| Organic/aqueous two–phase catalytic system with water-soluble organometallic complexes as catalysis is one of the frontier fields in the "Green Chemistry" that is progressing quickly recently. The study of olefin hydroformylation in two-phase catalytic system, the synthesis and characterization of phosphine and the study of their catalytic properties are very important in theory study and industrial application.The effects of reaction temperature, pressure, molar ratio of phosphine to rhodium, catalyst concentration, partial pressure ratio of CO to H2 and substrate concentration on the 1-butene hydroformylation catalyzed by water-soluble rhodium phosphine complex in two-phase catalytic system were investigated in detail. The results indicated that RhCI(CO)(TPPTS)2 showed excellent activity and good regioselectivity. Under the reaction conditions: 100(C, 2.5MPa, [TPPTS]/[Rh]=25, the TOF (Turnover Frequency) for aldehyde and selectivity for n-pentanal were up to 2500h-1 and 87.5%, respectively. The addition of organic and inorganic sodium salts, the structure and the concentration of surfactant and stirring rate could strongly influence the reaction activity and regioslectivity for linear aldehyde.BISBIS that shows higher regioselectivity for linear aldehyde in olefin hydroformylation has relatively not only wide natural bite angle (about 120() but also more flexible and can accommodate the bite angle with little additional strain energy. It preferentially occupies diequatorial sites and forms the rhodium complex of ee configuration, which has higher activity and regioselectivity for linear aldehyde formation at low molar ratio of BISBIS to rhodium. The effects of reaction parameter on the 1-butene hydroformylation catalyzed by RhCI(CO)(TPPTS)2— BISBIS in two-phase catalytic system were investigated. Under the optimum reaction conditions: 130(C, 2.5MPa, [BISBIS]/[Rh]=5, [1-butene]/[H2]/[CO]=1:1:1, [1-betene]/[Rh]=10400, the TOF and selectivity for linear aldehyde were 2987h-1 and 98%, respectively. The hydroformylation of 1-dodecene catalyzed by the assembly rhodium catalyst containing RhC1(CO)(TPPTS) 2 and BISBIS as well as different double long chain cationic surfactants was studied in organic/aqueous biphasic system. The assembly rhodium catalyst exhibited high activity and very high regioselectivity for linear aldehyde under the optimum reaction conditions: [Rh]=9.6×10-4mol/L, [BISBIS]/[Rh]=3, PH2/CO=1.0MPa, T=120(C, surfactant concentration=6.0×10-3mol/L. The TOF and the content of linear aldehyde in total aldehyde could reach about 500-680h-1 and 98-99%, respectively. Both the hydrogenation product dodecane and isomeric dodecene were less than 4%. The promotion by double long chain surfactants has not been reported in literature up to now. The addition of Na2HPO4 was favorable for the increase of the catalyst activity and regioselectivity in olefin hydroformylation. The addition of PhCH2OH and PhOCH3 to the Rh-TPPTS-CTAB system can also accelerate the reaction rate. In comparison, the effect of PhCH2OH on reaction rate is more effective than that of PhOCH3. The benzo-1, 4-dioxan and 3,4-dimethoxybenzene modified phosphines were firstly synthesized and characterized by 1H-NMR, 31P-NMR, and MS spectra. The effect of electronic and steric effect on catalytic properties were studied in detail, 3,4-dimethoxybenzene modified phosphines are much superior to traditional phosphine TPP (triphenylphosphine), the reason may be that the two dimethoxy act as " turn arm" which improves strongly the co-ordination of the olefin to catalytic active species and its sequent reactions. The corresponding water-soluble phosphines could be obtained by the sulfonation at mild condition, and the oxidation of phosphine could be avoided efficiently. The catalytic activity and regioselectivity and stability are much higher than TPPTS at low ratio of phosphine to rhodium when these water-soluble phosphine were used as ligand in the two-phase hydroformylation.
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