橡胶促进剂NS的绿色合成工艺与应用研究进展

橡胶硫化促进剂按照化学结构可以分为醛胺类、秋兰姆类、硫脲类、二硫代氨基甲酸盐类、噻唑类、胍类、黄原酸盐类和次磺酰胺类等，其中次磺酰胺类促进剂具有抗烧焦时间长、硫化活性大、硫化平坦性高、力学性能优良等优点，应用最为广泛。促进剂NS（N-叔丁基-2-苯并噻唑次磺酰胺，TBBS）与其他次磺酰胺类促进剂相比，因在硫化过程中不产生致癌毒性物质亚硝胺，被誉为“标准促进剂”。本文回顾了以次氯酸钠为氧化剂合成促进剂NS的传统方法；综述了催化氧化法、氯气氧化法、电解氧化法和双氧水氧化法等绿色合成工艺；简要概述了微通道反应器在合成促进剂NS方面的工业应用。同时简介了促进剂NS在天然橡胶、丁苯橡胶、二氧化硅填充橡胶的改性剂以及合成氨基磷酸酯等领域的应用。

Progress in clean synthesis technology and application of rubber accelerator NS

Ulfonamides rubber vulcanization accelerators can be divided into aldehydes, thiurams, thioureas, dithiocarbamates, thiazoles, guanidines, xanthates, and sulfenamides according to their chemical structure. Among them, sulfenamide accelerators have the advantages of long anti-scorch time, high vulcanization activity, high vulcanization flatness, and excellent mechanical properties, and are most widely used. Compared with the other sulfenamide accelerators, accelerator NS (N-tert-butyl-2-benzothiazolesulfenamide, TBBS) does not produce carcinogenic toxic nitrosamines in the process of vulcanization, so it is known as“standard accelerator”. The traditional method for synthesis of accelerator NS with sodium hypochlorite as oxidant is reviewed, and the green synthetic processes such as catalytic oxidation, chlorine oxidation, electrolytic oxidation and hydrogen peroxide oxidation are summarized. A brief overview of the application of the microreactor in the synthesis accelerator NS is provided. At the same time, the applications of accelerator NS in the fields of natural rubber, styrene-butadiene rubber, silica-filled rubber modifier and synthetic phosphoramidate were also introduced.