Citation: Yi Wang, Zhan-bin Feng, Hong-li Zuo, Bing Yu, Nan-ying Ning, Ming Tian, Li-qun Zhang. Preparation of Thermally Reversible Silicone Rubber/Carbon Nanotubes Composite with High Electrical Conductivity Based on Diels-Alder Reaction[J]. Acta Polymerica Sinica, ;2019, 50(5): 485-495. doi: 10.11777/j.issn1000-3304.2019.18280 shu

Preparation of Thermally Reversible Silicone Rubber/Carbon Nanotubes Composite with High Electrical Conductivity Based on Diels-Alder Reaction

State Key Laboratory of Organic-Inorganic Composites, Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029

Corresponding author: Nan-ying Ning, ningny@mail.buct.edu.cn Ming Tian, tianm@mail.buct.edu.cn
Received Date: 29 December 2018
Revised Date: 30 January 2019
Available Online: 18 March 2019

An emerging and crucial type of high-value-added functional materials, conductive elastomer composites (CEC) have found extensive applications in the fields of military and civil electromagnetic shielding/protection by virtue of their excellent electromagnetic shielding function and environmental sealing performance. However, practical uses of CEC materials can be largely compromised by such disadvantages as difficult rubber recovery, poor interfacial adhesion, and costly conductive fillers. In this study, methyl vinyl silicone rubber (SiR) with high vinyl content (20%, 30% and 50%) was firstly synthesized through an anionic ring-opening reaction, and as-prepared SiR was grafted with furan functional groups via the thiol-ene click chemical reaction to afford furan-grafted SiR (SiR-Fu). SiR-Fu/CNTs composites were then prepared by solution blending of SiR-Fu and carbon nanotubes (CNTs), during which Diels-Alder reaction occurred with SiR-Fu as the diene and CNTs as the dienophiles, giving rise to reversible covalent cross-linking networks throughout the resulting composites. SEM images showed that diameters of most CNTs in SiR-Fu/5wt% CNTs and SiR-Fu/10wt% CNTs composites were significantly larger than those of the raw CNTs due to a SiR layer coated on the nanotube surface, indication of the DA reaction between CNTs and SiR-Fu. However, CNTs tended to agglomerate when being further increased to 20 wt% and some of them showed little change in diameter as compared with the initial values, so that no DA reaction took place in that case. In addition, the gel content of SiR-Fu/5wt% CNTs and SiR-Fu/10wt% CNTs composites was 73% and 90%, respectively, suggesting an enhanced degree of DA reaction at increasing CNTs content within a certain range, while it decreased to 24.5% at 20 wt% CNTs addition for the reduced degree of DA reaction caused by CNTs agglomeration. Therefore, composites with 5 wt% and 10 wt% CNTs showed better interfacial adhesion, higher mechanical strength, greater electrical conductivity, and favorable thermal reversibility. Particularly, the electrical conductivity and tensile strength of SiR-Fu/10wt% CNTs composite reached 0.9 S/cm and 2.3 MPa, respectively, much improved than those of the neat SiR (2.5 × 10⁻¹⁴ S/cm and 0.2 MPa). Moreover, the initial tensile strength, elongation at break, and electrical conductivity could be retained at 77%, 88%, and 86%, respectively, after composite reprocessing.
- Conductive elastomer composite,
- Silicone rubber,
- Diels-Alder reaction,
- Thermo-reversibility,
- Carbon nanotubes
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