Sodium carbonate and carboxymethyl cellulose powders are compressed into two-component tablets with three mass ratios,97%:3%,95%:5% and 93%:7%.The dissolution tests for two-component tablets and reference pure sodium ...Sodium carbonate and carboxymethyl cellulose powders are compressed into two-component tablets with three mass ratios,97%:3%,95%:5% and 93%:7%.The dissolution tests for two-component tablets and reference pure sodium carbonate tablets are carried out at various temperatures.The dissolution process of each tablet is measured by electrical conductivity tracking method and the concentration of dissolved sodium carbonate is quanti fied with calibrated conductivity-concentration converting equation of sodium carbonate.The quanti fied dissolution data is fitted with both surface reaction model and diffusion layer model and the results clearly show that surface reaction model is suggested as the appropriate dissolution model for all measured tablets.Therefore,it is determined that carboxymethyl cellulose is a stable element to remain the dissolution mechanism of tablet unchanged.The dissolution rate constant quanti fied with surface reaction model presents that carboxymethyl cellulose-sodium carbonate two-component tablets obtain signi ficant higher dissolution rate constant than pure sodium carbonate tablet and higher proportion of carboxymethyl cellulose leads to apparent higher dissolution rate constant.The results prove for the usage of carboxymethyl cellulose in most practical applications at a relative low-level,the effect of carboxymethyl cellulose is effective and positive for two-component tablet to enhance the dissolution process and improve dissolution rate constant and this effect is speculated coming from its dynamic physical transforming process in water including dilation and conglutination.展开更多
Tbe N - methylmorpholine - N - oxide (NMMO) - water solvent was used to dissolve the cellulose that was achieved by means of hydrothermolysis. Sample B, RS and WS used here were made from beech, rice straw and wheat s...Tbe N - methylmorpholine - N - oxide (NMMO) - water solvent was used to dissolve the cellulose that was achieved by means of hydrothermolysis. Sample B, RS and WS used here were made from beech, rice straw and wheat straw respectively. They could be completely dissolved in the NMMO - water system. A commercial a - cellulose was employed in the comparative experiment. The entire dissolving process was Investigated. At a given temperature, the vacuum condition applied to the mixture of the cellulose and NMMO - water was very important in order to accelerate the dissolution of cellulose and shorten the dissolving period. After dissolution, degree of polymerization (DP) of all samples was measured by viscometry. Longer dissolving time and higher temperature could cause the degradation of the dissolved cellulose. N- propyl gallate could prevent the degradation of cellulose during the process of dissolution.展开更多
Cellulose pulps were directly dissolved in a green solvent of sodium hydrate/urea/thiourea/water with different composition for the purpose to prepare new regenerated cellulose fibers or films. The results showed that...Cellulose pulps were directly dissolved in a green solvent of sodium hydrate/urea/thiourea/water with different composition for the purpose to prepare new regenerated cellulose fibers or films. The results showed that the highest solubility of cellulose in the solvent with the composition of 8/8/6.5/77.5. The results revealed that the pulp feeding sequence, stirring rate, pre-treatment of pulp and pulp size affected the cellulose concentration in the green solvent. Accordingly, the more effective dissolution method was proposed in order to get higher concentration of cellulose. Furthermore, the properties of solution prepared by different kinds of pulps in the solvent were investigated by ARES rheometer. Rheologieal analyses indicated that all cellulose aqueous solutions in their high concentration were pseudoplastic fluids and sensitive to temperature and tended to transform to gel when temperature increased.展开更多
Cellulose nanofibrils(CNFs)were obtained through one-step mechano-partial dissolution by ball milling in N,N-dimethyl acetamide with a low concentration of LiCl from agricultural waste bagasse pith(BP).Compared with f...Cellulose nanofibrils(CNFs)were obtained through one-step mechano-partial dissolution by ball milling in N,N-dimethyl acetamide with a low concentration of LiCl from agricultural waste bagasse pith(BP).Compared with fibrous cellulose,parenchyma cellulose(PC)is less uniform in diameter and less aligned,causing PC to dissociate into CNFs during this process without pretreatment.The results showed that the CNFs prepared from PC of BP had a diameter of 30-200 nm and a length of several micrometers.The as-obtained CNFs,along with dissolved cellulose,formed a wet-stable and highly transparent nanopaper in a sorbitol aqueous solution bath,which exhibited a high strain of 101%and a low Young's modulus of 4.3 MPa owing to the addition of the plasticizer sorbitol.This type of nanopaper with favorable transparency,high tensile property,and low Young's modulus has great potential for use as electronic skin and medical dressing material.展开更多
Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose ...Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose graft copolymers were characterized by FTIR, ^1 H-NMR and XRD spectroscopy. The results show that AmimCl dissolved cellulose directly by destroying intermolecular and intramolecular hydrogen bonds in cellulose and the crystalline form of cellulose was transformed from cellulose Ⅰ to cellulose Ⅱ after regeneration from AmimCl. The best synthetic condition of the cellulose-graft-P (2-hydroxyethyl methacrylate) was that cellulose 0.5 g, 2-hydroxyethyl methacrylate 3.00 g and initiator ammonium persulfate 0.05 g reacted for 180 min at 60℃; the rate of grafting reached 77.3%.展开更多
The effect of ionic liquids(ILs) on the solubility of cellulose was investigated by changing their anions and cations. The structural variation included 11 kinds of cations in combination with 4 kinds of anions. The i...The effect of ionic liquids(ILs) on the solubility of cellulose was investigated by changing their anions and cations. The structural variation included 11 kinds of cations in combination with 4 kinds of anions. The interaction between the IL and cellobiose, the repeating unit of cellulose, was clarified through nuclear magnetic resonance(NMR) spectroscopy. The reason for different dissolving capabilities of various ILs was revealed. The hydrogen bonding interaction between the IL and hydroxyl was the major force for cellulose dissolution. Both the anion and cation in the IL formed hydrogen bonds with cellulose. Anions associated with hydrogen atoms of hydroxyls, and cations favored the formation of hydrogen bonds with oxygen atoms of hydroxyls by utilizing activated protons in imidazolium ring. Weakening of either the hydrogen bonding interaction between the anion and cellulose, or that between the cation and cellulose, or both, decreases the capability of ILs to dissolve cellulose.展开更多
Catalytic conversion of sustainable cellulose to the value-added chemicals and high quality biofuel has been recognized as a perfect approach for the alleviation of the dependence on the non-renewable fossil resources...Catalytic conversion of sustainable cellulose to the value-added chemicals and high quality biofuel has been recognized as a perfect approach for the alleviation of the dependence on the non-renewable fossil resources. Previously, we successfully de- signed and explored novel and efficient cooperative ionic liquid pairs for this renewable material, which has advantages of high reactor efficiency than current technologies because of the dissolution and in situ catalytic decomposition mechanism. Here, the determinant of this process is further studied by the intensive investigation on the relationship between the cellulose conversion and the properties of ionic liquid catalyst and solvent. Scanning electron microscope (SEM), thermogravimetric analysis (TG) and elemental analysis were used for the comparative characterization of raw cellulose and the residues. The re- suits demonstrate that this consecutive dissolution and in situ catalysis process is much more dependent on the dissolution ca- pability of ionic liquid solvent, while comparatively, the effect of in situ acid catalysis is relatively insignificant.展开更多
Cellulose is abundant in nature,with the advantages of low-cost,biodegradable and biocompatible,low density and high strength.However,the development and application of cellulose has been lagging behind its potential ...Cellulose is abundant in nature,with the advantages of low-cost,biodegradable and biocompatible,low density and high strength.However,the development and application of cellulose has been lagging behind its potential due to its unique properties.Cellulose has a large quantity of hydroxyl groups which can easily form hydrogen bond networks.The huge hydrogen bond network makes it extremely difficult to dissolve or melt cellulose,thus limiting the effective use of cellulose resources.To dissolve cellulose,the key is to break the hydrogen bonds.This article sums up recent studies on the dissociation or breakage of the intramolecular and intermolecular hydrogen bonds in the dissolution of cellulose.展开更多
It is nowadays well-known that ionic liquids can dissolve cellulose. However, little systematic data has been published that shed light onto the influence of the ionic liquid structure on the dissolution of cellulose....It is nowadays well-known that ionic liquids can dissolve cellulose. However, little systematic data has been published that shed light onto the influence of the ionic liquid structure on the dissolution of cellulose. We have conducted 1H NMR spec- troscopy of ethanol in a large number of ionic liquids, and found an excellent correlation of the data obtained with the hydro- gen acceptor properties (B-values). With this tool in hand, it is possible to distinguish between cellulose-dissolving and non-dissolving ionic liquids. A modulating effect of both, the anion of the non-dissolving ionic liquid and its cation was found in solubility studies with binary ionic liquid mixtures. The study was extended to other non-dissolving liquids, namely water and dimethylsulfoxide, and the effect of the cation was also investigated.展开更多
According to the Kamlet-Abraham-Taft(KAT)polarity parameters(α,β,π*),polymers and solvents can be categorized as hydrogen-bond(H-bond)acidic(α>β)or H-bond basic(α<β).Recently,we proposed a quantitative hy...According to the Kamlet-Abraham-Taft(KAT)polarity parameters(α,β,π*),polymers and solvents can be categorized as hydrogen-bond(H-bond)acidic(α>β)or H-bond basic(α<β).Recently,we proposed a quantitative hydrogen bonding(QHB)analysis to predict the solubility of polymers in ionic liquids(ILs)using the product ofΔαΔβ<0 as an indicator,whereΔαis the difference between the H-bond acidic parameters of the polymer and IL,andΔβis the difference in their basicity,while the prerequisite of the“complementary”principle(i.e.,that one component is H-bond acidic and the other is basic)is satisfied.Here,the applicability of QHB analysis was first confirmed by testing the solubilities of carefully chosen polymer/deep eutectic solvent(DES)pairs,as the DESs were eutectic mixtures dominated by hydrogen bonding interactions.Then,our attention focused on the solubility of cellulose in DESs.Our testing results as well as the typical published results were summarized,which indicate that the potential DESs for cellulose dissolution and regeneration must be of the H-bond basic type because the“complementary”principle should be satisfied as a prerequisite.However,the H-bond basic DESs investigated in this study do not show the superior solubility of cellulose that has been commonly observed for H-bond basic ILs,even if the criterion ofΔαΔβ<0 is satisfied for both DESs and ILs.Possible reasons for this discrepancy are given to understand the varying effectiveness in cellulose dissolution for H-bond basic DESs and ILs.展开更多
The manipulation of hydrogen bonding within protic ionic liquids is conducive to conquering the robust hydrogen bonding interactions in cellulose for its effective dissolution,but it is a great challenge to establish ...The manipulation of hydrogen bonding within protic ionic liquids is conducive to conquering the robust hydrogen bonding interactions in cellulose for its effective dissolution,but it is a great challenge to establish the delicate bal-ance of hydrogen bonding network between solvent and cellulose.Herein,we proposed the concept of“hydrogen bond producers”for urea molecules in 1,1,3,3-tetramethylguanidinium methoxyacetate acid([TMGH][MAA])to enhance the dissolution of cellulose.The optimization of physicochemical properties for[TMGH][MAA]solvent as a function of urea concentration revealed a remark-able increase in cellulose solubility from 13%to 17%(w/w)by adding only 0.25 wt%urea,highlighting the efficiency of[TMGH][MAA]as a power-ful solvent for the dissolution of cellulose.The experimental and simulation results verified that the significant improvement on dissolution of cellulose was attributed to the hydrogen bonding interaction of urea molecules with ion pairs and part of free ions,reducing the interference with the active ions bonded to cellulose.Furthermore,the considerable enhancement on compre-hensive properties of regenerated cellulose films demonstrated the effectiveness of[TMGH][MAA]/urea solvent.The concept of“hydrogen bond producers”presented here opens a new avenue for significantly enhancing the dissolu-tion of natural cellulose,promoting the sustainable development in large-scale processing of cellulose.展开更多
基金the Institute of Particle and Science Engineering,University of Leeds and Procter & Gamble Newcastle Innovation Centre(UK) for partially funding the project
文摘Sodium carbonate and carboxymethyl cellulose powders are compressed into two-component tablets with three mass ratios,97%:3%,95%:5% and 93%:7%.The dissolution tests for two-component tablets and reference pure sodium carbonate tablets are carried out at various temperatures.The dissolution process of each tablet is measured by electrical conductivity tracking method and the concentration of dissolved sodium carbonate is quanti fied with calibrated conductivity-concentration converting equation of sodium carbonate.The quanti fied dissolution data is fitted with both surface reaction model and diffusion layer model and the results clearly show that surface reaction model is suggested as the appropriate dissolution model for all measured tablets.Therefore,it is determined that carboxymethyl cellulose is a stable element to remain the dissolution mechanism of tablet unchanged.The dissolution rate constant quanti fied with surface reaction model presents that carboxymethyl cellulose-sodium carbonate two-component tablets obtain signi ficant higher dissolution rate constant than pure sodium carbonate tablet and higher proportion of carboxymethyl cellulose leads to apparent higher dissolution rate constant.The results prove for the usage of carboxymethyl cellulose in most practical applications at a relative low-level,the effect of carboxymethyl cellulose is effective and positive for two-component tablet to enhance the dissolution process and improve dissolution rate constant and this effect is speculated coming from its dynamic physical transforming process in water including dilation and conglutination.
文摘Tbe N - methylmorpholine - N - oxide (NMMO) - water solvent was used to dissolve the cellulose that was achieved by means of hydrothermolysis. Sample B, RS and WS used here were made from beech, rice straw and wheat straw respectively. They could be completely dissolved in the NMMO - water system. A commercial a - cellulose was employed in the comparative experiment. The entire dissolving process was Investigated. At a given temperature, the vacuum condition applied to the mixture of the cellulose and NMMO - water was very important in order to accelerate the dissolution of cellulose and shorten the dissolving period. After dissolution, degree of polymerization (DP) of all samples was measured by viscometry. Longer dissolving time and higher temperature could cause the degradation of the dissolved cellulose. N- propyl gallate could prevent the degradation of cellulose during the process of dissolution.
文摘Cellulose pulps were directly dissolved in a green solvent of sodium hydrate/urea/thiourea/water with different composition for the purpose to prepare new regenerated cellulose fibers or films. The results showed that the highest solubility of cellulose in the solvent with the composition of 8/8/6.5/77.5. The results revealed that the pulp feeding sequence, stirring rate, pre-treatment of pulp and pulp size affected the cellulose concentration in the green solvent. Accordingly, the more effective dissolution method was proposed in order to get higher concentration of cellulose. Furthermore, the properties of solution prepared by different kinds of pulps in the solvent were investigated by ARES rheometer. Rheologieal analyses indicated that all cellulose aqueous solutions in their high concentration were pseudoplastic fluids and sensitive to temperature and tended to transform to gel when temperature increased.
基金The authors are grateful for the financial support from the National Natural Science Foundation of China(Grant No.51963012)Special Foundation for Excellent Youth Scholars of Yunnan Province,China(Nos.YNWR-QNBJ-2020-039 and YNWR-QNBJ-2020-045).
文摘Cellulose nanofibrils(CNFs)were obtained through one-step mechano-partial dissolution by ball milling in N,N-dimethyl acetamide with a low concentration of LiCl from agricultural waste bagasse pith(BP).Compared with fibrous cellulose,parenchyma cellulose(PC)is less uniform in diameter and less aligned,causing PC to dissociate into CNFs during this process without pretreatment.The results showed that the CNFs prepared from PC of BP had a diameter of 30-200 nm and a length of several micrometers.The as-obtained CNFs,along with dissolved cellulose,formed a wet-stable and highly transparent nanopaper in a sorbitol aqueous solution bath,which exhibited a high strain of 101%and a low Young's modulus of 4.3 MPa owing to the addition of the plasticizer sorbitol.This type of nanopaper with favorable transparency,high tensile property,and low Young's modulus has great potential for use as electronic skin and medical dressing material.
基金supported by the 11th Five-Year Plan of the National Scientific and Technological Support Projects of China (Grant No. 2006BAD18B10)the Major Project of Chinese National Programs for Fundamental Research and Development (973 Program) (Grant No. 2010CB732204)
文摘Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose graft copolymers were characterized by FTIR, ^1 H-NMR and XRD spectroscopy. The results show that AmimCl dissolved cellulose directly by destroying intermolecular and intramolecular hydrogen bonds in cellulose and the crystalline form of cellulose was transformed from cellulose Ⅰ to cellulose Ⅱ after regeneration from AmimCl. The best synthetic condition of the cellulose-graft-P (2-hydroxyethyl methacrylate) was that cellulose 0.5 g, 2-hydroxyethyl methacrylate 3.00 g and initiator ammonium persulfate 0.05 g reacted for 180 min at 60℃; the rate of grafting reached 77.3%.
基金supported by the National Natural Science Foundation of China (51425307, 51573196, 21374126)the Program of Taishan Industry Leading Talents (Shandong Province)
文摘The effect of ionic liquids(ILs) on the solubility of cellulose was investigated by changing their anions and cations. The structural variation included 11 kinds of cations in combination with 4 kinds of anions. The interaction between the IL and cellobiose, the repeating unit of cellulose, was clarified through nuclear magnetic resonance(NMR) spectroscopy. The reason for different dissolving capabilities of various ILs was revealed. The hydrogen bonding interaction between the IL and hydroxyl was the major force for cellulose dissolution. Both the anion and cation in the IL formed hydrogen bonds with cellulose. Anions associated with hydrogen atoms of hydroxyls, and cations favored the formation of hydrogen bonds with oxygen atoms of hydroxyls by utilizing activated protons in imidazolium ring. Weakening of either the hydrogen bonding interaction between the anion and cellulose, or that between the cation and cellulose, or both, decreases the capability of ILs to dissolve cellulose.
基金supported by the National Natural Science Foundation of China (N21336002, 51306191, 21276094)the Natural Science Foundation of Guangdong Province, China (2015A030311048)
文摘Catalytic conversion of sustainable cellulose to the value-added chemicals and high quality biofuel has been recognized as a perfect approach for the alleviation of the dependence on the non-renewable fossil resources. Previously, we successfully de- signed and explored novel and efficient cooperative ionic liquid pairs for this renewable material, which has advantages of high reactor efficiency than current technologies because of the dissolution and in situ catalytic decomposition mechanism. Here, the determinant of this process is further studied by the intensive investigation on the relationship between the cellulose conversion and the properties of ionic liquid catalyst and solvent. Scanning electron microscope (SEM), thermogravimetric analysis (TG) and elemental analysis were used for the comparative characterization of raw cellulose and the residues. The re- suits demonstrate that this consecutive dissolution and in situ catalysis process is much more dependent on the dissolution ca- pability of ionic liquid solvent, while comparatively, the effect of in situ acid catalysis is relatively insignificant.
基金supported by the National Natural Science Foundation of China (No.51373191,51172247,51472253)the Chinese Academy of Sciences Visiting Professorships.
文摘Cellulose is abundant in nature,with the advantages of low-cost,biodegradable and biocompatible,low density and high strength.However,the development and application of cellulose has been lagging behind its potential due to its unique properties.Cellulose has a large quantity of hydroxyl groups which can easily form hydrogen bond networks.The huge hydrogen bond network makes it extremely difficult to dissolve or melt cellulose,thus limiting the effective use of cellulose resources.To dissolve cellulose,the key is to break the hydrogen bonds.This article sums up recent studies on the dissociation or breakage of the intramolecular and intermolecular hydrogen bonds in the dissolution of cellulose.
基金supported by the BASF SE. A.S. is indebted to the Deutsche Forschungsgemeinschaft (DFG) for funding within the SPP 1191 Priority Programme Ionic Liquids (STA1027/2-1 to /2-3)
文摘It is nowadays well-known that ionic liquids can dissolve cellulose. However, little systematic data has been published that shed light onto the influence of the ionic liquid structure on the dissolution of cellulose. We have conducted 1H NMR spec- troscopy of ethanol in a large number of ionic liquids, and found an excellent correlation of the data obtained with the hydro- gen acceptor properties (B-values). With this tool in hand, it is possible to distinguish between cellulose-dissolving and non-dissolving ionic liquids. A modulating effect of both, the anion of the non-dissolving ionic liquid and its cation was found in solubility studies with binary ionic liquid mixtures. The study was extended to other non-dissolving liquids, namely water and dimethylsulfoxide, and the effect of the cation was also investigated.
基金the National Natural Science Foundation of China(No.21973105)the National Key R&D Program of China(No.2020YFC1910301).
文摘According to the Kamlet-Abraham-Taft(KAT)polarity parameters(α,β,π*),polymers and solvents can be categorized as hydrogen-bond(H-bond)acidic(α>β)or H-bond basic(α<β).Recently,we proposed a quantitative hydrogen bonding(QHB)analysis to predict the solubility of polymers in ionic liquids(ILs)using the product ofΔαΔβ<0 as an indicator,whereΔαis the difference between the H-bond acidic parameters of the polymer and IL,andΔβis the difference in their basicity,while the prerequisite of the“complementary”principle(i.e.,that one component is H-bond acidic and the other is basic)is satisfied.Here,the applicability of QHB analysis was first confirmed by testing the solubilities of carefully chosen polymer/deep eutectic solvent(DES)pairs,as the DESs were eutectic mixtures dominated by hydrogen bonding interactions.Then,our attention focused on the solubility of cellulose in DESs.Our testing results as well as the typical published results were summarized,which indicate that the potential DESs for cellulose dissolution and regeneration must be of the H-bond basic type because the“complementary”principle should be satisfied as a prerequisite.However,the H-bond basic DESs investigated in this study do not show the superior solubility of cellulose that has been commonly observed for H-bond basic ILs,even if the criterion ofΔαΔβ<0 is satisfied for both DESs and ILs.Possible reasons for this discrepancy are given to understand the varying effectiveness in cellulose dissolution for H-bond basic DESs and ILs.
基金Science and Technology Department of Sichuan Province,Grant/Award Number:2022YFH0094National Natural Science Foundation of China,Grant/Award Numbers:51973141,52033005,U21A2090。
文摘The manipulation of hydrogen bonding within protic ionic liquids is conducive to conquering the robust hydrogen bonding interactions in cellulose for its effective dissolution,but it is a great challenge to establish the delicate bal-ance of hydrogen bonding network between solvent and cellulose.Herein,we proposed the concept of“hydrogen bond producers”for urea molecules in 1,1,3,3-tetramethylguanidinium methoxyacetate acid([TMGH][MAA])to enhance the dissolution of cellulose.The optimization of physicochemical properties for[TMGH][MAA]solvent as a function of urea concentration revealed a remark-able increase in cellulose solubility from 13%to 17%(w/w)by adding only 0.25 wt%urea,highlighting the efficiency of[TMGH][MAA]as a power-ful solvent for the dissolution of cellulose.The experimental and simulation results verified that the significant improvement on dissolution of cellulose was attributed to the hydrogen bonding interaction of urea molecules with ion pairs and part of free ions,reducing the interference with the active ions bonded to cellulose.Furthermore,the considerable enhancement on compre-hensive properties of regenerated cellulose films demonstrated the effectiveness of[TMGH][MAA]/urea solvent.The concept of“hydrogen bond producers”presented here opens a new avenue for significantly enhancing the dissolu-tion of natural cellulose,promoting the sustainable development in large-scale processing of cellulose.