A method for preparing a bio-based polyarylate
High-performance, low-toxicity, and sustainable bio-based polyarylates were prepared by interfacial polycondensation reaction of bisguaiacol and 2,5-furandicarboxylic acid chloride. This solved the safety and non-renewability problems of traditional petroleum-based monomers, and enabled the preparation and widespread application of high-performance polyarylates.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- MODERN TEXTILE TECH INNOVATION CENT (JIANHU LAB)
- Filing Date
- 2026-03-20
- Publication Date
- 2026-06-30
AI Technical Summary
The petroleum-based monomers used in the preparation of existing polyarylates, such as bisphenol A, have safety and non-renewable issues, making them difficult to apply to food contact products and medical implants. Furthermore, traditional methods for preparing bio-based polyarylates do not involve the reaction of bio-based bisphenols and furanyl chloride as monomers.
Bio-based polyarylates were prepared by interfacial polycondensation reaction using guaiacol and 2,5-furandicarboxylic acid chloride as raw materials. An oil-water interface reaction was formed by alkaline aqueous solution and organic solvent to generate polyarylate solid particles. Subsequent washing and drying yielded a white powder product.
The prepared bio-based polyarylates have high glass transition temperatures, excellent heat resistance and mechanical properties, and are safe and sustainable, making them suitable for fields such as electronics, food packaging, and medical devices.
Abstract
Description
Technical Field
[0001] This application relates to a method for preparing a bio-based polyarylate, belonging to the field of high-performance polymer technology. Background Technology
[0002] Polyarylates are a class of high-performance engineering plastics with excellent thermal stability, mechanical properties, light transmittance, and chemical corrosion resistance, and are widely used in electronics, automotive manufacturing, optical devices, and medical devices. Traditional polyarylate preparation mainly uses petroleum-based raw materials for extrusion, with bisphenol A (4,4'-dihydroxydiphenylpropane) and terephthaloyl chloride as core monomers. However, bisphenol A has endocrine-disrupting properties and poses potential hazards to human health and the environment. Furthermore, monomers such as terephthaloyl chloride rely on non-renewable petroleum resources. Therefore, polyarylates prepared from these monomers have safety issues and cannot be used in food contact products, medical implants, and other similar products.
[0003] Given the aforementioned safety concerns and non-renewable nature of these substances, a series of biomass-based diphenols have been developed in recent years, such as isosorbide, carvacrol, 4,4'-methylenebis(5-isopropyl-2-methylphenol), bio-based biphenyl, and 2,5-furandicarboxylic acid chloride (FDCA). For example, CN102796250A discloses a bio-based polyarylate and its preparation method, which involves esterifying 2,5-furandicarboxylic acid chloride with bisphenolic acid or bisphenolic ester under the catalysis of an esterifying enzyme, followed by polycondensation of the esterified product under the catalysis of a heteropolyacid salt to obtain the bio-based polyarylate. CN118812829A introduces bio-based furandicarboxylic acid chloride into a liquid crystal polyester, resulting in a bio-based liquid crystal polyarylate with a low melting point, high glass transition temperature, high mechanical strength, and good gas barrier properties. However, none of the aforementioned literature addresses the preparation of polyarylates using bio-based bisphenol and furandicarboxylic acid chloride as monomers. Summary of the Invention
[0004] In view of this, this application first provides a method for preparing bio-based polyarylates, which can achieve the preparation of high-performance, low-toxicity, sustainable, environmentally friendly, and mechanically excellent polyarylates with high safety.
[0005] Specifically, this application is implemented through the following scheme: A method for preparing a bio-based polyarylate, comprising the following steps: Step 1: Dissolve guaiacol in an alkaline aqueous solution to obtain an aqueous phase system; Step 2: Dissolve 2,5-furandicarboxylic acid chloride in an organic solvent to obtain an oil phase system; Step 3: Under stirring, the oil phase system is slowly added to the aqueous phase system. The reaction temperature and time are controlled to complete the interfacial reaction. During the reaction, the monomer undergoes a condensation reaction at the oil-water interface, and the generated polyarylate precipitates out in the form of solid particles. After the reaction is completed, stirring is stopped, the mixture is allowed to stand and separate into layers, the solid products are filtered and separated, and then washed and dried to obtain a white powder product, which is the bio-based polyarylate.
[0006] The bio-based polyarylates prepared by the above method have a glass transition temperature of 120~180 ℃, a number average molecular weight of 30000~80000 g / mol, and a tensile strength of 60~90 MPa. They have excellent heat resistance and mechanical properties, and do not contain bisphenol A, thus meeting the requirements for green, environmentally friendly, and safe applications.
[0007] Furthermore, as a preferred option: In step one, The alkaline aqueous solution is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, and the molar ratio of guaiacol to sodium hydroxide or potassium hydroxide is 1:2 to 2.2. In this case, the preparation process of the aqueous phase system in step one can be specifically set as follows: Guaifenesin, sodium hydroxide, or potassium hydroxide are taken at a molar ratio of 1:2 to 2.2 respectively; first, sodium hydroxide or potassium hydroxide is dissolved in deionized water to obtain an alkaline aqueous solution; then, guaiacol is added and stirred until completely dissolved to obtain a clear aqueous phase system.
[0008] The dissolution temperature is 20 ~ 40 ℃.
[0009] In the aqueous system, the concentration of guaiacol is 0.1 ~ 0.5 mol / L.
[0010] In step two, The organic solvent is at least one of dichloromethane, trichloromethane, 1,2-dichloroethane, and carbon tetrachloride.
[0011] In the oil phase system, the concentration of 2,5-furandicarboxylic acid chloride is 0.1 ~ 0.5 mol / L.
[0012] In step three, The molar ratio of guaiacol in the aqueous phase system to 2,5-furandicarboxylic acid chloride in the oil phase system is 1:0.9~1.1.
[0013] The oil phase system is added to the aqueous phase system at a dropping rate of 1 to 5 mL / min.
[0014] The stirring speed is 200 ~ 800 r / min, the reaction temperature is 0 ~ 30 ℃, and the time is 0.5 ~ 3 h.
[0015] The washing process includes washing with deionized water, washing with dilute hydrochloric acid, and washing with anhydrous ethanol. The washing process includes at least one step, with the steps of washing with deionized water, washing with dilute hydrochloric acid, and washing with anhydrous ethanol performed sequentially until the washing solution is neutral after washing.
[0016] The drying process is vacuum drying, with a drying temperature of 60-80℃ and a drying time of 12-24 hours.
[0017] The bio-based polyarylates prepared by the above method can be used in electronics, food packaging, medical devices, medium- and high-performance fibers, and environmentally friendly packaging materials.
[0018] Compared with the prior art, this application has the following advantages: 1) This application replaces traditional petroleum-based bisphenol monomers such as bisphenol A with renewable, estrogen-free guaiacol monomers, which has the dual advantages of safety and green sustainability, reducing biotoxicity and environmental risks; while furan-dicarboxylic chloride has better bio-based environmental friendliness. The two achieve interfacial reaction in different phases to realize the preparation of high-performance, low-toxicity bio-based polyarylates.
[0019] 2) The preparation conditions of this application are mild, and the preparation of polyarylates is basically completed at room temperature or medium and low temperature. Existing polyarylate synthesis equipment can be directly used for preparation without major modifications. The resulting product has a high molecular weight and glass transition temperature, which reduces the overall cost of product upgrade and modification. Detailed Implementation
[0020] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the technical solutions of this application will be further described in detail below with reference to specific examples in the embodiments of this application. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit the technical solutions of this application. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0021] Example 1
[0022] This embodiment provides a bio-based polyarylate, and the preparation process is as follows: Step 1: Weigh out bisguaiacol (i.e., 4,4'-dihydroxy-3,3'-dimethoxybiphenyl, C) in a 1:2 molar ratio. 14 H 14O4 (molecular weight 246.25) and sodium hydroxide were added. Sodium hydroxide was dissolved in deionized water to obtain an alkaline aqueous solution. Diguaiacol was added to the alkaline aqueous solution and stirred at 30 °C until completely dissolved to obtain a sodium guaiacol aqueous solution with a concentration of 0.1 mol / L.
[0023] Step 2: Weigh 2,5-furandicarboxylic acid chloride, dissolve it in dichloromethane, and stir until completely dissolved to obtain an oil phase solution with a concentration of 0.1 mol / L of 2,5-furandicarboxylic acid chloride.
[0024] Step 3: Add the sodium guaiacol obtained in the above steps to the reactor. Under a stirring rate of 200 r / min, add the oil phase solution obtained in Step 2 slowly dropwise to the reactor at a rate of 1 mL / min, with a feeding ratio of sodium guaiacol to oil phase solution of 1:1. After the addition is complete, carry out the interfacial polycondensation reaction at 0 °C for 3 h.
[0025] Step 4: Collect the solid product obtained in Step 3, wash it 3 times with deionized water, then wash it once with 0.1 mol / L dilute hydrochloric acid, and finally wash it twice with anhydrous ethanol. The washing solution was found to be neutral. Place the obtained product in a vacuum drying oven at 70 ℃ and dry it for 18 h to obtain the finished product.
[0026] Tests showed that the finished product obtained by the above method, namely bio-based polyarylate, has a number-average molecular weight of 35,000 g / mol, a tensile strength of 63 MPa, and a glass transition temperature of 133 ℃.
[0027] Example 2
[0028] This embodiment provides a bio-based polyarylate, and the preparation process is as follows: Step 1: Weigh out bisguaiacol (i.e., 4,4'-dihydroxy-3,3'-dimethoxybiphenyl, C) in a molar ratio of 1:2.05. 14 H 14 O4 (molecular weight 246.25) and potassium hydroxide were prepared. The potassium hydroxide was dissolved in deionized water to obtain an alkaline aqueous solution. Diguaiacol was added to the alkaline aqueous solution and stirred at 25 °C until completely dissolved to obtain a 0.2 mol / L potassium guaiacol aqueous solution.
[0029] Step 2: Weigh 2,5-furandicarboxylic acid chloride, dissolve it in chloroform, and stir until completely dissolved to obtain an oil phase solution with a concentration of 0.2 mol / L of 2,5-furandicarboxylic acid chloride.
[0030] Step 3: Add the potassium guaiacol aqueous solution obtained in the above steps to the reactor. Under a stirring rate of 300 r / min, add the oil phase solution obtained in Step 2 slowly dropwise to the reactor at a feeding ratio of 1:1 (potassium guaiacol aqueous solution to oil phase solution) at a rate of 2 mL / min. After the addition is complete, carry out the interfacial polycondensation reaction at 10 °C for 0.5 h.
[0031] Step 4: Collect the solid product obtained in Step 3, wash it 3 times with deionized water, then wash it once with 0.1 mol / L dilute hydrochloric acid, and finally wash it twice with anhydrous ethanol. The washing solution was found to be neutral. Place the obtained product in a vacuum drying oven at 70 ℃ and dry it for 18 h to obtain the finished product.
[0032] Tests showed that the finished product obtained by the above method, namely bio-based polyarylate, has a number-average molecular weight of 42,000 g / mol, a tensile strength of 65 MPa, and a glass transition temperature of 141 ℃.
[0033] Example 3
[0034] This embodiment provides a bio-based polyarylate, and the preparation process is as follows: Step 1: Weigh out bisguaiacol (i.e., 4,4'-dihydroxy-3,3'-dimethoxybiphenyl, C) in a molar ratio of 1:2.1. 14 H 14 O4 (molecular weight 246.25) and sodium hydroxide were added. Sodium hydroxide was dissolved in deionized water to obtain an alkaline aqueous solution. Diguaiacol was added to the alkaline aqueous solution and stirred at 35 °C until completely dissolved to obtain a sodium guaiacol aqueous solution with a concentration of 0.3 mol / L.
[0035] Step 2: Weigh 2,5-furandicarboxylic acid chloride and dissolve it in 1,2-dichloroethane. Stir until completely dissolved to obtain an oil phase solution with a concentration of 0.3 mol / L for 2,5-furandicarboxylic acid chloride.
[0036] Step 3: Add the sodium guaiacol obtained in the above steps to the reactor. Under a stirring rate of 400 r / min, add the oil phase solution obtained in Step 2 slowly dropwise to the reactor at a volume ratio of 1:1 (sodium guaiacol aqueous solution to oil phase solution) at a rate of 3 mL / min. After the addition is complete, carry out the interfacial polycondensation reaction at 20 °C for 1.5 h.
[0037] Step 4: Collect the solid product obtained in Step 3, wash it 3 times with deionized water, then wash it once with 0.1 mol / L dilute hydrochloric acid, and finally wash it twice with anhydrous ethanol. The washing solution was found to be neutral. Place the obtained product in a vacuum drying oven at 70 ℃ and dry it for 18 h to obtain the finished product.
[0038] Tests showed that the finished product obtained by the above method, namely bio-based polyarylate, has a number-average molecular weight of 58,000 g / mol, a tensile strength of 72 MPa, and a glass transition temperature of 152 ℃.
[0039] Example 4
[0040] This embodiment provides a bio-based polyarylate, and the preparation process is as follows: Step 1: Weigh out bisguaiacol (i.e., 4,4'-dihydroxy-3,3'-dimethoxybiphenyl, C) in a molar ratio of 1:2.15. 14 H 14 O4 (molecular weight 246.25) and potassium hydroxide were prepared. The potassium hydroxide was dissolved in deionized water to obtain an alkaline aqueous solution. Diguaiacol was added to the alkaline aqueous solution and stirred at 35 °C until completely dissolved to obtain a 0.4 mol / L potassium guaiacol aqueous solution.
[0041] Step 2: Weigh 2,5-furandicarboxylic acid chloride, dissolve it in carbon tetrachloride, and stir until completely dissolved to obtain an oil phase solution with a concentration of 0.4 mol / L for 2,5-furandicarboxylic acid chloride.
[0042] Step 3: Add the potassium guaiacol aqueous solution obtained in the above steps to the reactor. Under a stirring rate of 500 r / min, add the oil phase solution obtained in Step 2 slowly dropwise to the reactor at a feeding ratio of 1:1 (potassium guaiacol aqueous solution to oil phase solution) at a rate of 4 mL / min. After the addition is complete, carry out the interfacial polycondensation reaction at 30 °C for 2.5 h.
[0043] Step 4: Collect the solid product obtained in Step 3, wash it 3 times with deionized water, then wash it once with 0.1 mol / L dilute hydrochloric acid, and finally wash it twice with anhydrous ethanol. The washing solution was found to be neutral. Place the obtained product in a vacuum drying oven at 70 ℃ and dry it for 18 h to obtain the finished product.
[0044] Tests showed that the finished product obtained by the above method, namely bio-based polyarylate, has a number-average molecular weight of 69,000 g / mol, a tensile strength of 78 MPa, and a glass transition temperature of 159 ℃.
[0045] Example 5
[0046] This embodiment provides a bio-based polyarylate, and the preparation process is as follows: Step 1: Weigh out bisguaiacol (i.e., 4,4'-dihydroxy-3,3'-dimethoxybiphenyl, C) in a molar ratio of 1:2.2. 14 H 14O4 (molecular weight 246.25) and sodium hydroxide were added. Sodium hydroxide was dissolved in deionized water to obtain an alkaline aqueous solution. Diguaiacol was added to the alkaline aqueous solution and stirred at 30 °C until completely dissolved to obtain a sodium guaiacol aqueous solution with a concentration of 0.5 mol / L.
[0047] Step 2: Weigh 2,5-furandicarboxylic acid chloride, dissolve it in dichloromethane, and stir until completely dissolved to obtain an oil phase solution with a concentration of 0.1 mol / L of 2,5-furandicarboxylic acid chloride.
[0048] Step 3: Add the sodium guaiacol obtained in the above steps to the reactor. Under a stirring rate of 600 r / min, add the oil phase solution obtained in Step 2 slowly dropwise to the reactor at a feeding ratio of 1:1 (sodium guaiacol aqueous solution to oil phase solution) at a rate of 5 mL / min. After the addition is complete, carry out the interfacial polycondensation reaction at 0 °C for 2 h.
[0049] Step 4: Collect the solid product obtained in Step 3, wash it 3 times with deionized water, then wash it once with 0.1 mol / L dilute hydrochloric acid, and finally wash it twice with anhydrous ethanol. The washing solution was found to be neutral. Place the obtained product in a vacuum drying oven at 70 ℃ and dry it for 18 h to obtain the finished product.
[0050] Tests showed that the finished product obtained by the above method, namely bio-based polyarylate, has a number-average molecular weight of 75,000 g / mol, a tensile strength of 83 MPa, and a glass transition temperature of 173 ℃.
[0051] Example 6
[0052] This embodiment provides a bio-based polyarylate, and the preparation process is as follows: Step 1: Weigh out bisguaiacol (i.e., 4,4'-dihydroxy-3,3'-dimethoxybiphenyl, C) in a molar ratio of 1:2.2. 14 H 14 O4 (molecular weight 246.25) and potassium hydroxide were prepared. The potassium hydroxide was dissolved in deionized water to obtain an alkaline aqueous solution. Diguaiacol was added to the alkaline aqueous solution and stirred at 25 °C until completely dissolved to obtain a 0.4 mol / L potassium guaiacol aqueous solution.
[0053] Step 2: Weigh 2,5-furandicarboxylic acid chloride, dissolve it in chloroform, and stir until completely dissolved to obtain an oil phase solution with a concentration of 0.25 mol / L of 2,5-furandicarboxylic acid chloride.
[0054] Step 3: Add the potassium guaiacol aqueous solution obtained in the above steps to the reactor. Under a stirring rate of 800 r / min, add the oil phase solution obtained in Step 2 slowly dropwise to the reactor at a feeding ratio of 1:1 (potassium guaiacol aqueous solution to oil phase solution) at a rate of 4 mL / min. After the addition is complete, carry out the interfacial polycondensation reaction at 10 °C for 2.5 h.
[0055] Step 4: Collect the solid product obtained in Step 3, wash it 3 times with deionized water, then wash it once with 0.1 mol / L dilute hydrochloric acid, and finally wash it twice with anhydrous ethanol. The washing solution was found to be neutral. Place the obtained product in a vacuum drying oven at 70 ℃ and dry it for 18 h to obtain the finished product.
[0056] Tests showed that the finished product obtained by the above method, namely bio-based polyarylate, has a number-average molecular weight of 62,000 g / mol, a tensile strength of 75 MPa, and a glass transition temperature of 158 ℃.
[0057] Comparative Example 1
[0058] CN121226692A is used as Comparative Example 1. In Example 4, an aqueous phase was obtained by bisphenol A, sodium hydroxide aqueous solution, and triethylbenzylammonium chloride, and an organic phase was obtained by terephthaloyl chloride, isophthaloyl chloride, and dichloromethane. The aqueous phase and organic phase reacted at the interface and precipitated to obtain polyarylate.
[0059] The polyarylate obtained in Comparative Example 1 lacks sufficient biocompatibility, containing bisphenol A which has endocrine-disrupting properties, and the raw materials are non-renewable, lack bio-based properties, and have poor environmental performance. In contrast, the interfacial polycondensation reaction between potassium guaiacol aqueous solution and oil-phase solvent in this application not only boasts high biocompatibility and green, renewable raw materials, achieving a balance between performance and environmental friendliness, but also endows the finished product with higher overall application value in terms of tensile strength and glass transition temperature.
[0060] Comparative Example 2
[0061] Using CN102796250A as Comparative Example 2, 2,5-furandicarboxylic acid was esterified with bisphenolic acid or bisphenolic ester under the catalysis of esterification enzyme, and then the esterified product was subjected to polycondensation reaction under the catalysis of heteropoly acid salt to obtain heat-resistant bio-based polyarylate.
[0062] The polyarylate obtained in Comparative Example 2 suffers from drawbacks such as insufficient safety due to the presence of bisphenol A in the monomer, complex and demanding preparation process, and significant challenges in industrial production. In contrast, the interfacial polycondensation reaction between potassium guaiacol aqueous solution and oil-phase solvent in this application exhibits superior biosafety, a simpler and milder preparation process, and is more readily achievable for industrial production.
[0063] The above-mentioned scheme in this application uses guaiacol and 2,5-furandicarboxylic acid chloride as raw materials for interfacial polycondensation reaction. Guaifenesin itself has the characteristics of sustainability and green and safe sources. Combined with the effects of the finished product, it can be seen that this method can replace bisphenol A in the preparation of polyarylates without the non-renewable and safety issues of bisphenol A. Under a specific ratio of guaiacol monomers to 2,5-furandicarboxylic acid chloride, the prepared polyarylates have a high number-average molecular weight of over 35,000 g / mol and a tensile strength of over 63 MPa, giving the polyarylates good mechanical properties. Their glass transition temperature remains above 133℃, and they exhibit good thermal stability. Applying them to materials that come into direct contact with food, such as food packaging films, or to heat-sensitive or heat-generating devices such as electronic appliance casings, demonstrates excellent practicality and application effects.
[0064] The above-described embodiments are merely illustrative of several feasible implementations of the present invention, and their descriptions are relatively specific and detailed. However, they should not be construed as limiting the scope of the present invention, nor are the embodiments intended to limit the scope of protection in the claims of the present invention. For those skilled in the art, various modifications and improvements can be made without departing from the concept of the present invention. All equivalent implementations or changes that do not depart from the present invention should be included in the technology of the present invention.
Claims
1. A method for preparing a bio-based polyarylate, characterized in that, The steps are as follows: Step 1: Dissolve guaiacol in an alkaline aqueous solution to obtain an aqueous phase system; Step 2: Dissolve 2,5-furandicarboxylic acid chloride in an organic solvent to obtain an oil phase system; Step 3: Under stirring, the oil phase system is slowly added to the aqueous phase system. The reaction temperature and time are controlled. After the interfacial reaction is completed, the mixture is separated, washed, and dried to obtain a bio-based polyarylate with a glass transition temperature of 120-180 °C, a number-average molecular weight of 30,000-80,000 g / mol, and a tensile strength of 60-90 MPa.
2. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: In step one, the dissolution temperature is 20 ~ 40 ℃.
3. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: In the aqueous system, the concentration of guaiacol is 0.1 ~ 0.5 mol / L.
4. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: The alkaline aqueous solution is an aqueous solution of sodium hydroxide or potassium hydroxide, and the molar ratio of guaiacol to sodium hydroxide or potassium hydroxide is 1:2 to 2.
2.
5. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: In the oil phase system, the concentration of 2,5-furandicarboxylic acid chloride is 0.1 ~ 0.5 mol / L.
6. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: In step three, the molar ratio of guaiacol in the aqueous phase system to 2,5-furandicarboxylic acid chloride in the oil phase system is 1:0.9 ~ 1.
1.
7. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: The organic solvent is at least one of dichloromethane, trichloromethane, 1,2-dichloroethane, and carbon tetrachloride.
8. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: In step three, the stirring speed is 200 ~ 800 r / min, the reaction temperature is 0 ~ 30 ℃, and the time is 0.5 ~ 3 h.
9. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: In step three, the oil phase system is added to the aqueous phase system at a dropping rate of 1 to 5 mL / min.
10. The method for preparing a bio-based polyarylate according to claim 1, characterized in that: In step three, the washing process includes washing with deionized water, washing with dilute hydrochloric acid, and washing with anhydrous ethanol in sequence. The washing process includes at least one step until the washing solution is neutral after washing.