Method for synthesizing bisphenol a polyether
By using a composite catalyst composed of carbonates, amines, and organophosphorus compounds, and controlling the reaction conditions, the isomerization and decomposition problems in the synthesis of bisphenol A polyether were solved, resulting in a highly efficient bisphenol A polyether product with low hydroxyl value and light color.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- ZHEJIANG HUANGMA TECH CO LTD
- Filing Date
- 2025-05-30
- Publication Date
- 2026-05-21
AI Technical Summary
In existing methods for synthesizing bisphenol A polyethers, bisphenol A is prone to isomerization and decomposition reactions, resulting in a darker product color. Furthermore, high-temperature and strong-alkali catalysis leads to an increase in byproducts, affecting product quality.
A composite catalyst composed of carbonates, amines, and organophosphorus compounds is used to carry out the ring-opening polymerization of epoxides by controlling the reaction temperature and pressure, forming a composite active center and avoiding the adverse effects of strong base catalysts.
It effectively reduces the hydroxyl value of products, improves color, enhances product quality, reduces side reactions, and achieves higher catalytic efficiency and selectivity.
Smart Images
Figure CN2025098239_21052026_PF_FP_ABST
Abstract
Description
A method for synthesizing bisphenol A polyether Technical Field
[0001] This invention relates to the field of fine chemical synthesis technology, specifically to a method for synthesizing bisphenol A polyether. Background Technology
[0002] Bisphenol A polyether is produced by the addition polymerization reaction of bisphenol A and epoxides in the presence of a catalyst. It is a nonionic surfactant. Bisphenol A polyether products can be used as synthetic monomers for organic materials such as coatings, resins, adhesives, and glass fiber impregnators. It has wide applications in many fields such as automobile manufacturing, textiles, aerospace, petrochemicals, construction, and transportation.
[0003] Currently, existing bisphenol A polyethers are typically prepared using solvent dissolution and high-temperature melting methods. Solvent dissolution requires solvent removal, which is cumbersome and significantly increases production costs. Furthermore, most solvents are toxic and have a significant environmental impact. High-temperature melting methods typically involve adding bisphenol A to a reactor and heating it to its melting point using steam or an oil bath under inert gas protection. After melting, an epoxide is introduced, and the reaction proceeds under strong alkali catalysis. For example, the preparation processes of bisphenol A polyethylene ether reported in patents CN101367714B and CN107216453A both use KOH as a catalyst. The literature "Synthesis of Narrowly Distributed Bisphenol A Polyoxypropylene Ether" (Journal of Jiangnan University, 2012, Vol. 11, No. 2, pp. 212-215) describes the reaction of bisphenol A with NaOH in cyclohexane to prepare bisphenol A polyoxypropylene ether. The high-temperature melting method effectively overcomes the problems of cumbersome procedures and significant environmental impact associated with solvent dissolution methods. However, since the melting point of bisphenol A is around 158°C, the temperature of the heating medium must reach at least 160°C to melt bisphenol A without heating the solvent. The melted bisphenol A is very prone to isomerization and decomposition reactions under high temperature and strong alkali, which increases the amount of by-products and results in a high hydroxyl value of the product. At the same time, the product obtained by strong alkali catalysis at high temperature has a darker color and higher chroma, which greatly affects the product quality.
[0004] Therefore, it is essential to develop a method for synthesizing bisphenol A polyether to address the problems of isomerization and decomposition reactions of melted bisphenol A and the darkening of the product color. Summary of the Invention
[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide a method for synthesizing bisphenol A polyether. This method uses bisphenol A as an initiator and a composite catalyst to catalyze the ring-opening polymerization of epoxide alkane to obtain bisphenol A polyether with low hydroxyl value and light color, which greatly improves the product quality.
[0006] To solve the above problems, the technical solution adopted by the present invention is as follows:
[0007] A method for synthesizing bisphenol A polyether, comprising the following steps:
[0008] S1. Bisphenol A and the composite catalyst are added to the reaction vessel in sequence. After replacing the nitrogen gas, the reaction vessel is heated until the bisphenol A melts. After it has completely melted, stirring is started. The composite catalyst is composed of carbonate, amine compound and organophosphorus.
[0009] S2. Add epoxide alkane to the reactor and react, keeping the temperature until the pressure in the reactor no longer decreases;
[0010] S3. After the reaction is complete, the reaction vessel is cooled and degassed to obtain bisphenol A polyether.
[0011] In a preferred embodiment of the present invention, the mass percentages of carbonate, amine compound and organophosphorus in the composite catalyst are 3-20%: 4-45%: 35-93%.
[0012] More preferably, the carbonate is potassium carbonate and / or sodium carbonate.
[0013] More preferably, the amine compound is one or any combination of two or more of trimethylamine, triethylamine, and N,N-dimethylethylamine.
[0014] More preferably, the organophosphine is one or any combination of two or more of triisopropylphosphine, diphenylphosphine oxide, tributylphosphine, triphenylphosphine, and tritert-butylphosphine.
[0015] The above synthesis method employs a composite catalyst composed of carbonates, amines, and organophosphorus compounds to catalyze the ring-opening polymerization reaction. This effectively solves the problem of isomerization and decomposition of products under strong alkaline catalysts in existing technologies, while also effectively improving product color. The applicant's research found that carbonates such as potassium carbonate or sodium carbonate can form ethylene carbonate with ethylene oxide. Ethylene carbonate significantly increases the solubility of bisphenol A, which can lower the reaction temperature and promote the reaction to some extent. However, using only potassium carbonate or sodium carbonate results in relatively weak catalytic activity. Amines such as trimethylamine, triethylamine, and N,N-dimethylethylamine have low boiling points and are easily volatilized, effectively reducing the amount of catalyst residue in the product. Furthermore, amine catalysts exhibit high activity in the synthesis of low molecular weight bisphenol A polyethers. However, excessive use of amine catalysts during the reaction process carries the risk of increasing product color. Organophosphorus compounds such as triisopropylphosphine, diphenylphosphine oxide, tributylphosphine, triphenylphosphine, and tri-tert-butylphosphine are weak organic bases that follow anionic ring-opening polymerization mechanisms during reaction. However, their structures contain significant steric hindrance, which limits the distribution of the product. Furthermore, because the acidity of phenolic hydroxyl groups is stronger than that of alcoholic hydroxyl groups, the phenolic hydroxyl groups in bisphenol A preferentially bind to the aforementioned weakly basic catalysts, thus suppressing the self-polymerization side reaction of the epoxy monomer. Organophosphorus compounds, as catalysts, exhibit high catalytic activity and selectivity. This invention utilizes a composite catalyst prepared by compounding carbonates, amine compounds, and organophosphorus compounds in a specific ratio. The combined action of these three components forms a composite active center conducive to the reaction, achieving unexpected catalytic effects.
[0016] In the above synthesis method, the sum of the mass percentages of bisphenol A, the composite catalyst, and the epoxide is 100%. The epoxide is one or more of ethylene oxide, propylene oxide, and 1,2-epoxidebutane.
[0017] In a preferred embodiment of the present invention, the mass ratio of bisphenol A to the composite catalyst in step S1 is 1:0.0001 to 0.1.
[0018] In a preferred embodiment of the present invention, the mass ratio of bisphenol A to epoxide in step S2 is 1:0.35 to 10.
[0019] In a preferred embodiment of the present invention, the heating temperature in step S1 is 160–220°C. Here, heating refers to heating the reaction vessel to raise the temperature of the material inside to 160–220°C, preferably to 180°C.
[0020] As a preferred embodiment of the present invention, the specific operation of step S2 is as follows: a small amount of epoxide alkane is slowly added to the reactor. When the reaction temperature reaches 170°C, the epoxide alkane is steadily introduced to carry out the reaction, and the pressure of the reactor is controlled within 0.4 MPa. After the epoxide alkane is added, the temperature is kept warm and the reaction continues (referred to as continuous reaction) until the pressure of the reactor no longer decreases.
[0021] In a preferred embodiment of the present invention, the reaction temperature in step S2 is 150-180°C, preferably 170°C; and the pressure of the reactor is controlled within 0.4 MPa.
[0022] In a preferred embodiment of the present invention, in step S3, the material temperature is lowered to below 115°C before degassing.
[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0024] The synthesis method described in this invention involves compounding carbonates, amine compounds, and organophosphorus compounds in a specific ratio to form a composite catalyst, which is then applied to the ring-opening polymerization of epoxides using bisphenol A as an initiator to produce bisphenol A polyether. The three components in this composite catalyst work together to form a composite active center that facilitates the reaction, achieving higher catalytic efficiency and selectivity, and significantly improving the catalytic effect. Furthermore, because this composite catalyst is weakly alkaline, it effectively avoids the problem of isomerization and decomposition of products under strong alkaline catalysts in existing technologies. It also results in fewer side reactions, effectively reduces the hydroxyl value of the product, and improves the product color, greatly enhancing product quality. Attached Figure Description
[0025] Figure 1 is a schematic flowchart of the synthesis method of bisphenol A polyether according to the present invention. Detailed Implementation
[0026] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.
[0027] As shown in Figure 1, the method for synthesizing bisphenol A polyether provided by the present invention includes the following steps:
[0028] S1. Bisphenol A and the composite catalyst are added to the reactor in sequence. After replacing the air in the reactor with nitrogen, the reactor is heated to 160-220°C to melt the bisphenol A. After all the bisphenol A has melted, stirring is started. The mass ratio of bisphenol A to the composite catalyst is 1:0.0001-0.1. The composite catalyst is a mixture of carbonate, amine compound and organophosphorus in a mass percentage of 3-20%:4-45%:35-93%.
[0029] S2. Slowly add a small amount of alkyl epoxide to the reactor. When the reaction temperature reaches 150-180℃, start to steadily introduce alkyl epoxide to carry out the reaction, and control the pressure of the reactor to within 0.4MPa. After adding the alkyl epoxide, keep the temperature and continue the reaction until the pressure of the reactor no longer drops. The mass ratio of bisphenol A to alkyl epoxide is 1:0.35-10.
[0030] S3. After the reaction is complete, the temperature of the material in the reactor is lowered to below 115°C and then degassed to obtain the bisphenol A polyether product.
[0031] The synthesis method of bisphenol A polyether described in this invention will be further illustrated below through specific embodiments.
[0032] In the following examples, the residual amount of bisphenol A in the product was detected by high performance liquid chromatography, and the specific method is referred to Q / HMK 235-2017; the hydroxyl value was detected by GB / T 7383-2007, and the color was obtained by comparison with a standard colorimetric tube.
[0033] Example 1
[0034] A method for synthesizing bisphenol A polyether, comprising the following steps:
[0035] S1. Add 1000g of bisphenol A and 3.0g of composite catalyst (composed of 0.5g of potassium carbonate, 0.5g of trimethylamine and 2.0g of triisopropylphosphine) to the reactor in sequence, and replace the air in the reactor with nitrogen. Then heat the material in the reactor to 180°C. After all the bisphenol A has melted, start stirring.
[0036] S2. Slowly add a small amount of ethylene oxide to the reactor. When the reaction temperature reaches 150°C, start to steadily introduce ethylene oxide (total amount of ethylene oxide added is 351g). Control the pressure of the reactor to within 0.4MPa. After adding the ethylene oxide, keep the temperature and continue the reaction until the pressure no longer drops.
[0037] S3. After the reaction is complete, the temperature of the material in the reactor is lowered to below 115°C and then degassed for 30 minutes to obtain the bisphenol A polyether product.
[0038] The product prepared in this embodiment was analyzed by high performance liquid chromatography, and the results are as follows: the bisphenol A residue was 0 ppm; the color was No. 20 (Pt-Co unit); and the hydroxyl value determined by chemical method was 345 mg KOH / g.
[0039] Example 2
[0040] A method for synthesizing bisphenol A polyether, comprising the following steps:
[0041] S1. Add 1000g of bisphenol A and 6.5g of composite catalyst (composed of 0.2g sodium carbonate, 0.3g potassium carbonate, 2.0g N,N-dimethylethylamine and 4.0g triphenylphosphine) to the reactor in sequence, and replace the air in the reactor with nitrogen. Then heat the material in the reactor to 180°C. After all the bisphenol A has melted, start stirring.
[0042] S2. Slowly add a small amount of propylene oxide to the reactor. When the reaction temperature reaches 160℃, start to steadily introduce propylene oxide (total amount of propylene oxide added is 789g). Control the pressure of the reactor to within 0.4MPa. After adding the propylene oxide, keep the temperature and continue the reaction until the pressure no longer drops.
[0043] S3. After the reaction is complete, the temperature of the material in the reactor is lowered to below 115°C and then degassed for 30 minutes to obtain the bisphenol A polyether product.
[0044] The product prepared in this embodiment was analyzed by high performance liquid chromatography, and the results are as follows: the bisphenol A residue was 0 ppm; the color was No. 20 (Pt-Co unit); and the hydroxyl value determined by chemical method was 279 mg KOH / g.
[0045] Example 3
[0046] A method for synthesizing bisphenol A polyether, comprising the following steps:
[0047] S1. Add 1000g of bisphenol A and 3.9g of composite catalyst (composed of 0.4g of potassium carbonate, 1.0g of triethylamine and 2.5g of tributylphosphine) to the reactor in sequence, and replace the air in the reactor with nitrogen. Then heat the material in the reactor to 180°C. After all the bisphenol A has melted, start stirring.
[0048] S2. Slowly add a small amount of 1,2-epoxybutane to the reactor. When the reaction temperature reaches 170℃, start to steadily introduce 1,2-epoxybutane (the total amount of 1,2-epoxybutane added is 1263g). Control the pressure of the reactor to within 0.4MPa. After adding propylene oxide, keep the temperature and continue the reaction until the pressure no longer drops.
[0049] S3. After the reaction is complete, the temperature of the material in the reactor is lowered to below 115°C and then degassed for 30 minutes to obtain the bisphenol A polyether product.
[0050] The product prepared in this embodiment was analyzed by high performance liquid chromatography, and the results are as follows: the bisphenol A residue was 0 ppm; the color was 25 (Pt-Co unit); and the hydroxyl value determined by chemical method was 217 mg KOH / g.
[0051] Comparative Example 1
[0052] A method for synthesizing bisphenol A polyether, comprising the following steps:
[0053] S1. Add 1000g of bisphenol A and 4.2g of KOH to the reactor in sequence, and replace the air in the reactor with nitrogen. Then heat the material in the reactor to 180°C. After all the bisphenol A has melted, start stirring.
[0054] S2. Slowly add a small amount of ethylene oxide to the reactor. When the reaction temperature reaches 150°C, start to steadily introduce ethylene oxide (total amount of ethylene oxide added is 351g). Control the pressure of the reactor to within 0.4MPa. After adding the ethylene oxide, keep the temperature and continue the reaction until the pressure no longer drops.
[0055] S3. After the reaction is complete, the temperature of the material in the reactor is lowered to below 115°C and then degassed for 30 minutes to obtain the bisphenol A polyether product.
[0056] The product prepared in this embodiment was analyzed by high performance liquid chromatography, and the results are as follows: the residual amount of bisphenol A was 16730 ppm; the color was 65 (Pt-Co unit); and the hydroxyl value determined by chemical method was 348 mg KOH / g.
[0057] By comparing Example 1 and Comparative Example 1, it can be seen that, compared with strong base catalysts, the bisphenol A polyether prepared by the composite catalyst described in this invention for the ring-opening polymerization of epoxides has no bisphenol A residue, better color, and lower hydroxyl value, indicating that the synthesis method of this invention greatly improves the product quality of bisphenol A polyether.
[0058] Comparative Examples 2-4
[0059] The difference between Comparative Examples 2-4 and Example 1 is that potassium carbonate, trimethylamine, and triisopropylphosphine were used as catalysts separately, while other reaction conditions were exactly the same. Specifically, the catalyst dosage of Comparative Examples 2-4 and the bisphenol A residue, color, and hydroxyl value of the prepared bisphenol A polyethers are shown in Table 1.
[0060] Table 1 shows the catalyst dosage, bisphenol A residue, color, and hydroxyl value of the products obtained in Comparative Examples 2–4.
[0061] By comparing Comparative Example 2 and Example 1, it can be seen that the bisphenol A polyether prepared by using potassium carbonate catalyst alone has a better color, but the bisphenol A residue is high and the hydroxyl value is relatively high. According to the analysis and detection standards of hydroxyl value, the higher the hydroxyl value, the smaller the molecular weight. This indicates that although the product prepared by using potassium carbonate catalyst alone has a better color, the product quality is not as good as the composite catalyst used in Example 1.
[0062] Comparing Comparative Example 3 and Example 1, it is evident that using only trimethylamine as a catalyst results in a lower hydroxyl value for the bisphenol A polyether. A lower hydroxyl value, according to hydroxyl value analysis standards, indicates a larger molecular weight, suggesting that trimethylamine, as a catalyst, facilitates a more complete reaction of the epoxide alkane. However, the bisphenol A residue is higher, and the color is also poorer, indicating that while the product obtained using only trimethylamine as a catalyst has a better color, its quality is not as good as that of the composite catalyst used in Example 1.
[0063] By comparing Comparative Example 4 and Example 1, it can be seen that the bisphenol A polyether prepared by using only triisopropylphosphine catalyst has no bisphenol A residue, but the color is relatively poor and the hydroxyl value is relatively high. According to the analysis and detection standard of hydroxyl value, the larger the hydroxyl value, the smaller the molecular weight. This indicates that although the product prepared by using only triisopropylphosphine catalyst has no bisphenol A residue, the product quality is not as good as the composite catalyst used in Example 1.
[0064] The above analysis shows that the composite catalyst of the present invention has shown excellent performance in the preparation of bisphenol A polyether. The three components form a composite active center that is conducive to the reaction, thereby achieving a synergistic effect of 1+1+1>3 and realizing an unexpected catalytic effect.
[0065] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.
Claims
1. A method of synthesizing a bisphenol A polyether, characterized by: Includes the following steps: S1. Bisphenol A and the composite catalyst are added to the reaction vessel in sequence. After replacing the nitrogen gas, the reaction vessel is heated until the bisphenol A melts. After it has completely melted, stirring is started. The composite catalyst is composed of carbonate, amine compound and organophosphorus. S2. Add epoxide alkane to the reactor and react, keeping the temperature until the pressure in the reactor no longer decreases; S3. After the reaction is complete, the reaction vessel is cooled and degassed to obtain bisphenol A polyether.
2. The method of synthesis of bisphenol A polyether according to claim 1, characterized by that: The mass percentages of carbonates, amines, and organophosphorus compounds in the composite catalyst are 3–20% : 4–45% : 35–93%.
3. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized in that: The carbonate is potassium carbonate and / or sodium carbonate.
4. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized by the fact that: The amine compound is one or any combination of two or more of trimethylamine, triethylamine, and N,N-dimethylethylamine.
5. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized by the fact that: The organophosphine is one or any combination of two or more of the following: triisopropylphosphine, diphenylphosphine oxide, tributylphosphine, triphenylphosphine, and tritert-butylphosphine.
6. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized by the fact that: In step S1, the mass ratio of bisphenol A to the composite catalyst is 1:0.0001 to 0.
1.
7. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized by the fact that: The mass ratio of bisphenol A to epoxide in step S2 is 1:0.35 to 10.
8. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized by the fact that: The heating temperature in step S1 is 160–220°C.
9. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized by the fact that: The reaction temperature in step S2 is 150–180 °C.
10. The method of synthesis of bisphenol A polyether according to claim 1 or 2, characterized by the fact that: In step S3, the material temperature is lowered to below 115°C before degassing.