Biomass-based polyfuran high molecular material and preparation method thereof

Abstract

The application belongs to the field of biomass-based green polymer materials, and specifically discloses a biomass-based polyfuran polymer material and a preparation method thereof. The biomass-based polyfuran polymer material is synthesized by using double-(5-formylfurfuryl) ether (OBMF) as a raw material, which is an etherization product downstream of HMF. The polymer material contains furan rings, carbon-carbon chains and C-O-C groups in the molecular skeleton. The C-O-C group is easy to hydrolyze under the condition of an acid catalyst, and can be recycled at 100%. In addition, the length of the carbon-carbon chain can be adjusted, so as to realize the flexibility adjustment of the material. The material has an absorption signal in the visible or ultraviolet region. The structure of the polymer material is different from the currently reported polyfuran-based polymer materials, and the polymer material can have advantages in the field of photoelectric materials, and can also be used in the fields of energy materials, catalytic materials, packaging materials, adsorption materials and the like.

Description

Technical Field

[0001] The present invention belongs to the field of biomass-based green polymer materials, and the specific material is a biomass-based polyfuran polymer material and a preparation method thereof. Background Art

[0002] The Ministry of Industry and Information Technology, the Ministry of Ecology and Environment, the Ministry of Emergency Management, and the National Standards Administration jointly issued the "Action Plan for Improving Standards to Lead the Optimization and Upgrading of the Raw Materials Industry (2025-2027)". The action plan clearly classifies biodegradable materials as advanced basic materials and bio-based new materials as key strategic materials. It requires that the high-quality development of key industrial chains be promoted, application scenarios and industrial research and development be closely integrated, and the development and implementation of key standards be promoted simultaneously.

[0003] Biomass-based materials refer to a new class of materials, such as bioplastics and biomass-based functional polymers, manufactured using renewable biomass or raw materials derived from biomanufacturing through biological, chemical, and physical methods. These materials differ from traditional chemical products produced from non-renewable petrochemical resources like coal and oil. Bio-based materials offer the advantages of renewable raw materials, reduced carbon emissions, and energy conservation. Some products are also biodegradable, making them a key development direction for the new materials industry.

[0004] The bio-based polymer materials with a higher market value include polylactic acid, polyhydroxy fatty acids, polyglycolic acid, polybutylene succinate (PBS), etc., which are mainly fatty polymers. Due to the lack of rigid aromatic rings in their molecular structure, their mechanical properties (such as strength, modulus, creep resistance, etc.) and heat resistance (such as thermomechanical properties, heat deformation temperature, etc.) 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.

[0005] If bio-based polymers are to partially replace and supplement petroleum-based polymers, they urgently need to incorporate rigid aromatic rings into their molecular structures. 5-Hydroxymethylfurfural (HMF), the only bio-based platform compound with a ring structure, has become a hot topic in recent industry research. Its downstream derivatives, 2,5-furandicarboxylic acid (FDCA) and tetrahydrofuran dimethanol (THFDM), possess rigid aromatic rings that can be polymerized with monomers such as diols and diamines to produce novel bio-based synthetic polymers with excellent performance. For example, 100% renewable furandicarboxylic acid polyester (PEF), prepared from FDCA and bio-based ethylene glycol, exhibits excellent barrier properties, heat resistance, and mechanical properties, making it a viable alternative to PET in films and soft drink bottles, extending the shelf life of packaging products. Another example is the melt polycondensation of THFDM, 1,4-butanediol, and succinic acid to create a biodegradable copolymer that addresses the rapid degradation and poor mechanical properties of conventional biodegradable plastics (PBS), enhancing the versatility of PBS in packaging applications.

[0006] Currently, bio-based polyfuran materials have a relatively small market share. However, as HMF costs decrease, their application in the bio-based materials sector holds enormous potential. The development and upgrading of process technologies for producing novel and more competitive polyfuran materials using HMF and its derivatives require continuous investment and R&D. Summary of the Invention

[0007] The object of the present invention is to provide a biomass-based polyfuran polymer material, which is composed of a carbon-carbon chain, a furan ring, and a COC bond, and has a molecular structure as shown below:

[0008] It is a backbone carbon-carbon chain;

[0009] The backbone carbon-carbon chain consists of carbon-carbon single bonds and carbon-carbon double bonds.

[0010] The molecular weight of the polymer material is 1,000-1,000,000, preferably 2,000-100,000.

[0011] The polymer material has an absorption signal in the visible light or ultraviolet light region or in the ultraviolet-visible region.

[0012] The synthetic raw materials of the polymer material are bis-(5-formylfurfuryl) ether and ketone.

[0013] Furthermore, the types of ketones include monoketones, diketones, and polyketones. Monoketones are preferably acetone and cyclohexanone. Diketones are preferably diacetyl, hexanedione, and pentanedione. Polyketones are compounds having 4 or more carbon atoms and 3 or more carbonyl groups, preferably hexanetrione and heptantrione.

[0014] Furthermore, the polymer material preparation process is: bis-(5-formylfurfuryl) ether and ketone are placed in a solvent, reacted in the presence of a catalyst at a certain temperature for a period of time to obtain the polymer material.

[0015] Furthermore, the catalyst includes one or more of an alkali catalyst, a metal oxide catalyst or a metal salt catalyst.

[0016] Furthermore, the base catalyst includes an inorganic base; preferably, the inorganic base includes one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate.

[0017] Furthermore, the metal oxide catalyst includes one or more of titanium oxide, vanadium oxide, cerium oxide, zirconium oxide, and tungsten oxide.

[0018] Furthermore, the metal salt catalyst includes one or both of vanadium chloride and chromium chloride.

[0019] Furthermore, the molar ratio of bis-(5-formylfurfuryl) ether to ketone is less than 1.5,

[0020] Furthermore, the molar ratio of the bis-(5-formylfurfuryl) ether to the ketone is 1 to 0.5.

[0021] Preferably, the molar ratio of the bis-(5-formylfurfuryl) ether to the ketone is 0.53-0.81.

[0022] Furthermore, the temperature in the preparation method is less than or equal to 250 degrees Celsius.

[0023] Furthermore, the temperature in the preparation method is less than or equal to 200 degrees Celsius.

[0024] Preferably, the temperature in the preparation method ranges from 50 degrees Celsius to 200 degrees Celsius.

[0025] Furthermore, the reaction time in the preparation method ranges from 0.5h to 600h.

[0026] Preferably, the reaction time in the preparation method ranges from 6 h to 72 h.

[0027] Furthermore, the solvent in the preparation method is water, an organic solvent or a mixture of the two.

[0028] Furthermore, the organic solvent includes alcohols, acetonitrile, ketones, halogenated alkanes, esters, and ethers, preferably alcohols, acetonitrile, 1,4-dioxane, and halogenated alkanes.

[0029] Furthermore, the alcohols include methanol and isopropanol; the ketones include acetone; the halogenated alkanes include dichloromethane and chloroform; the esters include ethyl acetate; and the ethers include 4-dioxane.

[0030] The beneficial effects of the present invention are:

[0031] This invention provides a biomass-based polyfuran polymer material and its preparation method. Using bis-(5-formylfurfuryl) ether (OBMF), a downstream etherification product of HMF, as a raw material, the synthesized polymer material contains a furan ring, a carbon-carbon chain, and a COC group in its molecular skeleton. The COC group is easily hydrolyzed under acid catalyst conditions, allowing 100% recycling. Furthermore, the carbon-carbon chain length can be adjusted, thereby achieving material flexibility. The material exhibits absorption signals in the visible and ultraviolet regions. This material differs from the structure of previously reported polyfuran-based polymer materials and has advantages in the field of optoelectronic materials. It can also be used in energy materials, catalytic materials, packaging materials, adsorption materials, and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 1 is a high performance liquid chromatography analysis chart of the condensation process of OBMF and acetone in Example 1;

[0033] Figure 2 The infrared spectra of OBMFA and OBMF in Example 1 are shown below:

[0034] Figure 3 For Example 1 OBMFA 13 C-NMR visible spectrum;

[0035] Figure 4 UV-visible spectra of OBMFA and OBMF in Example 1;

[0036] Figure 5 UV-visible spectra of OBMFH and OBMFC of Examples 5 and 6;

[0037] Figure 6 These are the infrared spectra of OBMFH and OBMFC in Examples 5 and 6. DETAILED DESCRIPTION

[0038] The invention is further described in detail below using the biomass-based polyfuran polymer material and its preparation method as an example. The protection content of this patent is not limited to the specific implementation methods, but is limited by the claims.

[0039] Example 1

[0040] 50 ml of ultrapure water and 125 ml of methanol were added to a round-bottom flask, followed by 0.7 g of Na₂CO₃ and 0.5 g of OBMF. After complete dissolution, 0.2 g of acetone was added and the mixture was magnetically stirred at 50°C for 48 hours. After the reaction, the mixture was washed with methanol / water and then ultrapure water, filtered, and the resulting solid was dried at 70°C. This solid was designated OBMFA, with a yield of 85%.

[0041] The consumption of raw materials in the preparation process was detected by high performance liquid chromatography, and it was found that the raw materials were completely consumed within 10 hours ( Figure 1 ).

[0042] The C=O, C=C, furan ring ( Figure 2 ), which is consistent with the predicted structure. The OBMFA structure is as follows:

[0043]

[0044] The structure of the material was analyzed by ultraviolet spectroscopy and it was found that the absorption range of the material is mainly in the ultraviolet region (200-700nm) ( Figure 3 ).

[0045] The molecular weight range of the material analyzed by GPC is 2000-100,000

[0046] Example 2

[0047] 50 ml of ultrapure water and 200 ml of methanol were added to a round-bottom flask, followed by 0.1 g of NaOH and 0.5 g of OBMF. After complete dissolution, 0.3 g of acetone was added and magnetically stirred at 50°C for 36 hours. After the reaction, the mixture was washed with a methanol / water solution and then filtered with ultrapure water. The resulting solid was dried at 70°C for an 88% yield. The structure and properties of the material were analyzed using infrared, ultraviolet, and nuclear magnetic resonance spectroscopy, yielding results similar to those in Example 1.

[0048] Example 3

[0049] 50 ml of ultrapure water and 125 ml of methanol were added to a round-bottom flask, followed by 0.8 g of NaHCO and 0.5 g of OBMF. After complete dissolution, 0.3 g of acetone was added and magnetic stirring was performed at 90 degrees Celsius for 36 hours. After the reaction, the mixture was washed with methanol / water and then filtered with ultrapure water. The resulting solid was dried at 70 degrees Celsius for a yield of 92%. The structure and properties of the material were analyzed using infrared, ultraviolet, and nuclear magnetic resonance spectroscopy, and the results were similar to those in Example 1.

[0050] Example 4

[0051] 50 ml of ultrapure water and 125 ml of methanol were added to a round-bottom flask, followed by 0.7 g of Na₂CO₃ and 0.5 g of OBMF. After complete dissolution, 0.2 g of acetone was added and the mixture was magnetically stirred at 50°C for 12 hours, followed by 6 hours at 200°C. After the reaction, the mixture was washed with ultrapure water, filtered, and dried at 70°C. The structure and properties of the material were analyzed using infrared, ultraviolet, and nuclear magnetic resonance spectroscopy (NMR), yielding 96% results similar to those in Example 1.

[0052] Example 5

[0053] 50ml ultrapure water and 125ml methanol were added to a round-bottom flask, followed by 0.7g Na2CO3 and 0.5g OBMF. After complete dissolution, 0.3g hexanedione was added and magnetically stirred at 50 degrees Celsius for 24h. After the reaction was completed, the mixture was washed with methanol / water and then filtered with ultrapure water. The solid obtained by filtration was dried at 70°C. The material was recorded as OBMFH with a yield of 90%. The structure and properties of the material were analyzed by infrared and ultraviolet methods. The results are as follows Figure 5 、 6 The structural formula of OBMFH is as follows:

[0054] Example 6

[0055] 50ml of ultrapure water and 125ml of methanol were added to a round-bottom flask, followed by 0.7g of Na2CO3 and 0.5g of OBMF. After they were completely dissolved, 0.35g of cyclohexanone was added and magnetically stirred at 50 degrees Celsius for 24 hours. After the reaction was completed, the mixture was washed with methanol / water and then filtered with ultrapure water. The filtered solid was dried at 70°C. The material was recorded as OBMFC with a yield of 90%. The structure and properties of the material were analyzed by infrared and ultraviolet methods. The results are as follows Figure 5 、 6 The structural formula of OBMFC is as follows:

[0056] Example 7

[0057] 50 ml of ultrapure water and 125 ml of 1,4-dioxane were added to a round-bottom flask, followed by 0.7 g of NaCO and 0.5 g of OBMF. After complete dissolution, 0.2 g of acetone was added and the mixture was magnetically stirred at 50°C for 72 hours. After the reaction, the mixture was washed with ultrapure water and filtered. The resulting solid was dried at 70°C with a yield of 89%. Structural analysis using infrared and ultraviolet spectroscopy revealed similar results to those in Example 1.

[0058] Example 8

[0059] 50 ml of ultrapure water and 125 ml of acetonitrile were added to a round-bottom flask, followed by 0.7 g of NaCO and 0.5 g of OBMF. After complete dissolution, 0.2 g of acetone was added and the mixture was magnetically stirred at 50°C for 72 hours. After the reaction, the mixture was washed with ultrapure water and filtered. The resulting solid was dried at 70°C with a yield of 95%. Structural analysis using infrared and ultraviolet spectroscopy revealed similar results to those in Example 1.

[0060] Effect Examples

[0061] Example 1: OBMFA was insoluble in both methanol and water. An appropriate amount of this solid sample was placed in a reactor, and 30 ml of a 15% hydrochloric acid solution was added. Stirring at room temperature revealed that the solid did not dissolve. The reactor was sealed and heated to 150°C for 2 hours. Afterwards, the temperature was lowered to room temperature, the reactor was opened, and 60 ml of methanol was added. No solids were found in the liquid, indicating depolymerization of the solid material.

[0062] With the above-described preferred embodiments of the present invention as inspiration, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A biomass-based polyfuran polymer material, characterized by: The molecular structural formula of the polymer material is: ,in It is a skeleton carbon-carbon chain; the synthetic raw materials of the polymer material are bis-(5-formylfurfuryl) ether and ketone; the molecular weight of the polymer material is 1000-1 million.

2. A method for preparing a biomass-based polyfuran polymer material according to any one of claim 1, characterized in that: The method comprises the following steps: placing bis-(5-formylfurfuryl) ether and ketone in a solvent, heating and reacting under the action of a catalyst, washing and drying, and obtaining a biomass-based polyfuran polymer material.

3. The method for preparing the biomass-based polyfuran polymer material according to claim 2, wherein: The ketone includes one or more of monoketone, diketone and polyketone; The monoketone includes acetone and cyclohexanone; The diketones include diacetyl, hexanedione, and pentanedione; The polyketone is a compound having 4 or more carbon atoms and 3 or more carbonyl groups.

4. The method for preparing the biomass-based polyfuran polymer material according to claim 2, wherein: The catalyst includes one or more of a base catalyst, a metal oxide catalyst or a metal salt catalyst; The base catalyst includes an inorganic base; the inorganic base includes one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate; The metal oxide catalyst includes one or more of titanium oxide, vanadium oxide, cerium oxide, zirconium oxide, and tungsten oxide; The metal salt catalyst includes one or both of vanadium chloride and chromium chloride.

5. The method for preparing the biomass-based polyfuran polymer material according to claim 2, wherein: The molar ratio of the bis-(5-formylfurfuryl) ether to the ketone is less than 1.

5.

6. The method for preparing the biomass-based polyfuran polymer material according to claim 2, wherein: The temperature of the heating reaction is less than or equal to 250 degrees Celsius; and the reaction time is between 0.5h and 600h.

7. The method for preparing the biomass-based polyfuran polymer material according to claim 2, wherein: The reaction solvent is one or both of water and an organic solvent; the organic solvent includes alcohols, acetonitrile, ketones, halogenated alkanes, esters, and ethers.

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