Polyfurandicarboxylic acid glycol ester resin and preparation method and application thereof
By using ethylene carbonate as an inhibitor in the preparation of poly(ethylene furanate dicarboxylate) resin and controlling its proportion in ethylene glycol, the problem of high acetaldehyde production was solved, and the separation and purification difficulty and energy consumption were reduced.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-23
- Publication Date
- 2026-03-27
AI Technical Summary
During the high-temperature esterification reaction of poly(ethylene furanate dicarboxylate) resin, the side reaction of ethylene glycol to acetaldehyde is severe, which increases the difficulty of purification and the production cost.
Ethylene carbonate was used as an inhibitor, and its proportion in ethylene glycol was controlled within the range of 0.05% to 0.6%, thereby reducing the amount of acetaldehyde generated through low-compression polymerization.
It effectively reduces acetaldehyde content, simplifies the separation and purification process, and reduces energy consumption and production costs.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of organic polymer compound technology, and in particular to a poly(ethylene furanate) resin, its preparation method, and its application. Background Technology
[0002] Polyethylene terephthalate (PEF) resin is a biodegradable plastic synthesized by the condensation polymerization of furanyl dicarboxylic acid (FDCA) and ethylene glycol. Its rigid furan rings in its molecular structure endow it with mechanical strength and thermal stability surpassing those of traditional petroleum-based plastic polyethylene terephthalate (PET). Using 2,5-furanyl dicarboxylic acid (FDCA) and ethylene glycol (EG), synthesized from renewable resources such as lignocellulose and corn, as key monomers, PEF exhibits low permeability to oxygen and carbon dioxide, giving it disruptive potential in the food packaging field and making it one of the best-performing biodegradable materials currently on the market.
[0003] However, during the high-temperature esterification reaction of poly(ethylene furanate dicarboxylate) resin (PEF) in a strongly acidic environment (in the presence of furanate dicarboxylic acid), ethylene glycol (EG) undergoes a strong side reaction, generating acetaldehyde (ACE) and water. The mixture of high-content ethylene glycol (EG), ACE, water, and other gases is extracted and condensed by a vacuum system and then needs to be centrally separated and purified by an EG recovery device to meet emission requirements. However, the higher the ACE content in this EG purification process, the greater the purification difficulty and energy consumption, which greatly increases production costs. Therefore, it is urgent to reduce the amount of acetaldehyde produced during the esterification process. Summary of the Invention
[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a poly(ethylene furanate) resin, its preparation method, and its application.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a method for preparing polyethylene furanate resin, comprising the following steps: S1. 2,5-furandicarboxylic acid, ethylene glycol, catalyst and inhibitor are mixed and esterified to obtain the esterified product; S2. The esterified product obtained in S1 is subjected to a low-compression polymerization reaction to obtain the polyurethane difuranate resin. The inhibitor is ethylene carbonate (CAS No.: 96-49-1). According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, in the mixture of ethylene glycol and inhibitor, the chromatographic peak area of the inhibitor is 0.05%~0.6% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0006] In the preparation method of polyethylene furanate dicarboxylate resin of the present invention, ethylene carbonate is used as an inhibitor, which can inhibit the generation of acetaldehyde, a byproduct, during the high-temperature esterification reaction of 2,5-furandicarboxylic acid and ethylene glycol, thereby reducing the acetaldehyde content and reducing the difficulty of separating and purifying polyethylene furanate dicarboxylate resin.
[0007] It should be noted that the present invention does not particularly limit the source of the inhibitor ethylene carbonate, which can be an impurity present in ethylene glycol or directly added ethylene carbonate. The present invention has found that as long as the chromatographic peak area of the inhibitor ethylene carbonate / (chromatographic peak area of the inhibitor ethylene carbonate + chromatographic peak area of ethylene glycol) meets the range defined by the present invention, it is acceptable.
[0008] Optionally, the ratio of the peak area of the inhibitor to (peak area of the inhibitor + peak area of the ethylene glycol) can be any one or any two of the following values: 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, and 0.6%.
[0009] The chromatographic peak area can be calculated using a gas chromatograph. The specific test method for the chromatographic peak area is as follows: Before the S1 esterification reaction, the inhibitor raw material is dissolved in ethylene glycol raw material and mixed. According to the GB / T14571.2-2018 standard, the peak area is calculated by gas chromatograph. The integral area of the chromatographic peak is the chromatographic peak area.
[0010] The chromatographic peak area of the inhibitor and its percentage of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol can be controlled by adjusting the dosage of the inhibitor.
[0011] In a preferred embodiment of the preparation method of the poly(ethylene furanate dicarboxylate) resin of the present invention, the chromatographic peak area of the inhibitor is 0.1% to 0.4% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0012] In a preferred embodiment of the preparation method of the poly(ethylene furanate dicarboxylate) resin of the present invention, the chromatographic peak area of the inhibitor is 0.2% to 0.3% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0013] In a preferred embodiment of the preparation method of the poly(ethylene furanate dicarboxylate) resin of the present invention, according to the GB / T14571.2-2018 standard, the retention time of ethylene glycol is 10.3~10.7 min, and the retention time of the inhibitor is 14.5~15.0 min.
[0014] In a preferred embodiment of the preparation method of the poly(ethylene furanate dicarboxylate) resin of the present invention, in step S1, the esterification reaction is as follows: the mixed components are heated to 200°C~220°C under a nitrogen atmosphere and reacted for 3h~5h.
[0015] In a preferred embodiment of the preparation method of the polyethylene furanate dicarboxylate resin of the present invention, step S2 specifically includes the following steps: within 30 minutes, the pressure of the reaction system is reduced to below 50 Pa, and the reaction is continued at 245℃~255℃ for 3.5h~5h until the intrinsic viscosity reaches 1.4 dL / g~1.6 dL / g, nitrogen gas is introduced, and the mixture is extruded and granulated to obtain the polyethylene furanate dicarboxylate resin.
[0016] In a preferred embodiment of the preparation method of the polyethylene furanate dicarboxylate resin of the present invention, in step S1, the catalyst includes at least one of tetrabutyl titanate and tetraisopropyl titanate. In practical applications, the amount of catalyst can be 10 to 5000 ppm of the theoretical yield weight of the polyethylene furanate dicarboxylate resin.
[0017] Secondly, the present invention provides a method for preparing the poly(ethylene furanate) resin, which yields a poly(ethylene furanate) resin.
[0018] Specifically, the intrinsic viscosity of the polyethylene furanate resin prepared by the method of the present invention is 1.4 dL / g to 1.6 dL / g.
[0019] Thirdly, the present invention provides the application of the above-mentioned polyethylene furanate resin in the preparation of films, foamed materials or injection molded parts.
[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: The preparation method of the poly(ethylene furanate) resin of the present invention uses ethylene carbonate as an inhibitor to suppress the formation of acetaldehyde from ethylene glycol during the high-temperature esterification reaction, thereby reducing the acetaldehyde content in the poly(ethylene furanate) resin and effectively reducing the difficulty of separation and purification. Detailed Implementation
[0021] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.
[0022] Unless otherwise specified, all other materials, reagents, etc. used in the examples and comparative examples are commercially available.
[0023] 2,5-Furandicarboxylic acid, manufactured by Shaoxing Huafu New Material Technology Co., Ltd. Ethylene glycol, manufactured by CNOOC Shell Petrochemicals Co., Ltd.; according to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of ethylene carbonate is 0.01% of the sum of the chromatographic peak areas of ethylene carbonate and ethylene glycol.
[0024] Example 1 This embodiment provides a method for preparing polyethylene furanate dicarboxylate resin, comprising the following steps: S1. Dissolve 20.5 g of inhibitor (ethylene carbonate) in 8.2 kg of ethylene glycol to obtain an inhibitor / ethylene glycol solution; The inhibitor / ethylene glycol solution, 13.7 kg of 2,5-furandicarboxylic acid, and 8 g of catalyst (tetrabutyl titanate) were added to the reactor and mixed. After purging with nitrogen, the temperature was raised to 210±2℃. The pressure inside the reactor was controlled at atmospheric pressure. After reacting for 4 h, the esterified product was obtained. S2. Within 30 minutes, reduce the pressure of the reactor to below 50 Pa, and continue the reaction at 245±2℃ for 3.5~5.0 h until the intrinsic viscosity reaches 1.5 dL / g. Then, purge with nitrogen, press out and granulate to obtain polyethylene furanate dicarboxylate resin. In the above preparation method, the molar ratio of 2,5-furandicarboxylic acid to ethylene glycol is 1:1.5.
[0025] According to GB / T14571.2-2018 standard, the chromatographic peak areas of the inhibitor and ethylene glycol were obtained by chromatograph. The chromatographic conditions were as follows: the sample to be tested was a mixed solution of ethylene glycol and inhibitor (i.e., the inhibitor / ethylene glycol solution in step S1); the initial temperature of the chromatograph was 80℃, held for 5 min, and then increased to 230℃ at a rate of 10℃ / min; the carrier gas flow rate was 1 mL / min; the column size was (30 m × 0.32 mm × 1.8 μm), and an Agilent DB-624 column was selected; nitrogen was used as the carrier gas; the injection volume was 0.6~0.8 μL; the vaporization chamber temperature was 300℃; the detector temperature was 300℃; and the retention time was 30 min. The chromatogram was then obtained.
[0026] In the chromatogram, the retention time of ethylene glycol is 10.5 min, and the peak area is 792502888; the retention time of the inhibitor (ethylene carbonate) is 14.8 min, and the peak area is 1986223. The ratio of the peak area of the inhibitor to the peak area of ethylene glycol is 1986223 / (1986223 + 792502888) = 0.25%. The retention time of ethylene glycol is 10.3–10.7 min, and the retention time of the inhibitor is 14.5–15.0 min.
[0027] Example 2 This embodiment provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor is different. According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.05% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0028] Example 3 This embodiment provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor is different. According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.1% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0029] Example 4 This embodiment provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor is different. According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.2% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0030] Example 5 This embodiment provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor is different. According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.3% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0031] Example 6 This embodiment provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor is different. According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.4% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0032] Example 7 This embodiment provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor is different. According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.6% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0033] Example 8 This embodiment provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that: the catalyst is tetraisopropyl titanate; and the molar ratio of 2,5-furanate dicarboxylic acid to ethylene glycol is 1:2.0.
[0034] According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.5% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0035] Comparative Example 1 This comparative example provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor used is 0 (i.e., no inhibitor is added). At this time, the chromatographic peak area of ethylene carbonate is 0.01% of the sum of the chromatographic peak areas of ethylene carbonate and ethylene glycol. The ethylene carbonate is derived from impurities in ethylene glycol.
[0036] Comparative Example 2 This comparative example provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the amount of inhibitor is different. According to GB / T14571.2-2018 standard, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor is 0.8% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
[0037] Comparative Example 3 This comparative example provides a method for preparing poly(ethylene furanate dicarboxylate) resin, which is basically the same as that in Example 1, except that the chromatographic peak area of the inhibitor is kept to be 0.25% of the sum of the chromatographic peak areas of the inhibitor and 1,4-butanediol. The only difference is that the type of inhibitor is different, and the inhibitor is 1,3-dioxane-2-methanol.
[0038] Performance testing The esterified water collected by vacuum system during the esterification reaction of each embodiment and comparative example (esterification reaction start ≥10 min) was used as the test sample. According to GB / T14571.2-2018 standard, the chromatographic peak area of acetaldehyde and the chromatographic peak area of ethylene glycol were obtained by chromatograph. The yield of acetaldehyde (%) = acetaldehyde peak area / ethylene glycol peak area × 100%.
[0039] The specific testing method includes the following steps: The initial temperature of the chromatograph is 80℃, held for 5 min, and then increased to 230℃ at a rate of 10℃ / min. The carrier gas flow rate is 1 mL / min. The chromatographic column specifications are (30m × 0.32mm × 1.8μm), using an Agilent DB-624 column. Nitrogen is used as the carrier gas, with an injection volume of 0.6~0.8μL. The vaporization chamber temperature is 300℃, the detector temperature is 300℃, and the retention time is 30 min, yielding the chromatogram. The retention time of acetaldehyde is 6.7~7.3 min, and the retention time of ethylene glycol is 10.3~10.7 min.
[0040] Table 1 Performance of each embodiment and comparative example As shown in Table 1, the yield of acetaldehyde in Examples 1-8 was <2%, indicating that the preparation method of the present invention can effectively reduce the acetaldehyde content in polyethylene furanate resin. Meanwhile, Comparative Example 2 shows that when the inhibitor content is too high, the inhibitor's reaction is reversible, which weakens its inhibitory effect on acetaldehyde formation, resulting in a higher acetaldehyde yield. Furthermore, Comparative Example 3 reveals that using 1,3-dioxane-2-methanol as an inhibitor is insufficient to effectively reduce acetaldehyde production.
[0041] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A method for producing a polyethylenefurandicarboxylate resin, characterized by, The method comprises the following steps: S1, mixing 2,5-furan dicarboxylic acid, ethylene glycol, a catalyst and an inhibitor to perform an esterification reaction to obtain an esterification product; S2, performing a low-pressure polycondensation reaction on the esterification product obtained in S1 to obtain the poly(ethylene furandicarboxylate) resin; The inhibitor is vinyl carbonate; According to the standard GB / T14571.2-2018, based on the chromatographic purity of ethylene glycol, the chromatographic peak area of the inhibitor in the mixture of the inhibitor and ethylene glycol is 0.05%-0.6% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
2. The method for producing a polyethylene furanoate resin according to claim 1, wherein The chromatographic peak area of the inhibitor is 0.1%-0.4% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
3. The method for producing a polyethylene furanoate resin according to claim 2, wherein The chromatographic peak area of the inhibitor is 0.2%-0.3% of the sum of the chromatographic peak areas of the inhibitor and ethylene glycol.
4. The method for producing polyethylenefurandicarboxylate resin according to claim 1, wherein In the step S1, the esterification reaction is: after the mixed components are heated to 200-220℃ under a nitrogen atmosphere, the reaction is continued for 3-5h.
5. The method for producing polyethylenefurandicarboxylate resin according to claim 1, wherein The step S2 specifically comprises the following steps: within 30min, the pressure of the reaction system is reduced to below 50Pa, and the reaction is continued at 245-255℃ for 3.5-5h until the intrinsic viscosity reaches 1.4-1.6dL / g, nitrogen is filled, and the product is pressed and granulated to obtain the poly(ethylene furandicarboxylate) resin.
6. The method for producing polyethylenefurandicarboxylate resin according to claim 1, wherein In the step S1, the catalyst comprises at least one of tetrabutyl orthotitanate and tetraisopropyl orthotitanate.
7. The poly(ethylene furandicarboxylate) resin prepared by the method of any one of claims 1-6.
8. The poly(ethylene furandicarboxylate) resin of claim 7 for use in the preparation of a film, a foamed material or an injection-molded part.