Cloud Points of Water-soluble Polyether Phosphites and Their Application in the Biphasic Hydroformylation of Higher Olefins  

作　　者：刘晓忠 王艳华 孔凡志 金子林 

机构地区：[1]State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, Liaoning 116012, China

出　　处：《Chinese Journal of Chemistry》2003年第5期494-499,共6页中国化学（英文版）

基　　金：ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 990 60 0 1)

摘　　要：Water soluble polyether phosphites alkyl polyethylene glycol o phenylene phosphite (APGPPs) were easily prepared via alcoholysis of phosphorus chloride with polyoxyethylene alkyl ether. With appropriate HLB (hydrophile lypophile balance), the phosphites possess clear cloud points below 100 ℃. Addition of some inorganic salts decreases cloud points of the phosphites. When the phosphites have long polyether chain binding to short chain alkyl group, their cloud points could be extrapolated from figure of dependence of cloud points on addition of inorganic salts. Utilizing octylpolyglycol phenylene phosphite (OPGPP) (APGPP, R: Octyl)/Rh complex formed in situ as catalyst, over 90% conversion of 1 decene was obtained, avoiding the limitation of water insolubility of substrates. Preliminary results indicated that micellar catalysis and thermoregulated phase transfer catalysis (TRPTC) coexist in the reaction system. Below cloud point, micellar catalysis induced by polyether phosphites may be existed. When temperature is increased to above cloud point of the phosphites, this reaction works mainly in TRPTC. The catalysts could be easily separated by simple decantation, but followed by considerable loss in activity after three successive reaction runs. Preliminary results indicated hydrolysis of OPGPP happened during the reaction, which may explain for the bad loss in activity. The catalyst was reused up to seven times without clear decrease in activity when OPGPP/Rh ratio was increased to 50.Water soluble polyether phosphites alkyl polyethylene glycol o phenylene phosphite (APGPPs) were easily prepared via alcoholysis of phosphorus chloride with polyoxyethylene alkyl ether. With appropriate HLB (hydrophile lypophile balance), the phosphites possess clear cloud points below 100 ℃. Addition of some inorganic salts decreases cloud points of the phosphites. When the phosphites have long polyether chain binding to short chain alkyl group, their cloud points could be extrapolated from figure of dependence of cloud points on addition of inorganic salts. Utilizing octylpolyglycol phenylene phosphite (OPGPP) (APGPP, R: Octyl)/Rh complex formed in situ as catalyst, over 90% conversion of 1 decene was obtained, avoiding the limitation of water insolubility of substrates. Preliminary results indicated that micellar catalysis and thermoregulated phase transfer catalysis (TRPTC) coexist in the reaction system. Below cloud point, micellar catalysis induced by polyether phosphites may be existed. When temperature is increased to above cloud point of the phosphites, this reaction works mainly in TRPTC. The catalysts could be easily separated by simple decantation, but followed by considerable loss in activity after three successive reaction runs. Preliminary results indicated hydrolysis of OPGPP happened during the reaction, which may explain for the bad loss in activity. The catalyst was reused up to seven times without clear decrease in activity when OPGPP/Rh ratio was increased to 50.

关 键 词：HYDROFORMYLATION higher olefins micellar catalysis thermoregulated phase  transfer catalysis 

分 类 号：O643.3[理学—物理化学]