Pd(OH)_(2)/CeO_(2)在六苄基六氮杂异伍兹烷和四乙酰基二苄基六氮杂异伍兹烷催化氢解脱苄反应中的应用

Pd(OH)_(2)/CeO_(2) Catalyst for Hydrogenolytic Debenzylation Reaction of Hexabenzylhexaazaisowurtzitane and Tetraacetyl-dibenzyl-hexaazaisowurtzitane

Pd(OH)_(2)催化剂对六硝基六氮杂异伍兹烷(CL-20)的制备具有关键作用。选择CeO_(2)为催化剂载体,用沉积-沉淀法制备8种Pd(OH)_(2)/CeO_(2)催化剂,考察制备温度、浸渍时间、碱源、沉淀pH及载体结构对Pd(OH)_(2)/CeO_(2)催化氢解脱苄反应活性的影响。结果表明:Pd(OH)_(2)/CeO_(2)可同时作为六苄基六氮杂异伍兹烷(HBIW)和四乙酰基二苄基六氮杂异伍兹烷(TADBIW)氢解脱苄反应的催化剂,并表现出优异的催化活性,产物收率分别可达91%和95%;将其用于HBIW氢解脱苄反应,在金属Pd用量为底物HBIW质量的0.10%时,TADBIW的产率最高可达91%;将其用于TADBIW氢解脱苄反应,Pd用量为底物TADBIW质量的0.28%时,产率可达87%;所用研究方法使用少量Pd催化剂高效地催化HBIW和TADBIW的氢解脱苄反应,为低成本制备CL-20拓宽了道路。

Palladium hydroxide catalysts play a key role in the preparation of hexanitrohexaazais-owurtzitane(CL-20).Eight kinds of Pd(OH)_(2)/CeO_(2) catalysts,for which two kinds of CeO_(2) are used as catalyst support,were prepared by deposition-precipitation method.The effects of the preparation temperature,immersion time,the kinds of alkali,pH and the structure of support on the catalytic performance of Pd(OH)_(2)/CeO_(2) are investigated.Pd(OH)_(2)/CeO_(2) catalysts exhibit excellent catalytic activity in the hydrogenolytic debenzylation reaction of both hexabenzylhexaazaisowurtzitane(HBIW)and tetraacetyl-dibenzyl-hexaazaisowurtzitane(TADBIW),and the yields of products can reach 91%and 95%,respectively.When the amount of Pd used in catalyst is 0.10%(wt/wt)of HBIW substrate,the yield of TADBIW reachs 91%.When the amount of Pd is 0.28%(wt/wt)of TADBIW substrate,the yield of the product is as high as 87%.In this research,a small amount of Pd catalyst is used to efficiently catalyze the hydrogenolytic debenzylation reaction of HBIW and TADBIW,which broadens the way for low-cost preparation of CL-20.