Chen Guojing, Wang Bingbing, Lin Hongtu, Peng Wenfeng, Zhang Fuquan, Li Gaorong, Ke Dongbin, Liao Jianhe, Liao Lusheng
School of Materials Science and Engineering, Hainan University, Haikou 570228, China.
Key Laboratory of Tropical Crop Products Processing of Ministry of Agriculture and Rural Affairs, Agricultural Products Processing Research Institute of Chinese Academy of Tropical Agricultural Sciences, Zhanjiang 524002, China.
Polymers (Basel). 2022 May 27;14(11):2180. doi: 10.3390/polym14112180.
It well-known that the superior performance of natural rubber (NR) compared to its synthetic counterpart mainly derives from nonisoprene components and naturally occurring network, which varies during the progress of the maturation and thereby results in technically graded rubber with different properties. However, identifying the roles of these two factors in the forming of excellent performance of NR is still a challenge as they change simultaneously during the maturation process. Here, influences of naturally occurring networking and nonisoprene degradation on the components, structures and properties of NR were systematically investigated by tailored treatments of maturation. It was found that the maturation-induced formation of natural network structure contributes to the increase in initial plastic value, Mooney viscosity and gel content for un-crosslinked NR, while the decomposition of nonisoprene components plays a dominant role in improving the mechanical properties of vulcanized NR. Stress-strain curve and Mooney-Rivlin analysis demonstrate that the biodegradation of the nonisoprene components significantly boost the vulcanization process, which significantly increases the number of chemical cross-link networks and effective cross-link density of the material, greatly improving the mechanical properties of NR vulcanizates. This resulted in the tensile strength of TSR 10CV being able to reach 22.6 MPa, which is significantly improved compared to 15.8 MPa of TSR 3CV. Evidenced by tubular model fitting, the increase in chemical cross-linking points effectively reduces the movable radius of the molecular chain under dynamic loading, making the molecular chain more difficult to move, which suppresses the entropy change under dynamic loading and consequently endows NR excellent dynamic mechanical properties. This resulted in a significant decrease in the temperature rising of TSR 10CV to 3.3 °C, while the temperature rising of TSR 3CV was still as high as 14.5 °C. As a minor factor, the naturally occurring network improves the mechanical properties of vulcanizates in the form of sacrificial bonds.
众所周知,天然橡胶(NR)相较于合成橡胶具有更优异的性能,这主要源于非异戊二烯成分和天然存在的网络结构,其在成熟过程中会发生变化,从而产生具有不同性能的技术分级橡胶。然而,确定这两个因素在NR优异性能形成过程中的作用仍然是一项挑战,因为它们在成熟过程中会同时发生变化。在此,通过对成熟过程进行定制处理,系统地研究了天然网络结构和非异戊二烯降解对NR的成分、结构和性能的影响。研究发现,成熟诱导形成的天然网络结构有助于提高未交联NR的初始塑性值、门尼粘度和凝胶含量,而非异戊二烯成分的分解在改善硫化NR的机械性能方面起主导作用。应力-应变曲线和门尼-里夫林分析表明,非异戊二烯成分的生物降解显著促进了硫化过程,这显著增加了材料的化学交联网络数量和有效交联密度,极大地提高了NR硫化胶的机械性能。这使得TSR 10CV的拉伸强度能够达到22.6 MPa,与TSR 3CV的15.8 MPa相比有显著提高。通过管状模型拟合证明,化学交联点的增加有效地减小了动态载荷下分子链的活动半径,使分子链更难移动,从而抑制了动态载荷下的熵变,进而赋予NR优异的动态力学性能。这导致TSR 10CV的温度上升显著降低至3.3 °C,而TSR 3CV的温度上升仍高达14.5 °C。作为一个次要因素,天然存在的网络结构以牺牲键的形式改善了硫化胶的机械性能。