styrene-butadiene rubber (HSBR) as the backbones, 2-ureido-4-pyrimidinone (UPy-NCO) and 4,4’4’’-(1,3,5,2,4,6-trioxaborocyclohexane-2,4,6-triyl) triaryl chlorides (aryl-boronic esters) (BE) serving as hydrogen bond and boronate ester crosslinking agents, respectively. The synergistic effects of dynamic hydrogen and boron ester bonds endow HSBR-UPy15%-BE5% with excellent mechanical properties, with a tensile strength of 5.3 MPa, a elongation at break of 281.0%, and a Young’s modulus and toughness reaching 25.9 MPa and 13.3 MJ/m3, respectively. Furthermore, the dynamic boronate ester and hydrogen bonds provide the material with excellent self-healing and welding capabilities. HSBR-UPy5%-BE5%, HSBR-UPy10%-BE5%, and HSBR-UPy15%-BE2% achieve self-healing efficiencies of up to 100% after healing at 60℃ for 24 h, and self-welding efficiencies of 100% at room temperature and 60℃ after welding for 24 h. Additionally, the multiple interactions including hydrogen, coordination, and hydrophobic interactions between HSBR-UPy-BE and the substrate confer the material with excellent adhesion properties to metals, glass, and PE substrates. Furthermore, based on HSBR-UPy10%-BE5% and graphite powder as a conductive medium, a conductive double crosslinked SBR composite material (GP/HSBR-UPy-BE) was prepared through ultrasonic dispersion and hot pressing, which can be used as a strain sensor, successfully achieving real-time monitoring of heart rate and electromyographic signals.

     

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