内环双酚亚磷酸酯类抗氧剂HP-10的合成研究

研究了以2,2′-亚甲基双(4,6-二叔丁基苯酚)(简称双酚Z)与三氯化磷为原料,经一级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)亚磷酸酯一氯化物;与异辛醇二级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)异辛烷氧基亚磷酸酯(简称HP-10)。一级酯化工艺条件:n(双酚Z)∶n(三氯化磷)=1.0∶1.3,催化剂0.2g,反应时间2.0h,温度85.0℃;二级酯化工艺条件:异辛醇6.5g,缚酸剂13.0g,反应时间4.0h,温度85.0℃。合成HP-10收率达84.3%,熔点147.5～148.2℃,经IR1、H NMR、13 C NMR、LC-MS谱图解析,与HP-10结构相符,产物质量分数大于97.0%。

STUDY ON SYNTHESIS OF CYCLIC BISPHENOL PHOSPHITE ANTIOXIDANT HP-10

2,2′-Methylene bis(4,6-di-tert-butylphenyl) iso-octanol phosphate(called HP-10) was prepared by 2,2′-methylene bis(4,6-di-tert-butylphenol)(called bisphenol Z) with phosphorus trichloride as first-order esterification reaction to give 2,2′-methylene bis(4,6-di-tert-butylphenol) phosphorochlorodite which,in turn,was reacted with iso-octanol.The first-order esterification was conducted under the following conditions: the molar ratio of bisphenol Z to phosphorus trichloride of 1.0∶1.3,0.2 g catalyst,reaction time 2.0 h and reaction temperature 85.0 ℃.The second-order esterification was conducted under the following conditions: the amounts of iso-octanol and proton acceptor were 6.5 g and 13.0 g,respectively,the reaction time 4.0 h and the reaction temperature 85.0 ℃.The yield of the product reached up to 84.3% with the melting point of 147.5-148.2 ℃.The structure of the product was confirmed by IR,1H NMR,13C HMR and LC-MS.The purity of the product was up to 97.0% determined by HPLC.The yield of the product was improved by regulating the amount of the proton acceptor to absorb hydrogen chloride.