Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge.Herein,we report the immobilization of TsDPEN on SBA‐15 with...Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge.Herein,we report the immobilization of TsDPEN on SBA‐15 with an ionic liquid(IL)linkage via the one‐pot reaction of imidazole‐TsDPEN‐N‐Boc with 3‐(trimethoxysilyl)propyl bromide in the SBA‐15 mesopores.After coordination to Rh,the chiral solid catalysts could efficiently catalyze quinoline transfer hydrogenation,achieving 97%conversion with 93%ee,which was comparable to their homogeneous counterparts.The chiral solid catalyst with the IL linkage afforded much higher turnover frequency than that without the IL linkage(93 h^(–1)vs.33 h^(–1)),attributed to the phase transfer and formate‐enriching ability of the IL linkage.Furthermore,the effect of the pH on the reaction rate of the solid catalyst was investigated,preventing reaction rate retardation during the catalytic process.The tuning of the linkage group is an efficient approach for catalytic activity improvement of immobilized chiral catalysts.展开更多
A group of grafted PET fibers with different graft yield are formed by grafting acrylamide onto the PET main chains. The structure of grafted fibers are studied by scanning electronic microscope ( SEM ), infra-red spe...A group of grafted PET fibers with different graft yield are formed by grafting acrylamide onto the PET main chains. The structure of grafted fibers are studied by scanning electronic microscope ( SEM ), infra-red spectrophotometer ( IR ), and differential scanning calorimetry(DSC). At the same time, the moisture regain, dyeability, strength, and elongation at break of the samples are measured and their relations with structural changes are discussed. Compared with ungrafted fiber, shape of the fiber cross-section, IR characteristic absorption peaks, and melting behavior of the grafted fibers have been changed, causing the fiber dyeability and moisture regain to be increased, and mechanical properties to be changed.展开更多
Various polysulfonamide （PSA） statistical copolymers were synthesized by polycondensation of three aromatic diamines and terephthaloyl chloride. The inherent viscosities of the resulting PSA copolymers range from 1....Various polysulfonamide （PSA） statistical copolymers were synthesized by polycondensation of three aromatic diamines and terephthaloyl chloride. The inherent viscosities of the resulting PSA copolymers range from 1.54 to 1.66 dL/g. The precipitated PSA copolymers with feed content of p-phenylene diamine （PPD） being less than 50% （mole fraction） can be redissolved in N-methyl-2-pryrrolidone （NMP） or N, N-dimethylacetamide （DMAc） with lithium chloride of WLiC1 ： 0.02. All of the PSA copolymers exhibit enhanced tensile strength in comparison with PSA and still maintain excellent thermal stability in either air or nitrogen atmosphere展开更多
文摘Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge.Herein,we report the immobilization of TsDPEN on SBA‐15 with an ionic liquid(IL)linkage via the one‐pot reaction of imidazole‐TsDPEN‐N‐Boc with 3‐(trimethoxysilyl)propyl bromide in the SBA‐15 mesopores.After coordination to Rh,the chiral solid catalysts could efficiently catalyze quinoline transfer hydrogenation,achieving 97%conversion with 93%ee,which was comparable to their homogeneous counterparts.The chiral solid catalyst with the IL linkage afforded much higher turnover frequency than that without the IL linkage(93 h^(–1)vs.33 h^(–1)),attributed to the phase transfer and formate‐enriching ability of the IL linkage.Furthermore,the effect of the pH on the reaction rate of the solid catalyst was investigated,preventing reaction rate retardation during the catalytic process.The tuning of the linkage group is an efficient approach for catalytic activity improvement of immobilized chiral catalysts.
文摘A group of grafted PET fibers with different graft yield are formed by grafting acrylamide onto the PET main chains. The structure of grafted fibers are studied by scanning electronic microscope ( SEM ), infra-red spectrophotometer ( IR ), and differential scanning calorimetry(DSC). At the same time, the moisture regain, dyeability, strength, and elongation at break of the samples are measured and their relations with structural changes are discussed. Compared with ungrafted fiber, shape of the fiber cross-section, IR characteristic absorption peaks, and melting behavior of the grafted fibers have been changed, causing the fiber dyeability and moisture regain to be increased, and mechanical properties to be changed.
基金the National Natural Science Foundation of China (No. 50973059)the Scientific Research Foundation of 2009 Graduate School of Shanghai University
文摘Various polysulfonamide （PSA） statistical copolymers were synthesized by polycondensation of three aromatic diamines and terephthaloyl chloride. The inherent viscosities of the resulting PSA copolymers range from 1.54 to 1.66 dL/g. The precipitated PSA copolymers with feed content of p-phenylene diamine （PPD） being less than 50% （mole fraction） can be redissolved in N-methyl-2-pryrrolidone （NMP） or N, N-dimethylacetamide （DMAc） with lithium chloride of WLiC1 ： 0.02. All of the PSA copolymers exhibit enhanced tensile strength in comparison with PSA and still maintain excellent thermal stability in either air or nitrogen atmosphere
