Structure, preparation and properties of liquid fluoroelastomers with different end groups

Abstract

In order to design and prepare liquid fluoroelastomers with different end groups, and reveal the relationship between the molecular chain structure and properties, we studied on the oxidation degradation method and functional group conversion method to prepare carboxyl-terminated and hydroxyl-terminated liquid fluoroelastomers, respectively. The reaction mechanisms were also deduced. Furthermore, the curing system was created for liquid fluoroelastomers, and systematically analyzed their properties. The sequence type and content of the –CC– and oxygen-containing groups in the samples were measured and characterized by attenuated total reflectance/Fourier transform infrared (ATR-FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H-NMR), ¹⁹F-NMR spectroscopy and chemical titration, the molecular weights of liquid fluoroelastomers were measured by gel permeation chromatography (GPC). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to examine the thermal properties, while a viscometer was used to measure the dynamic viscosity of the liquid fluoroelastomers. Then the mechanical and surface properties of the cured samples were examined by universal testing machine and contact angle measurement instrument, respectively. The results show that carboxyl-terminated liquid fluoroelastomer with 2.71 wt% carboxyl terminal groups can be prepared by oxidation degradation method. When lithium aluminium hydride (LiAlH₄) was used as the reducing agent, it can efficiently convert carboxyl group to hydroxyl group with a conversion rate of more than 95%. In addition, it can be seen that the dynamic viscosity of the liquid fluoroelastomers were all decreased with the increase of temperature, and it is similar to about 10 Pa s at 70 °C. Compared with carboxyl-terminated liquid fluoroelastomers, hydroxyl-terminated liquid fluoroelastomers has higher curing reactivity, higher glass transition temperature (T_g) and thermal decomposition temperature (T_d), and better mechanical properties of cured samples. The two types of liquid fluoroelastomers with distinct end groups presented distinct hydrophilicity.