CN111019004A - Method for preparing cellulose nanocrystals by hydrolyzing acidic eutectic solvent under catalysis of metal salt - Google Patents
Method for preparing cellulose nanocrystals by hydrolyzing acidic eutectic solvent under catalysis of metal salt Download PDFInfo
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Abstract
The invention relates to a method for preparing cellulose nanocrystals by catalyzing hydrolysis of an acidic eutectic solvent with a metal salt, belonging to the field of preparation of natural high polymer materials. The cellulose nanocrystal is prepared by catalyzing and hydrolyzing 1-10 parts by mass of cellulose pulp under the catalysis of 1-8 parts by mass of metal salt in a eutectic system composed of 50 parts by mass of oxalic acid dihydrate and 10-50 parts by mass of choline chloride, wherein the reaction time is 4-10 hours, and the reaction temperature is 70-85 ℃. The reaction condition is mild, and the operation is simple. The cellulose nanocrystals are prepared by one step by using the acidic eutectic solvent, and the steps of machining treatment and the like are omitted. The prepared cellulose nanocrystal has good thermal stability and good dispersion stability in water.
Description
Technical Field
The invention relates to the field of preparation of natural high polymer materials, in particular to a method for preparing cellulose nanocrystals by catalyzing hydrolysis of an acidic eutectic solvent with a metal salt.
Background
Cellulose is one of the most abundant natural high molecular polymers in nature, has been used as a material for thousands of years, and is still widely used in the fields of papermaking, building, textile and the like due to abundant sources and excellent performance. Cellulose nanocrystals are rigid rod-like cellulose with a diameter of 1-100nm and a length of tens to hundreds of nanometers. Compared with common non-nano cellulose, due to the characteristics of high purity, high crystallinity, high Young's modulus, high strength and the like of the cellulose nanocrystals, the cellulose nanocrystals show extremely high Young's modulus, strength and other properties in material synthesis, so that the cellulose nanocrystals are widely applied to reinforced nano composite materials, and the mechanical and load-bearing properties of the composite materials are remarkably improved; in addition, the biological material has the characteristics of light weight, degradability, biocompatibility, reproducibility and the like, and the biological medicine is widely applied to wound coating materials, synthetic blood vessel hydrophobic modification, drug carriers and the like.
The eutectic solvent is a novel green reaction solvent consisting of a hydrogen bond acceptor and a hydrogen bond donor or a quaternary ammonium salt and a metal salt substance, has the advantages of simple preparation, low price and degradability, and is widely applied to the fields of organic synthesis, material preparation, gas separation and the like.
The existing cellulose nanocrystal preparation mainly adopts an acid hydrolysis method, although the used raw materials are various and the product properties are different, the main preparation principle and the method are basically consistent, namely the processes of cellulose swelling treatment, acid hydrolysis, washing, drying, crushing and the like are adopted, at present, the acid hydrolysis step mainly adopts inorganic acids such as sulfuric acid and the like, and the defects of large water consumption, more generated waste liquid, environment friendliness and the like exist. Eutectic systems have also been reported before the use of eutectic systems for the preparation of cellulose nanocrystals, patent 201610150536.0 discloses a method of preparing cellulose nanocrystals using a eutectic reagent as a pretreatment means followed by mechanical means, the mechanical means used including: sonication, high pressure homogenization, grinding, and the like. The method solves the problems of long preparation period, low yield and low product thermal stability caused by using concentrated acid to prepare the cellulose nanocrystals, but the whole steps are complicated. If the method can realize one-step preparation of the cellulose nanocrystals by hydrolyzing the cellulose by using the eutectic solvent, and omits the measures of moistening the cellulose, post-processing mechanical processing and the like, the reaction efficiency can be obviously improved, and the cost can be saved.
Disclosure of Invention
The invention mainly aims to improve the hydrolysis reaction activity of cellulose nanocrystals prepared by hydrolyzing an acidic eutectic solvent, and realize one-step preparation of the cellulose nanocrystals by using the acidic eutectic solvent without performing early moistening treatment and later mechanical treatment.
In order to achieve the above object, the present invention improves the hydrolysis reaction activity by introducing a catalyst into the eutectic system, and specifically comprises the following steps:
(1) adding 50 parts by mass of oxalic acid dihydrate and 10-50 parts by mass of choline chloride into a reactor at the temperature of 0-40 ℃, heating to 70-85 ℃, stirring for 5-10 min to form a eutectic solvent, adding 1-8 parts by mass of metal salt into the reactor, stirring for 5-10 min, adding 1-10 parts by mass of cellulose slurry, and continuously stirring for 4-10 h at the temperature of 70-85 ℃;
(2) adding 300-700 parts by mass of 70-95 ℃ distilled water into the reaction system in the step (1), centrifuging for 3-10 min at the rotating speed of 5000-10000 r/min while the solution is hot, pouring out the supernatant to keep a precipitate part, dispersing the obtained precipitate by 100-800 parts by mass of distilled water, centrifuging for 3-10 min at the rotating speed of 5000-10000 r/min, repeating the centrifugal washing process by using the distilled water for 3-8 times, and freeze-drying or spray-drying the washed solid to prepare the cellulose nanocrystal;
the metal salt is one or a mixture of more of ferric trichloride, ferric trichloride hexahydrate, ferric tribromide hexahydrate, aluminum trichloride hexahydrate and zinc dichloride.
The cellulose pulp is a mixture consisting of one or more of bleached wood pulp, bleached straw pulp, cotton pulp, dissolving pulp, secondary fiber, unbleached wood pulp or unbleached straw pulp.
The stirring is preferably mechanical stirring, and the stirring speed is 100 r/min-500 r/min.
And (3) concentrating the supernatant in the step (2) in a reduced pressure distillation mode, and taking a mixture obtained after concentration as a eutectic reaction solution to be reused for preparing the cellulose nanocrystals, wherein the repetition time is 3-6 times.
Has the advantages that:
(1) the method for preparing the cellulose nanocrystals has mild reaction conditions, does not need subsequent mechanical treatment compared with the original method (201610150536.0) for preparing the cellulose nanocrystals by using the eutectic solvent, and simplifies the preparation process; compared with the method of using the oxalic acid aqueous solution as the reaction reagent (201810047718.4), the reaction temperature is obviously reduced.
(2) The cellulose nanocrystal prepared by the method for preparing the cellulose nanocrystal has good thermal stability, and the thermal degradation temperature is more than 320 ℃; meanwhile, the dispersion stability in water is good.
Drawings
The FIGURE is a transmission electron micrograph of cellulose nanocrystals prepared according to example 1.
Detailed Description
Example 1
Adding 50g of oxalic acid dihydrate and 10g of choline chloride into a 250mL three-neck flask at the temperature of 25 ℃, heating the mixture by using an oil bath, heating the mixture to 85 ℃, mechanically stirring the mixture for 10min at the stirring speed of 100r/min to form a eutectic solvent, adding 1g of ferric chloride hexahydrate into the three-neck flask, stirring the mixture for 5min, adding 1g of bleached eucalyptus pulp, continuously stirring the mixture for 4h at the temperature of 85 ℃, diluting the reaction mixture by 300g of 95 ℃ distilled water, centrifuging the reaction mixture for 10min at the rotation speed of 10000r/min while the reaction is hot, pouring out supernatant liquid to retain a precipitate part, dispersing the obtained precipitate by 100g of distilled water, centrifuging the reaction mixture for 10min at the rotation speed of 10000r/min, repeating the centrifugation washing process by using the distilled water for 3 times, and freeze-drying the solid obtained after washing to obtain 0.75g of cellulose nanocrystals. The temperature of the obtained product with 5 percent of thermal decomposition weight loss is 321 ℃. The particle size distribution is about 230nm to 350 nm. The product was dispersed in water at a concentration of 1 wt% and left to stand for 30 days without settling.
Example 2
Adding 50g of oxalic acid dihydrate and 50g of choline chloride into a 250mL three-neck flask at the temperature of 25 ℃, heating the mixture by using an oil bath, heating the mixture to 70 ℃, mechanically stirring the mixture for 10min at the stirring speed of 500r/min to form a eutectic solvent, adding 8g of ferric trichloride hexahydrate into the three-neck flask, stirring the mixture for 5min, adding 10g of bleached straw pulp, continuously stirring the mixture for 10h at the temperature of 70 ℃, diluting the reaction mixture by 700g of 95 ℃ distilled water, centrifuging the reaction mixture for 10min at the rotation speed of 10000r/min while the reaction is hot, pouring out supernatant liquid to retain a precipitate part, dispersing the obtained precipitate by 800g of distilled water, centrifuging the reaction mixture for 10min at the rotation speed of 10000r/min, repeating the centrifugal washing process by using the distilled water for 8 times, and freeze-drying the solid obtained after washing to obtain 7.2g of cellulose nanocrystals. The temperature of the obtained product with 5 percent weight loss by thermal decomposition is 324 ℃. The particle size distribution is about 420nm to 510 nm. The product was dispersed in water at a concentration of 1 wt% and left to stand for 30 days without settling.
Example 3
Adding 50g of oxalic acid dihydrate and 20g of choline chloride into a 250mL three-neck flask at the temperature of 30 ℃, heating by using an oil bath, raising the temperature to 80 ℃, mechanically stirring for 5min at the stirring speed of 200r/min to form a eutectic solvent, adding 2g of aluminum trichloride into the three-neck flask, stirring for 5min, adding 3g of unbleached poplar wood pulp, continuously stirring for 6h at the temperature of 80 ℃, diluting the reaction mixture by 300g of 95 ℃ distilled water, centrifuging for 5min at the rotating speed of 8000r/min while hot, pouring out a supernatant to retain a precipitate part, dispersing the obtained precipitate by 600g of distilled water, centrifuging for 5min at the rotating speed of 8000r/min, repeating the centrifuging and washing process by the distilled water for 5 times, and spray drying the solid obtained after washing to obtain 2.05g of cellulose nanocrystals. The temperature of the obtained product with 5 percent of thermal decomposition weight loss is 322 ℃. The particle size distribution is 480 nm-590 nm. The product was dispersed in water at a concentration of 1 wt% and left to stand for 30 days without settling.
Example 4
Adding 50g of oxalic acid dihydrate and 25g of choline chloride into a 250mL three-neck flask at 25 ℃, heating by using an oil bath, raising the temperature to 80 ℃, mechanically stirring for 10min at the stirring speed of 300r/min to form a eutectic solvent, then adding 6g of zinc dichloride into the three-neck flask, stirring for 5min, adding 3g of cotton pulp, continuing stirring for 6h at 85 ℃, adding 600g of 85 ℃ distilled water into the reaction system, then centrifuging for 3min at 10000r/min while hot, pouring out supernatant liquid to keep a precipitate part, dispersing the obtained precipitate with 600g of distilled water, then centrifuging for 5min at 10000r/min, repeating the centrifugal washing process with distilled water for 3 times, and freeze-drying the solid obtained after washing to obtain 2.1g of cellulose nanocrystals. The temperature of the obtained product with 5 percent of thermal decomposition weight loss is 320 ℃. The particle size distribution is 570 nm-630 nm. The product was dispersed in water at a concentration of 1 wt% and left to stand for 30 days without settling.
Example 5
50g of oxalic acid dihydrate and 20g of choline chloride were charged into a 250mL three-necked flask at 25 ℃, then heating by using an oil bath, raising the temperature to 80 ℃, mechanically stirring for 10min at the stirring speed of 100r/min to form a eutectic solvent, then adding 2g ferric trichloride into a three-neck bottle, stirring for 10min, adding 2g unbleached straw pulp, continuing stirring for 7h at 80 ℃, diluting the reaction mixture with 500g distilled water at 80 ℃, centrifuging at 8000r/min for 6min, pouring out supernatant and retaining precipitate, dispersing the obtained precipitate with 500g of distilled water, centrifuging at 10000r/min for 6min, repeating the centrifuging and washing process with distilled water for 5 times, the solid obtained after washing was spray-dried to obtain 1.56g of cellulose nanocrystals. The temperature of the obtained product with 5 percent of thermal decomposition weight loss is 326 ℃. The particle size distribution is 265 nm-330 nm. The product was dispersed in water at a concentration of 1 wt% and left to stand for 30 days without settling.
Example 6
Adding 50g of oxalic acid dihydrate and 15g of choline chloride into a 250mL three-neck flask at the temperature of 25 ℃, heating by using an oil bath, raising the temperature to 80 ℃, mechanically stirring for 10min at the stirring speed of 100r/min to form a eutectic solvent, then adding 1g of ferric tribromide hexahydrate into the three-neck flask, stirring for 10min, adding 2g of bleached poplar wood pulp, continuing stirring for 10h at the temperature of 80 ℃, diluting the reaction mixture by 400g of 80 ℃ distilled water, then centrifuging for 5min at the rotating speed of 8000r/min while hot, pouring out a supernatant to retain a precipitate part, dispersing the obtained precipitate by 500g of distilled water, then centrifuging for 5min at the rotating speed of 8000r/min, repeating the centrifuging and washing process by the distilled water for 5 times, and freeze-drying the solid obtained after washing to obtain 1.55g of cellulose nanocrystals. The temperature of the obtained product with 5 percent of thermal decomposition weight loss is 322 ℃. The particle size distribution is 190 nm-270 nm. The product was dispersed in water at a concentration of 1 wt% and left to stand for 30 days without settling.
Example 7
50g of oxalic acid dihydrate and 50g of choline chloride were charged into a 250mL three-necked flask at 25 ℃, then heating by using an oil bath, raising the temperature to 70 ℃, mechanically stirring for 10min at the stirring speed of 500r/min to form a eutectic solvent, then 3g ferric chloride hexahydrate and 1g aluminum trichloride are added into a three-neck flask, stirred for 5min, then 5g bleached poplar pulp is added, the stirring is continued for 6h under the condition of 70 ℃, 500g distilled water with the temperature of 95 ℃ is used for diluting the reaction mixture, centrifuging at 10000r/min for 10min, pouring out supernatant and retaining precipitate, dispersing the obtained precipitate with 500g distilled water, centrifuging at 10000r/min for 10min, repeating the centrifuging and washing process with distilled water for 5 times, and freeze drying the washed solid to obtain 3.6g cellulose nanocrystal. The temperature of the obtained product with 5 percent weight loss by thermal decomposition is 324 ℃. The particle size distribution is 310 nm-485 nm. The product was dispersed in water at a concentration of 1 wt% and left to stand for 30 days without settling.
Claims (3)
1. A method for preparing cellulose nanocrystals by the hydrolysis of an acidic eutectic solvent catalyzed by a metal salt, the preparation method comprising the steps of:
(1) adding 50 parts by mass of oxalic acid dihydrate and 10-50 parts by mass of choline chloride into a reactor at the temperature of 0-40 ℃, heating to 70-85 ℃, stirring for 5-10 min to form a eutectic solvent, adding 1-8 parts by mass of metal salt into the reactor, stirring for 5-10 min, adding 1-10 parts by mass of cellulose slurry, and continuously stirring for 4-10 h at the temperature of 70-85 ℃;
(2) adding 300-700 parts by mass of 70-95 ℃ distilled water into the reaction system in the step (1), centrifuging for 3-10 min at the rotating speed of 5000-10000 r/min while the solution is hot, pouring out the supernatant to keep a precipitate part, dispersing the obtained precipitate by 100-800 parts by mass of distilled water, centrifuging for 3-10 min at the rotating speed of 5000-10000 r/min, repeating the centrifugal washing process by using the distilled water for 3-8 times, and freeze-drying or spray-drying the washed solid to prepare the cellulose nanocrystal;
the metal salt is one or a mixture of more of ferric trichloride, ferric trichloride hexahydrate, ferric tribromide hexahydrate, aluminum trichloride hexahydrate and zinc dichloride.
2. The method for preparing cellulose nanocrystals by the hydrolysis of the acidic eutectic solvent catalyzed by the metal salt as claimed in claim 1, wherein the cellulose pulp is one or more selected from bleached wood pulp, bleached straw pulp, cotton pulp, dissolving pulp, secondary fiber, unbleached wood pulp and unbleached straw pulp.
3. The method for preparing cellulose nanocrystals by the hydrolysis of the acidic eutectic solvent catalyzed by the metal salt as claimed in claim 1, wherein the stirring is mechanical stirring and the stirring speed is 100r/min to 500 r/min.
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Cited By (9)
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| CN112853794A (en) * | 2021-02-03 | 2021-05-28 | 江苏大学 | Method for preparing nano-cellulose microfibrils by pretreatment of ternary eutectic solvent |
| CN113278272A (en) * | 2021-06-04 | 2021-08-20 | 四川宽窄纸品有限责任公司 | Plant cellulose-based full-biodegradable material and preparation method thereof |
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| CN114181404A (en) * | 2021-12-17 | 2022-03-15 | 中国科学院上海高等研究院 | Ternary eutectic solvent and preparation method and application thereof |
| CN114751993A (en) * | 2022-04-13 | 2022-07-15 | 陕西科技大学 | Preparation method of cellulose nanocrystal capable of being dried and redispersed |
| CN114805615A (en) * | 2022-03-24 | 2022-07-29 | 华南农业大学 | Method for preparing cellulose nanocrystal by hydrolyzing acidic zinc chloride, cellulose nanocrystal prepared by method and application of cellulose nanocrystal |
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| CN112726253A (en) * | 2021-01-21 | 2021-04-30 | 天津科技大学 | Method for efficiently separating plant fibers by acidic eutectic solvent/metal salt multi-component system |
| CN112853794A (en) * | 2021-02-03 | 2021-05-28 | 江苏大学 | Method for preparing nano-cellulose microfibrils by pretreatment of ternary eutectic solvent |
| CN112853794B (en) * | 2021-02-03 | 2022-05-20 | 江苏大学 | Method for preparing nano-cellulose microfibrils by pretreatment of ternary eutectic solvent |
| CN113278272A (en) * | 2021-06-04 | 2021-08-20 | 四川宽窄纸品有限责任公司 | Plant cellulose-based full-biodegradable material and preparation method thereof |
| CN114181404A (en) * | 2021-12-17 | 2022-03-15 | 中国科学院上海高等研究院 | Ternary eutectic solvent and preparation method and application thereof |
| CN114181405A (en) * | 2021-12-17 | 2022-03-15 | 中国科学院上海高等研究院 | Eutectic solvent and preparation method and application thereof |
| CN114163684A (en) * | 2021-12-31 | 2022-03-11 | 浙江理工大学 | Method for directly extracting fibroin nanofibers from waste silkworm cocoons and recovering hydrolyzed silk protein and extracting solution |
| CN114163684B (en) * | 2021-12-31 | 2023-09-05 | 浙江理工大学 | Method for directly extracting silk fibroin nanofibers from waste cocoons and recovering hydrolyzed silk proteins and extracting solution |
| CN114805615A (en) * | 2022-03-24 | 2022-07-29 | 华南农业大学 | Method for preparing cellulose nanocrystal by hydrolyzing acidic zinc chloride, cellulose nanocrystal prepared by method and application of cellulose nanocrystal |
| CN114805615B (en) * | 2022-03-24 | 2023-09-15 | 华南农业大学 | Method for preparing cellulose nanocrystalline by acidic zinc chloride hydrolysis, prepared cellulose nanocrystalline and application thereof |
| CN114751993A (en) * | 2022-04-13 | 2022-07-15 | 陕西科技大学 | Preparation method of cellulose nanocrystal capable of being dried and redispersed |
| CN114751993B (en) * | 2022-04-13 | 2023-09-01 | 陕西科技大学 | Preparation method of cellulose nanocrystalline capable of being dried and redispersed |
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Application publication date: 20200417 |