CN108641102B - High-efficiency cellulose solvent system and application thereof - Google Patents
High-efficiency cellulose solvent system and application thereof Download PDFInfo
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Abstract
The invention discloses a high-efficiency cellulose solvent system which is formed by mixing ionic liquid and metal salt, can improve the solubility of cellulose under mild conditions, and an application of the system in preparing a cellulose film. The cellulose solvent system improves the dissolving effect of cellulose in the ionic liquid, particularly increases the maximum solubility of the cellulose and shortens the dissolving time of the cellulose; the metal salt is simply added, the dissolution is promoted through the synergistic effect of the ionic liquid and the salt, the operation is simple and convenient, and the ultralow temperature operation is not needed; toxic and harmful reagents are not used in the operation process, the process is environment-friendly and recyclable, and the economic feasibility of a novel solvent system is improved.
Description
Technical Field
The invention belongs to the field of cellulose dissolution, and particularly relates to a high-efficiency cellulose solvent system which is formed by mixing ionic liquid and metal salt, can improve the solubility of cellulose under a mild condition, and an application of the system in preparing a cellulose film.
Background
Cellulose is the most abundant renewable organic resource on the earth, has very wide sources, and exists in wood fiber raw materials such as wood, straw, bamboo, cotton, hemp and the like in a large amount. The cellulose is used for developing biomass base materials such as cellulose membranes, fibers, gels and the like and modifying and preparing cellulose derivatives such as hydroxymethyl cellulose and the like, and the cellulose derivative has wide application prospect in the fields of chemical industry, medicine, food, building, oilfield chemistry, biochemistry and the like. The development and utilization of novel highly efficient cellulose solvents are at the heart of impacting cellulose application and market competitiveness.
Cellulose is a linear macromolecule with a uniform structure formed by repeated connection of cellobiose units through beta-1, 4 glucosidic bonds, and the degree of polymerization can reach 10000 or higher. A large number of hydrogen bonds exist in cellulose molecules and among the cellulose molecules, molecular chains are arranged regularly in parallel, and the orientation degree is high, so that the cellulose has a compact structure and good chemical stability and is difficult to dissolve. Conventional cellulose solvents include cuprammonium, copper ethylenediamine, cadmium ethylenediamine, and the like solvent systems, as well as sodium hydroxide/carbon disulfide solvent systems (viscose process). Although the dissolving capacity is strong, heavy metal ions and CS can be discharged in the using process2And H2S and other toxic gases are not beneficial to sustainable development. In recent years, researchers have been working on the development of new green dissolution systems. For example, patent CN107304246A discloses a solvent system of sodium hydroxide and thiourea aqueous solution; CN107653502A cellulose was dissolved in a low temperature dissolution system of 5-10 wt% sodium hydroxide, 0-1 wt% lithium hydroxide and 8-15 wt% urea. Ionic Liquids (IL) are one of the new non-derivatised solvent systems that have been developed in recent years. Compared with other dissolving systems, IL is easy to recover, 100 percent of IL is composed of anions and cations, and the IL has the advantages of low vapor pressure, strong polarity, high dissolving capacity, non-volatility and the like. Swatloski et al (2002) first published a report on the ionic liquid 1-butyl-3-methylchloridic imidazolium chloride ([ C)4mim]Cl) was able to dissolve 10 wt% of the cellulose.
However, the existing cellulose dissolving system has the following disadvantages: although the sodium hydroxide/urea/lithium hydroxide dissolving system can dissolve 8 wt% of cellulose within 3min, the dissolving is carried out at a low temperature of-12 ℃, the dissolving condition is harsh, and industrial application is difficult to realize; the sodium hydroxide/thiourea system uses thiourea and alkaline solution, and the environmental protection requirement is difficult to achieve; in an ionic liquid dissolving system, ionic liquid with excellent dissolving performance is high in price, and ionic liquid with relatively low price is long in dissolving time and poor in dissolving effect.
Therefore, there is still a need to develop an environment-friendly, high-efficiency solvent system with excellent solubility, which is very beneficial to the high-efficiency utilization of cellulose resources.
Disclosure of Invention
In order to solve the problems of the prior art, according to one embodiment of the present invention, a high efficiency cellulose solvent system is provided, which is formed by mixing an ionic liquid and a metal salt,
wherein the ionic liquid is selected from the group consisting of 1-allyl-3-methylimidazolium chloride salt, 1-butyl-3-methylimidazolium chloride salt and 1-ethyl-3-methylimidazolium chloride salt, and the metal salt is selected from the group consisting of MgCl2、BaCl2、NaCl、Na2SO4、ZnCl2、LiCl、CaCl2One or more of (a).
Preferably, the ionic liquid is 1-allyl-3-methylimidazolium chloride.
Preferably, the metal salt is selected from MgCl2NaCl and Na2SO4One or more of (a).
Preferably, the metal salt is selected from MgCl2NaCl and Na2SO4When the metal salt is two metal salts, the mass ratio of the two metal salts is 1:9 to 5: 5.
Preferably, the addition amount of the metal salt is 0.1-2.5% of the weight of the ionic liquid.
According to one embodiment of the present invention there is provided the use of the high efficiency cellulose solvent system in the preparation of a cellulose film comprising the steps of:
(1) mixing ionic liquid and metal salt, heating and stirring to prepare an ionic liquid-metal salt homogeneous solution, namely a high-efficiency cellulose solvent system;
(2) removing impurities from the fiber raw material, and crushing to form a flocculent raw material;
(3) adding the flocculent raw material into the high-efficiency cellulose solvent system, and heating and dissolving to obtain a cellulose homogeneous phase solution;
(4) and diluting, coating and regenerating the cellulose homogeneous solution to obtain the cellulose film.
Preferably, the ionic liquid in the step (1) is an industrial ionic liquid with a market price of less than 1800 yuan/kg, and comprises 1-allyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole chloride salt and the like, and is preferably 1-allyl-3-methylimidazole chloride salt.
Preferably, the metal salt in step (1) is MgCl2、BaCl2、NaCl、Na2SO4、ZnCl2、LiCl、CaCl2One or more of the following; preferably MgCl2NaCl and Na2SO4One or more of; more preferably MgCl2NaCl and Na2SO4When the metal salt is two metal salts, the mass ratio of the two metal salts is 1:9 to 5: 5.
Preferably, the addition amount of the metal salt in the step (1) is 0.1-2.5% of the weight of the ionic liquid, the dissolving temperature is 50-90 ℃, the magnetic stirring speed is 100-300 rpm, and the time is 0.5-3 h.
Preferably, the fiber raw material in the step (2) is a raw material with high cellulose content, such as cotton linter, poplar pulp board, cotton pulp board, microcrystalline cellulose or alpha-cellulose.
Preferably, the polymerization degree of the flocculent raw material in the step (2) is 300-1200.
Preferably, in the step (3), the addition amount of the cellulose is 2-12% of the weight of the high-efficiency cellulose solvent system, preferably 4-6%, the dissolving temperature is 60-90 ℃, the magnetic stirring rotating speed is 100-300 rpm, and the time for dissolving the cellulose accounting for 5% of the weight of the high-efficiency cellulose solvent system is 40-150 min, preferably 50-140 min.
Preferably, the cellulose homogeneous solution is diluted in the step (4) to 2-4 wt%, the thickness of the membrane is 300-600 μm, the coagulating bath is acetone, ethanol or water, and the corresponding reverse phase solvent is used for soaking and washing for multiple times to remove the high-efficiency solvent system.
The technical scheme of the invention has the following beneficial effects:
according to the invention, through the preparation and use of a high-efficiency cellulose solvent system, the dissolving effect of cellulose in the ionic liquid with relatively low price is improved, especially the maximum solubility of the cellulose is increased, and the cellulose dissolving time is shortened; the metal salt is simply added, the dissolution is promoted through the synergistic effect of the ionic liquid and the salt, the operation is simple and convenient, and the ultralow temperature operation is not needed; toxic and harmful reagents are not used in the operation process, the process is environment-friendly and recyclable, and the economic feasibility of a novel solvent system is improved.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
The ionic liquid 100% consists of anions and cations, and the capacity of the ionic liquid to dissolve cellulose is closely related to the type of ions. In the dissolving process, the anions of the ionic liquid are accepted to form hydrogen bonds with hydrogen atoms on cellulose hydroxyl groups, and the hydrogen bonds of the cellulose are broken, so that the cellulose molecular aggregates are dissociated and dispersed into the solvent to be dissolved. In general, the greater the ability of the anion of an ionic liquid to accept hydrogen bonds, the greater its ability to solubilize cellulose. Therefore, compared with the ionic liquid chloride salt, the ionic liquid acetate salt has better dissolving effect on the cellulose and higher price.
The metal salt is beneficial to improving the hydrogen bond accepting capacity of the chloride ionic liquid, so that the dissolving effect of the chloride ionic liquid on cellulose is improved. The metal ions can act with cellulose molecular chains to promote dissolution. Preferably, the metal salt is a mixture of 1-2 salts selected from MgCl2、BaCl2、NaCl、Na2SO4、ZnCl2、LiCl、CaCl2The addition amount is 0.2-2.5% of the weight of the ionic liquid. When the amount of the metal salt added is less than 0.2%, the cellulose dissolution-promoting effect is almost the sameTo ignore; when the amount of the metal salt added exceeds 2.5%, the viscosity of the system increases, and dissolution of cellulose is inhibited. Preferably, in order to form the ionic liquid-metal salt homogeneous solution, the stirring speed is 100-300 rpm and the time is 0.5-3 h in the preparation process.
The reagents used in the examples of the present invention are all commercially available products.
Dissolution of cellulose
Example 1
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 1g of metal salt mixture (0.6g of magnesium chloride, 0.4g of sodium chloride) was added with stirring, the temperature was raised to 80 ℃ and the mixture was stirred at 150rpm for 2 hours. Weighing cotton linter (with the polymerization degree of 850) and adding the cotton linter into the mixed solution, and continuously stirring the mixture at 80 ℃ and 200rpm until the mixture cannot be dissolved to obtain a homogeneous solution in which the cotton linter is dissolved. The maximum solubility of the cotton linters, obtained by dividing the mass of the cotton linters by the mass of the ionic liquid, was found to be 8.6% by analysis, wherein the time to dissolve the cotton linters, which accounted for 5% of the mass of the ionic liquid, was measured to be 138 min.
Example 2
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 1g of metal salt mixture (0.6g of magnesium chloride, 0.4g of sodium chloride) was added with stirring, the temperature was raised to 80 ℃ and the mixture was stirred at 150rpm for 2 hours. Weighing a pulp plate (with the polymerization degree of 360) and adding the pulp plate into the mixed solution, and continuously stirring the mixture at 80 ℃ and 200rpm until the pulp plate cannot be dissolved to obtain a homogeneous solution in which the pulp plate is dissolved. The maximum solubility of cotton linters was found to be 9.4% by analysis, with a pulp sheet time of 86min measured for dissolution of 5% by mass of ionic liquid.
Example 3
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 2g of the metal salt mixture (1.5g of magnesium chloride, 0.5g of sodium chloride) were added with stirring, the temperature was raised to 85 ℃ and the mixture was stirred at 200rpm for 1.5 h. Weighing cotton linter (with the polymerization degree of 850) and adding the cotton linter into the mixed solution, and continuously stirring at 85 ℃ and 200rpm until the cotton linter cannot be dissolved to obtain a homogeneous solution in which the cotton linter is dissolved. The maximum solubility of the cotton linters was 11.5% by analysis, wherein the time to dissolve the cotton linters, which accounted for 5% by mass of the ionic liquid, was measured to be 55 min.
Example 4
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 2g of magnesium chloride was added with stirring, the temperature was raised to 85 ℃ and stirred at 200rpm for 1.5 h. Weighing cotton linter (with the polymerization degree of 850) and adding the cotton linter into the mixed solution, and continuously stirring at 85 ℃ and 200rpm until the cotton linter cannot be dissolved to obtain a homogeneous solution in which the cotton linter is dissolved. The maximum solubility of the cotton linters was found to be 10.2% by analysis, with a dissolution time of 72min measured for cotton linters which accounted for 5% by mass of the ionic liquid.
Example 5
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 2g of metal salt mixture (1.5g of zinc chloride, 0.5g of sodium sulfate) were added with stirring, the temperature was raised to 80 ℃ and the mixture was stirred at 200rpm for 1.5 h. Weighing cotton linter (with the polymerization degree of 850) and adding the cotton linter into the mixed solution, and continuously stirring at 85 ℃ and 200rpm until the cotton linter cannot be dissolved to obtain a homogeneous solution in which the cotton linter is dissolved. The maximum solubility of the cotton linters was found to be 9.2% by analysis, with the time to dissolve cotton linters accounting for 5% by mass of ionic liquid measured to be 115 min.
Example 6
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 2g of the metal salt mixture (1.5g of zinc chloride, 0.5g of sodium chloride) were added with stirring, the temperature was raised to 80 ℃ and the mixture was stirred at 200rpm for 2 h. 5g of cotton linter (with a polymerization degree of 850) is weighed and added into the mixed solution, and the stirring is continued at 80 ℃ and 200rpm until the solution is clear and transparent, so as to obtain a homogeneous solution in which the cotton linter is dissolved. The dissolution time of the cotton linters is 120min through time measurement.
Comparative example 1
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ for dissolution. The cotton linter (degree of polymerization: 850) was weighed out and added to the mixed solution, and stirring was continued at 85 ℃ and 200rpm until dissolution failed. The maximum solubility of the cotton linters was found to be 7.6% by analysis, wherein the time to dissolve the cotton linters, which accounted for 5% by mass of the ionic liquid, was measured to be 284 min.
Comparative example 2
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 5g of a metal salt mixture (3.5g of magnesium chloride, 1.5g of sodium chloride) were added with stirring, the temperature was raised to 85 ℃ and the mixture was stirred at 200rpm for 1.5h, the metal salt did not dissolve completely. Weighing cotton linter (with the polymerization degree of 850) and adding the cotton linter into the mixed solution, and continuously stirring at 85 ℃ and 200rpm until the cotton linter cannot be dissolved to obtain a homogeneous solution in which the cotton linter is dissolved. The maximum solubility of the cotton linters was found to decrease to 5.8% by analysis, where the time to dissolve the cotton linters at 5% by mass of ionic liquid was measured to be 265 min.
Comparative example 3
100g of ionic liquid 1-allyl-3-methylimidazolium chloride salt is weighed into a beaker and preheated to 60 ℃ to be liquid. 2g of the other metal salt mixture (1.5g of copper chloride, 0.5g of sodium chloride) were added with stirring, the temperature was raised to 85 ℃ and the mixture was stirred at 200rpm for 1.5 h. Weighing cotton linter (with the polymerization degree of 850) and adding the cotton linter into the mixed solution, and continuously stirring at 85 ℃ and 200rpm until the cotton linter cannot be dissolved to obtain a homogeneous solution in which the cotton linter is dissolved. It was found by analysis that the maximum solubility of the cotton linters hardly became 7.8%, wherein the extension of the time to dissolve the cotton linters, which accounted for 5% by mass of the ionic liquid, was measured to be 318 min.
Film preparation
Comparative Experimental example 1
The homogeneous solution prepared in comparative example 1, in which cotton linters were dissolved, was coated in an amount of 30g/10cm2After regeneration by an ethanol coagulating bath, washing and drying, a cellulose film with the tensile strength of 69MPa is obtained, wherein the cellulose film has the thickness of 320 mu m.
Experimental example 1
The homogeneous solution prepared in example 1, in which cotton linters were dissolved, was coated in an amount of 30g/10cm2After regeneration, washing and drying by an ethanol coagulating bath, a 350 mu m cellulose film is obtained, the tensile strength is 75MPa, and is equivalent to the conventional dissolved film forming strength.
Experimental example 2
The homogeneous solution prepared in example 7, in which cotton linters were dissolved, was coated in an amount of 30g/10cm2After regeneration, washing and drying by an ethanol coagulating bath, a 320 mu m cellulose film is obtained, the tensile strength is 69MPa, and the film strength is equivalent to that of a conventional dissolved film.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof, since the present invention is not limited thereto. Those skilled in the art can make various changes and modifications to the disclosed embodiments without departing from the scope of the present invention, and all such changes and modifications as would be obvious to one skilled in the art are intended to be included within the scope of the present invention.
Claims (5)
1. A high-efficiency cellulose solvent system, which is formed by mixing ionic liquid and metal salt,
wherein the ionic liquid is 1-allyl-3-methylimidazole chloride salt, and the metal salt is selected from MgCl2NaCl and Na2SO4Two of (1), or NaCl, Na2SO4And ZnCl2The mass ratio of the two metal salts is 1: 9-5: 5, and the addition amount of the metal salt is 0.2-2.5% of the weight of the ionic liquid.
2. Use of the high efficiency cellulose solvent system according to claim 1 for the preparation of a cellulose film comprising the steps of:
(1) mixing ionic liquid and metal salt, heating and stirring to prepare an ionic liquid-metal salt homogeneous solution, namely a high-efficiency cellulose solvent system;
(2) removing impurities from the fiber raw material, and crushing to form a flocculent raw material;
(3) adding the flocculent raw material into the high-efficiency cellulose solvent system, and heating and dissolving to obtain a cellulose homogeneous phase solution;
(4) diluting the cellulose homogeneous solution, coating, and regenerating by a coagulating bath to obtain a cellulose film;
wherein the ionic liquid in the step (1) is 1-allyl-3-methylimidazolium chloride, and the metal salt is selected from MgCl2NaCl and Na2SO4Two of (1), or NaCl, Na2SO4And ZnCl2The mass ratio of the two metal salts is 1:9 to 5: 5;
in the step (1), the addition amount of the metal salt is 0.2-2.5% of the weight of the ionic liquid, the dissolving temperature is 50-90 ℃, the magnetic stirring speed is 100-300 rpm, and the time is 0.5-3 h.
3. The use of the cellulose film according to claim 2, wherein the fiber material in step (2) is a material having a high cellulose content such as cotton linter, poplar pulp sheet, cotton pulp sheet, microcrystalline cellulose or α -cellulose; the polymerization degree of the flocculent raw materials is 300-1200.
4. The use of the cellulose film as claimed in claim 2, wherein the cellulose is added in an amount of 2-12 wt% of the high-efficiency cellulose solvent system in step (3), the dissolution temperature is 60-90 ℃, and the magnetic stirring speed is 100-300 rpm; dissolving cellulose accounting for 5 percent of the weight of the high-efficiency cellulose solvent system for 40min to 150 min;
and (3) diluting the cellulose homogeneous solution in the step (4) to 2-4 wt%, wherein the thickness of the membrane is 300-600 mu m, the coagulating bath is acetone, ethanol or water, and the corresponding reverse phase solvent is used for soaking and washing for multiple times to remove the solvent system.
5. The use of the cellulose film according to claim 4, wherein the cellulose is added in an amount of 4-6% by weight of the high efficiency cellulose solvent system in step (3); the time for dissolving the cellulose accounting for 5 percent of the weight of the high-efficiency cellulose solvent system is 50min to 140 min.
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| CN109337097B (en) * | 2018-10-29 | 2021-10-01 | 绍兴美标纺织品检验有限公司 | Solvent and method for preparing cellulose solution by using same |
| CN109158089B (en) * | 2018-11-07 | 2021-05-18 | 福州大学 | Ultrasonic-assisted sulfhydryl modified cellulose aerogel and preparation method thereof |
| CN110041564A (en) * | 2019-03-29 | 2019-07-23 | 北京林业大学 | The in-situ preparation method of cellulose antibacterial film, the cellulose antibacterial film by this method preparation and its application |
| CN111607106A (en) * | 2020-05-21 | 2020-09-01 | 浙江理工大学 | Dissolving of cellulose and preparation method of regenerated cellulose |
| CN113462031A (en) * | 2021-06-24 | 2021-10-01 | 南京林业大学 | Preparation method of cellulose-based plastic |
| CN114670299B (en) * | 2022-03-11 | 2023-05-23 | 华南理工大学 | High-strength anisotropic aerogel type wood structure and preparation method thereof |
| CN114702689B (en) * | 2022-05-19 | 2023-12-19 | 福建农林大学 | Preparation method of high-strength cellulose ionic gel |
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