Excellent Oxygen Barrier Property of Unfilled Natural Rubber/trans-Butadiene-co-Isoprene Rubber Vulcanizates under the Synergistic Effect of Crosslinking Density and Crystallization

The thermo-oxidative aging of rubber products is inevitable during their use and leads to product failure and can even endanger safety. Oxygen is an important factor that cannot be ignored during the thermo-oxidative aging process. Thus, the gas barrier property of rubber products is of significant concern. In this work, a strategy of crystallizing rubber in unfilled rubber composites was designed by firstly constructing a dual synergistic mechanism of crosslinking density and crystallization on the oxygen barrier properties. As a crystallizable polymer, trans-butadiene-co-isoprene rubber (TBIR) shows dendritic fibril crystals or spherulites in natural rubber (NR)/TBIR vulcanizates. Meanwhile, the vulcanizates containing TBIR have a higher crosslinking density than NR vulcanizates. These TBIR-rich crystals and high-crosslinking-density structures are distributed in vulcanizates like continuous islands. Contrary to what has been reported in the literature, the decrease in oxygen permeability of NR/TBIR is not only due to the high crosslinking density and free volume of the polymer matrix, but more importantly, the spherulites of TBIR play a role in blocking and prolonging the oxygen diffusion path during the diffusion of oxygen in the polymer composites. We propose that the compatible crystalline polymer can replace the lamellar filler, play the role of the oxygen barrier in rubber composites, reduce the diffusion and dissolution of oxygen, and achieve the effect of improving the thermo-oxidative aging property of the rubber composite. Future research will follow the morphology evolution of TBIR crystals, their crosslinking structure and density, and interactions between TBIR and NR on the oxygen barrier and thermo-oxidative aging property.