离子液体负载钌络合物的合成及其催化环烯烃开环易位聚合  

SYNTHESIS OF IONIC LIQUID-SUPPORTED RUTHENIUM COMPLEX AND RING-OPENING METATHESIS POLYMERIZATION OF CYCLOOLEFIN

作　　者：党靖雅[1] 陈凤香[1] 韩会景[1] 贺小华[1] 张以群[1] 谢美然[1] 

机构地区：[1]华东师范大学化学系,上海200062

出　　处：《高分子学报》2008年第4期343-349,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20474017)资助项目

摘　　要：设计合成了含离子液体的吡啶配体1,2-二甲基-3-乙氧基吡啶六氟磷酸盐咪唑离子液体,在丙酮∶石油醚=3∶1的混合溶剂制备了含咪唑的离子液体.该离子液体可以做配体与Grubbs第二代催化剂反应,制备离子液体负载的钌催化剂,利用(1H,13C,31P)-NMR、元素分析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)的振动峰由原来第二代催化剂的δ=19.2移至δ=16.27,在δ=-143.3处只出现PF6-中磷的信号峰,PCy3的信号消失,表明PCy3已经被置换完全,得到了新的催化剂.通过ICP测定含吡啶配体的离子液体负载的催化剂在混合物中的含量为14wt%.该催化剂在丙酮、甲醇、咪唑类离子液体等极性溶剂中易于溶解,解决了Grubbs催化剂在离子液体中不溶解的问题,实现了在纯离子液体中均相ROMP反应.考察了催化剂对不同极性单体在离子液体[BMIm]BF4中的开环易位聚合反应,非极性的环辛烯、含有中等极性取代基的5-羟基环辛烯单体以及含强极性取代基的5-腈基-2-降冰片烯单体的转化率分别为96%、73%和51.7%.利用凝胶渗透色谱(GPC)测定了聚合物的分子量及分子量分布.Ring-opening metathesis polymerization （ROMP） is a widespread tool for synthesizing well-defined andhighly functionalized polymers. The catalyst is an important factor which affects the ROMP of monomers. It is well-known that the ruthenium-based Grubbs＇ catalysts have good solubility in non-polar solvents such as CH2Cl2, benzene and toluene, but their solubility in polar solvents such as alcohol, acetone and ionic liquid was very poor, which limited their applications for ROMP in polar solvents. In this paper, an imidazolium salt-supported rutheniumcatalyst was synthesized, and its catalytic performance for ROMP of polar or nonpolar cycloolefinic monomers in ionic liquid [ BMIm] BF4 was investigated. A novel pyridyl ligand 2,3-dimethyl-l-[ 2-（4-pyridyloxy）ethyl] imidazolium hexafluorophosphate （4） was initially designed and synthesized, and its single crystal was obtained. The crystal is monoclinic with the parameters as follow： P21/c,a= 1.2469（5） nm,b = 1.6470（7） nm,c = 0.7943（3） nm,β=106.691（5）°, V = 1.5625 （11 ）nm^3. The pyridyl ligand was then used to coordinate with the second generation Grubbs＇ catalyst to get the first example of the ruthenium catalyst supported by imidazolium salt-contained pyridyl ligand （IL-cat 5）. The characterization of the synthesized ligand and the catalyst was carried out by NMR, ICP and elemental analysis. In ^1H-NMR spectroscopy, the signal of the benzylidene proton shifts from δH = 19.2 in thesecond generation Grubbs＇catalyst to δH = 16.3 in the novel catalyst IL-cat 5. In ^31 P-NMR spectroscopy, the signal of PF6^- in pyridyl ligand was observed at δp = - 143.3, while δp = 36.6 for PCy3 group was disappeared, which demonstrated the group of PCy3 was replaced by the pyridyl ligand completely. The content of IL-cat 5 in the mixture of prepared catalyst contained excess 4 was 14 wt% tested by ICP method. As expected, the novel catalyst IL-cat 5 issoluable in polar solvents including methanol acetone, and ionic liquid, thus ROMP in

关 键 词：开环易位聚合 吡啶基配体 离子液体负载钌催化剂 极性单体 

分 类 号：O641.4[理学—物理化学] O631.5[理学—化学]