A preparation method of a full-bio-based component (tannin-furfural) resin micro-nano sphere
By using tannic acid and furfural to replace traditional raw materials to prepare tannic acid-furfural resin micro-nanospheres, the non-renewable problem of phenolic resin materials was solved, the preparation of stable and controllable particle size bio-based micro-nanospheres was achieved, and its application in catalysis and adsorption fields was expanded.
Patent Information
- Application Number
- CN202310698900.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-06-13
- Publication Date
- 2025-10-24
- Estimated Expiration
- 2043-06-13
AI Technical Summary
The synthesis of existing phenolic resin materials relies on petroleum-based chemicals, which leads to non-renewability and toxicity, limiting their application areas. There is also a lack of methods for preparing fully bio-based resin micro-nanospheres with good structural stability.
Tannic acid is used to replace phenol, and furfural is used to replace formaldehyde. Tannic acid-furfural resin micro-nanospheres are prepared through mixing and curing treatment. The specific steps include heating at 160-180°C for 6-7 hours and using ammonia water, ethanol and water as solvents and catalysts.
Stable and size-controlled bio-based tannic acid-furfural resin micro-nanospheres were prepared, which have good metal chelating ability and catalyst carrier performance, are suitable for precious metal adsorption and catalysis, meet green production requirements, and are low-cost and high-efficiency.
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Figure CN116789920B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of phenolic resin material preparation, and particularly relates to a preparation method of full-biological-component tannic acid-furfural resin micro-nano balls. BACKGROUND
[0002] The information disclosed in this BACKGROUND section is only for the purpose of increasing the understanding of the general background of the application and does not necessarily constitute an admission by the patent applicant(s) that this information constitutes prior art.
[0003] As a synthetic polymer material, phenolic resin has been widely used in the fields of building, energy, catalysis and biomedical materials, etc. due to its advantages of simple preparation method, high mechanical strength, heat resistance, moisture resistance and other excellent performances. In the field of nanomaterials, phenolic resin micro-nano balls have attracted attention in the research of many frontier materials due to their controllable chemical structure and easy functionalization. However, the synthesis of phenolic resin materials is usually synthesized from petroleum-based chemicals such as common phenol and formaldehyde raw materials, both of which are non-renewable and toxic. With the shortage of petroleum-based resources and the requirement of environmental sustainability and green development, the resin materials synthesized from phenol and formaldehyde have been greatly limited in their application fields. How to develop a resin material synthesized from biological components has become a problem to be solved in the development of current resin materials, which is of great significance to expand its application field.
[0004] In the previous study, the inventors tried and developed a method for preparing lignin-based phenolic resin by replacing phenol with lignin. As known, lignin is a plant-based aromatic polymer with a three-dimensional network structure, containing a large number of aromatic ring structures, aldehyde groups and hydroxyl groups, which can provide aldehyde groups and hydroxyl groups required for phenolic condensation in the process of synthesizing phenolic resin with phenol and formaldehyde, to a certain extent, reducing the amount of phenol and formaldehyde. However, due to the complex molecular structure of lignin and large steric hindrance, the activity of lignin that can participate in the reaction is very low. In addition, it still uses highly toxic formaldehyde as a crosslinking agent in the condensation reaction, so that the synthesized lignin-based phenolic resin material is still a non-green material, and its structural stability is relatively poor. At the same time, the industry has not found a method for preparing full-biological resin micro-nano balls with good structural stability. SUMMARY
[0005] In order to solve the above problems, the application provides a preparation method of full-biological tannic acid-furfural resin micro-nano balls, which replaces phenol with tannic acid and replaces formaldehyde with furfural to synthesize tannic acid-furfural resin micro-nano balls.
[0006] In order to achieve the above purpose, the application adopts the following technical solutions:
[0007] The first aspect of the present application provides a preparation method of full-bio-based component (tannic acid-furfural) resin micro-nano-spheres, comprising:
[0008] tannic acid, furfural, ammonia, ethanol and water are uniformly mixed and subjected to solidification treatment to obtain tannic acid-furfural resin micro-nano-spheres;
[0009] The molar ratio of tannic acid to furfural is 1:0.06-1:0.4.
[0010] The solidification treatment is performed at 160-180 DEG C for 6-7 h.
[0011] The present application studies the second largest natural organic phenolic polymer-tannic acid in nature as a phenolic monomer, and combines the cross-linking reaction of tannic acid and furfural (furfural is considered to be one of the most high-value chemicals converted from biomass, and is a key chemical in the process of lignocellulosic biorefining, which can be converted from renewable agricultural and forestry resources such as grain crop residues and wood waste) to prepare a preparation method of full-bio-based component (tannic acid-furfural) resin micro-nano-spheres, which is of great significance for enriching the application of resin materials and realizing high-value utilization of bio-based materials.
[0012] The second aspect of the present application provides the tannic acid-furfural resin micro-nano-spheres prepared by the above method.
[0013] Advantages of the present application
[0014] (1) Tannic acid is a typical plant polyphenol derivative containing a large number of catechol and gallic phenol groups, and is considered to be a potential renewable alternative for preparing phenolic resin materials. Furfural is converted from biomass and is considered to be one of the most high-value chemicals, which can be converted from renewable agricultural and forestry resources (such as grain crop residues and wood waste). Therefore, the tannic acid and furfural used in the present application are not only green and sustainable, but also have a large amount of reserves in nature, and the use of tannic acid and furfural for preparing resin micro-nano-spheres meets the current requirements of green production.
[0015] (2) Compared with the phenol involved in the phenolic resin micro-nano spheres, the tannic acid-furfural resin micro-nano spheres produced by the technology have a large number of catechol and guaiacol groups in the structure of the tannic acid-furfural resin micro-nano spheres, and have many application advantages, such as being able to be chelated with different kinds of metal ions to form metal phenolic coordination polymers, endowing the tannic acid-furfural resin micro-nano spheres with many applications, especially as good noble metal adsorbents, catalyst carriers and carbon materials and the like. In addition, the preparation method of the application is simple and practical, and can obtain stable and particle size controllable bio-based tannic acid-furfural resin micro-nano spheres, has the characteristics of low cost and high efficiency, and is easier to popularize in actual industrial application.
[0016] (3) The tannic acid-furfural resin micro-nano spheres prepared by the application can be stably dispersed in different pH values (3, 7, 10) and different organic solutions (MeOH, EtOH and IPA), and can maintain stability for a long time. BRIEF DESCRIPTION OF DRAWINGS
[0017] The accompanying drawings, which form a part of the present description, are used to provide further understanding of the application, and the exemplary embodiments of the present application and their descriptions are used to explain the present application, and do not constitute improper limitations on the present application.
[0018] Figure 1 : Mechanism diagram of the application.
[0019] Figure 2 : (a)-(f) are scanning electron microscope images of the tannic acid-furfural resin micro-nano spheres prepared by adding 1.5 ml (Example 3), 2.0 ml and 3.0 ml (Example 4) of ammonia, respectively, (g)-(i) are size distribution thereof.
[0020] Figure 3 : Stable dispersion of the tannic acid-furfural resin micro-nano spheres prepared in Example 4 in different pH values (3, 7, 10) and different organic solutions (MeOH, EtOH and IPA).
[0021] Figure 4 : Stability photos of the tannic acid-furfural resin micro-nano spheres prepared by adding 1.5 ml (Example 3), 2.0 ml and 3.0 ml (Example 4) of ammonia, respectively, in anhydrous ethanol at room temperature and standing for 5 hours. DETAILED DESCRIPTION
[0022] It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the application. Unless otherwise specified, all technical and scientific terms used in the present application have the same meaning as generally understood by those skilled in the art to which the present application belongs.
[0023] The application discloses a preparation method of full-biological-component (tannic acid-furfural) resin micro-nano spheres.
[0024] Tannic acid and furfural are used as substrates, ammonia is used as a catalyst, and ethanol and deionized water are used as solutions; the tannic acid, the furfural, the ammonia, the ethanol and the deionized water are mixed, and then transferred into a reaction kettle, and solidification treatment is performed to obtain tannic acid-furfural resin micro-nano spheres.
[0025] In some embodiments, the molar ratio of the tannic acid to the furfural is 1:0.06-1:0.4, and the tannic acid-furfural resin micro-nano spheres in the ratio have the best spherical morphology and yield, and are beneficial to subsequent multifunctional applications of the micro-nano spheres.
[0026] In some embodiments, the addition amount of the ammonia (25wt%) is 0.9ml-4ml, and in order to obtain the best particle size and yield, the addition amount of the ammonia (25wt%) is 3ml.
[0027] In some embodiments, the volume ratio of the ethanol aqueous solution is water:ethanol=2:1, and the formed micro-nano spheres have the best morphology and uniformity.
[0028] In some embodiments, in the phenolic condensation reaction, centrifugal treatment is performed on the reaction liquid after solidification treatment, and then the reaction liquid is repeatedly washed with distilled water and alcohol, and dried in a vacuum drying box to obtain the tannic acid-furfural resin micro-nano spheres.
[0029] The application provides a tannic acid-furfural resin micro-nano sphere, which is prepared according to the above method. Phenolic condensation is performed using tannic acid and furfural, and a full-biological tannic acid-furfural resin micro-nano sphere can be prepared, which meets the requirements of green production. In addition, the rich hydroxyl groups in the tannic acid increase the active sites for loading noble metal ions, and the micro-nano sphere can be used as an effective reducing agent to realize in-situ formation of noble metal nanoparticles, so that the micro-nano sphere has the potential to be used as a noble metal catalyst carrier, a hydrogel / film filler and a candidate material of carbon material, and further plays a role in the fields of catalysts, nanomaterial additives, supercapacitors and the like.
[0030] The application will be further described in detail in combination with specific embodiments, and it should be pointed out that the specific embodiments are an explanation but not a limitation of the application.
[0031] Example 1
[0032] Take 0.6 g of tannic acid in total, add 3 ml of 99% furfural solution and 0.9 ml of 25wt% ammonia water, and mix well in deionized water (180 mL), then transfer the mixed solution to a sealed stainless steel autoclave lined with polytetrafluoroethylene, and heat at 160°C for 7h, then naturally cool to room temperature. The reaction solution is centrifuged at a speed of 9500 rpm, and the centrifuged solids are repeatedly washed with distilled water and ethanol, and dried in a vacuum drying oven to obtain tannic acid-furfural resin micro-nano spheres.
[0033] Example 2
[0034] Take 0.6 g of tannic acid in total, add 3 ml of 99% furfural solution and 0.9 ml of 25wt% ammonia water, and mix well in deionized water (180 mL), then transfer the mixed solution to a sealed stainless steel autoclave lined with polytetrafluoroethylene, and heat at 160°C for 7h, then naturally cool to room temperature. The reaction solution is centrifuged at a speed of 9500 rpm, and the centrifuged solids are repeatedly washed with distilled water and ethanol, and dried in a vacuum drying oven to obtain tannic acid-furfural resin micro-nano spheres.
[0035] Example 3
[0036] Take 0.6 g of tannic acid in total, add 3 ml of 99% furfural solution and 1.5 ml of 25wt% ammonia water, and mix well in an ethanol solution (120 mL of deionized water and 60 mL of ethanol), then transfer the mixed solution to a sealed stainless steel autoclave lined with polytetrafluoroethylene, and heat at 160°C for 7h, then naturally cool to room temperature. The reaction solution is centrifuged at a speed of 9500 rpm, and the centrifuged solids are repeatedly washed with distilled water and ethanol, and dried in a vacuum drying oven to obtain tannic acid-furfural resin micro-nano spheres.
[0037] Example 4
[0038] Take 0.6 g of tannic acid in total, add 3 ml of 99% furfural solution and 3 ml of 25wt% ammonia water, and mix well in an ethanol solution (120 mL of deionized water and 60 mL of ethanol), then transfer the mixed solution to a sealed stainless steel autoclave lined with polytetrafluoroethylene, and heat at 160°C for 7h, then naturally cool to room temperature. The reaction solution is centrifuged at a speed of 9500 rpm, and the centrifuged solids are repeatedly washed with distilled water and ethanol, and dried in a vacuum drying oven to obtain tannic acid-furfural resin micro-nano spheres.
[0039] Example 5
[0040] Take 0.6 g of tannic acid in total, add 4 ml of 99% furfural solution and 0.9 ml of 25wt% ammonia water, and mix well in an ethanol aqueous solution (120 mL of deionized water and 60 mL of ethanol), then transfer the mixed solution to a sealed stainless steel autoclave lined with polytetrafluoroethylene, and heat at 160°C for 7h, and then naturally cool to room temperature. The reaction solution is centrifuged at a speed of 9500 rpm, and the solid after centrifugation is repeatedly washed with distilled water and ethanol, and dried in a vacuum drying box to obtain tannic acid-furfural resin micro-nano balls.
[0041] The morphology of the tannic acid-furfural resin micro-nano balls of Examples 1-5 was recorded, as shown in the following table:
[0042]
[0043] The results show that the bio-based phenolic resin micro-nano balls prepared from tannic acid and furfural have uniform size and good spherical structure.
[0044] As Figure 3 shown, the tannic acid-furfural resin micro-nano balls prepared in Example 4 were stably dispersed (2 mg of tannic acid-furfural resin micro-nano balls dispersed in 100 ml of organic solution) in different pH values (3, 7, 10) and different organic solutions (MeOH, EtOH and IPA).
[0045] As Figure 4 shown, the tannic acid-furfural resin micro-nano balls (10 mg) prepared by adding 1.5 ml (Example 3), 2.0 ml and 3.0 ml (Example 4) of ammonia water were stably dispersed in anhydrous ethanol (100 ml) at room temperature for 5 hours.
[0046] Therefore, the tannic acid-furfural resin micro-nano balls prepared by the present application can be stably dispersed in different pH values (3, 7, 10) and different organic solutions (MeOH, EtOH and IPA), and can maintain stability for a long time.
[0047] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Those skilled in the art can make various modifications and changes to the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. A method for preparing a full-bio-based component tannic acid-furfural resin micro-nano-sphere, characterized in that, The application relates to a tannin-furfural resin micro-nano ball and a preparation method thereof. The molar ratio of tannin acid to furfural is 1:19.24 or 1:25.
66. The curing treatment is carried out at 160-180 DEG C for 6-7 hours. The average particle size of the tannin-furfural resin micro-nano ball is 773-1011 nm. The concentration of the ammonia water is 25-27 t%, and the adding amount is 0.9-4 ml.
2. The process for the preparation of full biobased component tannin-acetaldehyde resin micro- and nano-spheres according to claim 1, characterized in that, The adding amount of the ammonia water is 3 ml.
3. The process for the preparation of full biobased component tannin-acetaldehyde resin micro- and nano-spheres according to claim 2, characterized in that, The volume ratio of water to ethanol in the ethanol solution is 2:1-1.
2.
4. The process for the preparation of full biobased component tannin-acetaldehyde resin micro- and nano-spheres according to claim 1, characterized in that, The volume ratio of water to ethanol is 2:
1.
5. The process for the preparation of full biobased component tannin-acetaldehyde resin micro- and nano-spheres according to claim 4, characterized in that, The volume ratio of the furfural solution to ammonia water is 3-4:0.9-3.
6. The process for the preparation of full biobased component tannin-acetaldehyde resin micro- and nano-spheres according to claim 1, characterized in that, The curing treatment is carried out at 160 DEG C for 7 hours.
7. The process for the preparation of full biobased component tannin-acetaldehyde resin micro- and nano-spheres according to claim 1, characterized in that, After the curing treatment, the reaction liquid is subjected to centrifugal treatment, repeatedly washed with distilled water and alcohol, and vacuum dried to obtain the tannin-furfural resin micro-nano ball.
8. The process for the preparation of full biobased component tannin-acetaldehyde resin micro- and nano-spheres according to claim 1, characterized in that, The centrifugal treatment is carried out at a rotating speed of 9500-10000 rpm.
9. The process for the preparation of full biobased component tannin- furfural resin micro- and nano-spheres according to claim 8, characterized in that, 10. The tannin-furfural resin micro-nano ball prepared by the method in any one of claims 1-9.
11. The application of the tannin-furfural resin micro-nano ball in claim 9 in the preparation of a noble metal catalyst carrier, a hydrogel / film filler and carbon material.