Biomass-based polyfuran high polymer material with adjustable flexibility and preparation method thereof
The catalyst-promoted reaction of furan diformaldehyde with diketones or polyketones to form biomass-based polyfuran polymer materials, solving the problem of insufficient rigidity of bio-based fat materials, achieving the improvement of high flexibility and heat resistance, and expanding its application potential in many fields.
Patent Information
- Application Number
- CN202510430892.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-08
- Publication Date
- 2025-07-08
AI Technical Summary
The lack of rigid structure in the molecular structure of existing bio-based fat chain polymers, resulting in lower heat resistance and mechanical properties than petroleum-based polymer materials.
Under the action of the catalyst, furan diformaldehyde and diketones or polyketones undergo a hydroxyaldehyde condensation reaction at a temperature below 250°C to form a biomass-based polyfuran polymer material. Its molecular structure is alternately connected by carbon chains and furan rings, with a molecular weight of 10-1 million. The catalyst includes alkalis, metal oxides or metal salts.
It improves the flexibility and heat resistance of biomass-based polyfuran polymer materials, enhances the absorption capacity of ultraviolet and visible light, is suitable for energy materials, catalytic materials and packaging materials, and promotes the development of renewable energy technology.
Smart Images
Figure CN120271771A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of biomass-based polyfuran polymer materials, and specifically relates to a flexible and adjustable biomass-based polyfuran polymer material and a preparation method thereof. Background Art
[0002] It has become an irresistible trend to promote the diversification, sustainability, and environmental friendliness of China's energy. The raw materials of bio-based materials mainly come from renewable resources such as starch and cellulose, which use sunlight and carbon dioxide as energy and carbon sources. Using bio-based materials can reduce the dependence on petroleum resources.
[0003] Currently, the developed bio-based aliphatic chain polymer materials mainly include polylactic acid, polyhydroxy fatty acids, polyglycolic acid, polybutylene succinate (PBS), etc. In the molecular structure of bio-based aliphatic chain polymer materials, there is a lack of rigid aromatic rings, and their mechanical properties (such as strength, modulus, creep resistance, etc.) and heat resistance properties (such as thermomechanical properties, heat distortion temperature, etc.) are significantly lower than those of petroleum-based polymer materials such as polyethylene terephthalate (PET), aromatic nylon, polycarbonate, and epoxy resin. Summary of the Invention
[0004] The problems existing in the prior art are as follows: In the molecular structure of conventional bio-based aliphatic chain polymer materials, there is a lack of rigid structure, and their heat resistance and mechanical properties are significantly lower than those of petroleum-based polymer materials. In view of the above technical problems, the present invention provides a flexible and adjustable biomass-based polyfuran polymer material, which is a product obtained by the aldol condensation reaction of furan dialdehyde with diketone or polyketone under the action of a catalyst, and the reaction temperature is not higher than 250 °C, and more preferably, the reaction temperature is not higher than 150 °C. During the reaction process, the molar ratio of furan dialdehyde to diketone or polyketone is not greater than 1.5:1, and more preferably, the molar ratio of furan dialdehyde to diketone or polyketone is 0.5 - 1:1. The reaction time is 0.5 - 600 h, and more preferably, the reaction time is 2 - 50 h. The structural formula of the biomass-based polyfuran polymer material is formed by alternating carbon chains and furan rings, and the general structural formula of the biomass-based polyfuran polymer material is as follows:
[0005]
[0006] In the above general structural formula, the value of n is determined by the dosage of the reaction raw materials and the reaction conditions (reaction time, reaction temperature, etc.).
[0007] Preferably, the molecular weight of the biomass-based polyfuran polymer material is 1000 - 1,000,000.
[0008] Preferably, the molecular weight of the biomass-based polyfuran polymer material is 3000 - 100,000.
[0009] Preferably, the structural formula of the biomass-based polyfuran polymer material is as follows:
[0010]
[0011] In the above general structural formula, the value of n is determined by the amounts of reaction raw materials, reaction time, and reaction temperature, and the value of m is determined by the structural formula of the diketone, where m ≥ 4 and m is an integer.
[0012] Preferably, the diketone includes 2,3-butanedione, 2,5-hexanedione, 2,4-pentanedione, or 2,7-heptanedione.
[0013] Preferably, the polyketone has a carbon atom number greater than or equal to 4 and a carbonyl group number greater than or equal to 3, and the polyketone includes one or more of polybutanone, polypentanone, polyhexanone, and polyheptanone.
[0014] Preferably, the reaction solvent includes water, an organic solvent, or a mixture formed by water and an organic solvent.
[0015] Preferably, the organic solvent includes alcohol, cyanide, ketone, halogenated alkane, ester, or ether solvents.
[0016] Preferably, the organic solvent is methanol, dichloromethane, or acetonitrile.
[0017] Preferably, the catalyst used in the reaction includes one or more of a base, a metal oxide, or a metal salt.
[0018] Preferably, the metal oxide includes one or more of titanium oxide, vanadium oxide, cerium oxide, zirconium oxide, and tungsten oxide.
[0019] Preferably, the metal salt includes one or two of vanadium chloride and chromium chloride.
[0020] Preferably, the base includes one or more of Na2CO3, NaHCO3, and NaOH.
[0021] The biomass-based polyfuran polymer material obtained in the present invention can be used as an energy material, a catalytic material, a packaging material, an adsorption material, etc.
[0022] The present invention has the following beneficial effects:
[0023] (1) The biomass-based polyfuran polymer material obtained in the present invention has a molecular skeleton composed of aromatic rings and carbon-carbon chains, without heteroatoms, and is similar to the molecular skeleton of phenolic resin. Phenolic resin is formed by the polycondensation of phenol and formaldehyde, and the aromatic rings are connected by a carbon chain. Phenolic resin has strong rigidity, is brittle, and lacks flexibility. However, the biomass-based polyfuran polymer material obtained in the present invention has a lower carbon footprint. In the molecular structure, the aromatic furan rings are connected to double bonds, and the length of the carbon chain between the furan rings can be adjusted (by changing the type of diketone or polyketone), that is, the flexibility of the biomass-based polyfuran polymer material can be adjusted, thus overcoming the disadvantages of traditional phenolic resin with strong rigidity and brittleness. In addition, since this material is derived from renewable biomass resources, its production process is green and clean, meeting the current global demand for sustainable development materials.
[0024] (2) The solid ultraviolet-visible absorption signal of the biomass-based polyfuran polymer material obtained in the present invention can reach between 1.75 and 2.0, showing strong absorption ability for ultraviolet or visible light. This strong absorption signal makes it possible to detect low-concentration samples, especially suitable for trace analysis or scenarios with high sensitivity requirements. At the same time, due to its excellent light absorption performance, this material also has broad application prospects, especially in the field of solar cells. By applying this material to solar cells, the light energy conversion efficiency can be effectively improved, thus promoting the development of renewable energy technologies.
[0025] (3) The biomass-based polyfuran polymer material obtained in the present invention not only achieves an innovative breakthrough in molecular structure but also demonstrates significant advantages in functional properties. These characteristics endow it with broad application potential in multiple fields, providing a new direction for the research and development of future sustainable development materials. Description of the Drawings
[0026] Figure 1 : High-performance liquid chromatography analysis chart during the reaction process of Example 1.
[0027] Figure 2 : Infrared spectra of Example 1-2 and DFF.
[0028] Figure 3 : Ultraviolet-visible spectra of DFFB and DFFH obtained in Example 1 and Example 2 respectively.
[0029] Figure 4 : Thermogravimetric analysis chart of DFFB obtained in Example 1.
[0030] Figure 5 : High-performance liquid chromatography analysis chart during the reaction process of Example 2.
[0031] Figure 6 : Thermogravimetric analysis chart of DFFH obtained in Example 2. Detailed Embodiments
[0032] The present invention will be described in detail below in conjunction with embodiments. It should be understood that the following embodiments are only illustrative examples of the implementation modes of the present invention, rather than limiting the scope of the present invention.
[0033] Example 1
[0034] 25 mL of ultrapure water and 25 mL of methanol were added to a round-bottom flask, and then 0.9 g of Na2CO3 and 0.5 g of furandialdehyde (DFF) were added. After complete dissolution, 0.7 g of 2,3-butanedione was added, and the mixture was magnetically stirred at room temperature for 48 h. After the reaction was completed, it was washed by suction filtration with methanol-water and then with ultrapure water. The solid obtained by suction filtration was dried at 70 °C and denoted as DFFB. The chemical reaction equation for the above process is as follows:
[0035]
[0036] During the reaction process, a high-performance liquid chromatography analyzer was used to monitor the consumption of raw materials in the reaction process. It was found that most of the DFF was consumed within 17 h. The specific monitoring results are as shown in the appendix of the specification Figure 1 as shown.
[0037] The C=O, C=C, and furan ring functional groups in the molecular structure of the product DFFB were analyzed by infrared spectroscopy. The results are as shown in the appendix of the specification Figure 2 as shown. The infrared chromatogram analysis of DFF is as shown in the appendix of the specification Figure 2 as shown.
[0038] The solid ultraviolet spectrum analysis results of the product DFFB are as shown in the appendix of the specification Figure 3 as shown. The image shows that the absorption range of the product DFFB in the ultraviolet-visible light region is 200 - 800 nm. The solid ultraviolet-visible absorption signal (the larger the solid ultraviolet-visible absorption signal, the stronger the absorption ability of the sample to ultraviolet or visible light) is between 0.75 - 1.75.
[0039] It was analyzed by GPC that the molecular weight range of the product DFFB is 1000 - 100,000, and the molecular weight distribution index is 1.2.
[0040] The thermal stability of the material was analyzed by a thermogravimetric analyzer. The results are as Figure 4 shown. The DFFB material remained stable within 200 °C.
[0041] Example 2
[0042] Add 25 ml of ultrapure water and 25 ml of methanol to a round-bottom flask, then add 1.2 g of sodium carbonate and 0.5 g of DFF. After complete dissolution, add 0.7 g of 2,5-hexanedione, and stir magnetically at room temperature for 48 h. After the reaction is completed, remove the solvent on a rotary evaporator to obtain a solid material, dissolve it in methanol, filter to remove solid sodium carbonate, then rotary evaporate the filtrate to obtain a solid material, and dry it at 70 °C, denoted as DFFH. The chemical reaction equation for the above process is as follows:
[0043]
[0044] During the reaction process, a high-performance liquid chromatography analyzer was used to monitor the consumption of raw materials in the reaction process. It was found that most of the DFF was consumed within 5 h. The specific monitoring results are shown in the appendix of the specification Figure 5 as shown.
[0045] The C=O, C=C, and furan ring functional groups in the molecular structure of the product DFFH were analyzed by infrared spectroscopy. The results are shown in the appendix of the specification Figure 2 as shown.
[0046] The solid ultraviolet spectrum analysis results of the product DFFH are shown in the appendix of the specification Figure 3 as shown. The image shows that the absorption range of the product DFFH in the ultraviolet-visible light region is 200 - 700 nm, and the ultraviolet-visible absorption signal intensity is between 1.75 - 2.0.
[0047] Analysis by GPC shows that the molecular weight range of the product DFFH is 1000 - 100,000, and the molecular weight distribution index is 1.1.
[0048] The thermal stability of the material was analyzed by a thermogravimetric analyzer. The results are shown in Figure 6 as shown. The DFFH material remains stable within 200 °C.
[0049] Example 3
[0050] Add 25 ml of ultrapure water and 25 ml of methanol to a round-bottom flask, then add 0.8 g of NaHCO3 and 0.5 g of DFF. After complete dissolution, add 0.75 g of 2,5-hexanedione, and stir magnetically at room temperature for 50 h. After the reaction is completed, wash and filter with methanol-water, then wash and filter with ultrapure water. The solid obtained by filtration is dried at 70 °C to obtain DFFH-3.
[0051] The absorption range of the product DFFH-3 in the solid ultraviolet-visible light region is 200 - 700 nm, and the ultraviolet-visible absorption signal intensity is between 1.5 - 2.0.
[0052] Analysis by GPC shows that the molecular weight range of the product DFFH-3 is 1000 - 100,000, and the molecular weight distribution index is 1.1.
[0053] Example 4
[0054] Add 25 ml of ultrapure water and 25 ml of methanol into a round-bottom flask, then add 0.8 g of NaOH and 0.5 g of DFF. After it is completely dissolved, add 0.75 g of 2,5-hexanedione. Stir magnetically at 90 °C for 10 h. After the reaction is completed, wash and filter by methanol-water, then wash and filter by ultrapure water. The solid obtained by filtration is dried at 70 °C to obtain DFFH-4.
[0055] The absorption range of the product DFFH-4 in the solid ultraviolet-visible light region is 200 - 700 nm, and the ultraviolet-visible absorption signal intensity is between 1.5 - 2.0.
[0056] It can be known by GPC analysis that the molecular weight range of the product DFFH-4 is 1000 - 100,000, and the molecular weight distribution index is 1.1.
[0057] Example 5
[0058] Add 25 ml of ultrapure water and 25 ml of dichloromethane into a round-bottom flask, then add 0.8 g of Na2CO3 and 0.5 g of DFF. After it is completely dissolved, add 0.8 g of 2,5-hexanedione. Stir magnetically at room temperature for 4 h, then raise the temperature to 150 °C and react for 6 h. After the reaction is completed, wash and filter by methanol-water, then wash and filter by ultrapure water. The solid obtained by filtration is dried at 70 °C to obtain DFFH-5.
[0059] The absorption range of the product DFFH-5 in the solid ultraviolet-visible light region is 200 - 700 nm, and the ultraviolet-visible absorption signal intensity is between 1.5 - 2.0.
[0060] It can be known by GPC analysis that the molecular weight range of the product DFFH-5 is 1000 - 100,000, and the molecular weight distribution index is 1.1.
[0061] Comparative Example 1 is the same as Example 1, except that in Comparative Example 1, 2,3-butanedione is not added. It is found that DFF itself does not undergo a condensation reaction and no solid material can be obtained.
[0062] Comparative Example 2 is the same as Example 1, except that in Comparative Example 2, DFF is not added. It is found that the diketone itself does not undergo a condensation reaction and no solid material can be obtained.
[0063] Enlightened by the ideal embodiments of the present invention described above, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.
Claims
1. A flexible and adjustable biomass-based polyfuran polymer material, characterized in that, It is a product obtained by the aldol condensation reaction of furan dialdehyde with diketone or polyketone under the action of a catalyst. The structural formula of the biomass-based polyfuran polymer material is composed of a carbon chain formed by carbon-carbon bonds and furan rings alternatingly connected. The general structural formula of the biomass-based polyfuran polymer material is as follows: In the above general structural formula, the value of n is determined by the dosage of reaction raw materials and reaction conditions.
2. The flexible and adjustable biomass-based polyfuran polymer material according to claim 1, characterized in that, The molecular weight of the biomass-based polyfuran polymer material is 1,000 - 1,000,000.
3. The flexible and adjustable biomass-based polyfuran polymer material according to claim 2, characterized in that, The molecular weight of the biomass-based polyfuran polymer material is 3,000 - 100,000.
4. A flexible and adjustable biomass-based polyfuran polymer material according to claim 1, characterized in that, The structural formula of the biomass-based polyfuran polymer material is as follows: In the above general structural formula, the value of n is determined by the dosage of reaction raw materials and reaction conditions, and the value of m is determined by the structural formula of diketone, m ≥ 4, and m is an integer.
5. A flexible and adjustable biomass-based polyfuran polymer material according to claim 2, characterized in that The diketone includes 2,3-butanedione, 2,5-hexanedione, 2,4-pentanedione or 2,7-heptanedione.
6. A flexible and adjustable biomass-based polyfuran polymer material according to claim 1, characterized in that, The solvent for the reaction includes water, organic solvent or a mixed solution formed by water and organic solvent.
7. A flexible and adjustable biomass-based polyfuran polymer material according to claim 6, characterized in that, The organic solvent includes alcohol, cyanide, ketone, halogenated alkane, ester or ether solvent.
8. A flexible and adjustable biomass-based polyfuran polymer material according to claim 7, characterized in that, The organic solvent is methanol, dichloromethane or acetonitrile.
9. A flexible and adjustable biomass-based polyfuran polymer material according to claim 1, characterized in that, The catalyst used in the reaction includes one or more of alkali, metal oxide or metal salt.
10. A flexible and adjustable biomass-based polyfuran polymer material according to claim 1, characterized in that, The catalyst used in the reaction is one or several of Na2CO3, NaHCO3, NaOH.