Preparation method of bisphenol a-based diglyceryl ether compound

Abstract

The application discloses a preparation method of bisphenol A-based diglycidyl ether compounds, which uses bisphenol A diglycidyl ether and a phenol or alcohol compound with a multi-hydroxyl functional group as reaction substrates, and performs an epoxy group ring-opening reaction under the action of an organic amine catalyst. The method has high substrate applicability, does not need to add an organic solvent, has high atomic economic benefits, is safe and reliable, has a near 100% regional selectivity of the obtained target product, has a high yield, successfully solves the problems of poor reaction selectivity, complicated reaction steps, low yield and the need of using environment-harmful reagents in traditional synthesis of bisphenol A-based diglycidyl ether compounds, and has a good industrial application prospect.

Description

Technical Field

[0001] This invention relates to a method for preparing glycerol ether compounds, specifically a method for preparing bisphenol A diglycerol ether compounds, belonging to the field of organic synthesis technology. Background Technology

[0002] Bisphenol A diglyceride compounds are an important class of organic synthesis intermediates. Furthermore, due to their unique chemical properties, they have wide applications in the preparation of phenoxy resin composites, optoelectronic materials, new energy materials, and fine chemicals.

[0003] Because the epoxy functional group in bisphenol A diglycidyl ether compounds is highly reactive, it readily undergoes ring-opening reactions under acidic or alkaline conditions. Typically, after ring-opening, a new hydroxyl functional group forms. Due to variations in reaction conditions, this hydroxyl group may further attack the epoxy functional group, resulting in a ring-opening product with n>1. In the aforementioned reaction system, the reaction process is complex, requiring large amounts of organic solvents and reagents, exhibiting poor selectivity and significant product loss, which does not meet the requirements of modern green chemistry.

[0004] The methods for synthesizing bisphenol A diglycidyl ether compounds reported in the literature mainly include: (1) acid catalytic system: using Lewis acids (erbium trifluoromethanesulfonate, bismuth trichloride, etc.) or Brønsted acids (toluenesulfonic acid, salicylic acid, N-toluenesulfonylglycine, etc.) to achieve ring-opening of epoxy functional groups under the attack of nucleophiles; (2) basic ring-opening system: the common basic ring-opening method in the industry is to use basic compounds (sodium hydroxide, potassium hydroxide, sodium phenolate, etc.) to catalyze the ring-opening of epoxy functional groups, and then form the corresponding diglycidyl ether compounds under the attack of nucleophiles. Patent publication number CN104302686A discloses an esterified epoxy resin, its manufacturing method and a curable composition containing the esterified epoxy resin. Although the patent reports a method for preparing polyethers based on bisphenol A epoxy resin and diol compounds, the structure of the product is uncontrollable during the reaction process, and the average number ratio of chain groups is 10:90 to 90:10. In summary, the above methods generally use air-sensitive reagents (such as bismuth trichloride) or strong acids and bases, and also have drawbacks such as cumbersome experimental procedures, expensive and difficult-to-recycle catalysts, harsh reaction conditions, overlapping substrate applicability, low yield, poor selectivity, and significant environmental pollution.

[0005] To date, the efficient synthesis of bisphenol A diglycidyl ether compounds faces several challenges, including raw material quality, production safety, and product stability and purity. The synthesis technology is quite difficult, and currently only a few companies in the United States, Japan, Germany, and other countries are producing them. Meanwhile, my country currently relies mainly on imports for some high-end bisphenol A diglycidyl ether compound products.

[0006] To address the shortcomings of existing synthesis processes for bisphenol A diglycidyl ether compounds, the industry is focusing on researching new methods for synthesizing corresponding bisphenol A diglycidyl ether compounds using mild reaction conditions and efficient catalysis. These methods utilize stable, inexpensive, and readily available bisphenol A diglycidyl ethers and phenols or alcohols with polyhydroxy functional groups as building blocks. Summary of the Invention

[0007] To address the shortcomings of existing bisphenol A diglyceride ether synthesis techniques, such as cumbersome preparation steps, harsh conditions, low yield, poor selectivity, high cost, and significant environmental pollution, the present invention aims to provide a method for preparing bisphenol A diglyceride ether compounds that is simple and easy to implement, has mild preparation conditions, high yield, good selectivity, low cost, and is suitable for industrial-scale production.

[0008] To achieve the above-mentioned technical objectives, the present invention provides a method for preparing bisphenol A diglycidyl ether compounds, which involves mixing bisphenol A diglycidyl ether with a phenol or alcohol compound containing multiple hydroxyl groups and carrying out an epoxy ring-opening reaction under the action of an organic amine catalyst to obtain the compound.

[0009] As a preferred embodiment, the phenol or alcohol compound containing multiple hydroxyl groups has the structural expression R-OH, wherein R is selected from 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 3,5-dihydroxyphenyl, 4-(2-(4-hydroxyphenyl)-2-propyl)-phenyl, 4-(4-hydroxybenzyl)-phenyl, 4-((4-hydroxyphenyl)sulfonyl)phenyl, 4-(4-hydroxyphenyl)phenyl, 4-hydroxy-1-naphthyl, 5-hydroxy-1-naphthyl, 6-hydroxy-2-naphthyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, and 4-hydroxycyclohexyl. The base-catalyzed reaction expression of the bisphenol A diglycidyl ether with the phenol or alcohol compound containing multiple hydroxyl groups is shown in formula (1) below.

[0010]

[0011] As a preferred embodiment, the polyhydroxy phenol or alcohol compound is one of catechol, resorcinol, hydroquinone, pyrogallol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanediol.

[0012] As a preferred embodiment, the organic amine catalyst is at least one selected from triethylamine, 1,8-diazabicycloundec-7-ene, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethylbenzylaniline, N,N-dibenzylaniline, diisopropylethylamine, N-phenylpiperidine, and N-ethyl-N-benzylaniline. This preferred organic amine catalyst not only allows the epoxy ring-opening reaction between bisphenol A diglycidyl ether and polyhydroxyl-containing phenols or alcohols to proceed at lower temperatures, but also exhibits high conversion and high selectivity, while avoiding the use of solvents.

[0013] As a preferred embodiment, the molar ratio of bisphenol A diglycidyl ether to a polyhydroxy phenol or alcohol compound is 1:2.0 to 4.0.

[0014] As a preferred embodiment, the molar ratio of bisphenol A diglycidyl ether to the organic amine catalyst is 1:0.05-0.3. If the proportion of organic amine used is too low, below 5% of bisphenol A diglycidyl ether, the selectivity of the reaction and the yield of the target product will be significantly reduced. When the organic amine content is increased to 20% of bisphenol A diglycidyl ether, the yield and selectivity of the target product reach the optimal level. Further increasing the organic amine content will result in a slight decrease in the yield and selectivity of the target product. Therefore, the molar ratio of bisphenol A diglycidyl ether to the organic amine catalyst is further preferably 1:0.1-0.3.

[0015] As a preferred embodiment, the ring-opening reaction is carried out under nitrogen protection at a temperature of 25–100°C for a time of 3–12 h. A further preferred reaction temperature is 60–100°C, and most preferably 70–90°C. Within the preferred temperature and time range, appropriately increasing the reaction temperature and extending the reaction time is beneficial for increasing the yield of the target product; however, excessively high reaction temperatures and times will increase the impact of side reactions.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] (1) The preparation method is simple and easy to implement, the reaction conditions are mild, the process is easy to control, and it is safe and reliable.

[0018] (2) The substrate has wide applicability, does not require the addition of organic solvents, has high atom economy, and does not cause environmental pollution.

[0019] (2) It has high reaction efficiency, high yield, good selectivity, short reaction time, few impurities, low cost, and is suitable for large-scale production, with good industrial application prospects. Attached Figure Description

[0020] Figure 1 The target product obtained in Example 3 1 H NMR spectrum.

[0021] Figure 2 The target product obtained in Example 3 13 C10 NMR spectrum. Detailed Implementation

[0022] The present invention will be further described below with reference to embodiments thereof:

[0023] The structural analysis of the reaction products in the following embodiments of the present invention was performed using a gas chromatography-mass spectrometry (GC / MS) system (6890N / 5973N) equipped with an HP-5MS capillary column (30m × 0.45mm × 0.8μm) manufactured by Agilent Technologies, and a high-performance liquid chromatography (HPLC) system (Inertsil) manufactured by Agilent Technologies, equipped with an HP-5MS capillary column (30m × 0.45mm × 0.8μm). @ An ODS-3 column (5 μm, 4.6*250 mm), mobile phase: CH3CN:H2O = 9:1, and a Bruker Avance-III 500 NMR analyzer were used. The selectivity and yield of the target product were analyzed using the Bruker Avance-III 500 NMR analyzer.

[0024] Example 1

[0025] A series of parallel reactions were prepared. 340 mg (1 mmol) of bisphenol A diglycidyl ether and 220 mg (2 mmol) of hydroquinone were added to Schlenk tubes under nitrogen protection. Then, 15 mol% of an organic base (triethylamine, 1,8-diazabicycloundec-7-ene, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethylbenzylamine, N,N-dibenzylaniline, diisopropylethylamine, N-phenylpiperidine, N-ethyl-N-benzylaniline), was added to each Schlenk tube, and the mixture was stirred at 80 °C for 6 hours. Analysis by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) showed that the highest yield and selectivity of the target product were achieved when triethylamine was used as the base, with a selectivity of 95% and a yield of 92%.

[0026] Example 2

[0027] A series of parallel reactions were prepared. 340 mg (1 mmol) of bisphenol A diglycidyl ether and 220 mg (2 mmol) of hydroquinone were added to Schlenk tubes under nitrogen protection. Then, triethylamine was added to each Schlenk tube in different molar ratios (0 mol%, 1 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 30 mol%), and the reactions were stirred at 80 °C for 12 hours. Analysis by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) showed that the highest yield and selectivity of the target product were achieved when the triethylamine content was 15 mol%, with a selectivity of 95% and a yield of 92%. The specific data from parallel experiments with different molar ratios of triethylamine are as follows: 0 mol% (selectivity 60%, yield 3%), 1 mol% (selectivity 85%, yield 22%), 5 mol% (selectivity 88%, yield 56%), 10 mol% (selectivity 93%, yield 87%), 20 mol% (selectivity 94%, yield 91%), and 30 mol% (selectivity 92%, yield 85%).

[0028] Example 3

[0029] A series of parallel reactions were prepared. 340 mg (1 mmol) of bisphenol A diglycidyl ether and 220 mg (2 mmol) of hydroquinone were added to Schlenk tubes under nitrogen protection. Then, 15 mol% triethylamine was added to each Schlenk tube. The reactions were carried out at 25°C, 40°C, 60°C, 80°C, and 100°C with stirring for 12 hours each. Analysis by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) showed that the yield and selectivity of the target product were highest at a reaction temperature of 80°C, with a selectivity of 95% and a yield of 92%. Figure 1 and Figure 2 As shown, the product obtained in this embodiment was subjected to NMR analysis. 1 H NMR (400MHz, Acetone-d6): δ7.12-7.05(m,4H),6.86-6.79(m,6H),6.79-6.70(m,3H),4.29-4.20(m,2H),4.13-3.96(m,8H),1.57(s,6H); 13 C NMR (101MHz, Acetone-d6): δ157.64,157.61,154.08,153.07,152.28,151.08,144.00,143.98,128.4 2,116.59,116.56,116.39,116.27,114.72,70.77,70.69,70.10,70.05,69.38,69.34,42.17,31.34.

[0030] Example 4

[0031] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 220 mg (2 mmol) of resorcinol were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 92%, and the yield was 89%.

[0032] Example 5

[0033] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 252 mg (2 mmol) of pyrogallol were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was completed, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 96%, and the yield was 93%.

[0034] Example 6

[0035] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 456 mg (2 mmol) of bisphenol A were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 92%, and the yield was 87%.

[0036] Example 7

[0037] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 500 mg (2 mmol) of bisphenol S were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 91%, and the yield was 83%.

[0038] Example 8

[0039] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 320 mg (2 mmol) of 1,4-dihydroxynaphthalene were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was completed, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 94%, and the yield was 90%.

[0040] Example 9

[0041] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 500 mg (2 mmol) of 2,6-dihydroxynaphthalene were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 95%, and the yield was 91%.

[0042] Example 10

[0043] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 124 mg (2 mmol) of ethylene glycol were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 97%, and the yield was 94%.

[0044] Example 11

[0045] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 180 mg (2 mmol) of 1,4-butanediol were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 96%, and the yield was 91%.

[0046] Example 12

[0047] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 236 mg (2 mmol) of 1,6-hexanediol were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS), and further purified by column chromatography. The selectivity of the target product was 92%, and the yield was 85%.

[0048] Example 13

[0049] 340 mg (1 mmol) of bisphenol A diglycidyl ether and 232 mg (2 mmol) of 1,6-hexanediol were added to a Schlenk tube under nitrogen protection. Then, 15 mol% triethylamine was added to the Schlenk tube, and the reaction was carried out at 80 °C with stirring for 12 hours. After the reaction was complete, the product was analyzed by high performance liquid chromatography and gas chromatography-mass spectrometry (HPLC), and further purified by column chromatography. The selectivity of the target product was 90%, and the yield was 82%.

[0050] As can be seen from the above embodiments, the method of preparing corresponding bisphenol A diglycidyl ether compounds with different substituted functional groups by reacting bisphenol A diglycidyl ether with phenols or alcohols having polyhydroxy functional groups has the advantages of mild reaction conditions, inexpensive and readily available catalysts, and high regioselectivity. Furthermore, this method also has the advantages of wide substrate applicability and high yield, providing an efficient method for synthesizing bisphenol A diglycidyl ether derivatives with different substituted functional groups.

[0051] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A method for preparing a bisphenol A diglyceride compound, characterized in that: Bisphenol A diglycidyl ether is mixed with phenols and / or alcohols containing polyhydroxyl groups and subjected to an epoxy ring-opening reaction in the presence of a triethylamine catalyst to obtain the product. The polyhydroxyl-containing phenolic compound is one of catechol, resorcinol, hydroquinone, pyrogallol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; the polyhydroxyl-containing alcohol compound is one of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanediol.

2. The method for preparing a bisphenol A diglyceride compound according to claim 1, characterized in that: The molar ratio of the bisphenol A diglycidyl ether to the polyhydroxy phenol or alcohol compound is 1:2.0~4.

0.

3. The method for preparing a bisphenol A diglyceride compound according to claim 1 or 2, characterized in that: The molar ratio of bisphenol A diglycidyl ether to triethylamine catalyst is 1:0.05~0.

3.

4. The method for preparing a bisphenol A diglyceride compound according to claim 1, characterized in that: The conditions for the ring-opening reaction are: under nitrogen protection, the reaction temperature is 25~100℃, and the time is 3~12h.

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