CN113754899A - Carbon dioxide composite solvent and method for dissolving cellulose - Google Patents
Carbon dioxide composite solvent and method for dissolving cellulose Download PDFInfo
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- CN113754899A CN113754899A CN202110929737.1A CN202110929737A CN113754899A CN 113754899 A CN113754899 A CN 113754899A CN 202110929737 A CN202110929737 A CN 202110929737A CN 113754899 A CN113754899 A CN 113754899A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 107
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 107
- 239000002904 solvent Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000875 Dissolving pulp Polymers 0.000 title claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 96
- 239000001913 cellulose Substances 0.000 claims abstract description 96
- 230000002745 absorbent Effects 0.000 claims abstract description 21
- 239000002250 absorbent Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 150000007530 organic bases Chemical class 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 235000010980 cellulose Nutrition 0.000 claims description 91
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 38
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 15
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 5
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 5
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 5
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 4
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QFWZJBUYDUYIJQ-UHFFFAOYSA-M methylsulfinylmethane;tetrabutylazanium;fluoride Chemical compound [F-].CS(C)=O.CCCC[N+](CCCC)(CCCC)CCCC QFWZJBUYDUYIJQ-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/097—Sulfur containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
Abstract
The invention discloses a carbon dioxide composite solvent and a method for dissolving cellulose by using the same. The composite solvent comprises an organic solvent, organic alkali and a carbon dioxide absorbent, and the Henry constant of carbon dioxide in the carbon dioxide absorbent at normal temperature<1.0×107Solubility parameter of Pa or carbon dioxide absorbent<4.0×106Pa(1/2). The method for dissolving the cellulose comprises the steps of dissolving the cellulose in a carbon dioxide composite solvent to form a solid-liquid mixture, then introducing carbon dioxide, stirring and dissolving to obtain a cellulose solution. The invention adopts the polar aprotic solvent with lower Henry constant as the high-efficiency carbon dioxide absorbent, combines the organic base and the organic solvent of a carbon dioxide dissolving system to prepare the carbon dioxide composite solvent, and not only can improve the dissolving capacity of the celluloseThe high-concentration cellulose solution is obtained, the consumption of carbon dioxide can be effectively reduced, and the stability of the cellulose solution is improved.
Description
Technical Field
The invention belongs to the technical field of chemistry and materials, and particularly relates to a carbon dioxide composite solvent and a method for dissolving cellulose by using the carbon dioxide composite solvent.
Background
Cellulose is the most abundant natural polymer on earth and one of the most important renewable raw materials. The method is widely applied to the fields of paper making, packaging, food, medical treatment and the like. However, cellulose has a tough structure with high rigidity and high crystallinity due to the rigidity of cellulose molecules and a large number of intra-and intermolecular hydrogen bonding actions, and is infusible and extremely insoluble. This severely limited its processing and application. Therefore, the development of solvent systems that achieve efficient dissolution of cellulose under mild conditions has been a long-standing focus of research.
Systems that have been developed to date for use in cellulose dissolution include N-methylmorpholine-N-oxide systems, N-dimethylacetamide-lithium chloride systems, dimethylsulfoxide-tetrabutylammonium fluoride systems, ionic liquid systems, alkali/urea/water low temperature dissolution systems, and the like. Recently, people construct a novel cellulose dissolving system based on carbon dioxide, and realize the dissolution of cellulose by regulating and controlling the pressure of the carbon dioxide and efficiently mixing the system, but the system also has some obvious and inevitable defects. For example, chinese patent application (publication No. CN103694482A) discloses a method for dissolving cellulose in an underivatized form by adding alcohol under high pressure sealing conditions to form an ionic compound intermediate with organic base and carbon dioxide, wherein the intermediate has the ability to directly dissolve cellulose, but the high pressure sealing system has higher requirements for reaction equipment, and the obtained cellulose solution has poor stability and is easily precipitated after pressure relief. For another example, chinese patent application (publication No. CN110229354A) discloses that dissolution of cellulose is achieved in a derivatization mode under normal pressure open conditions, however, carbon dioxide gas needs to be continuously introduced into the system, a large amount of carbon dioxide needs to be consumed in the whole dissolution process, only a small amount of carbon dioxide is absorbed by the system and participates in the cellulose dissolution process, and the subsequent large-scale industrial production is not facilitated.
From the dissolving mechanism, the system is dissolved in an organic solvent through the action of the organic alkali and cellulose hydroxyl and the formation of a cellulose derivative ionic intermediate after absorbing carbon dioxide. The whole reaction is a gas-liquid-solid three-phase system comprising cellulose solid, organic alkali liquid and carbon dioxide gas. Obviously, the full contact of the three is beneficial to the reaction, especially the contact of the carbon dioxide gas with the cellulose and the organic base is the key of the whole reaction. The dissolution of the cellulose is realized by improving the contact of carbon dioxide gas with the cellulose and the organic alkali through high pressure and high efficiency mixing respectively under the high pressure closed condition (CN103694482A) or under the normal pressure open condition (CN110229354A) in a non-derivatization form. However, the disadvantages of these two methods are also evident.
Disclosure of Invention
The invention aims to provide a carbon dioxide composite solvent which can quickly dissolve cellulose and improve the dissolving capacity of the cellulose and the stability of a cellulose solution aiming at the problems in the prior art.
In order to achieve the above purpose, the technical solution of the present application is as follows: the carbon dioxide composite solvent comprises an organic solvent, organic alkali and a carbon dioxide absorbent, wherein the Henry constant of carbon dioxide in the carbon dioxide absorbent at normal temperature<1.0×107Solubility parameter of Pa or carbon dioxide absorbent<4.0×106Pa(1/2)。
The research and development personnel of the application find that the contact of carbon dioxide gas with cellulose and organic alkali is improved after theoretical analysis and practice prove, the key point is to improve the concentration of the carbon dioxide gas in an organic solvent, and the traditional high-pressure and high-efficiency mixing can achieve the purpose, but has obvious defects. The organic solvents such as DMSO used in the prior art have poor dissolving capacity for carbon dioxide, so the methods of increasing the pressure of carbon dioxide gas and efficiently mixing the carbon dioxide gas have poor effect on greatly increasing the concentration of carbon dioxide gas in the organic solvents. According to henry's law, the solubility of a gas in a solvent is proportional to the equilibrium pressure of the gas above the liquid surface at isothermal isobaric pressures, with a constant proportionality coefficient, called the henry constant. The smaller the henry constant, the stronger the solvent's ability to dissolve the gas. The research shows that the Henry constant of carbon dioxide in organic solvent such as DMSO is large (more than 1.0 multiplied by 10)7Pa), which fundamentally limits the dissolution of carbon dioxide, resulting in a concentration of carbon dioxide in the organic solvent that is not high and the contact of carbon dioxide with cellulose and organic base cannot be effectively achieved, and thus dissolution efficiency and solution stability are not high. According to the invention, the polar aprotic solvent with a low Henry constant is used as the high-efficiency carbon dioxide absorbent, and the carbon dioxide composite solvent is prepared by combining the organic alkali and the organic solvent of a carbon dioxide dissolving system, so that the carbon dioxide absorbent can increase the concentration of carbon dioxide in the composite solvent in the dissolving process, promote the heterogeneous reaction of solid, liquid and gas, realize the rapid dissolution of cellulose under the low-pressure closed condition, improve the dissolving capacity of the cellulose, obtain a high-concentration cellulose solution, effectively reduce the consumption of carbon dioxide and improve the stability of the cellulose solution.
In the carbon dioxide composite solvent, the carbon dioxide absorbent is a polar aprotic solvent. Preferably, the carbon dioxide absorbent is one or more selected from Propylene Carbonate (PC), Ethylene Carbonate (EC) and Sulfolane (SF).
In the carbon dioxide composite solvent, the mass ratio of the carbon dioxide absorbent to the organic solvent is (1-6): 10.
In the carbon dioxide composite solvent, the organic solvent is selected from polar aprotic organic solvents with the boiling point higher than 150 ℃. Preferably, the organic solvent is one or more selected from dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and N, N-dimethylacetamide (DMAc).
In the carbon dioxide composite solvent, the organic base is selected from organic bases with pKa > 20. Preferably, the organic base is selected from one or more of 1, 8-diazabicyclo-bis [5,4,0] -7-undecene (DBU), 1,5, 7-triazabicyclo [4,4,0] dec-5-ene (TBD), 1, 5-diazabicyclo [4,3,0] non-5-ene (DBN).
The invention also aims to provide a method for dissolving cellulose, which comprises the steps of dissolving cellulose in the carbon dioxide composite solvent to form a solid-liquid mixture, and then introducing carbon dioxide to stir and dissolve the mixture to obtain a cellulose solution.
In the above method for dissolving cellulose, the structural formula of the cellulose is as follows:
Preferably, the cellulose is selected from microcrystalline cellulose, alpha-cellulose, and one or more of cellulose separated from corncob, cotton, paper pulp, wood pulp, bamboo pulp and straws of agriculture and forestry.
In the method for dissolving cellulose, the molar ratio of the organic base in the carbon dioxide complex solvent to the cellulose anhydroglucose unit (AGU) is (2-5): 1.
In the method for dissolving cellulose, the pressure for stirring and dissolving is 0.1-1.0 MPa, and the temperature is 30-70 ℃.
In the method for dissolving cellulose, the cellulose concentration in the cellulose solution is 0.1-15 wt%.
Compared with the prior art, the polar aprotic solvent with a low Henry constant is used as the high-efficiency carbon dioxide absorbent, and the carbon dioxide composite solvent is prepared by combining the organic alkali and the organic solvent of a carbon dioxide dissolving system, so that the dissolving capacity of cellulose can be improved, the concentration and the stability of the cellulose can be improved, and the preparation method has a positive promoting effect on the preparation of novel industrial materials of the cellulose. The carbon dioxide composite solvent has universality in cellulose dissolution, has low requirements on temperature and pressure, and is beneficial to industrial production.
Drawings
In FIG. 1, a, b, c and d are photographs of cellulose solutions in example 1, example 7, example 10 and comparative example 1, respectively.
In FIG. 2, a, b, c, d are polarization photographs of the cellulose solutions in example 1, example 7, example 10 and comparative example 1 of the present invention, respectively.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to several preferred embodiments and accompanying drawings. It should be understood that the embodiments listed are some, but not all embodiments of the invention. On the basis of the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without any inventive work are within the scope of the present invention. The test methods for specific conditions in the following examples are generally carried out under conventional conditions, if not otherwise noted.
Example 1
A carbon dioxide composite solvent comprises 10.00g DMSO, 1.91g DBU and 1.00g Propylene Carbonate (PC), and CO at room temperature2Henry constant in PC is 0.68X 107Pa. 0.68g of pulp cellulose (DP. 755) was dissolved in the carbon dioxide composite solvent, and activated and dissolved at 50 ℃ by passing 0.5MPa of carbon dioxide, to obtain a cellulose solution having a cellulose concentration of 5 wt%, in which the molar ratio of DBU to cellulose anhydroglucose unit AGU was 3: 1.
Example 2
A carbon dioxide composite solvent comprises 10.00g of DMSO, 2.55g of DBN and 2.00g of Propylene Carbonate (PC), and CO at normal temperature2Henry constant in PC is 0.68X 107Pa. 1.10g of pulp cellulose (DP. 755) was dissolved in the carbon dioxide composite solvent, and activated and dissolved at 40 ℃ by passing 0.3MPa carbon dioxide, to obtain a cellulose solution having a cellulose concentration of 7 wt%, in which the molar ratio of DBN to AGU was 3: 1.
Example 3
Pulp cellulose (DP ═ 755) (2.10g) was dissolved in a carbon dioxide composite solvent of DMSO (10.00g), DBU (5.92g), and SF (3.00g), and CO was added at room temperature2Henry constant in SF of 0.86X 107Pa. Then introducing 0.6MPa carbon dioxide, activating and dissolving at 60 ℃ to obtain the cellulose with the concentration of 10 wt% cellulose solution with a DBU to AGU molar ratio of 3: 1.
Example 4
Pulp cellulose (DP ═ 755) (2.26g) was dissolved in a carbon dioxide composite solvent of DMSO (10.00g), DBU (4.25g), and PC (4.00g), and CO was added at room temperature2Henry constant in PC is 0.68X 107Pa. Then, carbon dioxide of 0.7MPa is introduced, and activated and dissolved at 50 ℃ to obtain a cellulose solution with the cellulose concentration of 11 wt%, wherein the molar ratio of DBU to AGU in the solution is 2: 1.
Example 5
Pulp cellulose (DP ═ 755) (1.43g) was dissolved in a carbon dioxide complex solvent of DMSO (10.00g), DBU (4.03g), and EC (5.00g), EC was solid at room temperature, and the solubility parameter of EC was 3.0 × 106Pa(1/2). Then, carbon dioxide of 0.2MPa is introduced, and activated and dissolved at 70 ℃ to obtain a cellulose solution with the cellulose concentration of 7 wt%, wherein the molar ratio of DBU to AGU in the solution is 3: 1.
Example 6
Pulp cellulose (DP ═ 755) (0.75g) was dissolved in a carbon dioxide complex solvent of DMF (10.00g), TBD (3.20g) and PC (1.00g), and then activated and dissolved at 50 ℃ by passing carbon dioxide of 0.1MPa to obtain a cellulose solution having a cellulose concentration of 5 wt% in which the molar ratio of DBU to AGU was 5: 1.
Example 7
Corncob cellulose (DP ═ 1440) (2.10g) was dissolved in a carbon dioxide composite solvent of DMSO (10.00g), DBU (5.92g), and PC (3.00g), and then activated and dissolved at 50 ℃ by passing carbon dioxide of 0.9MPa to obtain a cellulose solution having a cellulose concentration of 10 wt% in which the molar ratio of DBU to AGU was 3: 1.
Example 8
Corncob cellulose (DP ═ 1440) (1.35g) was dissolved in a carbon dioxide composite solvent of DMAc (10.00g), DBU (5.02g) and EC (3.00g), and then activated and dissolved at 60 ℃ by passing carbon dioxide of 0.4MPa to obtain a cellulose solution having a cellulose concentration of 7 wt% in which the molar ratio of DBU to AGU was 3: 1.
Example 9
Corncob cellulose (DP ═ 1440) (2.87g) was dissolved in a carbon dioxide composite solvent of DMSO (10.00g), DBU (8.10g), and SF (3.00g), and then carbon dioxide of 0.5MPa was introduced and activated and dissolved at 60 ℃ to obtain a cellulose solution having a cellulose concentration of 12 wt%, in which the molar ratio of DBU to AGU was 3:1 and the mass ratio of SF to DMSO was 3: 10.
Example 10
Microcrystalline cellulose (DP ═ 180) (4.56g) was dissolved in a carbon dioxide complex solvent of DMSO (10.00g), DBU (8.10g), and PC (3.00g), and then activated and dissolved at 60 ℃ by passing carbon dioxide of 1.0MPa, to obtain a cellulose solution having a cellulose concentration of 15 wt%, in which the molar ratio of DBU to AGU was 3: 1.
Example 11
Microcrystalline cellulose (DP ═ 180) (2.87g) was dissolved in a carbon dioxide complex solvent of DMSO (10.00g), DBU (8.10g), and EC (3.00g), and then activated and dissolved at 50 ℃ by passing carbon dioxide of 0.8MPa to obtain a cellulose solution having a cellulose concentration of 12 wt% in which the molar ratio of DBU to AGU was 3: 1.
Example 12
Microcrystalline cellulose (DP ═ 180) (1.24g) was dissolved in a carbon dioxide complex solvent of DMSO (10.00g), DBU (3.49g), and SF (3.00g), and then 0.7MPa carbon dioxide was introduced and activated and dissolved at 30 ℃ to obtain a cellulose solution having a cellulose concentration of 7 wt%, in which the molar ratio of DBU to AGU was 3:1 and the mass ratio of SF to DMSO was 3: 10.
Comparative example 1
0.22g of pulp cellulose (DP ═ 755) was dissolved in a mixed solvent of 10.00g of DMSO and 0.61g of DBU, followed by passing carbon dioxide of 0.5MPa and activated dissolution at 50 ℃ to obtain an incompletely dissolved cellulose solution having a cellulose concentration of 2 wt%, in which the molar ratio of DBU to cellulose anhydroglucose units (AGU) was 3: 1.
The photographs of the cellulose solutions in inventive example 1, example 7, example 10 and comparative example 1 are shown in fig. 1 as a, b, c and d, respectively. The polarization photographs of the cellulose solutions in inventive example 1, example 7, example 10 and comparative example 1 are shown in fig. 2 as a, b, c and d, respectively. As can be seen from the figure, examples 1, 7 and 10 can obtain clear and transparent solutions in which cellulose is completely dissolved, and undissolved cellulose crystals are not observed under a polarization microscope; the cellulose solution obtained in comparative example 1 was turbid, and a large amount of undissolved cellulose crystals were observed under a polarizing microscope. Therefore, compared with a solvent system without the carbon dioxide absorbent, the carbon dioxide composite solvent prepared by adding the carbon dioxide absorbent has stronger dissolving capacity on cellulose, and can realize efficient dissolution of the cellulose.
Claims (10)
1. The carbon dioxide composite solvent is characterized by comprising an organic solvent, an organic base and a carbon dioxide absorbent, wherein the Henry constant of carbon dioxide in the carbon dioxide absorbent at normal temperature<1.0×107Solubility parameter of Pa or carbon dioxide absorbent<4.0×106Pa(1/2)。
2. The carbon dioxide composite solvent as defined in claim 1, wherein the carbon dioxide absorbent is a polar aprotic solvent.
3. The carbon dioxide composite solvent as claimed in claim 1, wherein the carbon dioxide absorbent is selected from one or more of Propylene Carbonate (PC), Ethylene Carbonate (EC) and Sulfolane (SF).
4. The carbon dioxide composite solvent as claimed in claim 1, wherein the mass ratio of the carbon dioxide absorbent to the organic solvent is (1-6): 10.
5. The carbon dioxide composite solvent as claimed in claim 1, wherein the organic solvent is selected from polar aprotic organic solvents with boiling point higher than 150 ℃, and the organic solvent is selected from one or more of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and N, N-dimethylacetamide (DMAc).
6. The carbon dioxide composite solvent according to claim 1, wherein the organic base is selected from organic bases having pKa >20, and the organic base is selected from one or more of 1, 8-diazabicyclo-bis [5,4,0] -7-undecene (DBU), 1,5, 7-triazabicyclo [4,4,0] dec-5-ene (TBD), and 1, 5-diazabicyclo [4,3,0] non-5-ene (DBN).
7. A method for dissolving cellulose is characterized in that cellulose is dissolved in the carbon dioxide composite solvent as claimed in claim 1 to form a solid-liquid mixture, and then carbon dioxide is introduced into the solid-liquid mixture to be stirred and dissolved to obtain a cellulose solution.
8. The method of dissolving cellulose according to claim 7, wherein the cellulose has a structural formula as follows:
9. The method for dissolving cellulose according to claim 7, wherein the molar ratio of the organic base in the carbon dioxide composite solvent to the cellulose anhydroglucose unit (AGU) is (2-5: 1).
10. The method for dissolving cellulose according to claim 7, wherein the pressure for stirring and dissolving is 0.1 to 1.0MPa, and the temperature is 30 to 70 ℃.
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