Preparation method of equol-based biomass polyarylester

Abstract

The invention provides a preparation method of equol-based biomass polyarylester, and relates to the technical field of high polymer material synthesis and application, and the preparation method comprises the following steps: (1) water phase preparation, (2) oil phase preparation, (3) interfacial polymerization, and (4) post-treatment. Biomass 2, 5-furandicarboxylic acid and equol are taken as raw materials, efficient preparation of biomass equol-based polyarylester with high viscosity (1.5-3.0 dL / g), high glass transition temperature (higher than 230 DEG C) and high light transmittance (higher than 80%) is realized by adopting an interfacial polycondensation method, dependence of non-renewable petrochemical resources is reduced, carbon footprint is reduced, and meanwhile, the biomass equol-based polyarylester has the advantages of high yield, high yield and high quality. And comprehensive replacement of commercially available petroleum-based U-100 polyarylester is expected to be realized, and the method has far-reaching significance for reconstructing an energy supply system in China and constructing a green and low-carbon society.

Description

Technical Field

[0001] The present invention belongs to the technical field of synthesis and application of polymer materials, and particularly relates to a preparation method of equol-based biomass polyarylates. Background Art

[0002] Polyarylates are a class of thermoplastic polymers containing aromatic ring structures and ester bond structures. The main feature is that the polymer main chain structure is almost entirely composed of aromatic rings connected by ester bonds, having advantages such as high heat resistance, low dielectric constant, and high strength, and being widely used in the fields of aerospace, automotive lightweighting, electronics and electricity, etc.

[0003] According to the molecular structure differences, polyarylates can be divided into fully aromatic type (Vectra) and semi-aromatic type (U-100). The main manufacturers are DuPont Company in the United States and Celanese Corporation in the United States. Petroleum-based chemical monomers such as terephthaloyl chloride, bisphenol A, biphenol, and p-hydroxybenzoic acid can be used, and they can be prepared by methods such as melt polycondensation method, solution polycondensation method, and interfacial polycondensation method. With the global awareness of the shortage of petrochemical resources and sustainable development increasing, preparing biomass polyarylates using biomass renewable resources as raw materials has become an important measure to reduce the dependence on fossil resources.

[0004] Patents with publication numbers CN106519200A and CN119798628A have successively disclosed the preparation methods of furyl semi-biomass polyarylates, providing feasible solutions for the research and development of biomass polyarylate materials. However, the above patents still use petrochemical resources such as bisphenol A and terephthalic acid as raw materials to prepare polyarylates, and the preparation of fully biomass polyarylates has not been achieved.

[0005] The chemical name of equol is 7-hydroxy-3-(4-hydroxyphenyl)-chroman, which belongs to non-steroidal hormones. The molecule is composed of C14H15O3 ( Figure 1),(heterocyclic structure) contains two reactive hydroxyl groups and a relatively inert oxygen in its central pyran ring, and can be prepared by chemical synthesis (Bioorganic & Medicinal Chemistry, 2004, 12(6): 1559-1567.), microbial preparation (Journal of Food Processing and Preservation, 2019, 43(11): e14205.), and biosynthesis (Applied and Environmental Microbiology, 2013, 79(11): 3494-3502.). In recent years, researchers have focused on studying the pathways of equol production by natural microbial metabolism, and have successively isolated strains related to equol metabolism from the feces of animals such as humans, mice, monkeys, and pigs, such as Asaccharobacter celatus, Adlercreutziae - quolifaciens, Slackia isoflavoniconvertens, Enterorhabdus mucosicola. Some researchers have also achieved the preparation of low-cost equol from biomass resources such as soybeans and kudzu root through separation, purification, fermentation and other means, providing broad prospects for large-scale industrial production of equol. The research and development of its downstream derivatives has also become a key issue that needs to be solved urgently.

[0006] The molecular structure of equol is as follows:

[0007] Based on this, the present invention uses biomass 2,5-furandicarbonyl chloride and equol as raw materials, and prepares biomass polyarylate by interfacial polycondensation. Utilizing the high rigidity and asymmetric structure of the furan ring and pyran ring, the applicable range of biomass polyarylate can be expanded, and the light transmittance can be improved, which is expected to replace the traditional commercially available petroleum-based U-100 polyarylate in the applications such as display screens, smart wearables, and car headlight components.

[0008] The successful implementation of this patent can reduce the application of non-renewable fossil resources in the field of high-performance materials, and at the same time further improve some properties of traditional petroleum-based polyarylate, which is of great significance for expanding the multi-scenario applications of polyarylate. Summary of the Invention

[0009] In view of the unsustainability in the production of the above-mentioned high-performance polyarylate polymer materials and the contradiction between the glass transition temperature and the light transmittance, this application discloses an equol-based biomass polyester and its preparation method. Based on the high molecular rigidity and asymmetric structure of the furan ring and pyran ring, and by using the interfacial polycondensation technology, the preparation of biomass polyarylate polymer materials with high viscosity, high glass transition temperature and high light transmittance is realized, which is expected to replace petroleum-based polyarylates such as U-100 in the applications of high-end displays, optical lenses, automotive lamp covers, etc., and is of great significance for promoting the sustainable development of our country.

[0010] The present invention provides an equol-based biomass polyarylate and its preparation method, and the specific method is as follows: (1) Aqueous phase: Dissolve a certain mass of equol and sodium hydroxide in water. After the solution becomes clear and transparent, cool the reaction system to 0-20°C, and add 0.01-1 wt% of a phase transfer catalyst, and stir for 0.5-3 h; (2) Organic phase: Dissolve a certain mass of 2,5-furandicarbonyl chloride in dichloromethane, and stir at room temperature until it becomes clear and transparent; (3) Interfacial polymerization: Slowly drop the organic phase into the aqueous phase at a rate of 0.01-2 g / min, and react for 0.1-10 h at 20-40°C under strong stirring; (4) Post-treatment: After the reaction is completed, adjust the pH of the organic phase to 2-5 with dilute hydrochloric acid, and precipitate with a poor solvent of the product. The precipitated solid is washed repeatedly with water until it is neutral, and then dried to obtain the equol-based polyarylate.

[0011] Further, the molar ratio of equol to sodium hydroxide in the aqueous phase is 1:1-8, and the mass ratio of equol to water is 1:8-15; Further, the mass ratio of 2,5-furandicarbonyl chloride to dichloromethane in the organic phase is 1:5-12; Further, the phase transfer catalyst includes one or more of polyethylene glycol, cyclodextrin, triethylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, pyridine, tributylamine, tetramethylammonium hydroxide, didodecyldimethylammonium chloride, dioctyldimethylammonium bromide; Further, in the aqueous phase, the dosage of the phase transfer catalyst is 0.01-0.3 wt% of the equol addition amount, the stirring time is 0.5-1 h, and the reaction system temperature is 0-10°C; Further, in the interfacial polymerization, the dropping rate of the organic phase is 0.01-0.3 g / min, the reaction temperature is 25-35°C, and the reaction time after the dropping is completed is 1-5 h; Further, in the interfacial polymerization, the stirring rate is 200-600 rpm; Further, in the post-treatment, the pH of the organic phase is adjusted to 3 with dilute hydrochloric acid, and the poor solvent for the product is one or two of methanol, ethanol, and acetone; Further, in the post-treatment, the number of water washing times does not exceed 3 times; Further, in the post-treatment, drying is carried out in a forced-air oven at 120 °C for 2 h to obtain polyarylate in an absolutely dry state; Further, in the interfacial polymerization, the stirring rate is not less than 300 rpm. Beneficial effects

[0012] Using biomass 2,5-furandicarboxylic acid and equol as raw materials, high-viscosity (1.5 - 3.0 dL / g), high glass transition temperature (>230 °C), and high light transmittance (>80%) biomass equol-based polyarylate was efficiently prepared by interfacial polycondensation method. While reducing the dependence on non-renewable petrochemical resources and reducing the carbon footprint, it is also expected to fully replace commercially available petroleum-based U-100 polyarylate, which has far-reaching significance for reconstructing China's energy supply system and building a green and low-carbon society. Brief description of the drawings

[0013] Figure 1 Shows the molecular structure of the biomass equol-based polyarylate obtained in the preparation process of Example 1 in the present invention. Detailed implementation manners

[0014] The present invention will be further described below with reference to the drawings and examples.

[0015] Intrinsic viscosity: 0.2 g of the product is dissolved in 20 mL of pentafluorophenol solution, and it is measured in a 25 °C water bath by the one-point method. The calculation formula for intrinsic viscosity is: ; ; ; The relationship is: : Relative viscosity, : Specific viscosity, : Solvent efflux time, : Efflux time of polymer solution, : Concentration of polymer solution; In the examples, the glass transition temperature is characterized according to GB / T19466.2 - 2004; In the examples, the light transmittance is characterized according to ISO13468.1 - 2019. Examples

[0016] (1) Aqueous phase: Dissolve equol (24.2 g, 0.1 mol) and sodium hydroxide (12.0 g, 0.3 mol) in 200 mL of water. After the solution becomes clear and transparent, cool the reaction system to 3 °C, and add 0.02 g of triethylbenzylammonium chloride, then stir for 1 h; (2) Organic phase: Dissolve 2,5-furandicarbonyl chloride (19.3 g, 0.1 mol) in 120 mL of dichloromethane, and stir at room temperature until clear and transparent; (3) Interfacial polymerization: Slowly add the organic phase dropwise to the aqueous phase at a rate of 1 g / min, and react at 28 °C with a rotation speed of 500 rmp for 4 h; (4) Post-treatment: After the reaction is completed, adjust the pH of the organic phase to 3 with dilute hydrochloric acid, and precipitate with methanol. The precipitated solid is washed repeatedly with water until neutral, and finally the solid obtained by filtration is dried in a forced-air oven at 120 °C for 2 h to obtain the biomass equol-based polyarylate.

[0017] After testing, the intrinsic viscosity of the obtained product is 2.76 dL / g, the glass transition temperature is 237 °C, and the light transmittance is 84%. Example

[0018] (1) Aqueous phase: Dissolve equol (24.2 g, 0.1 mol) and sodium hydroxide (12.0 g, 0.3 mol) in 200 mL of water. After the solution becomes clear and transparent, cool the reaction system to 1 °C, and add 0.03 g of triethylbenzylammonium chloride, then stir for 1 h; (2) Organic phase: Dissolve 2,5-furandicarbonyl chloride (19.3 g, 0.1 mol) in 120 mL of dichloromethane, and stir at room temperature until clear and transparent; (3) Interfacial polymerization: Slowly add the organic phase dropwise to the aqueous phase at a rate of 1 g / min, and react at 32 °C with a rotation speed of 600 rmp for 5 h; (4) Post-treatment: After the reaction is completed, adjust the pH of the organic phase to 3 with dilute hydrochloric acid, and precipitate with methanol. The precipitated solid is washed repeatedly with water until neutral, and finally the solid obtained by filtration is dried in a forced-air oven at 120 °C for 2 h to obtain the biomass equol-based polyarylate.

[0019] After testing, the intrinsic viscosity of the obtained product is 2.94 dL / g, the glass transition temperature is 238 °C, and the light transmittance is 82%. Example

[0020] (1) Aqueous phase: Dissolve equol (24.2 g, 0.1 mol) and sodium hydroxide (12.0 g, 0.3 mol) in 200 mL of water. After the solution becomes clear and transparent, cool the reaction system to 3 °C, and add 0.02 g of triethylbenzylammonium chloride, then stir for 1 h; (2) Oil phase: Dissolve 2,5-furandicarbonyl chloride (19.3 g, 0.1 mol) in 120 mL of dichloromethane, and stir at room temperature until it becomes clear and transparent. (3) Interfacial polymerization: Slowly add the oil phase to the aqueous phase at a rate of 0.5 g / min, and react at 28 °C with a rotation speed of 500 rmp for 4 h. (4) Post-treatment: After the reaction, adjust the pH of the organic phase to 3 with dilute hydrochloric acid, precipitate with methanol, wash the precipitated solid repeatedly with water until neutral, and finally dry the solid obtained by filtration in a forced-air oven at 120 °C for 2 h to obtain biomass equol-based polyarylate.

[0021] After testing, the intrinsic viscosity of the obtained product is 2.88 dL / g, the glass transition temperature is 237 °C, and the light transmittance is 85%.

[0022] Comparative Example 1 (1) Aqueous phase: Dissolve bisphenol A (22.8 g, 0.1 mol) and sodium hydroxide (12.0 g, 0.3 mol) in 200 mL of water. After the solution becomes clear and transparent, cool the reaction system to 3 °C, and add 0.02 g of triethylbenzylammonium chloride, and stir for 1 h. (2) Oil phase: Dissolve 2,5-furandicarbonyl chloride (19.3 g, 0.1 mol) in 120 mL of dichloromethane, and stir at room temperature until it becomes clear and transparent. (3) Interfacial polymerization: Slowly add the oil phase to the aqueous phase at a rate of 1 g / min, and react at 28 °C with a rotation speed of 500 rmp for 4 h. (4) Post-treatment: After the reaction, adjust the pH of the organic phase to 3 with dilute hydrochloric acid, precipitate with methanol, wash the precipitated solid repeatedly with water until neutral, and finally dry the solid obtained by filtration in a forced-air oven at 120 °C for 2 h to obtain biomass equol-based polyarylate.

[0023] After testing, the intrinsic viscosity of the obtained product is 2.48 dL / g, the glass transition temperature is 216 °C, and the light transmittance is 71%.

[0024] Comparative Example 2: Use U-100 produced by the commercially available Japanese Unitika Ltd. as the raw material and test it.

[0025] After testing, the intrinsic viscosity of the obtained product is 2.33 dL / g, the glass transition temperature is 195 °C, and the light transmittance is 68%.

[0026] Table 1 Performance summary of biomass equol-based polyarylate Intrinsic viscosity (dL / g) Glass transition temperature (°C) Light transmittance (%) Example 1 2.76 237 84 Example 2 2.94 238 82 Example 3 2.88 237 85 Comparative Example 1 2.48 216 71 Comparative Example 2 2.33 195 68 Result analysis: As can be seen from Table 1, comparing Examples 1 to 3 with Comparative Example 1: Compared with the semi-biomass furanyl polyarylate, under the dual action of the furan ring and the pyran ring, the glass transition temperature and light transmittance of the product obtained from the biomass equol-based polyarylate of the present invention are both significantly improved, and the raw materials are all derived from renewable resources; comparing Example 1 with Comparative Example 2: Compared with U-100 produced by the commercially available Japanese Unitika Ltd., in addition to the raw materials being of biomass origin, the intrinsic viscosity of the biomass equol-based polyarylate of the present invention is increased by 18.4%, the glass transition temperature is increased by 21.5%, and the light transmittance is increased by 23.5%.

[0027] Although the specific embodiments of the present invention have been described above in conjunction with the accompanying drawings, it is not a limitation to the protection scope of the present invention. Those skilled in the art should understand that, based on the technical solutions of the present invention, various modifications or deformations that can be made by those skilled in the art without creative efforts are still within the protection scope of the present invention.

Claims

1. A preparation method of equol-based biomass polyarylate, characterized in that, It includes the following steps: (1) Aqueous phase: Dissolve a certain mass of equol and sodium hydroxide in water. After the solution becomes clear and transparent, cool the reaction system to 0 - 20 °C, and add a phase transfer catalyst of 0.01 - 1 wt%, and stir for 0.5 - 3 h; (2) Organic phase: Dissolve a certain mass of 2,5-furandicarbonyl chloride in dichloromethane, and stir at room temperature until it becomes clear and transparent; (3) Interfacial polymerization: Slowly add the organic phase to the aqueous phase at a rate of 0.01 - 2 g / min. Under strong stirring, react at 20 - 40 °C for 0.1 - 10 h; (4) Post-treatment: After the reaction is completed, adjust the pH of the organic phase to 2 - 5 with dilute hydrochloric acid, and precipitate with a poor solvent of the product. The precipitated solid is washed repeatedly with water until neutral, and then dried to obtain equol-based polyarylate.

2. The preparation method of equol-based biomass polyarylate according to claim 1, characterized in that, In the aqueous phase, the molar ratio of equol to sodium hydroxide is 1:1 - 8, and the mass ratio of equol to water is 1:8 - 15.

3. The preparation method of equol-based biomass polyarylate according to claim 1, characterized in that, In the organic phase, the mass ratio of 2,5-furandicarbonyl chloride to dichloromethane is 1:5 - 12.

4. The preparation method of equol-based biomass polyarylate according to claim 1, characterized in that, The phase transfer catalyst includes one or several of polyethylene glycol, cyclodextrin, triethylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, pyridine, tributylamine, tetramethylammonium hydroxide, didodecyldimethylammonium chloride, dioctyldimethylammonium bromide.

5. The preparation method of the equol-based biomass polyarylate according to claim 1, wherein In the aqueous phase, the dosage of the phase transfer catalyst is 0.01 - 0.3 wt% of the equol addition amount, the stirring time is 0.5 - 1 h, and the reaction system temperature is 0 - 10 °C.

6. The preparation method of the equol-based biomass polyarylate according to claim 1, characterized in that, In the interfacial polymerization, the dropping rate of the organic phase is 0.01 - 0.3 g / min, the reaction temperature is 25 - 35 °C, and the reaction time after the dropping is completed is 1 - 5 h.

7. The preparation method of equol-based biomass polyarylate according to claim 1, characterized in that, In the interfacial polymerization, the stirring rate is 200 - 600 rpm.

8. The preparation method of equol-based biomass polyarylate according to claim 1, characterized in that, In the post-treatment, adjust the pH of the organic phase to 3 with dilute hydrochloric acid, and the poor solvent of the product is 1 - 2 of methanol, ethanol, and acetone.

9. The preparation method of the equol-based biomass polyarylate according to claim 1, characterized in that, In the post-treatment, the number of water washing times does not exceed 3 times; dry in a forced-air oven at 120 °C for 2 h to obtain the completely dry polyarylate.

10. The preparation method of equol-based biomass polyarylate according to claim 1, characterized in that, In the interfacial polymerization, the stirring rate is not less than 300 rpm.

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