钝化氯磺酸法高选择性硫酸酯化的新技术研究

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

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 oC；老化15 min，此时硫酸酯化率达到98.4 %，NPPS选择性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，该方法更简便、高效和廉价；因此该法有望推广到其它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。

Abstract:

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 polyproxylene ether sulfate (NPPS), one of the extended surfactant was highly selectively synthesized from nonylphenol polyproxylene ether (NPP) by using the aforementioned technique. The influential factors such as dosages of sulfation agent, ageing temperatures and ageing times were systematically investigated. The selectivity of sulfation could reach to 100 % and the maximum yield was as high as 98.4 % under the optimal conditions of 1.3:1 molar ration of HSO3Cl to NPP at 35 oC reacting 15 min. And fortunately DMF could be simply recovered and reused. The experimental results showed that it was difficult to obtain high sulfation selectivity by only using chlorosulfonic acid as sulfation agent. And it is also showed that compared with sulfamic acid as sulfation agent, this technique was much simple, 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.