|本期目录/Table of Contents|

[1]薛香菊,刘 杨,鲍 翠,等.硫化促进剂N-环己基-2-苯并噻唑次磺酰胺合成工艺过程探究[J].合成橡胶工业,2023,6:476-481.
　XUE Xiang-ju,LIU Yang,BAO Cui,et al.Study on synthesis process of vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide[J].China synthetic rubber industy,2023,6:476-481.
点击复制

硫化促进剂N-环己基-2-苯并噻唑次磺酰胺合成工艺过程探究(PDF)

《合成橡胶工业》[ISSN:1000-1255/CN:62-1036/TQ]

期数:
2023年6期
页码:
476-481
栏目:
出版日期:
2023-11-15

文章信息/Info

Title:
Study on synthesis process of vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide
文章编号:
1000-1255（2023）06-0476-06
作者:
薛香菊; 刘 杨; 鲍 翠; 逯宇宙; 杨春霞; 单 鑫
山东尚舜化工有限公司，山东 菏泽 274300
Author(s):
XUE Xiang-ju;  LIU Yang;  BAO Cui;  LU Yu-zhou;  YANG Chun-xia;  SHAN Xin
Shandong Sunsine Chemical Co Ltd, Heze 274300, China
关键词:
硫化促进剂; N-环己基-2-苯并噻唑次磺酰胺; 2-巯基苯并噻唑; 环己胺; 氧化法; 合成工艺; 游离胺
Keywords:
vulcanization accelerator;  N-cyclohexyl-2-benzothiazole sulfenamide;  2-mercaptobenzothiazole;  cyclohexylamine;  oxidation method;  synthesis process;  free amine
分类号:
TQ 325.1
DOI:
DOI:10.19908/j.cnki.ISSN1000-1255.2023.06.0476
文献标识码:
A
摘要:
以硫化促进剂2-巯基苯并噻唑（M）和环己胺为原料，采用次氯酸钠氧化法合成了N-环己基-2-苯并噻唑次磺酰胺（CBS），考察了合成工艺过程中反应体系的外观变化、液相中环己胺含量、固相中游离胺含量及固相熔点，同时提出了反应机理。结果表明，反应机理主要是促进剂M先与环己胺反应生成促进剂M环己胺盐，在氧化剂次氯酸钠的作用下胺盐中的硫氢键和氮氢键经交叉偶联反应和脱氢反应形成硫氮键，从而生成促进剂CBS。当氧化剂次氯酸钠加入量较少时，在反应前期阶段反应体系内液相相对较少，反应体系整体上呈膏状；随着次氯酸钠加入量的不断增加，固液两相逐渐分离，液相中环己胺质量浓度先由0.120 g/mL逐渐降低至0.045 g/mL，后又逐渐升高至0.092 g/mL，固相中游离胺质量分数由37.12%逐渐下降至0.15%；当次钠酸钠完全加入时，促进剂CBS质量分数可高达98.9%。
Abstract:
N-cyclohexyl-2-benzothiazole sulfenamide (CBS) was synthesized with vulcanization accelerator 2-mercaptobenzothiazole (M) and cyclohexylamine as raw materials via the oxidation ca-talyzed by sodium hypochlorite, the appearance change of the reaction system, the content of cyclohexylamine in the liquid phase and free amine in the solid phase, and the melting point of the solid phase were investigated during the synthesis process, and at the same time, the reaction mechanism was proposed. The results showed that the reaction mechanism was mainly the reaction of promoter M with cyclohexylamine to give promoter M cyclohexylamine salt, of which the sulfur hydrogen bond and nitrogen hydrogen bond underwent cross-coupling reaction and dehydrogenation reaction to form sulfur nitrogen bond under the action of oxidant sodium hypochlorite, followed by the generating of accelerator CBS. When the addition amount of oxidant sodium hypochlorite was small, there was relatively little li-quid phase in the reaction system in the early stage of the reaction and the overall reaction system was paste-like; with the increasing addition amount of sodium hypochlorite, the solid-liquid phases separated gradually and mass concentration of cyclohexylamine in liquid phase decreased gradually from 0.120 g/mL to 0.045 g/mL and then increased gradually to 0.092 g/mL, and mass fraction of free amine in the solid phase decreased gradually from 37.12% to 0.15%; when sodium hyponatrate was completely added, mass fraction of vulcanization accelerator CBS could be up to 98.9%.

参考文献/References

［1］ 张新民. 2009年中国橡胶助剂工业科技发展报告［M］. 北京： 中国商业出版社， 2009： 1-8.［2］ Heidemn G, Noordemeer J W M, Datta R N, et al. Zinc loaded clay as activator in sulfur vulcanization： A new route for zinc oxide reduction in rubber compounds［J］. Rubber Chemistry and Technology, 2004, 77（2）： 336-355.［3］ 中国化工学会橡胶专业委员会. 橡胶助剂手册［M］. 北京： 化学工业出版社, 2002： 378-379.［4］ Svarz J J, Hunter W E, Goretta L A, et al. Amine derivatives of mercapto-benzothjiazole： US, 3600398［P］. 1971-08-17.［5］ Toukan S S. Manufecture of sulfanamides： US, 4258197［P］. 1981-03-24.［6］ Zen L H, Eisenhuth L, Bergfeld M. Process for the production of thiazolyl-2-sulphenanides： US, 4670556［P］. 1987-06-02.［7］ 张怀猛, 刘斌. 一种提高双氧水法合成CBS收率的方法［J］.中国橡胶, 2021, 37（6）： 40-42.［8］ Wuest A, Van O T. Process for preparing benzothiazolesulphenamides： US, 4751301 A［P］. 1988-06-14.［9］ 朱言萍. 硫化促进剂CBS工艺优化研究［J］. 煤炭与化工, 2016, 39（1）： 72-74.［10］ 刘万兴, 刘秀峥. 钴盐催化合成橡胶硫化促进剂CBS工艺的探讨［J］. 云南化工, 2019, 46（2）： 64-68.［11］ He Muxue, Cheng Shiyan, Pan Yongzhou, et al. Electrochemically mediated S—N bond formation： Synthesis of sulfenamides［J］. Chinese Journal of Organic Chemistry, 2021, 41（6）： 2354-2360.［12］ Taniguchi N. Copper-catalyzed oxidative synthesis of sulfinamides using thiols or disulfides with amines［J］. Europe Journal of Organic Chemistry, 2016, 2016： 2157-2162.［13］ Wei Zhaoxin, Wang Renjie, Zhang Yonghong, et al. Electrochemical synthesis of N-acyl/sulfonylsulfenamides using potassium iodide as mediator［J］. Chinese Journal of Organic Che-mistry, 2022, 42： 3730-3739.［14］ Eisenhuth L, Bergfeld M. Process for the preparation of benzothiazolyl-2-sulphenamides： US, 5436346［P］. 1995-07-25.［15］ Davis F A, Friedman A J, Kluger E W, et al. Chemistry of the sulfur-nitrogen bond. 12. Metal-assisted synthesis of sulfenamide derivatives from aliphatic and aromatic disulfides［J］. Journal of Organic Chemistry, 1977, 42（6）： 967-972.［16］ 王浩, 于萍, 杜丽丽, 等. 促进剂N-环己基-2-苯并噻唑次磺酰胺的混合氧化法合成工艺［J］. 合成橡胶工业, 2018, 41（3）： 167-171.［17］ 中国石油和化学工业联合会. GB/T 21184—2007 橡胶配合剂 次磺酰胺促进剂试验方法［S］. 北京： 中国标准出版社, 2008： 1-8.［18］ Subcommittee D 11.11 on Chemical Analysis of ASTM Committee D 11 on Rubber and Rubber-like Materials. D 1519-95 （2023）： Standard test method for rubber chemicals—Determination of melting range［S］. West Conshohocken： American Society for Testing and Materials, 2023：1-4.

备注/Memo

备注/Memo:
无
更新日期/Last Update: 2023-11-15