钝化氯磺酸法高选择性硫酸酯化的新技术  

A Novel Technique to Enhance Selectivity of Sulfation Against Sulfonation Using Katastaltic Chlorosulfonic Acid

作　　者：何志强[1] 金光勇[1] 方云[1] 陈骥[1] 

机构地区：[1]江南大学化学与材料工程学院食品胶体与生物技术教育部重点实验室,江苏无锡214122

出　　处：《精细化工》2013年第7期725-728,765,共5页Fine Chemicals

基　　金："十一五"国家科技支撑计划项目(2007BAE52B01);江苏省精细石油化工重点实验室开放基金项目(KF0903)~~

摘　　要：采用DMF钝化氯磺酸活性的方法开发了一种对同时含有醇羟基和芳香环的有机原料实现高选择性硫酸酯化的方法。运用该技术以壬基酚聚氧丙烯醚(NPP)为原料高选择性制备了一类Extended表面活性剂——壬基酚聚氧丙烯醚硫酸盐(NPPS)。探索了反应参数对选择性硫酸酯化的影响,优化后得到较佳的工艺条件为:n(HSO3Cl)/n(NPP)=1.3,老化温度35℃,老化时间15 min,此时硫酸酯化率达到98.4%,NPPS选择性达100%,且DMF钝化剂经简单回收后可重复使用。与非钝化氯磺酸法相比,该法实现了高选择性硫酸酯化;与氨基磺酸法相比,该法更简便、高效和廉价;因此,该法有望推广到其他同时含有醇羟基和芳香环原料的高选择性硫酸酯化反应中。A new sulfation technique was developed using DMF-katastaltic chlorosulfonic acid as sulfation/sulfonation agent which showed higher selectivity of sulfation against sulfonation for the feedstocks containing both aromatic ring and hydroxyl intramolecularly.Nonylphenol polyoxypropylene ether sulfate（NPPS）,one of the extended surfactants was highly selectively synthesized from nonylphenol polyproxylene ether（NPP） by using the aforementioned technique.The influential factors such as dosage of sulfation agent,ageing temperature and ageing time were systematically investigated.The selectivity of sulfation could reach 100% and the maximum yield was as high as 98.4% under the optimal conditions of 1.3：1 molar ratio of HSO3Cl to NPP at 35 ℃ reacting for 15 min.And fortunately DMF could be simply recovered and reused.The experimental results show that it was difficult to obtain high sulfation selectivity by only using chlorosulfonic acid as sulfation agent.And it is also shown that,compared with sulfamic acid as sulfation agent,this technique was much simpler,more efficient and more inexpensive.It is expected that the novel technique is a hopeful sulfation method with high sulfation selectivity for the other feedstocks containing both aromatic ring and hydroxyl intramolecularly.

关 键 词：氯磺酸 钝化剂 氨基磺酸 选择性硫酸酯化 烷基酚聚氧丙烯醚 Extended表面活性剂 

分 类 号：TQ423.4[化学工程]