Octylamine regulating the mechanical robustness of natural rubber by involving in the construction of crosslinking network.

The formation of three dimensional network structure is critical in determining mechanical properties of natural rubber (NR). Consequently, it is vital to regulate crosslinking network of NR by controlling vulcanization process. Inspired by our previous studies on contribution of non-rubber components (NRCs) to the excellent properties of NR, we find octylamine in NRCs decreases the activation energy (Ea) of vulcanization from 82.73 kJ/mol to 44.34 kJ/mol, thereby reducing vulcanization time from 18.67 min to 2.71 min. From microscopic perspective, octylamine tends to coordinate with zinc ions to improve dispersion of ZnO in NR. And octylamine promotes ring-opening reaction of S8 to favor formation of polysulfide intermediates. Therefore, the incorporation of octylamine remarkably improves vulcanization efficiency, which contributes to the formation of a more homogeneous network with higher crosslinking density, enhancing remarkably the strength and toughness of NR. As a result, the tensile strength and fracture energy of samples are as high as 31.15 MPa and 68.88 kJ/m2, respectively. In addition, even with a 60 % reduction in ZnO content, the NR samples still maintain high vulcanization efficiency and excellent mechanical properties after the addition of octylamine, which provides a green and feasible way to alleviate the environmental pollution caused by ZnO.

Mechanically Robust Elastomers Enabled by a Facile Interfacial Interactions-Driven Sacrificial Network.

Strength and toughness are usually mutually exclusive for materials. The sacrificial bond strategy is used to address the trade-off between strength and toughness. However, the complex construction process of sacrificial network limits the application of sacrificial network. This work develops a facile strategy to construct an interfacial interactions-driven sacrificial network. The authors' group finds that there are the interfacial interactions between arginines (A) aggregates and molecular chains. Such interfacial interactions result in the mechanical properties of samples having a strong dependence on extension rates, which shows that A aggregates construct a network structure by interfacial interactions. The interfacial interactions between A aggregates and chains improve the strength of samples; while the A aggregate network driven by interfacial interactions preferentially ruptures to dissipate large energy for the improvement of fracture toughness, which can be considered as a sacrificial network. Therefore, their designed elastomers have both high strength and high toughness. This work provides an easier strategy for the construction of sacrificial networks, which can promote the industrial application of sacrificial networks in elastomer materials.

MXene Enabling the Long-Term Superior Thermo-Oxidative Resistance for Elastomers.

The ability of long-term thermo-oxidative resistance is very important for elastomers in application. However, many conventional antioxidants are difficult to realize the long-term thermo-oxidative resistance. To overcome this limitation, a design strategy is introduced by combing elastomers with MXene and natural rubber (NR) is chosen as a model material. MXene is efficient in absorbing oxygen and the generated free radicals in the NR matrix and can inhibit the diffusion of oxygen toward the interior. Moreover, MXene, like graphene and carbon black, absorbs molecular chains, inhibiting the migration of MXene toward the surface of the sample. Such characteristics of MXene endow NR/MXene with the long-term outstanding thermo-oxidative resistance. For example, after three days of the thermo-oxidative process for NR/MXene, the tensile strength is 19 MPa and the retention of tensile strength is 63%, which far exceeds the effects of conventional antioxidants. This work not only provides a good guide for the universal design of elastomers with long-term thermo-oxidative resistance but also expands the application of MXene.

Effect of protein on the thermogenesis performance of natural rubber matrix.

Under high-speed strain, the thermogenesis performance of natural rubber products is unstable, leading to aging and early failure of the material. The quality of rubber latex and eventually that of the final products depends among others on the protein content. We found that when the protein is almost removed, the heat generated by the vulcanized rubber increases rapidly. After adding soy protein isolate to the secondary purification rubber, the heat generation of the vulcanized rubber is reduced, and the heat generation is the lowest when the added amount is 2.5-3.0 phr, which on account of protein promotes the construction of a vulcanization network and increases the rigidity of the rubber chain, resulting in a decrease in the potential frictional behavior of the rubber chain during the curl up-extension process.

Mimicking the Mechanical Robustness of Natural Rubber Based on a Sacrificial Network Constructed by Phospholipids.

Mechanical strength and toughness are usually mutually exclusive, but they can both appear in natural rubber (NR). Previous studies ascribe such excellent properties to highly cis stereoregularity of NR. To our surprise, after the removal of non-rubber components (NRC) by centrifugation, the strength and toughness of NR decrease dramatically. It is still a challenge for us to make out for the problem of how NRC affect the properties of NR. Our group ascribes the superior mechanical robustness of NR to NRC. To further verify such a viewpoint, we add phospholipids (phosphatidylcholines) into NR without NRC. Phosphatidylcholines construct a sacrificial network, which ruptures preferentially upon deformation to dissipate energy. Moreover, some of phosphatidylcholines participate in the vulcanization reaction, which further improves the mechanical strength and energy dissipation. As a result, the mechanical strength and toughness of samples are as high as 21.1 MPa and 49.6 kJ/m2, respectively, which have reached the same level as that of NR. Therefore, this work not only imitates the excellent mechanical robustness of NR but also further provides a rational design for elastomers with excellent mechanical robustness.