Homogeneous acetylation of cellulose in 1-allyl-3-methyl-imidazolium chloride(AMIMCl) was carried out. Acetic anhydride and acetyl chloride were used as acetylating agents in the absence and presence of pyridine. The ...Homogeneous acetylation of cellulose in 1-allyl-3-methyl-imidazolium chloride(AMIMCl) was carried out. Acetic anhydride and acetyl chloride were used as acetylating agents in the absence and presence of pyridine. The degree of substitution(DS) of the products and the distribution of substituents were determined by titration and {} 13C NMR techniques respectively. It was observed that acetyl chloride reacted faster than {anhydride}. Further, pyridine accelerated the reactions when anhydride was used as the acetylating agent, while it slowed down the reactions when acetyl chloride was used. An interesting distribution of DS_ C-2 DS_ C-3 for substitutes was observed in the product with acetic anhydride/pyridine system.展开更多
Cellulose acetates with low degree of substituent(DS) were homogeneously synthesized in an ionic liquid,1-allyl-3-methyl-imidazolium chloride(AmimC1).Under mild reaction conditions,cellulose monoacetates(CMA) with the...Cellulose acetates with low degree of substituent(DS) were homogeneously synthesized in an ionic liquid,1-allyl-3-methyl-imidazolium chloride(AmimC1).Under mild reaction conditions,cellulose monoacetates(CMA) with the DS in a range from 0.34 to 1.60 were obtained.NMR analysis shows that the distribution of acetyl moieties among the three OH groups of anhydroglucose unit is C6■C3>C2 for the synthesized CMA.The water solubility measurement shows that the CMA samples with the DS ranging from 0.65 to 1.06 are readily dissolved in water.The relationship between the structure and water solubility of CMA was briefly discussed.展开更多
At relatively high cellulose mass concentrations(8%,10%,and 12%),homogeneous acetylation of cellulose was carried out in an ionic liquid,1-allyl-3-methylimidazolium chloride(AmimCl).Without using any catalyst,cellulos...At relatively high cellulose mass concentrations(8%,10%,and 12%),homogeneous acetylation of cellulose was carried out in an ionic liquid,1-allyl-3-methylimidazolium chloride(AmimCl).Without using any catalyst,cellulose acetates(CAs)with the degree of substitution(DS)in a range from 0.4 to 3.0 were synthesized in one-step.The effects of reaction time,temperature and molar ratio of acetic anhydride/anhydroglucose unit(AGU) in cellulose on DS value of CAs were investigated.The synthesized CAs were characterized by means of FT-IR, NMR,and solubility,mechanical and thermal tests.After the acetylation,the used ionic liquid AmimCl was easily recycled and reused.This study shows the potential of the homogeneous acetylation of cellulose at relatively high concentrations in ionic liquids in future industrial applications.展开更多
Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneo...Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneous catalysts(isolated active sites)and heterogeneous catalysts(stable and easy to separate),and are thus predicted to be able to bridge the homo-and heterogeneous catalysis.This prediction was first experimentally demonstrated in 2016.In this mini-review,we summarize the few homogeneous catalysis progresses reported recently where SACs have exhibited promising application:a)Rh/ZnO and Rh/CoO SAC have been used successfully in hydroformylation of olefin of which the activity are comparable to the homogeneous Wilkinson’s catalyst;b)a Pt/Al2O3 SAC has shown excellent performance in hydrosilylation reaction;and c)M-N-C SACs(M=Fe,Co etc.)have been applied in the activation of C–H bonds.All of these examples suggest that fabrication of suitable SACs could provide a new avenue for the heterogenization of homogeneous catalysts.These pioneering works shed new light on the recognition of single-atom catalysis in bridging the homo-and heterogeneous catalysis.展开更多
文摘Homogeneous acetylation of cellulose in 1-allyl-3-methyl-imidazolium chloride(AMIMCl) was carried out. Acetic anhydride and acetyl chloride were used as acetylating agents in the absence and presence of pyridine. The degree of substitution(DS) of the products and the distribution of substituents were determined by titration and {} 13C NMR techniques respectively. It was observed that acetyl chloride reacted faster than {anhydride}. Further, pyridine accelerated the reactions when anhydride was used as the acetylating agent, while it slowed down the reactions when acetyl chloride was used. An interesting distribution of DS_ C-2 DS_ C-3 for substitutes was observed in the product with acetic anhydride/pyridine system.
文摘Cellulose acetates with low degree of substituent(DS) were homogeneously synthesized in an ionic liquid,1-allyl-3-methyl-imidazolium chloride(AmimC1).Under mild reaction conditions,cellulose monoacetates(CMA) with the DS in a range from 0.34 to 1.60 were obtained.NMR analysis shows that the distribution of acetyl moieties among the three OH groups of anhydroglucose unit is C6■C3>C2 for the synthesized CMA.The water solubility measurement shows that the CMA samples with the DS ranging from 0.65 to 1.06 are readily dissolved in water.The relationship between the structure and water solubility of CMA was briefly discussed.
基金Supported by the National Basic Research Program of China(2009CB219901)
文摘At relatively high cellulose mass concentrations(8%,10%,and 12%),homogeneous acetylation of cellulose was carried out in an ionic liquid,1-allyl-3-methylimidazolium chloride(AmimCl).Without using any catalyst,cellulose acetates(CAs)with the degree of substitution(DS)in a range from 0.4 to 3.0 were synthesized in one-step.The effects of reaction time,temperature and molar ratio of acetic anhydride/anhydroglucose unit(AGU) in cellulose on DS value of CAs were investigated.The synthesized CAs were characterized by means of FT-IR, NMR,and solubility,mechanical and thermal tests.After the acetylation,the used ionic liquid AmimCl was easily recycled and reused.This study shows the potential of the homogeneous acetylation of cellulose at relatively high concentrations in ionic liquids in future industrial applications.
基金supported by National Natural Science Foundation of China(21606222,21776270)Postdoctoral Science Foundation(2017M621170,2016M601350)~~
文摘Single-atom catalysis,the catalysis by single-atom catalysts(SACs),has attracted considerable attention in recent years as a new frontier in the heterogeneous catalysis field.SACs have the advantages of both homogeneous catalysts(isolated active sites)and heterogeneous catalysts(stable and easy to separate),and are thus predicted to be able to bridge the homo-and heterogeneous catalysis.This prediction was first experimentally demonstrated in 2016.In this mini-review,we summarize the few homogeneous catalysis progresses reported recently where SACs have exhibited promising application:a)Rh/ZnO and Rh/CoO SAC have been used successfully in hydroformylation of olefin of which the activity are comparable to the homogeneous Wilkinson’s catalyst;b)a Pt/Al2O3 SAC has shown excellent performance in hydrosilylation reaction;and c)M-N-C SACs(M=Fe,Co etc.)have been applied in the activation of C–H bonds.All of these examples suggest that fabrication of suitable SACs could provide a new avenue for the heterogenization of homogeneous catalysts.These pioneering works shed new light on the recognition of single-atom catalysis in bridging the homo-and heterogeneous catalysis.
