摘要
仲丁基二硫醚是一种对称烷基二硫化物,是生产农药、染料、医药的重要的化工原料和中间体。随着对该产品认识的深入和下游产品的开发,其市场需求量正逐年增加,而国内生产仅停留在实验室规模,国外工业化生产产率也较低,因此,对仲丁基二硫醚合成工艺的开发具有重要的实际意义。本课题组受三门峡奥科化工有限公司的委托,开展了仲丁基二硫醚的新工艺研究。主要研究工作如下：
由合成法实验测定了硫化钠在水、乙醇-水、甲醇-水、二甲基亚砜-水、N,N-二甲基甲酰胺-水、1,4-二氧六环-水、四氢呋喃-水等体系中的溶解度,实验结果表明：当w=20%时硫化钠的溶解度数据符合DMF-水>水>甲醇-水>二氧六环-水>DMSO-水>乙醇-水,运用Apelblat三参数方程关联实验数据,并给出相关的模型参数和相关系数。所有数据点的实验值和计算值相比较,相对误差小于4.7%,说明实验测得溶解度数据运用Apelblat三参数溶解度方程关联时实验值和计算值吻合良好。
探索了以硫化钠、硫和仲丁基溴为原料合成仲丁基二硫醚的工艺路线。以分析纯、工业硫化钠为原料,四丁基溴化钱为相转移催化剂合成仲丁基二硫醚,通过单因素实验、正交实验研究了反应温度、硫化钠与硫的摩尔比、二硫化钠与仲丁基溴的摩尔比、溶剂量、催化剂量、滴加速度对反应收率和选择性的影响,单因素实验最佳工艺条件为：n(Na2S):n(S)=1.25:1,n(Na2S2):n(C4H9Br)=l:1.8,反应温度为25℃,滴加速度为4h,反应时间为10h,收率为91.64%；正交实验得到各因素的影响顺序大小为：催化剂量>n(Na2S):n(S)>反应温度>n(Na2S2): n(C4H9Br)>滴加时间,最优水平组合为：n(Na2S):n(S)= 1:0.5,n(Na2S2):n(C4H9Br)=1：1.75,温度25℃,催化剂0.5%,滴加时间0h。优化工艺组合方案下,产物的平均收率为92.04%。产品气相浓度大于95%,反应选择性达到95%以上。
反应后的水相无需再添加催化剂可经循环使用3次,减少了废水的排放量,也节省了催化剂。通过对单因素和正交实验最佳条件下的工艺进行物料衡算和经济核算得出生产单位产品正交实验最佳工艺条件下的工艺原料消耗少,成本低,更适于工业化。
利用红外光谱、核磁共振谱和气相色谱等分析方法对硫化钠法合成仲丁基二硫醚进行了表征,红外光谱和1HNMR谱确定了物质的结构,表明为目标产物,气相色谱利用标样保留时间来定性,用于反应后产品含量的确定。
Di-sec butyl disulfide is a symmetrical disulfide. As an important pharmaceutical intermediate and chemical material, it can be used to synthesize a variety of pesticides dyes and medcine. In recent years, di-sec butyl disulfide has a good market demand with its deep realization and development of down-stream products. But its scale of production is very low at home and abroad. So the study on production technology of di-sec butyl disulfide is very significative. Commissioned by Sanmenxia Aoke Chmical Engineering Co. Ltd, synthesis of di-sec butyl disulfide was carried out in this study. The work was as follows.
The solubility of sodium sulfide in water and methanol-water, ethanol-water, dimethyl formamide-water, dimethylsulfoxide-water, tetrahydrofuran-water,1, 4-dioxane-water had been determined by synthetic method. It can be observed that the solubility in selected solvents follow the order DMF-water> water> methanol-water>1,4-dioxane-wate>DMSO-water> ethanol-water on the whole. By using Apelblat three parameters solubility equation to correlate the experimental data, and comparing the calculated value with experimental value, the related deviations were within 4.7%.
2-brombutane and sodium sulfide, sulfur as materials were used. The optimal technology conditions were obtained by single-factor and orthogonal designs. The effects of mole ratio of sodium sulfide to sulfur, the amount of catalysis, the amount of solvent, temperature on the result of reaction were studied. The optimal technology conditions of single-factor were:the amount of catalysis 2%, the mole ratio of sodium sulfide to sulfur 1.25:1, the mole ratio of sodium disulfide to 2-brombutane 1:1.8, the reaction temperature 25℃, the drop time 4 hours, the reaction time 10 hours and the yield 91.64%. The factors followed the order the amount of catalysis> the mole ratio of sodium disulfide to sulfur>the reaction temperature>the mole ratio of sodium disulfide to 2-brombutan>the drop time. And the optimal technology conditions of orthogonal designs were:the amount of catalysis 0.5%, the mole ratio of sodium disulfide to sulfur 1:0.5, the reaction temperature 25℃, the mole ratio of sodium disulfide to 2-brombutan 1:1.75 and the drop time 0 hour. The selectivity and purity of di-sec butyl disulfide is up to 95% and 99.5% respectively. The average yield was 92.04% under the optimal conditions. The process is applicable to the industrial preparation of di-sec butyl disulfide.
The inorganic phase solution could be recycled three times in reaction. So the amount of waste water and catalyst were on the decrease. The economic technology conditions were obtained by material accounting and cost accounting. The optimal technology conditions by orthogonal designs were more suitable for industrial production due to low consumption of raw materials and low cost.
The structure of di-sec butyl disulfide prepared was charactered by IR and 1HNMR.The result showed that the structure of product was in good agreement with the authentic sample. And GC was used for the measurement of crude di-sec butyl disulfide and monitoring the progress of the reaction.
引文
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