Synthesis Of Novel Polyether Functionalized Ionic Liquids And Its Application In Homogeneous Catalysis

In this paper,21 kinds of polyether functionalized ionic liquid were designed and synthesized containing tetramethylguanidine salt,imidazole salt,pyridine salt,piperidine salt,morpholine salt,pyrrolidine salt and triethylamine salt.The structures were characterized by 1H NMR,13 C NMR and electrospray ionization mass spectrometry and the solubility,viscosity,thermal stability and phase stability of liquid were observed and analyzed.Based on the concept of "phosphine ligand?catalyst?and ionic liquid integration",39 kinds of phosphine functionalized polyether ionic liquids were prepared by intruducing two kinds of sulfonic acid type water-soluble phosphine ligand TPPTS and 2,7-bis?SO₃Na?Xantphos into polyether functionalized ionic liquids.The structures were characterized by 1H NMR,13 C NMR,31 P NMR and electrospray ionization mass spectrometry.The properties of the solubility,thermal stability and phase transition were analyzed.Based on the phosphine functionalized polyether ionic liquid,constructed phosphine functionalized polyether ionic liquid /organic two-phase catalytic system and phosphine functionalized polyether ionic liquid / alcohol homogeneous catalytic system,then applied them to the 1-octene hydroformylation reaction.Different phosphine functionalized polyether ionic liquids and the length of different polyether chains were investigated for affects of catalytic activity,selectivity and service life.The results show that the activity and selectivity of monophosphine?TPPTS?functionalized polyether ionic liquid in rhodium-catalyzed hydroformylation of 1-octene under phosphine functionalized polyether ionic liquid / organic two-phase catalytic system,which was related to the cationic structures,and the catalytic activity of Rh with [Ph?EO?16MiCH]3[TPP?SO₃-?3] was the highest,TOF was 2717 h-1,The catalyst can be reused 15 times,the turnover number was reached 40,000.The active and optionally was generally low in the rhodium catalyzed hydroformylation of 1-octene under bisphosphine?2,7-bis?SO₃Na?Xantphos?phosphine functionalized polyether ionic liquid / alcohol homogeneous catalytic system,the highest TOF was 437 h-1;under phosphine functionalized polyether ionic liquid / alcohol homogeneous catalytic system,the catalytic activity and selectivity of monophosphoric?TPPTS?functionalized polyether ionic liquid with different cations did not change much.The turn over frequency were all high,both in the range of 10000-25000 h-1.when(CH3?EO?4MiCH3]3[TPP?SO₃-?3] was used as the catalyst carrier in the cycling of the catalyst,the cumulative TON value was 20000.Under the functionalized polyether ionic liquid / ethanol homogeneous system,the catalytic effect of phosphine functionalized polyether guanidinium ionic liquid was significant,chemical selectivity and regioselectivity were above 93%,and the cumulative value of TON were between 3200 and 3500 h-1,in the presence of(CH3?EO?4TMG]2[Xantphos?SO₃-?2] as the catalyst carrie catalyst can be repeated for 7 times,the turnover number was more than30,000.