含吡啶配体的钌催化剂合成及在离子液体中开环易位聚合反应

合成了离子液体负载的钌催化剂, 考察了该催化剂在离子液体中对极性环烯烃单体的开环易位聚合(ROMP)反应规律. 首先设计合成含离子液体的吡啶配体1,2-二甲基-3-己氧基吡啶六氟磷酸盐咪唑离子液体配体, 利用其与Grubbs第二代催化剂配位反应, 制备离子液体负载的钌催化剂, 通过1H, 13C NMR等方法对合成的化合物和催化剂进行表征. 催化剂中与钌连接的苯亚甲基上氢(RuCH—Ph) 的振动峰由原来Grubbs第二代催化剂的δ 19.2移至δ 18.6, 表明得到了新的催化剂, ICP测定催化剂混合物中纯催化剂的质量分数为36.2%. 该催化剂易溶于丙酮、甲醇及咪唑类离子液体等极性溶剂, 解决了Grubbs催化剂不溶于离子液体的问题, 实现了在纯离子液体中均相ROMP反应. 考察了催化剂对极性单体5-羟基环辛烯在离子液体BMIm]BF4中的ROMP反应规律, 研究了离子液体中ROMP反应动力学.

Synthesis of Pyridyl-based Ionic Liguid Supported Ruthenium Complex and Kinetics of Ring-opening Metathesis Polymerization in Ionic Liguid

Ring-opening metathesis polymerization(ROMP)is a widespread tool to synthesize well-defined and highly functionalized polymers.The catalyst is a key factor which affects the polymerization behavior.The Grubbs' catalysts have good solubility in non-polar solvents such as CH2Cl2,benzene,THF,and toluene,but their solubility in polar solvents such as alcohol,acetone,and ionic liquid is usually very poor,which limited their application for ROMP in polar solvents.In this paper,the pyridyl-based imidazolium salt-s...