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

Abstract 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 °C. 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.