A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic ...A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.展开更多
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 (hy...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.展开更多
Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics, activated by modified methylaluminoxane（MMAO）, were tested in the polymerization of higher α-olefin（1-hexene, 1-decene and 1-hexadec...Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics, activated by modified methylaluminoxane（MMAO）, were tested in the polymerization of higher α-olefin（1-hexene, 1-decene and 1-hexadecene） under suitable conditions. The polymerization results indicated the possibility of precise microstructure control, depending on catalyst structure, polymerization temperature, monomer concentration and types of monomers, which in turn strongly affects the resultant polymer properties. Naphthyl-α-diimine nickel complex bearing chiral bulky sec-phenethyl groups in the o-naphthyl position showed good catalytic activity, and resulted in branched polymers（42-88/1000 C） with high molecular weights（Mn：（4.3-15.2） × 10^4 g·mol^-1） and narrow molecular weight distribution（Mw/Mn = 1.13-1.29, RT）, which suggested a living polymerization. The increasing steric hindrance of catalyst leads to enhance insertion for 2,1-insertion of α-olefin and the chain-walking reaction.展开更多
Polyether moiety was introduced to the phosphinite and the phosphinite modified rhodium complex formed in situ was highly active in the hydroformylation of higher olefins in organic monophase system. After reaction, ...Polyether moiety was introduced to the phosphinite and the phosphinite modified rhodium complex formed in situ was highly active in the hydroformylation of higher olefins in organic monophase system. After reaction, on cooling to room temperature, the catalyst could precipitate out from organic phase and was easily separated by decantation and reused six times without obvious decreasing in activity.展开更多
文摘A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 990 60 0 1)
文摘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.
基金financially supported by the Fundamental Research Funds for the Central Universities (WK2060200025)Advanced Catalysis and Green Manufacturing Collaborative Innovation Center (ACGM2016-06-01)Yixing Taodu Ying Cai Program
文摘Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics, activated by modified methylaluminoxane（MMAO）, were tested in the polymerization of higher α-olefin（1-hexene, 1-decene and 1-hexadecene） under suitable conditions. The polymerization results indicated the possibility of precise microstructure control, depending on catalyst structure, polymerization temperature, monomer concentration and types of monomers, which in turn strongly affects the resultant polymer properties. Naphthyl-α-diimine nickel complex bearing chiral bulky sec-phenethyl groups in the o-naphthyl position showed good catalytic activity, and resulted in branched polymers（42-88/1000 C） with high molecular weights（Mn：（4.3-15.2） × 10^4 g·mol^-1） and narrow molecular weight distribution（Mw/Mn = 1.13-1.29, RT）, which suggested a living polymerization. The increasing steric hindrance of catalyst leads to enhance insertion for 2,1-insertion of α-olefin and the chain-walking reaction.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29906001)and the Research Institute of Petroleum Processing.
文摘Polyether moiety was introduced to the phosphinite and the phosphinite modified rhodium complex formed in situ was highly active in the hydroformylation of higher olefins in organic monophase system. After reaction, on cooling to room temperature, the catalyst could precipitate out from organic phase and was easily separated by decantation and reused six times without obvious decreasing in activity.
