六氟环氧丙烷的合成及主副反应机理研究  

Synthesis of Hexafluoropropylene Oxide and its Reaction Mechanism

作　　者：尹红[1] 王刚[1] 戴思远 袁慎峰[1] 陈志荣[1] 

机构地区：[1]浙江大学化学工程与生物工程学院,浙江杭州310027

出　　处：《高校化学工程学报》2015年第4期830-836,共7页Journal of Chemical Engineering of Chinese Universities

基　　金：浙江省重点科技创新团队计划(2011R50007)

摘　　要：以六氟丙烯(HFP)为原料,次氯酸钠饱和水溶液为氧化剂,1,1,2-三氟三氯乙烷(F-113)为溶剂,甲基三辛基氯化铵(TOMAC)为相转移催化剂进行两相法合成六氟环氧丙烷(HFPO)的工艺研究。考察了次氯酸钠水溶液加入方式、反应温度、催化剂用量、次氯酸钠溶液与F-113体积比和反应时间对反应的影响。结果表明:当次氯酸钠水溶液采用缓慢加入法,反应温度为-12℃,催化剂用量为2.5 g,水油相体积比为1,反应时间为2 h时,原料转化率91.3%,六氟环氧丙烷收率84.5%,选择性92.5%。运用量子化学理论在DFT/u B3LYP/6-31+G(d,p)水平计算得到了主反应六氟环氧丙烷生成过程的中间体和过渡态。通过19F-NMR和1H-NMR分析反应水相中生成物,验证了副反应产物Na F、CF3COONa、CF3CF2COONa和CF3CFHCOONa的生成机理。Hexafluoropropylene oxide was synthesized by using hexafluoropropylene （raw material）, sodium hypochlorite （oxidant）, 1,1,2-trichlorotrifluoroethane （solvent） and trioctylmethylammonium chloride （phase-transfer catalyst）, and the effects of sodium hypochlorite aqueous solution adding approach, reaction temperature, catalyst dosage, sodium hypochlorite solution/1,1,2-trichlorotrifluoroethane volume ratio and reaction time on the oxidation process was investigated. The results show that when sodium hypochlorite is slowly added under reaction temperature of-12℃, and the catalyst dosage is 2.5g with aqueous/organic phase volume ratio of 1 and reaction time of 2 h, the conversion of hexafluoropropylene is 91.3% and the yield and selectivity ofhexafluoropropylene oxide can reach to 84.5% and 92.5%, respectively. The formation mechanism of the byproducts SNaF, CF3COONa, CF3CFzCOONa and CF3CFHCOONa is proved by 19F-NMR and 1H-NMR, and the intermediates and transition states of the reaction were obtained by quantum chemical calculation on DFT/uB3LYP/6-31＋G（d, p）.

关 键 词：六氟丙烯 六氟环氧丙烷 量子化学 过渡态 

分 类 号：X52[环境科学与工程—环境工程]