类米氏酮光引发剂的合成及在ATRP中的应用

摘要

以4,4'-二甲基二苯甲酮为原料,经过溴化、选择性胺化、O-烷基化等反应,依次合成了4-(溴甲基)-4'-[双(羟乙基)氨基]二苯甲酮与4-(腰果酚基甲基)-4'-[双(羟乙基)氨基]二苯甲酮两个功能性的类米氏酮光引发剂,收率分别为58%和46%.在4-(溴甲基)-4'-[双(羟乙基)氨基]二苯甲酮中含有苄溴基团,因此该化合物还可作为 ATRP或 SET-LRP引发剂.同时,利用4-(溴甲基)-4'-[双(羟乙基)氨基]二苯甲酮作引发剂进行了腰果酚单体的 AGET ATRP聚合反应,得到相应的腰果酚均聚物(Mn=20.2 kDa,PDI=1.11).小分子化合物的结构用1H-NMR进行了表征.%By using 4,4'-dimethyl benzophenone as starting material,two functional Michler's ketone-like photoinitiators,4-(bro-momethyl)-4'-[bis(hydroxyethyl)amino]benzophenone and 4-(cardanolylmethyl)-4'-[bis(hydroxyethyl)amino]benzophenone were synthesized via bromination,selective amination and O-alkylation.The yields were 58%and 46%,respectively.The compound 4-(bromomethyl)-4'-[bis(hydroxyethyl)amino]benzophenone could act as an ATRP or SET-LRP initiator,because there was an benzyl bromide group in this compound.Furthermore,AGET ATRP polymerization of cardanyl methacrylate was conducted by using 4-(bromomethyl)-4'-[bis(hydroxyethyl)amino]benzophenone as the initiator,leading to the corresponding cardanol-based ho-mopolymer(Mn=20.2 kDa,PDI=1.11).Structures of the synthesized small molecules were characterized by 1H-NMR.