聚二(2-甲基-4-羟基-5-叔丁基苯)硫醚的合成

介绍了四步法合成聚二(2 甲基 4 羟基 5 叔丁基苯)硫醚:①以异丁烯和间甲酚为原料,以浓硫酸为催化剂合成3 甲基 6 叔丁基苯酚,并将剩余釜底液继续与间甲酚反应使3 甲基 6 叔丁基苯酚的收率接近100%;②硫磺与氯气反应合成二氯化硫,收率80%以上;③3 甲基 6 叔丁基苯酚与二氯化硫发生缩合反应生成二(2 甲基 4 羟基 5 叔丁基苯)硫醚,采用加入辅助溶剂法收率达到92%;④二(2 甲基 4 羟基 5 叔丁基苯)硫醚同氧气发生氧化偶联反应合成聚二(2 甲基 4 羟基 5 叔丁基苯)硫醚。氧化偶联反应的最佳条件:n〔二(2 甲基 4 羟基 5 叔丁基苯)硫醚〕/n(氧气)=2 5～3 0,n(氯化亚铜)∶n〔二(2 甲基 4 羟基 5 叔丁基苯)硫醚〕=1∶140,n(氯化亚铜)∶n(四甲基乙二胺)=1∶1 3的铜 胺络合物为催化剂,温度50℃,压力0 2MPa,反应时间2～3h,然后减压蒸出溶剂,最后得到淡黄色的聚二(2 甲基 4 羟基 5 叔丁基苯)硫醚,收率>99%。

Synthesis of Poly[di(2-methyl-4-hydroxy-5-t-butylphenyl)sufide]

Poly〔di(2-methyl-4-hydroxy-5-t-butylphenyl) sufide〕(Ⅰ) was synthesized via four-step reactions.Firstly,3-methyl-6-t-butylphenol(Ⅱ) was formed by reaction of isobutylene with cresol using sulfuric acid as catalyst and then by reaction of the by-products with cresol.Thus the total yield of Ⅱ was nearly 100%.Secondly,sulfur dichloride was prepared by the reaction of sulfur with chlorine,and the yield is over 80%.Thirdly,di (2-methyl-4-hydroxy-5-t-butylphenyl) sufide(Ⅲ) was synthesized from Ⅱ and sulfur dichloride in 92% yield through adding auxiliary solvent.Finaly,Ⅰ was obtained through oxidative coupling of Ⅲ with pure gaseous oxygen.The optimized reaction conditions are n(Ⅲ)/n(O_2)= 2.5～3.0,n(CuCl)∶n(Ⅲ)=1∶140,and n(CuCl)∶n(tetramethylethylenediamine)=1∶1.3 as catalyst at 50 ℃ under 0.2 MPa for 2～3 h.The yield of final product Ⅰ was > 99%.