Biomass-based polyfuran conjugated polymer material and application thereof
By synthesizing biomass-based polyfuran conjugated polymers with continuous conjugated structures, the problem of insufficient performance of bio-based polymers has been solved, enabling their application in the fields of optoelectronics and catalysis, especially exhibiting high selectivity in photocatalysis.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-02
- Publication Date
- 2026-04-10
AI Technical Summary
The poor mechanical and heat resistance properties of existing bio-based polymer materials limit their application range, and the diversified design of biomass resources has not been fully explored.
Using 2,5-furandicarboxaldehyde and acetone as raw materials, a biomass-based polyfuran conjugated polymer material with a continuous conjugated structure was synthesized under specific conditions through alkaline catalysts, metal oxide catalysts, or metal salt catalysts. The material contains carbon-carbon single bonds, carbon-carbon double bonds, and furan rings.
The prepared polymeric material has absorption signals in the infrared, ultraviolet and visible light regions, and has excellent thermal stability and photoactivity. It can catalyze the conversion of benzylamine to N-benzylbenzylamine with high selectivity, and can be applied to optoelectronic materials, energy materials and catalyst materials.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of biomass-based green polymer materials, and specifically relates to a biomass-based polyfuran conjugated polymer material. BACKGROUND
[0002] The production and preparation of traditional polymer materials cannot be separated from petrochemical resources, but the limited and non-renewable petrochemical resources are the main obstacle to the sustainable development of polymer materials. Biomass resources are a kind of carbon-containing resources with abundant reserves and short renewable cycle, and the annual output is estimated to be 1.7×10 11 It is of great significance to synthesize polymer materials from biomass resources. At present, the marketable biomass-based polymer materials mainly include polylactic acid, polyhydroxy fatty acid, polyglycolic acid, polybutylene succinate (PBS), etc., which are mainly fatty polymers. The mechanical properties (such as strength, modulus, creep resistance, etc.) and heat resistance (such as thermal mechanical properties, heat distortion temperature, etc.) of the fatty polymers are significantly lower than those of petroleum-based polymer materials such as polyethylene terephthalate (PET), aromatic nylon, polycarbonate and phenolic resin, which seriously limits their application range.
[0003] As one of the lignocellulose-based bio-based platform compounds with a cyclic structure, hydroxymethylfurfural (HMF) has become a research hotspot in recent years. Its downstream derivatives, 2,5-furan dicarboxylic acid (FDCA), furan dicarboxaldehyde, and tetrahydrofuran dimethanol (THFDM), are important monomers that can be polymerized with diols, diamines, and diacids to produce new bio-based polyfuran synthetic materials with excellent performance. At present, 100% renewable furan dicarboxylic acid polyester (PEF) is prepared using FDCA and bio-based ethylene glycol, which has excellent barrier properties, heat resistance, and mechanical properties, and can replace PET to be applied to thin films and soft drink bottles, thereby extending the shelf life of packaging products. For example, a biodegradable copolymer is obtained by melt polycondensation of raw materials containing THFDM, 1, 4-butanediol, and succinic acid, which solves the problems of traditional biodegradable plastics PBS, such as too fast degradation speed and poor mechanical properties, and improves the versatility of PBS in the packaging field. 2,5-furan dicarboxaldehyde (DFF) is one of the important oxidation derivatives of HMF, which has typical chemical properties of aldehydes. DFF can be used as an intermediate for fine chemicals such as medicines, macrocyclic ligands, antibacterial agents, adhesives, and organic conductors, and is also an important furan-based polymer monomer. DFF can be synthesized with different diamines to form Schiff bases and with urea to form new biomass-based resins. Due to the rigid structure of DFF, it can be polymerized with different rigid aromatic diamines to obtain furan-based organic polymer porous materials. For example, furan dicarboxaldehyde can be condensed with diamine compounds to obtain biomass-based polyimine thermosetting elastomers (Green Chem., 2019, 21, 1596-1601); furan dicarboxaldehyde is condensed with undecylenic aldehyde to obtain furan-based diene monomers, and the double bonds are further polymerized to obtain a novel furan-based polymer material, which exhibits excellent thermal stability, excellent hydrophobicity, and significant photoactivity (ACS Sustainable Chem. Eng. 2024, 12, 13798-13809). Although the current research on DFF-based polymers has proved their performance potential, the diversified design and exploration of the molecular skeleton of DFF-based polymers still need to be deepened. SUMMARY
[0004] The present application aims to provide a biomass-based polyfuran conjugated polymer material.
[0005] The molecular skeleton of the polymer material consists of carbon-carbon single bonds, carbon-carbon double bonds, furan rings, and carbonyl groups, and contains a continuous conjugated structure of carbonyl groups, carbon-carbon double bonds, and furan rings in the skeleton, and the structural formula is as shown below: .
[0006] The synthesis raw material of the polymer material is 2,5-furan dicarboxaldehyde and acetone.
[0007] The molecular weight of the polymer material is 300-10 million, preferably 500-1 million.
[0008] The polymer material has absorption signals in the infrared, ultraviolet, and visible light regions.
[0009] The preparation process of the polymer material is to mix furan dimethyl formaldehyde and acetone in a certain proportion, and the catalyst used is one or more of alkali catalyst, metal oxide catalyst, or metal salt catalyst, and the reaction is carried out at a certain temperature for a period of time.
[0010] The alkali catalyst in the preparation process contains inorganic bases, preferably one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate.
[0011] The metal oxide catalyst in the preparation process includes one or more of titanium oxide, vanadium oxide, cerium oxide, zirconium oxide, and tungsten oxide.
[0012] The metal salt catalyst in the preparation process includes one or both of vanadium chloride and chromium chloride.
[0013] The molar ratio of furan dimethyl formaldehyde to acetone in the preparation process is less than 1.5, preferably 1 to 0.5.
[0014] The reaction temperature in the preparation process is less than 250°C, preferably less than 150°C.
[0015] The reaction time in the preparation process ranges from 0.5h to 600h, preferably 2h to 50h.
[0016] The reaction solvent in the preparation process is water, an organic solvent, or a mixture of the two.
[0017] The organic solvent includes alcohols, acetonitrile, ketones, halogenated alkanes, esters, and ethers. Preferably, it includes alcohols, acetonitrile, and halogenated alkanes.
[0018] Preferably, the reaction solvent is a water / organic solvent mixture; the volume ratio of water to organic solvent in the water / organic solvent mixture is 1:1; and the organic solvent includes one of methanol, acetonitrile, and 1,4-dioxane.
[0019] The polymer material can be used in the fields of optoelectronic materials, energy materials, and catalyst materials.
[0020] Further, the polymer material can be used to catalyze the conversion of benzylamine to N-benzylidene benzylamine.
[0021] The application introduces a novel biomass-based polyfuran conjugated polymer material and a preparation method thereof, which is different from the polyfuran-based compounds and conjugated polymer materials reported in the literature. Specifically, the material introduced in the application has a continuous conjugated structure, a plurality of continuous conjugated structures composed of carbonyl groups, carbon-carbon double bonds and furan ring double bonds, and has absorption in the infrared region, the ultraviolet region and the visible light region, and can be used in the fields of photoelectric materials, energy materials, catalyst materials and the like, and has good effects, for example, the application is applied to the catalysis of benzylamine to N-benzylidene benzylamine, and 20 mg of benzylamine can be almost completely converted in 2 min under 450 nm light, normal pressure and oxygen atmosphere, and the selectivity of N-benzylidene benzylamine reaches 95%. The preparation process of the material is relatively simple, the raw material is furan dicarboxaldehyde and acetone, and the catalyst is an alkali catalyst, a metal oxide catalyst or a metal salt catalyst, and the polymer material can be obtained after a period of reaction. BRIEF DESCRIPTION OF DRAWINGS
[0022] Figure 1 It is a high performance liquid chromatogram of the condensation process of DFF of Example 1 and acetone; Figure 2 It is an infrared spectrum of DFFA of Example 1; Figure 3 It is a solid nuclear magnetic resonance spectrum of DFFA of Example 1; 13 C-NMR spectrum; Figure 4 It is an ultraviolet-visible spectrum of DFF and DFFA of Example 1; Figure 5 It is an ultraviolet-visible absorption spectrum of DFFA of Examples 1, 5 and 6, Example 1 is marked as DFFA-methanol, Example 5 is marked as DFFA-acetonitrile, and Example 6 is marked as DFFA-1,4-dioxane; Figure 6 It is an ultraviolet-visible absorption spectrum of DFFA of Example 1 and DFFC of Comparative Example 2. DETAILED DESCRIPTION
[0023] The application will be further described in detail below taking the biomass-based polyfuran conjugated polymer material and its preparation as an example. The protection content of the patent is not limited by the specific implementation manner, but is limited by the claims.
[0024] Example 1
[0025] Na2CO3 catalyst: 25 ml of ultrapure water and 25 ml of methanol were added to a round-bottom flask, followed by 1.2 g of sodium carbonate and 0.5 g of DFF. After complete dissolution, 0.4 g of acetone was added, and magnetic stirring was performed at room temperature for 48 h. After the reaction was completed, the product was washed with methanol water (1:1) and then with ultrapure water, and the obtained solid (DFFA) was dried at 70°C. The yield of the product was about 90%.
[0026] The consumption of raw materials in the preparation process was detected by high-performance liquid chromatography. It was found that DFF was completely consumed within 5 h, and the amount of remaining acetone did not change, as shown in Figure 1 .
[0027] The C=O bond in the obtained solid material was shifted to a lower wave number compared to DFF, and the C=C bond was very obvious ( Figure 2 ), indicating that the structure had an electron conjugated structure, which was consistent with the predicted structure, as shown in the formula: .
[0028] The obtained solid material was detected by 13 C-NMR ( Figure 3 ), and it was found that there were three types of structures in the molecular structure: C=O, C=C, and furan ring, which were consistent with the predicted structure.
[0029] UV spectroscopy analysis of the structure showed that the material had an absorption range mainly in the ultraviolet-visible region (200-600 nm) ( Figure 4 ).
[0030] GPC analysis of the molecular weight of the material showed that the molecular weight range was 700-100,000.
[0031] Example 2
[0032] NaOH catalyst: 25 ml of ultrapure water and 25 ml of methanol were added to a round-bottom flask, followed by 0.1 g of NaOH and 0.5 g of DFF. After complete dissolution, 0.5 g of acetone was added, and magnetic stirring was performed at room temperature for 12 h. After the reaction was completed, the product was washed with methanol water (1:1) and then with ultrapure water, and the obtained solid was dried at 70°C. The structure and properties of the material were analyzed by infrared, ultraviolet, and nuclear magnetic resonance methods, and the results were similar to those of Example 1.
[0033] Example 3
[0034] Na2CO3 catalyst: 25 ml of ultrapure water and 25 ml of methanol were added to a round-bottom flask, then 0.8 g of Na2CO3 and 0.5 g of DFF were added, and after complete dissolution, 0.35 g of acetone was added, and magnetic stirring was carried out at room temperature for 50 h. After the reaction was completed, the reaction mixture was washed with methanol water (1:1) and then filtered, and the obtained solid was washed with ultrapure water and filtered, and the obtained solid was dried at 70°C. The structure and properties of the material were analyzed by infrared, ultraviolet, and nuclear magnetic resonance, and the results were similar to those of Example 1.
[0035] Example 4
[0036] Reaction temperature: 25 ml of ultrapure water and 25 ml of methanol were added to a round-bottom flask, then 0.8 g of Na2CO3 and 0.5 g of DFF were added, and after complete dissolution, 0.35 g of acetone was added, and magnetic stirring was carried out at room temperature for 3 h, and then the temperature was raised to 150°C and the reaction was carried out for 6 h. After the reaction was completed, the reaction mixture was washed with methanol water (1:1) and then filtered, and the obtained solid was washed with ultrapure water and filtered, and the obtained solid was dried at 70°C. The structure and properties of the material were analyzed by infrared, ultraviolet, and nuclear magnetic resonance, and the results were similar to those of Example 1.
[0037] Example 5
[0038] Reaction solvent acetonitrile: 25 ml of ultrapure water and 25 ml of acetonitrile were added to a round-bottom flask, then 1.2 g of sodium carbonate and 0.5 g of DFF were added, and after complete dissolution, 0.4 g of acetone was added, and magnetic stirring was carried out at room temperature for 48 h. After the reaction was completed, the reaction mixture was filtered with ultrapure water, and the obtained solid was dried at 70°C. The structure of the material was analyzed by ultraviolet spectroscopy, and it was found that the light absorption range of the material was significantly increased compared to the material in Example 1, and there was obvious absorption in the ultraviolet-visible-near infrared region (marked as DFFA-acetonitrile). Figure 5
[0039] Example 6
[0040] Reaction solvent 1,4-dioxane: 25 ml of ultrapure water and 25 ml of 1,4-dioxane were added to a round-bottom flask, then 1.2 g of sodium carbonate and 0.5 g of DFF were added, and after complete dissolution, 0.4 g of acetone was added, and magnetic stirring was carried out at room temperature for 48 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the obtained solid was washed with water and centrifuged, and then dried at 70°C. The structure of the material was analyzed by ultraviolet spectroscopy, and it was found that the light absorption range of the material was significantly increased compared to the material in Example 1, and there was obvious absorption in the ultraviolet-visible-near infrared region (marked as DFFA-1,4-dioxane). Figure 5
[0041] Example 7
[0042] Application in catalysis: DFFA-acetonitrile was used as catalyst to catalyze the conversion of benzylamine to N-benzylidene benzylamine. A small amount of sample was taken as catalyst, about 5 mg, which was able to convert 20 mg of benzylamine almost completely in 1.5 h under 450 nm light irradiation and normal pressure oxygen atmosphere, and the selectivity of N-benzylidene benzylamine reached 95%.
[0043] Comparative Example 1
[0044] 25 ml of ultrapure water and 25 ml of methanol were added to a round-bottom flask, followed by 0.8 g of Na2CO3 and 0.5 g of DFF, which were magnetically stirred at room temperature for 48 h. After the reaction was completed, no solid material was generated, and high-performance liquid chromatography analysis of the reaction process found that the amount of raw material had almost no change, indicating that DFF itself would not polymerize.
[0045] Comparative Example 2
[0046] Comparative cyclic ketone: 25 ml of ultrapure water and 25 ml of methanol were added to a round-bottom flask, followed by 0.8 g of Na2CO3 and 0.5 g of DFF, which were completely dissolved, and then 0.7 g of cyclohexanone was added. The mixture was magnetically stirred at room temperature for 12 h. After the reaction was completed, the mixture was washed and filtered with methanol water (1:1), and then washed and filtered with ultrapure water. The solid obtained by filtration (DFFC) was dried at 70°C. The structure and properties of the material were analyzed by infrared and ultraviolet methods, and the results were as follows Figure 6 The characterization results confirmed that the structure of the obtained material was as shown in the figure: the light absorption range of DFFC was narrower than that of DFFA, and the light absorption intensity was lower.
[0047] Comparative Example 3
[0048] DFFC was used as catalyst to catalyze the conversion of benzylamine to N-benzylidene benzylamine. A small amount of sample was taken as catalyst, about 5 mg, which was able to convert 20 mg of benzylamine almost completely in 1.5 h under 450 nm light irradiation and normal pressure oxygen atmosphere, but the selectivity of N-benzylidene benzylamine was only 80%.
[0049] The above only describes the preferred embodiments of the present application, and it should be noted that those of ordinary skill in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.
Claims
1. A biomass-based polyfuran conjugated polymer material, characterized in that: The framework of polymer materials consists of carbon-carbon single bonds, carbon-carbon double bonds, furan rings, and carbonyl groups. The framework contains multiple sets of continuous conjugated structures composed of carbonyl groups, carbon-carbon double bonds, and furan ring double bonds. The structural formula is as follows: .
2. The biomass-based polyfuran conjugated polymer material according to claim 1, characterized in that: The raw materials for synthesizing the biomass-based polyfuran conjugated polymer are furan diformaldehyde and acetone.
3. The biomass-based polyfuran conjugated polymer material according to claim 1, characterized in that: The molecular weight of molecular materials is 3 million to 1 million.
4. A method for preparing a biomass-based polyfuran conjugated polymer material according to any one of claims 1-3, characterized in that: The process includes the following steps: reacting furan-diformaldehyde and acetone in a solvent under the action of a catalyst by heating to obtain a biomass-based polyfuran conjugated polymer material.
5. The method for preparing a biomass-based polyfuran conjugated polymer material according to claim 4, characterized in that: The catalyst includes one or more of the following: an alkaline catalyst, a metal oxide catalyst, or a metal salt catalyst; the alkaline catalyst includes one or more of the following: sodium hydroxide, sodium carbonate, and sodium bicarbonate; the metal oxide catalyst includes one or more of the following: titanium oxide, vanadium oxide, cerium oxide, zirconium oxide, and tungsten oxide; and the metal salt catalyst includes one or two of the following: vanadium chloride and chromium chloride.
6. The method for preparing a biomass-based polyfuran conjugated polymer material according to claim 4, characterized in that: The molar ratio of furanyl dicarboxaldehyde and acetone is less than 1.
5.
7. The method for preparing a biomass-based polyfuran conjugated polymer material according to claim 4, characterized in that: The heating reaction temperature is below 250°C, and the reaction time is from 0.5 h to 600 h.
8. The method for preparing a biomass-based polyfuran conjugated polymer material according to claim 4, characterized in that: The solvent is water, an organic solvent, or a mixture of both; the organic solvent includes alcohols, acetonitrile, ketones, haloalkanes, esters, and ethers.
9. The method for preparing a biomass-based polyfuran conjugated polymer material according to claim 4, characterized in that: The reaction solvent is a water / organic solvent mixture; the volume ratio of water to organic solvent in the water / organic solvent mixture is 1:1; the organic solvent includes one of methanol, acetonitrile, and 1,4-dioxane.
10. The application of a biomass-based polyfuran conjugated polymer material according to any one of claims 1-3 in optoelectronic materials, energy materials, and catalyst materials.