【作者】 司晓宁；

【导师】 袁存光； 于剑峰；

【作者基本信息】 中国石油大学 ， 应用化学， 2008， 硕士

【摘要】 有机锡化物是制备烷基酯的最有效的催化剂,其中以二丁基二甲氧基锡(DBDMOS)的催化效果最好。本文研究了以二丁基氧化锡(DBOS)为原料制备DBDMOS的反应体系及合成的条件,并将合成所得产物应用于某些引入甲氧基反应体系的催化反应中,研究了其作为催化剂使用的性能。实验研究确定用DBOS、甲醇作原料,在氨基甲酸甲酯(MC)分解反应催化作用下反应合成DBMOS,确定了DBDMOS的制备条件:MC、甲醇、DBOS的物质的量之比为3:3:1、反应温度180.0℃、反应时间5h,在此条件下DBDMOS的产率达到理论产率的86%。采用甲醇-正己烷混合溶剂萃取的方法提纯合成的DBDMOS粗产品。分别用IR、1H-NMR及ICP-MS等现代仪器手段测定了原料DMOS和产品DBDMOS的结构,通过谱图与标准谱图的对照分析,确定DBOS已经成功的转化为DBDMOS。将实验合成的DBDMOS作为催化剂应用到碳酸二甲酯(DMC)的合成实验及脂肪酸甲酯酯交换反应中。在DMC合成实验中,用DBDMOS作催化剂,与以DBOS为催化剂的效果比较,催化效果明显,适宜的反应温度基本一致,但DMC的产率大大提高、催化剂用量大大减少、反应时间缩短了近一半。脂肪酸甲酯与甲醇在本文获得的产品DBDMOS的催化作用下反应,可以生成烃类和DMC,该催化反应在低温条件下,以四氢呋喃为溶剂,DMC的产率为0.47%,这一反应体系为生物油脂的矿物化和DMC的合成提供了新途径,为国内外首次研究。本文的总体研究成果对尿素法合成碳酸二烷基酯反应及有机合成中通过亲核取代作用引入-OCH3基团的催化反应体系具有重要的应用价值。更多还原

【Abstract】 One of organictin compounds, dibutyltin dimethoxide(DBDMOS), is the most effective catalyst for preparing alkyl ester. In this paper, the reaction system and perpatation conditions of DBDMOS from dibutyltin oxide(DBOS) were mainly studied. The products were applied in some catalytic reactions to study the catalytic properties, which methoxyl group was introduced. A process with DBOS and methanol(MeOH) as raw materials for making DBDMOS was determined, and the decomposition and catalysis of alkyl carbamate(MC) were compared. Operating conditions which influence the preparation condition of DBDMOS were measured as following: Reaction temperature 180.0℃, reaction time 5h, the material quantity tatio was MeOH:MC:DBOS=3:3:1. Under the conditions, the yield of DBDMOS exceeds 86%.The primary products was purification via methanol and n-hexane extraction. The products and raw materials have been characterized by means of IR, 1H-NMR and ICP-MS. The results indicate that dibutyltin dimethoxide has been prepared. To examine the activity of DBDMOS, the product was used as catalyst for the dimethyl carbonate(DMC) synthesis reaction and the transesterification reaction of fatty acid methyl ester. In the process of DMC synthesis reaction, the catalytic property of DBDMOS is better than that of DBOS as catalyst. The amount of catalyst obviously reduced, reaction time reduced by half, while the yield of DMC increased. But the reaction temperatures of two reactions are similar. With DBDMOS as catalyst, tetrahydrofuran as the solvent and low temperature, hydrocarbon and DMC were prepared from fatty acid methyl ester and MeOH and the yield of DMC exceeds 0.47%. This reaction system was studied for the first time to provide a new method which to mineralize of biodiesel and synthesis of DMC. The results have important value in the technics of the preparation of dialkyl carbonate, as well as the organic reactions of introduction the -OCH3 group via nucleophilic substitution.更多还原