脲二酮的开环及氨酯化反应  

Ring-Opening and Carbamate Reaction of Uretedione

作　　者：杨鹏飞[1,2] 赵超[1] 李天铎[1,3] 

机构地区：[1]山东轻工业学院轻工助剂省重点实验室 [2]山东轻工业学院分析测试中心 [3]山东轻工业学院科技处,山东济南250353

出　　处：《高分子材料科学与工程》2011年第11期129-132,共4页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(20676074)

摘　　要：用在线红外光谱跟踪1,3-双(3-氨基甲酸甲酯基-4-甲基苯基)脲二酮的开环反应,研究了温度、催化剂等对脲二酮开环反应的影响;同时,进行了脲二酮开环-氨酯化反应,用核磁共振(NMR)表征了产物甲苯-二(2-甲基-4-乙基)氨基甲酸酯的结构。结果表明,温度为80℃、催化剂三正丁基膦用量为m(cat)/m(uretedione)=4/100时,脲二酮开环反应比较完全;在三正丁基膦的催化下,可能会发生异氰酸酯三聚反应,导致异氰酸酯基浓度呈现先增大后减小的变化规律。此外,与乙醇反应时,脲二酮的开环、氨酯化同时进行,氨酯化速率大于开环速率,使产物具有规整的结构。Ring-opening reaction of 1,3-bis（3-methyl carbamyl-4-methyl phenyl）uretedione was investigated with in-situ Fourier transform infrared spectrum（FT-IR）,and the effects of temperature and catalyst on the reaction was discussed.Carbamate reaction of ring-opened uretedione was also studied,and the product of tolylene-bis-（2-methyl-4-ethyl）carbamate was characterized with IR and nuclear magnetic resonance spectrum（NMR）.It shows that ring-opening reaction carries on completely when the reaction temperature is 80 ℃ and the mass percent of tri-n-butyl phosphine is m（cat）/m（uretedione）=4/100.Trimerization of isocyanate may be also happened in the presence of tri-n-butyl phosphine,which leads to the-NCO concentration first larger and then smaller.Furthermore,the ring-opening reaction and carbamate reaction happens together when reacting with alcohol.The rate of carbamate reaction is faster than that of ring-opening reaction,which enables good structure regularity of the product.

关 键 词：脲二酮 开环反应 氨酯化反应 甲苯-2 4-二异氰酸酯 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]