The capability of the synthesized heteropoly complexes of rare earths {K10 [(O39W11Si) Ln(Gly)3Ln(SiW11O39)]?H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy)} as the catalyst promoter in the synthesis of the ethyl acetate was ...The capability of the synthesized heteropoly complexes of rare earths {K10 [(O39W11Si) Ln(Gly)3Ln(SiW11O39)]?H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy)} as the catalyst promoter in the synthesis of the ethyl acetate was studied. The results showed that the quantity of H2SO4 used for synthesizing the ethyl acetate can be reduced by 75% and the yield reached 98% at the optional condition.展开更多
Polymerization of 4-vinylpyridine by complex catalyst of neodymium chloride was studied. The influence of Al/Nd (molar ratio), concentration of catalyst, reaction time and temperature on polymerization of 4-vinylpyrid...Polymerization of 4-vinylpyridine by complex catalyst of neodymium chloride was studied. The influence of Al/Nd (molar ratio), concentration of catalyst, reaction time and temperature on polymerization of 4-vinylpyridine was investigated. The results show that different kinds of ligand in the rare earth complex have an effect on the catalytic activity of the complex. The catalytic activity of the rare earth complex is higher than that of simple rare earth chloride. The catalytic activity of polymer-supported catalyst is higher than those of the similar small molecular system.展开更多
Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through s...Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through salt metathesis. This complex was successfully used to initiate the ring-opening polymerization of ε-caprolactone. The initiation conditions in different temperature, monomer-to-initiator ratio and time were investigated. Under the condition： [ε-caprolactone]：[catalyst] = 600, 56 ℃, toluene： 2 ml, poly（ε-caprolactone） （PCL） with Mw = 11,2782 and PDI = 1.96 was achieved.展开更多
Three new bridging complexes of rare earth and cobalt cluster were synthesized and characterized via ICP, IR and TG techniques. The structure of the complexes was speculated as： two rare earth atoms were bridged with...Three new bridging complexes of rare earth and cobalt cluster were synthesized and characterized via ICP, IR and TG techniques. The structure of the complexes was speculated as： two rare earth atoms were bridged with four CF3COO–, and rare earth atoms were coordinated with cobalt carbonyl clusters to form a steady structure. Application of the complexes as the catalyst precursors was explored for Fischer-Tropsch synthesis. The study showed that the bridging complexes of rare earth and cobalt cluster had large molecular size and were difficult to enter pore path of γ-Al2O3, so they were dispersed on the surface of γ-Al2O3 support. In addition, the performance of Co（Ce）/ γ-Al2O3 was the best among the catalysts with complex as precursor and maintained 77.7% CO conversion at 220 oC for 80 operation hours.展开更多
The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerizati...The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerization, while P-CH2SOCH3. NdCl3 can catalyze the polymerization of butadiene. The content of cis-1,4-polybutadiene is more than 95%.展开更多
The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H<sub>2</sub>salen)<sub>2</sub>Cl<sub>3</sub>·2C<sub>2&l...The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H<sub>2</sub>salen)<sub>2</sub>Cl<sub>3</sub>·2C<sub>2</sub>H<sub>7</sub>OH/Al(i-Bu)<sub>3</sub>) at room temperature was investigated. The influences of ligand structure, catalyst composition, polymerization temperature, polymerization time, the concentration of catalyst and monomer, and the polymerization solvent on the polymerization of isocyanates were studied. It was found that under the polymerization conditions, examined La(H<sub>2</sub>salen<sub>A</sub>)<sub>2</sub>Cl<sub>3</sub>·2C<sub>2</sub>-H<sub>7</sub>OH/Al(i-Bu)<sub>3</sub> (H<sub>2</sub>salen<sub>A</sub>= N,N′-disalicylideneethylene diamine) is a fairly high efficient catalyst for the polymerization of n-hexyl isocyanate (n-HexNCO) to prepare high molecular weight poly(n-hexyl isocyanate) (PHNCO) with narrower molecular weight distribution at room temperature. PHNCO could be prepared with yield of 74.0%, number-average molecular weight (M <sub>n</sub>) of 40.20×10<sup>4</sup> and MWD of 1.79 under the following optimum conditions: [Al]/[La] = 30 (molar ratio), [n-HexNCO]/[La] = 100 (molar ratio), [n-HexNCO] = 3.43 mol/L polymerization at 20°C for 12 h in toluene. In the same polymerization conditions, poly (n-octyl isocyanate) (PONCO) with yield of 67.3%, and poly(n-butyl isocyanate) (PBNCO) with yield of 45.5%, could be prepared respectively. The kinetics of the polymerization of n-HexNCO was also investigated and found to be first-order with respect to both monomer and catalyst concentrations.展开更多
文摘The capability of the synthesized heteropoly complexes of rare earths {K10 [(O39W11Si) Ln(Gly)3Ln(SiW11O39)]?H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy)} as the catalyst promoter in the synthesis of the ethyl acetate was studied. The results showed that the quantity of H2SO4 used for synthesizing the ethyl acetate can be reduced by 75% and the yield reached 98% at the optional condition.
文摘Polymerization of 4-vinylpyridine by complex catalyst of neodymium chloride was studied. The influence of Al/Nd (molar ratio), concentration of catalyst, reaction time and temperature on polymerization of 4-vinylpyridine was investigated. The results show that different kinds of ligand in the rare earth complex have an effect on the catalytic activity of the complex. The catalytic activity of the rare earth complex is higher than that of simple rare earth chloride. The catalytic activity of polymer-supported catalyst is higher than those of the similar small molecular system.
基金The authors acknowledge the financial supports from National Nature Science Foundation（Nos. 20674071, 20774078 and 20434020） ；the Special Funds for Major State Basic Research Projects （No.2005CB623802）.
文摘Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through salt metathesis. This complex was successfully used to initiate the ring-opening polymerization of ε-caprolactone. The initiation conditions in different temperature, monomer-to-initiator ratio and time were investigated. Under the condition： [ε-caprolactone]：[catalyst] = 600, 56 ℃, toluene： 2 ml, poly（ε-caprolactone） （PCL） with Mw = 11,2782 and PDI = 1.96 was achieved.
基金supported by the National Natural Science Foundation of China (20661001, 21061008)the Key Grant of Inner Mongolia Natural Science Foundation of China (200408020201)
文摘Three new bridging complexes of rare earth and cobalt cluster were synthesized and characterized via ICP, IR and TG techniques. The structure of the complexes was speculated as： two rare earth atoms were bridged with four CF3COO–, and rare earth atoms were coordinated with cobalt carbonyl clusters to form a steady structure. Application of the complexes as the catalyst precursors was explored for Fischer-Tropsch synthesis. The study showed that the bridging complexes of rare earth and cobalt cluster had large molecular size and were difficult to enter pore path of γ-Al2O3, so they were dispersed on the surface of γ-Al2O3 support. In addition, the performance of Co（Ce）/ γ-Al2O3 was the best among the catalysts with complex as precursor and maintained 77.7% CO conversion at 220 oC for 80 operation hours.
文摘The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerization, while P-CH2SOCH3. NdCl3 can catalyze the polymerization of butadiene. The content of cis-1,4-polybutadiene is more than 95%.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20304011, 20774078 & 20434020)the Special Funds for Major Basic Research Projects (Grant No. 2005CB623802)
文摘The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H<sub>2</sub>salen)<sub>2</sub>Cl<sub>3</sub>·2C<sub>2</sub>H<sub>7</sub>OH/Al(i-Bu)<sub>3</sub>) at room temperature was investigated. The influences of ligand structure, catalyst composition, polymerization temperature, polymerization time, the concentration of catalyst and monomer, and the polymerization solvent on the polymerization of isocyanates were studied. It was found that under the polymerization conditions, examined La(H<sub>2</sub>salen<sub>A</sub>)<sub>2</sub>Cl<sub>3</sub>·2C<sub>2</sub>-H<sub>7</sub>OH/Al(i-Bu)<sub>3</sub> (H<sub>2</sub>salen<sub>A</sub>= N,N′-disalicylideneethylene diamine) is a fairly high efficient catalyst for the polymerization of n-hexyl isocyanate (n-HexNCO) to prepare high molecular weight poly(n-hexyl isocyanate) (PHNCO) with narrower molecular weight distribution at room temperature. PHNCO could be prepared with yield of 74.0%, number-average molecular weight (M <sub>n</sub>) of 40.20×10<sup>4</sup> and MWD of 1.79 under the following optimum conditions: [Al]/[La] = 30 (molar ratio), [n-HexNCO]/[La] = 100 (molar ratio), [n-HexNCO] = 3.43 mol/L polymerization at 20°C for 12 h in toluene. In the same polymerization conditions, poly (n-octyl isocyanate) (PONCO) with yield of 67.3%, and poly(n-butyl isocyanate) (PBNCO) with yield of 45.5%, could be prepared respectively. The kinetics of the polymerization of n-HexNCO was also investigated and found to be first-order with respect to both monomer and catalyst concentrations.
