CN111100212A - Sulfate nanocellulose and preparation method thereof - Google Patents
Sulfate nanocellulose and preparation method thereof Download PDFInfo
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- CN111100212A CN111100212A CN201911164470.0A CN201911164470A CN111100212A CN 111100212 A CN111100212 A CN 111100212A CN 201911164470 A CN201911164470 A CN 201911164470A CN 111100212 A CN111100212 A CN 111100212A
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- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/14—Preparation of cellulose esters of organic acids in which the organic acid residue contains substituents, e.g. NH2, Cl
Abstract
The invention relates to the field of cellulose materials, and discloses sulfate nanocellulose and a preparation method thereof. The method comprises the following steps: the cellulose reacts in the organic solution of sulfamic acid for 3 to 24 hours to prepare the sulfate ester nano-cellulose. The invention provides another feasible method for preparing the nano-cellulose, and the obtained nano-cellulose has higher yield, high product crystallinity and excellent performance. The method provided by the invention has the advantages of short treatment time and simple process, and is suitable for industrial mass production. The nano-cellulose product obtained by the invention contains high-concentration functional groups on the surface, has good redispersibility in water, and has wide application prospects in the fields of nano-composite materials, medical high polymer materials, wearable equipment, super-adsorption and the like.
Description
Technical Field
The invention relates to the field of cellulose materials, and particularly relates to sulfate nanocellulose and a preparation method thereof.
Background
Cellulose is a natural renewable high-molecular polymer which is most abundant and widely distributed in nature. Nanocellulose is a cellulosic material with a dimension less than 100nm in one of three dimensions. The nano-cellulose has small-size effect, surface interface effect and macroscopic quantum tunneling effect, shows unique optical, electrical, magnetic and chemical properties, is known as the most promising material in the century, has attracted high attention of various governments and scientific circles, and has wide application prospect in the fields of new material research and new technology.
Cellulose is the main component of plant cell walls and is also one of the most abundant renewable organic resources on earth. The cellulose can be used for producing clean energy, and high-performance materials and high value-added chemicals can be produced to replace products from fossil resources. Because adjacent cellulose microfibrils are chemically cross-linked or physically intertwined together, efficient nano defibrination is always a difficulty in high-value utilization of cellulose.
The preparation method of the nano-cellulose mainly comprises a physical method, a chemical method and a biological method. The physical methods mainly comprise a high-pressure homogenization method, a micro-jet method, a disc mill, an ultrasonic method and the like, and the physical methods have the main defect of high energy consumption, and can be as high as 25KWh/kg sometimes. The chemical method adopts high-concentration inorganic acid, such as sulfuric acid, hydrochloric acid, phosphoric acid and the like, for acidolysis, and has the defects of serious cellulose hydrolysis, low yield, strong corrosion of acid liquid on equipment, high difficulty in recycling hydrolysis products and the like. The enzyme price of the biological method is expensive, the reaction condition is harsh, the reaction efficiency is low, and the reaction time is long. In order to realize the industrial production of the nano-cellulose, an efficient and simple preparation method of the nano-cellulose must be developed.
The charged anionic groups are introduced to the surfaces of the cellulose microfibrils, electrostatic repulsion is formed between adjacent microfibrils, hydrogen bonding between cellulose molecules is destroyed, and energy consumption during defibration can be reduced. Akira Isogai et al oxidatively modify cellulose by a TEMPO catalytic oxidation method, and although carboxyl groups can be introduced on the surfaces of microfibrils, the concentration of the carboxyl groups does not exceed 1.8mmol/g of cellulose at most, the TEMPO reagent used in the method has high toxicity, and the reaction condition needs to be carried out under a specific pH, so that the operation is complex. Therefore, a method is needed to be invented, so that charged groups are introduced to the surfaces of the microfibrils as much as possible, the energy consumption of mechanical defibration is low, and the nanocellulose is efficiently prepared.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide sulfate nanocellulose and a preparation method thereof.
The invention aims to provide a sulfate nanocellulose product with new functions and characteristics and an efficient preparation method thereof.
The sulfate nano cellulose product provided by the invention is in the form of suspension, aerogel or powder, contains high-concentration functional groups on the surface, and has good redispersibility in water.
The invention also aims to provide a preparation method of the sulfate nanocellulose. The method comprises the following steps: adding cellulose raw material into the reaction solution, continuously stirring and reacting for a certain time at a certain temperature, washing, centrifuging and dispersing the reaction product to obtain sulfate nanocellulose suspension, and freeze-drying to obtain aerogel-like and powdery nanocellulose. The reaction solution is N' N-dimethylformamide of sulfamic acid or dimethyl sulfoxide mixed solution.
The method provided by the invention has the advantages of short treatment time and simple process, and is suitable for industrial mass production. The obtained sulfate nano-cellulose material has wide application prospect in the fields of nano-composite materials, medical high polymer materials, wearable equipment, super-adsorption and the like.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of sulfate nanocellulose, which comprises the following steps:
(1) adding sulfamic acid into an organic solvent, and uniformly stirring to obtain a sulfamic acid solution;
(2) adding cellulose into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, heating the mixed solution under a stirring state for reflux reaction, cooling to room temperature, centrifuging to obtain a precipitate, and obtaining a gel-like solid;
(3) and (3) washing the gel-like solid in the step (2) to obtain a washed gel-like solid, adding the washed gel-like solid into water, uniformly dispersing to obtain a nanocellulose suspension, and drying to obtain the sulfate nanocellulose.
Further, the organic solvent in the step (1) is N' N-dimethylformamide or dimethyl sulfoxide; the mass percentage concentration of the sulfamic acid solution is 2-15 wt%.
Further, the cellulose in the step (2) is purified cellulose; the cellulose is one of bamboo pulp cellulose, bagasse pulp cellulose, bacterial cellulose, short cotton linter, commercialized microcrystalline cellulose and the like.
Furthermore, in the mixed solution in the step (2), the concentration of the cellulose is 0.008-0.02 g/mL.
Further, in the mixed liquor in the step (2), the solid content of the cellulose is 0.05-0.2%.
Further, the temperature of the reflux reaction in the step (2) is 60-160 ℃, and the time of the reflux reaction is 3-24 hours.
Further, the rotation speed of the centrifugation in the step (2) is 3000-6000rpm, and the centrifugation time is 5-30 minutes.
Further, the washing in the step (3) is washing with a mixed solution of N 'N-dimethylformamide, N' N-dimethylformamide and isopropanol and water in sequence; the mixed solution of the N 'N-dimethylformamide and the isopropanol is formed by uniformly mixing the N' N-dimethylformamide and the isopropanol; the volume ratio of the N' N-dimethylformamide to the isopropanol is 1: 1.
Preferably, the number of washing in step (3) is 1 to 5.
Further, the uniformly dispersing mode in the step (3) comprises ultrasonic dispersing, homogenizer dispersing and stirring dispersing; the time for uniform dispersion is 5-30 minutes.
Preferably, the manner of uniform dispersion is ultrasonic dispersion.
Further, the drying manner in the step (3) comprises vacuum freeze drying; the drying time is 12-48 hours.
The invention provides sulfate nanocellulose prepared by the preparation method.
The preparation method provided by the invention has the advantages that the used reagent has low toxicity and simple operation, and the prepared nano-cellulose has good appearance and is convenient for industrial production. The sulfate nanocellulose prepared by the method contains high-concentration functional groups on the surface, has good redispersibility in water, and has wide application prospects in the fields of nano composite materials, medical high polymer materials, wearable equipment, super-adsorption and the like.
The sulfate nanocellulose provided by the invention contains high-concentration functional groups, and the functional groups are sulfate groups.
The invention provides a method for preparing nano-cellulose by using D-glucose as a chain high molecular compound bonded by β -1,4 glucoside bonds, wherein each glucose contains 3 hydroxyl groups on C2, C3 and C6.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the sulfate nanocellulose prepared by the invention has the advantages of high purity and uniform size distribution;
(2) according to the preparation method of the sulfate nanocellulose, the content of the functional groups of the obtained sulfate nanocellulose can be regulated and controlled by regulating the using amount of sulfamic acid; the nano-cellulose reduces energy consumption and production cost in the preparation process, has simple and easy operation process, does not need expensive equipment, and is suitable for industrial mass production.
Drawings
FIG. 1 is an AFM image of the sulfate nanocellulose prepared in example 1.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of sulfate nanocellulose comprises the following steps:
(1) adding 50mL of N, N-dimethylformamide into a 100mL three-neck flask, then adding 1g of sulfamic acid into the three-neck flask, and uniformly stirring to completely dissolve solids to obtain a sulfamic acid solution;
(2) adding 0.8g of microcrystalline cellulose into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, transferring the mixed solution into an oil bath pot, heating to 120 ℃ under a stirring state to perform reflux reaction, wherein the reflux reaction time is 3 hours, cooling to room temperature, centrifuging to obtain a precipitate, and removing the reaction solution to obtain a gel-like solid;
(3) washing the gelatinous solid in the step (2) by using N 'N-dimethylformamide, a mixed solution of N' N-dimethylformamide and isopropanol and deionized water in sequence, the mixed solution of the N 'N-dimethylformamide and the isopropanol is a liquid formed by uniformly mixing the N' N-dimethylformamide and the isopropanol, the volume ratio of the N' N-dimethylformamide to the isopropanol is 1:1, the washing times are all 3 times, after each washing, the mixture is centrifuged for 10 minutes at the rotating speed of 3000rpm to remove supernatant liquid, so as to obtain washed gel-like solid, the washed gel-like solid is added into water, and (3) uniformly dispersing by using ultrasonic for 15 minutes to obtain a nano cellulose suspension, and freeze-drying in vacuum for 48 hours to obtain the sulfate nano cellulose.
The obtained gel-like solid was dispersed with ultrasound for 15 minutes to obtain a nanocellulose suspension, the Zeta potential of which was-60 mV, demonstrating that it was a stable suspension. And (4) carrying out vacuum freeze drying on the suspension for 48 hours to obtain the nano cellulose aerogel with a three-dimensional network structure. Dispersing the aerogel in deionized water by ultrasonic wave for 15 minutes, wherein the prepared nano-cellulose has better redispersibility; characterized by an atomic force microscope (as shown in figure 1), the diameter of the material is 10 nm-20 nm, and the length of the material is about 200 nm-600 nm.
Example 2
A preparation method of sulfate nanocellulose comprises the following steps:
(1) adding 50mL of dimethyl sulfoxide into a 100mL three-neck flask, then adding 1g of sulfamic acid into the three-neck flask, and uniformly stirring to completely dissolve solids to obtain sulfamic acid solution;
(2) adding 0.8g of microcrystalline cellulose into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, transferring the mixed solution into an oil bath pot, heating to 150 ℃ under a stirring state to perform reflux reaction, wherein the reflux reaction time is 3 hours, cooling to room temperature, centrifuging to obtain a precipitate, and removing the reaction solution to obtain a gel-like solid;
(3) washing the gelatinous solid in the step (2) by using N 'N-dimethylformamide, a mixed solution of N' N-dimethylformamide and isopropanol and deionized water in sequence, the mixed solution of the N 'N-dimethylformamide and the isopropanol is a liquid formed by uniformly mixing the N' N-dimethylformamide and the isopropanol, the volume ratio of the N' N-dimethylformamide to the isopropanol is 1:1, the washing times are all 3 times, after each washing, the mixture is centrifuged for 10 minutes at the rotating speed of 3000rpm to remove supernatant liquid, so as to obtain washed gel-like solid, the washed gel-like solid is added into water, and (3) carrying out ultrasonic dispersion uniformly for 10 minutes to obtain a nano cellulose suspension, and carrying out vacuum freeze drying for 48 hours to obtain the sulfate nano cellulose.
The obtained gel-like solid was dispersed with ultrasound for 10 minutes to obtain a nanocellulose suspension, the Zeta potential of which was-76 mV, demonstrating that it was a stable suspension. And (4) carrying out vacuum freeze drying on the suspension for 48 hours to obtain the nano cellulose aerogel with a three-dimensional network structure. Dispersing the aerogel in deionized water by ultrasonic wave for 15 minutes, wherein the prepared nano-cellulose has better redispersibility; characterized by an atomic force microscope, the diameter is 10nm to 30nm, and the length is about 200nm to 700nm, as shown in FIG. 1.
Example 3
A preparation method of sulfate nanocellulose comprises the following steps:
(1) adding 50mL of N' N-dimethylformamide into a 100mL three-neck flask, then adding 2.5g of sulfamic acid into the three-neck flask, and uniformly stirring to completely dissolve solids to obtain sulfamic acid solution;
(2) adding 1g of short linter into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, transferring the mixed solution into an oil bath pot, heating the mixed solution to 80 ℃ under a stirring state to perform reflux reaction, wherein the reflux reaction time is 8 hours, cooling the mixed solution to room temperature, centrifuging the mixed solution to obtain a precipitate, and removing a reaction solution to obtain a gel-like solid;
(3) washing the gelatinous solid in the step (2) by using N 'N-dimethylformamide, a mixed solution of N' N-dimethylformamide and isopropanol and deionized water in sequence, the mixed solution of the N 'N-dimethylformamide and the isopropanol is a liquid formed by uniformly mixing the N' N-dimethylformamide and the isopropanol, the volume ratio of the N' N-dimethylformamide to the isopropanol is 1:1, the washing times are all 5 times, after each washing, the mixture is centrifuged for 5 minutes at the rotating speed of 6000rpm to remove supernatant liquid to obtain washed gel-like solid, the washed gel-like solid is added into water, and (3) uniformly dispersing by using ultrasonic for 15 minutes to obtain a nano cellulose suspension, and freeze-drying in vacuum for 24 hours to obtain the sulfate nano cellulose.
The obtained gel-like solid was dispersed with ultrasound for 15 minutes to obtain a nanocellulose suspension, the Zeta potential of which was-72 mV, demonstrating that it was a stable suspension. And (3) carrying out vacuum freeze drying on the suspension for 24 hours to obtain the nano cellulose aerogel with a three-dimensional network structure. The aerogel is dispersed in deionized water by ultrasonic wave for 20 minutes, and the prepared nano-cellulose has good redispersibility, and the diameter of the nano-cellulose is 20 nm-40 nm and the length of the nano-cellulose is about 300 nm-800 nm as represented by an atomic force microscope, which can be seen in fig. 1.
Example 4
A preparation method of sulfate nanocellulose comprises the following steps:
(1) adding 50mL of N' N-dimethylformamide into a 100mL three-neck flask, then adding 2.5g of sulfamic acid into the three-neck flask, and uniformly stirring to completely dissolve solids to obtain sulfamic acid solution;
(2) adding 1g of bacterial cellulose into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, transferring the mixed solution into an oil bath pot, heating the mixed solution to 80 ℃ under a stirring state to perform reflux reaction, cooling the mixed solution to room temperature for 24 hours, centrifuging to obtain precipitates, and discarding the reaction solution to obtain a gel-like solid;
(3) washing the gelatinous solid in the step (2) by using N 'N-dimethylformamide, a mixed solution of N' N-dimethylformamide and isopropanol and deionized water in sequence, the mixed solution of the N 'N-dimethylformamide and the isopropanol is a liquid formed by uniformly mixing the N' N-dimethylformamide and the isopropanol, the volume ratio of the N' N-dimethylformamide to the isopropanol is 1:1, the washing times are all 3 times, after each washing, the mixture is centrifuged for 10 minutes under the condition that the rotating speed is 5000rpm so as to remove supernatant liquid, so as to obtain washed gel-like solid, the washed gel-like solid is added into water, and (3) uniformly dispersing by using ultrasonic for 30 minutes to obtain a nano cellulose suspension, and freeze-drying in vacuum for 24 hours to obtain the sulfate nano cellulose.
The obtained gel-like solid was dispersed with ultrasound for 30 minutes to obtain a nanocellulose suspension, the Zeta potential of which was-80 mV, demonstrating that it was a stable suspension. And (3) carrying out vacuum freeze drying on the suspension for 24 hours to obtain the nano cellulose aerogel with a three-dimensional network structure. The aerogel is dispersed in deionized water by ultrasonic wave for 15 minutes, and the prepared nano-cellulose has good redispersibility, is characterized by an atomic force microscope, has a diameter of 10 nm-20 nm and a length of about 200 nm-800 nm, and can be shown in figure 1.
Example 5
A preparation method of sulfate nanocellulose comprises the following steps:
(1) adding 50mL of N' N-dimethylformamide into a 100mL three-neck flask, then adding 5g of sulfamic acid into the three-neck flask, and uniformly stirring to completely dissolve solids to obtain sulfamic acid solution;
(2) adding 1g of bacterial cellulose into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, transferring the mixed solution into an oil bath pot, heating the mixed solution to 100 ℃ under a stirring state to perform reflux reaction, wherein the reflux reaction time is 8 hours, cooling the mixed solution to room temperature, centrifuging to obtain precipitates, and removing a reaction solution to obtain a gel-like solid;
(3) washing the gelatinous solid in the step (2) by using N 'N-dimethylformamide, a mixed solution of N' N-dimethylformamide and isopropanol and deionized water in sequence, the mixed solution of the N 'N-dimethylformamide and the isopropanol is a liquid formed by uniformly mixing the N' N-dimethylformamide and the isopropanol, the volume ratio of the N' N-dimethylformamide to the isopropanol is 1:1, the washing times are all 3 times, after each washing, the mixture is centrifuged for 10 minutes under the condition that the rotating speed is 5000rpm so as to remove supernatant liquid, so as to obtain washed gel-like solid, the washed gel-like solid is added into water, and (3) uniformly dispersing by using ultrasonic for 20 minutes to obtain a nano cellulose suspension, and freeze-drying in vacuum for 48 hours to obtain the sulfate nano cellulose.
The obtained gel-like solid was dispersed with ultrasound for 20 minutes to obtain a nanocellulose suspension, the Zeta potential of which was-68 mV, which was confirmed to be a stable suspension. And (4) carrying out vacuum freeze drying on the suspension for 48 hours to obtain the nano cellulose aerogel with a three-dimensional network structure. The aerogel is dispersed in deionized water by ultrasonic wave for 20 minutes, and the prepared nano-cellulose has good redispersibility, is characterized by an atomic force microscope, has a diameter of 10 nm-20 nm and a length of about 400 nm-2000 nm, and can be shown in figure 1.
Example 6
A preparation method of sulfate nanocellulose comprises the following steps:
(1) adding 50mL of N' N-dimethylformamide into a 100mL three-neck flask, then adding 7.5g of sulfamic acid into the three-neck flask, and uniformly stirring to completely dissolve solids to obtain sulfamic acid solution;
(2) adding 0.8g of bagasse pulp cellulose into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, transferring the mixed solution into an oil bath kettle, heating the mixed solution to 80 ℃ under a stirring state to perform reflux reaction, wherein the time of the reflux reaction is 3 hours, cooling the mixed solution to room temperature, centrifuging to obtain precipitates, and removing the reaction solution to obtain a gel-like solid;
(3) washing the gelatinous solid in the step (2) by using N 'N-dimethylformamide, a mixed solution of N' N-dimethylformamide and isopropanol and deionized water in sequence, the mixed solution of the N 'N-dimethylformamide and the isopropanol is a liquid formed by uniformly mixing the N' N-dimethylformamide and the isopropanol, the volume ratio of the N' N-dimethylformamide to the isopropanol is 1:1, the washing times are all 5 times, after each washing, the mixture is centrifuged for 10 minutes under the condition that the rotating speed is 5000rpm so as to remove supernatant liquid, so as to obtain washed gel-like solid, the washed gel-like solid is added into water, and (3) uniformly dispersing by using ultrasonic for 15 minutes to obtain a nano cellulose suspension, and freeze-drying in vacuum for 24 hours to obtain the sulfate nano cellulose.
The obtained gel-like solid was dispersed with ultrasound for 15 minutes to obtain a nanocellulose suspension, the Zeta potential of which was-92 mV, demonstrating that it was a stable suspension. And (3) carrying out vacuum freeze drying on the suspension for 24 hours to obtain the nano cellulose aerogel with a three-dimensional network structure. The aerogel is dispersed in deionized water by ultrasonic wave for 15 minutes, and the prepared nano-cellulose has good redispersibility, and the diameter of the nano-cellulose is 20 nm-40 nm and the length of the nano-cellulose is about 100 nm-800 nm as represented by an atomic force microscope, which can be seen in fig. 1.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of sulfate nanocellulose is characterized by comprising the following steps:
(1) adding sulfamic acid into an organic solvent, and uniformly stirring to obtain a sulfamic acid solution;
(2) adding cellulose into the sulfamic acid solution obtained in the step (1), uniformly mixing to obtain a mixed solution, heating the mixed solution under a stirring state for reflux reaction, cooling to room temperature, centrifuging to obtain a precipitate, and obtaining a gel-like solid;
(3) and (3) washing the gel-like solid in the step (2) to obtain a washed gel-like solid, adding the washed gel-like solid into water, uniformly dispersing to obtain a nanocellulose suspension, and drying to obtain the sulfate nanocellulose.
2. The method for preparing sulfate nanocellulose according to claim 1, wherein the organic solvent of step (1) is N, N-dimethylformamide or dimethyl sulfoxide; the mass percentage concentration of the sulfamic acid solution is 2-15 wt%.
3. The method for preparing sulfate nanocellulose according to claim 1, wherein the cellulose of step (2) is purified cellulose; the cellulose is one of bamboo pulp cellulose, bagasse pulp cellulose, bacterial cellulose, short cotton linter and commercialized microcrystalline cellulose.
4. The method for preparing sulfate nanocellulose according to claim 1, wherein the concentration of cellulose in the mixed solution in step (2) is 0.008 to 0.02 g/mL.
5. The method for preparing sulfate nanocellulose according to claim 1, wherein the temperature of the reflux reaction in step (2) is 60 to 160 ℃, and the time of the reflux reaction is 3 to 24 hours.
6. The method for preparing sulfate nanocellulose as claimed in claim 1, wherein the rotation speed of the centrifugation in step (2) is 3000-6000rpm, and the time of the centrifugation is 5-30 minutes.
7. The method for preparing sulfate nanocellulose according to claim 1, wherein the washing in step (3) is washing with N 'N-dimethylformamide, a mixed solution of N' N-dimethylformamide and isopropanol, and water in this order; the mixed solution of the N 'N-dimethylformamide and the isopropanol is formed by uniformly mixing the N' N-dimethylformamide and the isopropanol; the volume ratio of the N' N-dimethylformamide to the isopropanol is 1: 1.
8. The method for preparing sulfate nanocellulose according to claim 1, wherein the manner of dispersing uniformly in step (3) includes ultrasonic dispersion, homogenizer dispersion and stirring dispersion; the time for uniform dispersion is 5-30 minutes.
9. The method for preparing sulfate nanocellulose according to claim 1, wherein the drying means of step (3) comprises vacuum freeze-drying; the drying time is 12-48 hours.
10. A sulfate nanocellulose produced by the production method of any one of claims 1 to 9.
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