A method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol

Abstract

The application discloses a method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl) phenol, which comprises the following steps: taking a Bronsted acidic ionic liquid as a catalyst, taking a propylene glycol fatty acid ester as an additive, and reacting 3-(2-hydroxy-2-propyl) phenol with hydrogen peroxide to generate resorcinol. The method can efficiently and stably produce resorcinol from 3-(2-hydroxy-2-propyl) phenol through a one-step method, and the product yield is high.

Description

TECHNICAL FIELD

[0001] The present application relates to a synthesis method of resorcinol, in particular to a synthesis method of resorcinol from 3-(2-hydroxy-2-propyl)phenol. BACKGROUND

[0002] Resorcinol is a colorless or white needle-like crystal or powder, mainly used in rubber industry, wood low-temperature adhesive, dye and pharmaceutical industries. At present, the main methods for producing resorcinol in industry are: benzene sulfonation alkali fusion method, m-phenylenediamine method and cumene oxidation method. The benzene sulfonation alkali fusion method uses a large amount of sulfonating agent, the equipment is easy to corrode, and the environmental pollution is relatively serious, which is facing elimination. The m-phenylenediamine method has high process risk, and many nitro compound explosion accidents have occurred in related production manufacturers. The cumene oxidation method is only mastered by a few Japanese enterprises, and the process flow is as follows:

[0003]

[0004] In this process, 3-(1-hydroperoxy-1-methylethyl)-α,α-dimethylbenzyl alcohol HHP and DHP are prepared by air oxidation of m-diisopropylbenzene, and then DHP is cracked to generate resorcinol; at the same time, HHP also cracks to generate 3-(2-hydroxy-2-propyl)phenol, i.e. DCS. Since 3-(2-hydroxy-2-propyl)phenol is inevitably generated in the reaction system, it is of great significance to study the effective utilization of 3-(2-hydroxy-2-propyl)phenol. Converting 3-(2-hydroxy-2-propyl)phenol into resorcinol can realize the high value-added utilization of the by-product.

[0005] Patent CN115448818B reports a reaction of converting 3-(2-hydroxy-2-propyl)phenol into SHP with hydrogen peroxide in the presence of sulfuric acid, then the pure product is obtained by silica gel column chromatography separation, and then SHP is decomposed to obtain resorcinol under the catalysis of sulfuric acid. The reaction process is long, there are many by-products, the intermediates need to be further separated and purified, and the reaction time is relatively long. DHP or SHP is easy to be re-decomposed into 3-(2-hydroxy-2-propyl)phenol in the reaction system. In addition, under the reaction conditions of strong acid, resorcinol and m-isopropylphenol will undergo alkylation reaction, which reduces the product yield.

[0006] Therefore, there is an urgent need in the art for a method for efficiently, conveniently and directly utilizing 3-(2-hydroxy-2-propyl)phenol to prepare resorcinol. SUMMARY

[0007] In order to solve the above technical problems, the present application provides a method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl) phenol. The method can efficiently and stably produce resorcinol from 3-(2-hydroxy-2-propyl) phenol, and the product yield is high.

[0008] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0009] A method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl) phenol, characterized in that it comprises the process of reacting 3-(2-hydroxy-2-propyl) phenol and hydrogen peroxide to generate resorcinol with a Br nsted acidic ionic liquid as a catalyst and a propylene glycol fatty acid ester as an additive.

[0010] In some embodiments, the Br nsted acidic ionic liquid is a sulfonic acid type ionic liquid, preferably [TEBSA][HSO4], and the structural expression is as follows:

[0011]

[0012] The preparation method of the ionic liquid [TEBSA][HSO4] is simple and known to those skilled in the art, and the raw materials are widely available and inexpensive. For details, refer to the specific method for synthesis in the master's thesis "Zheng Xianfeng. Process research on synthesis of N-substituted amides by Ritter reaction. Diss. Nanjing University of Technology, 2010".

[0013] Preferably, the addition amount of the Br nsted acidic ionic liquid is 0.5-2% of the mass of 3-(2-hydroxy-2-propyl) phenol.

[0014] In some embodiments, the propylene glycol fatty acid ester is at least one of the substances with the following structural expression:

[0015]

[0016] wherein n is 8-16;

[0017] Preferably, the amount of the propylene glycol fatty acid ester is 1-5% of the mass of the catalyst.

[0018] In some embodiments, the molar ratio of 3-(2-hydroxy-2-propyl) phenol to hydrogen peroxide is 1:(1-10), preferably 1:(2-5);

[0019] Preferably, the mass concentration of the hydrogen peroxide is 2-30%, preferably 3-10%.

[0020] In some embodiments, the reaction temperature is 20-70℃, and the reaction time is 3-20 min. In some embodiments, the reaction temperature is 20-70℃, and the reaction time is 3-20 min.

[0021] In some embodiments, the feeding process of the reaction is that 3-(2-hydroxy-2-propyl) phenol is mixed with the promoter in an organic solvent to obtain an organic phase, a catalyst and hydrogen peroxide are mixed to obtain an aqueous phase, and then the aqueous phase is added to the organic phase for reaction.

[0022] In some embodiments, the organic solvent is ketone, preferably one or more of acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK).

[0023] In some embodiments, the amount of the organic solvent is 4-25 times the mass of 3-(2-hydroxy-2-propyl) phenol.

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] (1) The m-dihydroxybenzene can be obtained by one-step reaction, the reaction yield is high, the by-products are few, the cost is low, and the method is suitable for industrial production;

[0026] (2) The reaction can be carried out using low-concentration hydrogen peroxide as raw material, thereby improving the intrinsic safety level of the reaction;

[0027] (3) The introduction of the promoter strengthens the mass transfer, reduces the proportion of intermediate product peroxide SHP in the reaction system, and directly obtains m-dihydroxybenzene by one-step reaction with high yield. DETAILED DESCRIPTION

[0028] The present application will be further described below through specific examples, and the examples described in the present application are only used to illustrate the present application and do not limit the scope of the present application.

[0029] In the following examples of the present application, the main raw material information is as follows, and other raw materials and reagents can be generally obtained through conventional commercial channels unless otherwise specified:

[0030] 3-(2-hydroxy-2-propyl) phenol, purity 98wt%, Beijing Inokai Co., Ltd.

[0031] 1,2-propanediol monododecanoate, Nantong Haitianyuan Chemical Co., Ltd.

[0032] 1,2-propanediol monohexadecanoate, Shanghai Jinjile Industrial Co., Ltd.

[0033] propylene glycol monostearate, Nantong Chenrun Chemical Co., Ltd.

[0034] MIBK: methyl isobutyl ketone, Shanghai Aldrin Biochemical Technology Co., Ltd.

[0035] Hydrogen peroxide, 27.5% aqueous solution, Luxi Chemical Co., Ltd., and the conventional preparation of hydrogen peroxide with the required concentration is based on this.

[0036] [TEBSA][HSO4] ionic liquid preparation method:

[0037] A 200 mL round bottom flask was charged with 0.1 mol 1,4-butanesultone, 0.1 mol triethylamine and 50 mL acetonitrile, and the reaction was refluxed for 10 hours. After the reaction was completed, a white solid was obtained by filtration, washed with ethyl acetate to remove non-ionic residues, and dried in vacuum to obtain an intermediate (yield 85%). Then, the intermediate (23.7 g, 0.1 mol) was added to a 250 mL three-necked flask, 10 mL of 10 mol / L dilute sulfuric acid was added dropwise, and the reaction was stirred at 80°C for 6 hours. After the reaction was completed, the water was evaporated to obtain NNN-triethyl-N-butylsulfate ammonium bisulfate salt [TEBSA][HSO4] (yield 99%).

[0038]

[0039] The detection method involved in the following examples of the present application:

[0040] (1) HPLC method

[0041] The present application uses high performance liquid chromatography to analyze the reaction conversion rate and selectivity, and the chromatographic analysis conditions are as follows:

[0042] Instrument model: LC-6A high performance liquid chromatograph (Shimadzu)

[0043] Analysis column: CLC-SIL 150*6.0mm (Shimadzu)

[0044] Preparation column: Zorbax SIL 250*9.4mm (column bang)

[0045] Mobile phase: water: methanol: isopropanol: isopropyl cyclohexane (60-90°C) = 15:3:3:60 (v / v)

[0046] Flow rate: 0.7 ml / min

[0047] Column temperature: room temperature

[0048] UV detector (Shimadzu SPD-6AV UV-visible spectrophotometer detector) wavelength: 235 nm;

[0049] (2) Peroxide titration

[0050] Preparation of hydrogen peroxide concentration detection: refer to national standard GB / T 1616-2014 and GB / T32102-2015.

[0051] (3) Raw material conversion rate calculation method

[0052] 3-(2-hydroxy-2-propyl)phenol conversion rate = (molar amount of 3-(2-hydroxy-2-propyl)phenol feed - molar amount of 3-(2-hydroxy-2-propyl)phenol remaining in the oil phase after the reaction) / molar amount of 3-(2-hydroxy-2-propyl)phenol feed * 100%

[0053] Example 1

[0054] A 500 g MIBK solution of 4 wt% 3-(2-hydroxy-2-propyl)phenol as raw material was prepared, 1,2-propanediol hexadecanoate accounting for 0.3% of the mass of the raw material was added, and after being uniformly mixed, it was added to a 2 L stainless steel reaction kettle; then, an aqueous hydrogen peroxide solution was added to the reaction kettle, the amount of addition being 1.2 times the molar amount of the raw material, and the concentration of the hydrogen peroxide was 10 wt%; the temperature was maintained at 20°C, [TEBSA][HSO4] was added to the reaction kettle, the amount of addition being 0.5% of the mass of the raw material, and the reaction was started. After 20 min, the reaction liquid was cooled to room temperature, the oil and water were separated, the aqueous phase was extracted with MIBK to recover resorcinol, and the extraction phase was mixed with the oil phase of the reaction liquid, the contents of 3-(2-hydroxy-2-propyl)phenol, resorcinol, and byproducts in the oil phase were determined by HPLC, and the raw material conversion rate, product yield, and byproduct selectivity were calculated, and the results are shown in Table 1.

[0055] Example 2

[0056] A 500 g MIBK solution of 5 wt% 3-(2-hydroxy-2-propyl)phenol as raw material was prepared, propylene glycol monostearate accounting for 0.3% of the mass of the raw material was added, and after being uniformly mixed, it was added to a 2 L stainless steel reaction kettle; then, an aqueous hydrogen peroxide solution was added to the reaction kettle, the amount of addition being 1.6 times the molar amount of the raw material, and the concentration of the hydrogen peroxide was 8 wt%; the temperature was raised to 40°C, [TEBSA][HSO4] was added to the reaction kettle, the amount of addition being 1% of the mass of the raw material, and the reaction was started. After 8 min, the reaction liquid was cooled to room temperature, the oil and water were separated, the aqueous phase was extracted with MIBK to recover resorcinol, and the extraction phase was mixed with the oil phase of the reaction liquid, the contents of 3-(2-hydroxy-2-propyl)phenol, resorcinol, and byproducts in the oil phase were determined by HPLC, and the raw material conversion rate, product yield, and byproduct selectivity were calculated, and the results are shown in Table 1.

[0057] Example 3

[0058] A 500g 6.67wt% 3-(2-hydroxy-2-propyl)phenol MIBK solution was prepared as a raw material, 0.3% of the raw material by mass of propylene glycol monostearate was added, and after being uniformly mixed, it was added to a 2L stainless steel reaction kettle; then, an aqueous hydrogen peroxide solution was added to the reaction kettle, the addition amount was 2 times the molar amount of the raw material, and the hydrogen peroxide concentration was 6wt%; the temperature was raised to 60°C, [TEBSA][HSO4] was added to the reaction kettle, the addition amount was 1.5% of the mass of the raw material, and the reaction started. After 6 minutes, the reaction liquid was cooled to room temperature, oil and water were separated, the aqueous phase was extracted with MIBK to recover resorcinol, and the extract phase was mixed with the oil phase of the reaction liquid, the oil phase was determined by HPLC method to determine the content of 3-(2-hydroxy-2-propyl)phenol, resorcinol, and byproducts, and the raw material conversion rate, product yield, and byproduct selectivity were calculated, and the results are shown in Table 1.

[0059]

Example 4

[0060] A 500g 10wt% 3-(2-hydroxy-2-propyl)phenol MIBK solution was prepared as a raw material, 0.3% of the raw material by mass of propylene glycol monostearate was added, and after being uniformly mixed, it was added to a 2L stainless steel reaction kettle; then, an aqueous hydrogen peroxide solution was added to the reaction kettle, the addition amount was 3 times the molar amount of the raw material, and the hydrogen peroxide concentration was 4wt%; the temperature was raised to 70°C, [TEBSA][HSO4] was added to the reaction kettle, the addition amount was 2% of the mass of the reaction liquid, and the reaction started. After 4 minutes, the reaction liquid was cooled to room temperature, oil and water were separated, the aqueous phase was extracted with MIBK to recover resorcinol, and the extract phase was mixed with the oil phase of the reaction liquid, the oil phase was determined by HPLC method to determine the content of 3-(2-hydroxy-2-propyl)phenol, resorcinol, and byproducts, and the raw material conversion rate, product yield, and byproduct selectivity were calculated, and the results are shown in Table 1.

[0061]

Example 5

[0062] A 500g 25wt% 3-(2-hydroxy-2-propyl)phenol MIBK solution was prepared as a raw material, 0.3% of the raw material by mass of 1,2-propanediol monohexadecanoate was added, and after being uniformly mixed, it was added to a 2L stainless steel reaction kettle; then, an aqueous hydrogen peroxide solution was added to the reaction kettle, the addition amount was 5 times the molar amount of the raw material, and the hydrogen peroxide concentration was 3wt%; the temperature was raised to 40°C, [TEBSA][HSO4] was added to the reaction kettle, the addition amount was 1.5% of the mass of the raw material, and the reaction started. After 3 minutes, the reaction liquid was cooled to room temperature, oil and water were separated, the aqueous phase was extracted with MIBK to recover resorcinol, and the extract phase was mixed with the oil phase of the reaction liquid, the oil phase was determined by HPLC method to determine the content of 3-(2-hydroxy-2-propyl)phenol, resorcinol, and byproducts, and the raw material conversion rate, product yield, and byproduct selectivity were calculated, and the results are shown in Table 1.

[0063] Example 6

[0064] A 500g 10wt% 3-(2-hydroxy-2-propyl)phenol MIBK solution was prepared, 1,2-propanediol monododecanoate was added to the solution at a dosage of 0.3% of the mass of the raw material, and the mixture was uniformly mixed and then added to a 2L stainless steel reaction kettle. Subsequently, hydrogen peroxide aqueous solution was added to the reaction kettle at a dosage of 10 times the molar amount of the raw material, and the concentration of the hydrogen peroxide was 3wt%. The temperature was raised to 40°C, [TEBSA][HSO4] was added to the reaction kettle at a dosage of 1.5% of the mass of the raw material, and the reaction was started. After 3min, the reaction liquid was cooled to room temperature, the oil and water were separated, the aqueous phase was extracted with MIBK to recover the resorcinol, and the extraction phase was mixed with the oil phase of the reaction liquid. The content of 3-(2-hydroxy-2-propyl)phenol, resorcinol, and byproducts in the oil phase was determined by HPLC, and the raw material conversion rate, product yield, and byproduct selectivity were calculated. The results are shown in Table 1.

[0065] Example 7

[0066] A 500g 10wt% 3-(2-hydroxy-2-propyl)phenol MIBK solution was prepared, 1,2-propanediol monododecanoate was added to the solution at a dosage of 0.3% of the mass of the raw material, and the mixture was uniformly mixed and then added to a 2L stainless steel reaction kettle. Subsequently, hydrogen peroxide aqueous solution was added to the reaction kettle at a dosage of 5 times the molar amount of the raw material, and the concentration of the hydrogen peroxide was 3wt%. The temperature was raised to 40°C, [TEBSA][HSO4] was added to the reaction kettle at a dosage of 1.5% of the mass of the raw material, and the reaction was started. After 8min, the reaction liquid was cooled to room temperature, the oil and water were separated, the aqueous phase was extracted with MIBK to recover the resorcinol, and the extraction phase was mixed with the oil phase of the reaction liquid. The content of 3-(2-hydroxy-2-propyl)phenol, resorcinol, and byproducts in the oil phase was determined by HPLC, and the raw material conversion rate, product yield, and byproduct selectivity were calculated. The results are shown in Table 1.

[0067] Example 8

[0068] 500g 10wt% 3-(2-hydroxy-2-propyl)phenol in MIBK was prepared as raw material, 0.3% of propylene glycol monostearate based on the mass of the raw material was added, and after being mixed uniformly, it was added to a 2L stainless steel reaction kettle; then, hydrogen peroxide aqueous solution was added to the reaction kettle, and the addition amount was 5 times the molar amount of the raw material, and the concentration of hydrogen peroxide was 3wt%; the temperature was raised to 40℃, and [TEBSA][HSO4] was added to the reaction kettle, and the addition amount was 1.5% of the mass of the raw material; the reaction was started. After 8min, the reaction liquid was cooled to room temperature, and oil and water were separated, the water phase was extracted by MIBK to recover resorcinol, and the extraction phase was mixed with the oil phase of the reaction liquid, and the content of 3-(2-hydroxy-2-propyl)phenol, resorcinol and by-products in the oil phase was determined by HPLC method, and the raw material conversion rate, product yield and by-product selectivity were counted, and the results are shown in Table 1.

[0069] Comparative Example 1

[0070] Resorcinol was synthesized according to the method basically same as Example 7, the only difference was that 1,2-propanediol monododecanoate was not added. The raw material conversion rate, product yield and by-product selectivity were counted, and the results are shown in Table 1.

[0071] Comparative Example 2

[0072] Resorcinol was synthesized according to the method basically same as Example 7, the only difference was that [TEBSA][HSO4] was replaced by an equal amount of 98wt% sulfuric acid, and 1,2-propanediol monododecanoate was not added.

[0073] Table 1, analysis results

[0074]

[0075] In Table 1, the structure of the product of the alkylation of resorcinol and m-isopropenylphenol is as follows:

[0076]

[0077] From the test results in Table 1, it can be seen that the synthesis method of the present application has a raw material conversion rate of more than 96% and a product yield of more than 93%, and the content of typical by-products is very low.

[0078] The above only describes the preferred embodiments of the present application, and it should be pointed out that for ordinary skilled persons in the art, without departing from the method of the present application, several improvements and supplements can be made, and these improvements and supplements should also be considered as the protection range of the present application.

Claims

1. A method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol, characterized in that, This includes the process of using Brønsted acidic ionic liquid as a catalyst and propylene glycol fatty acid ester as an auxiliary agent to react 3-(2-hydroxy-2-propyl)phenol and hydrogen peroxide to produce resorcinol; The Brønsted acidic ionic liquid is [TEBSA][HSO4]; The propylene glycol fatty acid ester is at least one of the substances having the following structural expression: Where n is 8-16.

2. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 1, characterized in that, The amount of the Brønsted acidic ionic liquid added is 0.5-2% of the mass of 3-(2-hydroxy-2-propyl)phenol.

3. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 1, characterized in that, The amount of propylene glycol fatty acid ester used is 1-5% of the catalyst mass.

4. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to any one of claims 1-3, characterized in that, The molar ratio of 3-(2-hydroxy-2-propyl)phenol to hydrogen peroxide is 1:(1-10).

5. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 4, characterized in that, The molar ratio of 3-(2-hydroxy-2-propyl)phenol to hydrogen peroxide is 1:(2-5).

6. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 4, characterized in that, The hydrogen peroxide has a mass concentration of 2-30%.

7. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 6, characterized in that, The hydrogen peroxide has a mass concentration of 3-10%.

8. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to any one of claims 1-3, characterized in that, The reaction temperature is 20-70℃, and the reaction time is 3-20 min.

9. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to any one of claims 1-3, characterized in that, The reaction feeding process is as follows: first, 3-(2-hydroxy-2-propyl)phenol and the co-catalyst are mixed in an organic solvent to obtain an organic phase; then, the catalyst and hydrogen peroxide are mixed to obtain an aqueous phase; and finally, the aqueous phase is added to the organic phase to carry out the reaction.

10. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 9, characterized in that, The organic solvent is a ketone.

11. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 10, characterized in that, The organic solvent is one or more of acetone, methyl ethyl ketone, and methyl isobutyl ketone.

12. The method for synthesizing resorcinol from 3-(2-hydroxy-2-propyl)phenol according to claim 9, characterized in that, The amount of the organic solvent used is 4-25 times the mass of 3-(2-hydroxy-2-propyl)phenol.

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