Bio-based nano material and green preparation method thereof

Abstract

The invention relates to recycling of natural polymer materials, in particular to a bio-based nano material and a green preparation method thereof. The method specifically comprises the following steps: swelling a bio-based raw material in an aprotic solution containing an organic Lewis base, and activating hydroxyl on the surface of the bio-based material; and adding a modified compound capable of reacting with the oxygen anions into the reaction system, and reacting to obtain the bio-based nano material. The preparation method of the bio-based nano material is high in preparation efficiency, low in preparation cost, high in universality and environmentally friendly. The embodiment of the invention also provides the bio-based nano material prepared by the preparation method.

Description

Technical Field

[0001] The present invention relates to the reuse of natural polymer materials, specifically to a bio-based nanomaterial and a green preparation method thereof. Background Art

[0002] With the increasingly serious environmental problems caused by waste polymers, natural polymer materials have been widely studied and developed due to their advantages such as renewable, biodegradable, and rich reserves, in order to seek to replace traditional polymers. Among them, cellulose, chitin, and silk are the most common natural polymer materials at present. At the same time, nanomaterials prepared from bio-based raw materials such as cellulose, chitin, and silk have characteristics such as low density, high strength, and high aspect ratio; they also have a high specific surface area, a reactive surface, and good biocompatibility, and have great potential in the fields of medicine, tissue engineering, water treatment, membrane materials, etc.

[0003] At the present stage, there are various preparation methods for bio-based nanomaterials. Common methods include acid hydrolysis method, alkali treatment method, TEMPO oxidation method, deacetylation method, etc. However, these methods generally have disadvantages such as high energy consumption, serious pollution, and poor universality. Therefore, the existing methods are not conducive to environmental protection and the sustainable development strategy. Summary of the Invention

[0004] The purpose of the present invention is to provide a bio-based nanomaterial and a green preparation method thereof.

[0005] To achieve the purpose of the present invention, the technical solution adopted by the present invention is as follows:

[0006] A green preparation method of a bio-based nanomaterial:

[0007] (1) Swell the bio-based raw material in an aprotic solution containing an organic Lewis base to activate the hydroxyl groups on the surface of the bio-based material;

[0008] (2) Add a modified compound capable of reacting with an oxygen anion to the above reaction system, and a bio-based nanomaterial is obtained after the reaction.

[0009] The organic Lewis base refers to an organic compound having electron-rich properties, that is, pKaH + > 15 and / or an organic compound capable of efficiently extracting protons in the system; wherein, the mass ratio of the bio-based raw material to the organic Lewis base is 1:1 - 12.

[0010] The organic Lewis base is one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 4-dimethylaminopyridine (DMAP).

[0011] The aprotic solvent refers to a solvent that has no active protons in its molecules, has almost no acidity compared with water, has no amphoteric characteristics, and / or does not form hydrogen bonds with negative ions; wherein, the mass ratio of the organic Lewis base to the aprotic solvent is 1:1 - 10.

[0012] The aprotic solvent is one or more of amides, ketones, nitriles, pyridine, dimethyl sulfoxide (DMSO).

[0013] The modified compound capable of reacting with an oxygen anion is a compound that undergoes esterification and / or etherification with a hydroxyl group; wherein, the molar ratio of the biobased raw material to the modified compound is 1:1 - 6.

[0014] The modified compound capable of reacting with an oxygen anion is one or more of halogenated acid salts, ammonium salts, phosphates, acid anhydrides, acyl chlorides, epoxy compounds; a compound that is prone to undergo esterification and / or etherification with a hydroxyl group.

[0015] For example, sodium chloroacetate, sodium bromoacetate, sodium iodoacetate, 3-chloro-2-hydroxypropyltrimethylammonium chloride, diammonium hydrogen phosphate, chlorosulfonic acid, epichlorohydrin, succinic anhydride (SA), maleic anhydride (MA), phthalic anhydride (PA), camphoric anhydride (CA), diphenic anhydride (DA), etc.

[0016] The swelling time of the biobased raw material in the aprotic solution containing the organic Lewis base in step (1) is 24 - 120 h; the swelling temperature is 20 - 105 °C.

[0017] After the modified compound in step (1) reacts with the activated biobased material, the reaction product is washed and mechanically treated to obtain the biobased nanomaterial.

[0018] The biobased raw material includes one or more of green plants, the shells of crustaceans, the organs of mollusks, and animal protein products, etc.

[0019] The green plants include at least one of wood, plant branches and leaves, bagasse, Enteromorpha prolifera, fruits, vegetables, cotton, and green plants;

[0020] The shells of crustaceans include at least one of shrimp shells, crab shells, and the shells of insects;

[0021] The organs of mollusks include at least one of squid bones, the stomachs of squids, and the tunics of sea squirts;

[0022] The animal protein products include the silk of Bombyx mori and / or Antheraea pernyi, and the silk of spiders such as Nephila clavata and Araneus ventricosus;

[0023] Furthermore, in the above preparation method, when an organic Lewis base is selected to activate the surface hydroxyl groups of the bio-based raw material, the mass ratio of the bio-based raw material to the organic Lewis base is 1:1 - 12, optionally 1:3 - 7;

[0024] In the above preparation method, when an organic Lewis base is selected to activate the surface hydroxyl groups of the bio-based raw material, the mass ratio of the organic Lewis base to the aprotic solvent is 1:1 - 10, optionally 1:2 - 10.

[0025] In the above preparation method, when an acid anhydride compound is selected to react with the surface-activated hydroxyl groups of the bio-based raw material, the molar ratio of the bio-based raw material to the modification compound is 1:1 - 6, optionally 1:3 - 4.

[0026] The washing treatment refers to one of filtration or centrifugation until the organic Lewis base in the system is completely removed;

[0027] When the washing treatment is filtration, the treatment method is as follows: Place the reaction system in a common funnel and perform suction filtration washing with a coarse filter paper under negative pressure until the filtrate is neutral;

[0028] When the washing treatment is centrifugation, the treatment method is as follows: Place the reaction system in a centrifuge tube, perform centrifugal washing treatment 6 times, each treatment for 10 min, at a rotation speed of 10000 rpm / min, and take the lower layer precipitate for standby.

[0029] The mechanical treatment refers to one or more of shaking, ultrasonic treatment, high-speed homogenization, or cell crusher crushing;

[0030] When the mechanical treatment is shaking, the treatment method is as follows: Pick up the reaction system by hand and shake it violently up and down and oscillate it for 2 min.

[0031] When the mechanical treatment is ultrasonic treatment, the treatment method is as follows: Place the reaction system in an ultrasonic cleaner for ultrasonic treatment, continuously ultrasonic treat for 1 - 30 min, the ultrasonic treatment temperature is 10 - 40 °C, the ultrasonic power is 200 W, and the ultrasonic frequency is 50 - 2000 Hz;

[0032] When the mechanical treatment is high-speed homogenization, the treatment method is as follows: Rapidly treat the reaction system with a high-speed homogenizer, treat 1 - 10 times, each treatment for 1 - 10 min, and the power is 1400 W;

[0033] When the mechanical treatment is cell crusher crushing, the treatment method is as follows: Place the reaction system in a cell crusher and continuously crush for 1 - 30 min, and the crushing power is 300 W.

[0034] In the above preparation process, the aprotic solution of the organic Lewis base after the reaction can be recovered and purified by distillation, wherein the recovery rate of the organic Lewis base can exceed 60%, and the recovery rate of the aprotic solution can exceed 90%.

[0035] A bio-based nanomaterial prepared by the method, which is a bio-based nanomaterial with at least one of its three-dimensional dimensions in the nanoscale range (<100 nm) obtained by the method.

[0036] The average length of the bio-based nanomaterial is 500 - 5000 nm, and the average diameter is 6 - 25 nm.

[0037] Advantages of the present invention:

[0038] The preparation method of the bio-based nanomaterial of the present invention processes common bio-based raw materials at present (such as green plants, organs of mollusks, shells of crustaceans, and animal protein products), and uses an organic Lewis base as a proton-abstracting reagent, which can react with the hydroxyl groups on the surface of the bio-based raw material at a certain temperature to generate oxygen anions and activate the bio-based raw material. In addition, the organic Lewis base can also damage the loosely arranged amorphous regions in the bio-based raw material while retaining the tightly arranged crystalline regions, improving the accessibility of the modified molecules to the bio-based raw material and facilitating the reaction between the bio-based raw material and the modified molecules. Compared with the nanofibers prepared by other methods, this method can prepare customized hydrophilic or hydrophobic nanoscale bio-based materials with a high surface charge density (>30 mV) and long-term stability (>180 days) under weak shear force. At the same time, the organic Lewis base used as a proton-abstracting reagent in this method can be recovered by distillation and reused in the preparation of nanoscale bio-based materials. Moreover, the preparation method of the present invention has high efficiency, low energy requirement, low cost, strong universality, and is environmentally friendly. Description of the Drawings

[0039] Figure 1 It is a transmission electron microscope photograph of the cellulose nanofibers (CNF) prepared in Example 1 of the present invention.

[0040] Figure 2 It is a transmission electron microscope photograph of the ascidian cellulose nanofibers (T-CNF) prepared in Example 2 of the present invention.

[0041] Figure 3 It is a transmission electron microscope photograph of the shrimp shell chitin nanofibers (α-ChNF) prepared in Example 3 of the present invention.

[0042] Figure 4 It is a transmission electron microscope photograph of the squid bone chitin nanofibers (β-ChNF) prepared in Example 4 of the present invention.

[0043] Figure 5It is the transmission electron microscope photograph of the mulberry silk nanofibers (BSNF) prepared in Example 5 of the present invention.

[0044] Figure 6 It is the transmission electron microscope photograph of the spider silk nanofibers (SSNF) prepared in Example 6 of the present invention.

[0045] Figure 7 It is the solid-state nuclear magnetic carbon spectrum characterization of the cellulose nanofibers prepared in Example 1 of the present invention.

[0046] Figure 8 It is the ultraviolet-visible spectrum characterization of the cellulose nanofibers prepared in Example 1 of the present invention.

[0047] Figure 9 It is the surface negative charge characterization of the bio-based nanofibers prepared in Examples 1-8 of the present invention.

[0048] Figure 10 It is the Fourier transform infrared spectrum characterization of DBU and DMSO recovered in Example 9 of the present invention.

[0049] Figure 11 It is the transmission electron microscope photograph of the cellulose nanofibers prepared by reusing the DBU and DMSO recovered in Example 9 of the present invention for the preparation of cellulose nanofibers.

[0050] Figure 12 It is the comparison of the method described in Example 1 of the present invention with common biomass nanomaterial preparation methods in terms of energy consumption.

[0051] Figure 13 It is the water contact angle characterization of the cellulose nanofibers prepared in Example 1 and Example 3 of the present invention.

[0052] Specific implementation methods

[0053] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. Unless otherwise clearly stated, in the whole specification and claims, the term "comprise" or its variations such as "comprises" or "including" will be understood to include the stated elements or components, without excluding other elements or other components.

[0054] In addition, for better illustration of the present invention, numerous specific details are given in the following detailed implementation manners. Those skilled in the art should understand that the present invention can also be implemented without certain specific details. In some embodiments, raw materials, components, methods, means, etc. well-known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.

[0055] Example 1

[0056] 0.3 g of hardwood pulp board was pulverized into powder with a blender and dispersed in 9 g of DMSO. 1 g of DBU was added, and after stirring at 65 °C for 24 h, 0.6 g of succinic anhydride was added and reacted for 15 min. Then it was centrifugally washed 3 times with DMSO and then 3 times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min each time and the time was 10 min each time. Finally, the precipitate was dispersed in deionized water, shaken vigorously by hand for 2 min, and then centrifuged at a speed of 10,000 rpm / min for 10 min. The supernatant was taken to obtain a stably dispersed cellulose nanofiber suspension (see Figure 1 and Figures 7 - 9 ).

[0057] From Figure 1 and Figures 7 - 9 it can be seen that the method of the present invention can successfully prepare cellulose nanofibers with an average diameter of 12 nm, an aspect ratio > 10 2 and a surface charge of -37 mV. These nanofibers have no aggregation and precipitation after standing for 180 days, and the light transmittance at 400 - 800 nm is close to 100%. At the same time, the prepared cellulose nanofibers show a carbonyl peak at 1750 cm -1 in the Fourier transform infrared spectrum, proving that succinic anhydride has successfully modified the cellulose nanofibers.

[0058] In addition, from Figure 12 it can be seen that the method of the present invention can prepare nano-biomass materials under simple hand shaking, which has obvious advantages in terms of energy consumption compared with other common methods for preparing nano-biomass materials. From Figure 13 it can be seen that the nano-biomass materials prepared by the method of the present invention have high hydrophobicity.

[0059] Example 2

[0060] After bleaching 0.3 g of the ascidian tunic, it was pulverized into powder using a blender and dispersed in 9 g of DMSO. 1 g of TBD was added, and after stirring at 65 °C for 24 h, 0.6 g of succinic anhydride was added and reacted for 15 min. Then, it was centrifugally washed three times with DMSO and then three times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min and the time was 10 min each time. Finally, the precipitate was dispersed in deionized water and ultrasonically treated for 30 min with an ultrasonic power of 200 W and an ultrasonic frequency of 1000 Hz. After the ultrasonic treatment ended, centrifugation was performed using a centrifuge at a speed of 10,000 rpm / min for 10 min, and the supernatant was taken to obtain a stably dispersed suspension of ascidian cellulose nanofibers (see Figure 2 and Figure 9 ).

[0061] From Figure 2 and Figure 9 it can be seen that the method described in the present invention can successfully prepare ascidian cellulose nanofibers with an average diameter of 24 nm, an aspect ratio > 10 2 and a surface charge of -36 mV.

[0062] Example 3

[0063] After pulverizing 0.3 g of purified shrimp shells into powder using a blender, it was dispersed in 8 g of tetrahydrofuran (ether). 2 g of DBN was added, and after stirring at 65 °C for 120 h, 0.9 g of sodium chloroacetate was added and reacted for 15 min. Then, it was centrifugally washed three times with DMSO and then three times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min and the time was 10 min each time. Finally, the precipitate was dispersed in deionized water and subjected to cell disruption treatment for 20 min with a power of 300 W. After the cell disruption treatment ended, centrifugation was performed using a centrifuge at a speed of 10,000 rpm / min for 10 min, and the supernatant was taken to obtain a stably dispersed suspension of shrimp shell chitin nanofibers (see Figure 3 and Figure 9 ).

[0064] From Figure 3 and Figure 9 it can be seen that the method described in the present invention can successfully prepare shrimp shell chitin nanofibers with an average diameter of 5 nm, an aspect ratio > 10 2 and a surface charge of -41 mV.

[0065] In addition, from Figure 13 it can be known that the nanobiomass materials prepared by the method described in the present invention have high hydrophilicity.

[0066] Example 4

[0067] 0.3 g of purified squid bone was pulverized into powder using a blender and then dispersed in 8 g of acetone (ketone). 2 g of DBU was added, and after stirring at 65 °C for 120 h, 0.9 g of tetramethylammonium chloride was added and reacted for 15 min. Then it was centrifugally washed 3 times with DMSO and then 3 times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min for 10 min each time. Finally, the precipitate was dispersed in deionized water and ultrasonically treated for 30 min with an ultrasonic power of 200 W and an ultrasonic frequency of 1000 Hz. After the ultrasonic treatment ended, centrifugation was carried out at a speed of 10,000 rpm / min for 10 min, and the supernatant was taken to obtain a stably dispersed squid bone chitin nanofiber suspension (see Figure 4 and Figure 9 ).

[0068] From Figure 4 and Figure 9 it can be seen that the method described in the present invention can successfully prepare squid bone chitin nanofibers with an average diameter of 11 nm, an aspect ratio > 10 2 and a surface charge load of 35 mV.

[0069] Example 5

[0070] 0.3 g of degummed mulberry silk was pulverized into powder using a blender and then dispersed in 8 g of dimethylacetamide (amide). 2 g of TMG was added, and after stirring at 85 °C for 72 h, 0.9 g of diphenic anhydride was added and reacted for 15 min. Then it was centrifugally washed 3 times with DMSO and then 3 times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min for 10 min each time. Finally, the precipitate was dispersed in deionized water, and the concentration of the dispersion was controlled to be 0.3 wt%, and high-pressure homogenization was carried out 4 times for 10 min each time with a power of 1400 W. After the homogenization treatment ended, centrifugation was carried out at a speed of 10,000 rpm / min for 10 min, and the supernatant was taken to obtain a stably dispersed mulberry silk nanofiber suspension (see Figure 5 and Figure 8 ).

[0071] From Figure 5 and Figure 9 it can be seen that the method described in the present invention can successfully prepare silk fibroin nanofibers with an average diameter of 35 nm and a surface charge load of -31 mV.

[0072] Example 6

[0073] 0.3 g of degummed Nephila spider silk was pulverized into powder using a blender and then dispersed in 9 g of N,N-dimethylformamide (amide type). 1 g of DMAP was added, and the mixture was stirred at 85 °C for 72 h. Then, 0.9 g of phthalic anhydride was added and reacted for 15 min. Subsequently, it was centrifugally washed 3 times with DMSO and then 3 times with deionized water. During this process, the centrifuge speed was 10,000 rpm / min for 10 min each time. Finally, the precipitate was dispersed in deionized water, and the concentration of the dispersion was controlled to be 0.3 wt%. It was subjected to high-pressure homogenization treatment 4 times, 10 min each time, with a power of 1400 W. After the homogenization treatment was completed, centrifugation was carried out using a centrifuge at a speed of 10,000 rpm / min for 10 min, and the supernatant was taken to obtain a stably dispersed spider silk nanofiber suspension (see Figure 6 and Figure 8 ).

[0074] From Figure 6 and Figure 9 it can be seen that the method described in the present invention can successfully prepare spider silk protein nanofibers with an average diameter of 18 nm and a surface charge of -40 mV.

[0075] Example 7

[0076] 0.3 g of hardwood pulp board was pulverized into powder using a blender and then dispersed in 9 g of DMSO. 1 g of TBD was added, and the mixture was stirred at 65 °C for 24 h. Then, 0.7 g of sodium chloroacetate was added and reacted for 30 min. Subsequently, it was centrifugally washed 3 times with DMSO and then 3 times with deionized water. During this process, the centrifuge speed was 10,000 rpm / min for 10 min each time. Finally, the precipitate was dispersed in deionized water and shaken vigorously by hand for 2 min, and then centrifuged using a centrifuge at a speed of 10,000 rpm / min for 10 min, and the supernatant was taken to obtain a stably dispersed cellulose nanofiber suspension (see Figure 9 ).

[0077] From Figure 9 it can be seen that the method described in the present invention can successfully prepare cellulose nanofibers with a surface charge of 37 mV.

[0078] Example 8

[0079] 0.3 g of hardwood pulp board was pulverized into powder with a blender and dispersed in 9 g of DMSO. 1 g of TMG was added, and after stirring at 65 °C for 24 h, 1.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added and reacted for 30 min. Then it was centrifugally washed 3 times with DMSO and then 3 times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min and the time was 10 min each time. Finally, the precipitate was dispersed in deionized water, shaken vigorously by hand for 2 min, and then centrifuged at 10,000 rpm / min for 10 min. The supernatant was taken to obtain a stably dispersed cellulose nanofiber suspension (see Figure 9 ).

[0080] As can be seen from Figure 9 , the method of the present invention can successfully prepare cellulose nanofibers with a surface charge load of -35 mV.

[0081] Example 9

[0082] 0.3 g of hardwood pulp board was pulverized into powder with a blender and dispersed in 9 g of DMSO. 1 g of DBU was added, and after stirring at 65 °C for 24 h, it was centrifuged, and the reaction solvent (the DMSO and DBU mixture) was poured out and denoted as Solvent 1. Then it was centrifugally washed 3 times with DMSO and 3 times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min and the time was 10 min each time. Finally, the precipitate was dispersed in deionized water, and the concentration of the dispersion was controlled to be 0.3 wt%. It was subjected to high-pressure homogenization treatment 4 times, 10 min each time, with a power of 1400 W. After the homogenization treatment was completed, it was centrifuged at 10,000 rpm / min for 10 min, and the supernatant was taken to obtain a stably dispersed cellulose nanofiber suspension.

[0083] Solvent 1 and 10 ml of cyclohexane were added to a separatory funnel and extracted 3 times. Then the lower-layer solution was transferred to a single-neck flask to assemble a distillation device, and the mixture was heated to 200 °C by an oil bath and distilled at 200 °C until no liquid flowed out. The distillate was DMSO and the residue was DBU.

[0084] Finally, 0.3 g of hardwood pulp board was pulverized into powder with a blender and dispersed in 9 g of recycled DMSO. Then 1 g of recycled DBU was added, and after stirring at 65 °C for 24 h, 0.9 g of phthalic anhydride was added and reacted for 15 min. Then it was centrifugally washed 3 times with DMSO and then 3 times with deionized water. During the process, the centrifuge speed was 10,000 rpm / min and the time was 10 min each time. Finally, the precipitate was dispersed in deionized water, shaken vigorously by hand for 2 min, and then centrifuged at 10,000 rpm / min for 10 min. The supernatant was taken to obtain the cellulose nanofiber suspension prepared from recycled DBU and DMSO (see Figure 10 and Figure 11 ).

[0085] As can be seen from Figure 10 and 11 , the aprotic solution of the organic Lewis base used in the method of the present invention can be recovered and purified by distillation, and the recovered solution can be reused for the preparation of nano-biological materials.

Claims

1. A green preparation method of a bio-based nanomaterial, characterized in that: (1) Swell the bio-based raw material in an aprotic solution containing an organic Lewis base to activate the hydroxyl groups on the surface of the bio-based material; (2) Add a modified compound capable of reacting with an oxygen anion to the above reaction system, and obtain a bio-based nanomaterial after the reaction.

2. The preparation method according to claim 1, characterized in that: The organic Lewis base refers to an organic compound with electron-rich properties, that is, pKaH + > 15 and / or capable of efficiently extracting protons in the system; wherein, the mass ratio of the bio-based raw material to the organic Lewis base is 1:1 - 12.

3. The preparation method according to claim 2, characterized in that: The organic Lewis base is one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 4-dimethylaminopyridine (DMAP).

4. The preparation method according to claim 1, characterized in that: The aprotic solvent refers to a solvent without active protons in the molecule, having almost no acidity compared with water, no amphoteric characteristics, and / or not forming hydrogen bonds with anions; wherein, the mass ratio of the organic Lewis base to the aprotic solvent is 1:1-10.

5. The preparation method according to claim 4, characterized in that: The aprotic solvent is one or more of amides, ketones, nitriles, pyridine, dimethyl sulfoxide (DMSO).

6. The preparation method according to claim 1, characterized in that: The modified compound capable of reacting with an oxygen anion is a compound that undergoes esterification and / or etherification with a hydroxyl group; wherein, the molar ratio of the bio-based raw material to the modified compound is 1:1-6.

7. The preparation method according to claim 6, characterized in that: The modified compound capable of reacting with an oxygen anion is one or more of halogenated acid salts, ammonium salts, phosphates, acid anhydrides, acyl chlorides, epoxy compounds.

8. The preparation method according to any one of claims 1-7, characterized in that: The swelling time of the bio-based raw material in the aprotic solution containing an organic Lewis base in step (1) is 24-120 h; the swelling temperature is 20-105 °C.

9. The preparation method according to any one of claims 1-7, characterized in that: After the modified compound reacts with the activated bio-based material in step (1), the reactants are washed and mechanically treated to obtain a bio-based nanomaterial.

10. A bio-based nanomaterial prepared by the method according to claim 1, characterized in that: A bio-based nanomaterial with at least one of the three-dimensional dimensions in the nanoscale (<100 nm) prepared by the method according to claim 1.

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