以溴酸根插层锌铝水滑石为载体构建新溴源体系  

New Reagent System for Bromination Built with Zn/Al-BrO_3^--LDHs as Carrier

作　　者：王力耕[1] 郑飞翔[1] 蒋晨星 倪哲明[1] 

机构地区：[1]浙江工业大学化学工程学院,杭州310032

出　　处：《硅酸盐学报》2015年第5期672-677,共6页Journal of The Chinese Ceramic Society

基　　金：浙江省2014公益性技术应用研究

摘　　要：以溴酸根插层锌铝水滑石(Zn/Al-Br O3–-LDHs)为载体,与Br-等还原剂构建形成新型溴源体系。为实现溴源体系在实际应用中的有效控溴,对Zn/Al-Br O3–-LDHs中Br O3–的释放行为进行了研究,并考察了温度、交换离子类型、p H值等因素对Br O3–释放行为的影响。结果表明:升高温度会加快Br O3–的释放,交换离子的交换性越强,Br O3–释放得越快,在p H值为9.0的磷酸盐缓冲溶液中的释放速率要比在p H值为4.0的磷酸盐缓冲溶液中快。采用4种动力学模型对水滑石中Br O3–的释放过程进行动力学拟合,结果表明:LDHs-Br O3–中Br O3–的释放行为符合Bhaskar方程,属粒内扩散控制过程。用LDHs-Br O3–/Br–构建的溴源体系合成了3,5-二溴-2-氨基苯甲酸甲酯,收率为94.7%,纯度为99.8%。A reagent system for bromination was prepared with Zn/Al-Br O3–-LDHs as a carrier and bromide ion as an appropriate reductant. The release behavior of Br O3– was investigated to achieve the controlled release of bromine in practical application. Also, the effects of temperature, type of ion exchanger and p H value on the release behavior were investigated. The results indicate that the release rate becomes more rapidly when the temperature and the anionic exchanging capacity increase, and the Br O3– releases more quickly in a phosphate buffer solution at p H value of 9.0 rather than in a phosphate buffer solution at p H value of 4.0. To analyze the release property of Br O3–, the release profiles were fitted by four theoretical models. The fitting results indicate that the release behavior follows the Bhaskar equation, showing that the release of Br O3– is controlled by intraparticle diffusion. The bromination reagent system was applied for the green synthesis of 3,5-dibromine-2-amino methyl benzoate, which is a key intermediate material for preparing cough medicine like bromhexine and ambroxol at an isolated yield of 94.7% and a purity of 99.8%.

关 键 词：溴酸根 水滑石 释放 溴源体系 控溴 

分 类 号：O611.4[理学—无机化学]