Alicyclic ethoxylated sodium bisphenol sulfonate and preparation method thereof

Abstract

The present invention relates to the field of fine chemical technology, particularly to the field of IPC C07C303. More specifically, it relates to a cycloaliphatic ethoxylated sodium bisphenol sulfonate and a preparation method thereof. The general structural formula is shown in Formula 1: wherein X comprises one of O, CH2, and (CH3)2C, and R comprises an unsaturated ring. The preparation method comprises the following steps: S1, an etherification reaction: adding a cycloolefin, an ethoxylated bisphenol compound, and an acidic catalyst to a reaction solvent, heating the reaction, and removing the solvent, catalyst, and excess cycloolefin to obtain an alicyclic ethoxylated bisphenol intermediate; S2, a sulfonation neutralization reaction: cooling the intermediate, adding a sulfonating reagent dropwise for reaction, and post-treating the intermediate to obtain the product. The preparation method is simple and mild, and the product has good water solubility and surface activity.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals, in particular to the field of IPC C07C303, and more specifically to an alicyclic ethoxylated sodium bisphenol sulfonate and a preparation method thereof. Background Art

[0002] Sodium alkyl diphenyl ether disulfonate is a type of gemini surfactant, with a molecular structure containing two hydrophobic groups, two hydrophilic groups, and a linking group. Compared to traditional surfactants, this type of catalyst has a lower critical micelle concentration, better low-temperature solubility and solubilization properties, and better acid, alkali, and hard water resistance. It is widely used in industries such as emulsion polymerization, industrial cleaning, textiles, and water-based coatings.

[0003] Chinese invention patent CN101185866A discloses a class of gemini anionic surfactants and their preparation methods. These surfactants have two synthetic routes: an alkylation reaction, using alkyl bromide and diphenyl ether as raw materials, catalyzed by the Lewis acid AlCl3, to produce the intermediate alkyl diphenyl ether; and a phase transfer catalytic reaction, using alkylphenol and oxyethylene ether as raw materials, catalyzed by the phase transfer catalyst hexadecyltrimethylammonium bromide, to produce alkylphenol oxyethylene ether. The resulting intermediate is sulfonated and neutralized to yield the gemini anionic surfactant. This class of surfactants exhibits good surface activity and synergistic effects with other surfactants, promising widespread application in tertiary oil recovery. However, their adsorption capacity is high and their dispersibility is still insufficient. Summary of the Invention

[0004] The first aspect of the present invention provides an alicyclic ethoxylated sodium bisphenol sulfonate, the general structural formula of which is shown in Formula 1: 1; wherein X includes one of O, CH2, and (CH3)2C, and R includes an unsaturated ring.

[0005] The unsaturated ring has 8 to 14 carbon atoms.

[0006] Preferably, the unsaturated ring has 10-12 carbon atoms.

[0007] More preferably, the unsaturated ring has 10 or 12 carbon atoms.

[0008] The second aspect of the present invention provides a method for preparing alicyclic ethoxylated sodium bisphenol sulfonate, comprising the following steps:

[0009] S1, etherification reaction: adding a cycloolefin, an ethoxylated bisphenol compound, and an acidic catalyst to a first solvent, heating for reaction, and removing the solvent, catalyst, and excess cycloolefin to obtain an alicyclic ethoxylated bisphenol intermediate;

[0010] S2, sulfonation neutralization reaction: the above intermediate is mixed with the second solvent, cooled and then dropwise added with a sulfonation reagent for reaction, and the product is obtained after post-treatment.

[0011] Preferably, the cycloolefin comprises tricyclodecene or tetracyclododecene.

[0012] Preferably, the ethoxylated bisphenol compound includes one of ethoxylated bisphenol A, ethoxylated bisphenol F and ethoxylated dihydroxy diphenyl ether.

[0013] The acidic catalyst includes at least one of concentrated sulfuric acid, anhydrous hydrofluoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, macroporous sulfonic acid resin, and perfluorosulfonic acid resin.

[0014] Preferably, the acidic catalyst comprises at least one of chlorosulfonic acid and sulfur trioxide.

[0015] The amount of the acidic catalyst used is 5 to 30% of the mass of the cycloolefin.

[0016] Preferably, the amount of the acidic catalyst is 5 to 15% of the mass of the cycloolefin.

[0017] More preferably, the amount of the acidic catalyst is 5-10% of the mass of the cycloolefin.

[0018] The reaction temperature in S1 is 30-120° C. and the reaction time is 6-24 h.

[0019] Preferably, the reaction temperature in S1 is 70-90° C. and the reaction time is 6-8 h.

[0020] The molar ratio of the cycloolefin to the ethoxylated bisphenol compound is (2-5):1.

[0021] The present application has found that the molar ratio of the cycloolefin to the ethoxylated bisphenol compound is (2-5):1, which can increase the yield of the alicyclic ethoxylated bisphenol intermediate to more than 50%, while also improving the purity of the intermediate and reducing the difficulty of post-processing. This may be because the acidic protons (H+) in the etherification reaction form OH bonds with the oxygen atoms in the alcohol molecules, thereby increasing the reaction rate of the protonated alcohol molecules and improving the stability of the protonated alcohol molecules, thereby facilitating subsequent nucleophilic attacks and forming new OC bonds.

[0022] Preferably, the molar ratio of the cycloolefin to the ethoxylated bisphenol compound is (2.5-3):1.

[0023] The molar ratio of the sulfonating agent to the alicyclic ethoxylated bisphenol intermediate is (2-4):1.

[0024] Preferably, the molar ratio of the sulfonating agent to the alicyclic ethoxylated bisphenol intermediate is (2-3):1.

[0025] The first solvent includes at least one of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetonitrile, toluene, and xylene.

[0026] Preferably, the first solvent comprises at least one of toluene and xylene.

[0027] The second solvent includes at least one of dichloromethane, chloroform, dichloroethane, tetrachloroethane, nitromethane, and nitroethane.

[0028] Preferably, the second solvent comprises at least one of dichloromethane and dichloroethane.

[0029] Beneficial effects

[0030] 1. The process for preparing alicyclic ethoxylated sodium bisphenol sulfonate in this application is simple and easy to operate.

[0031] 2. The molar ratio of cycloolefin and ethoxylated bisphenol compound is (2-5):1, which can improve the alicyclic ethoxylation

[0032] The yield of the bisphenol intermediate reaches more than 50%, while the purity of the intermediate is improved and the difficulty of post-processing is reduced.

[0033] 3. The molar ratio of the sulfonating agent to the alicyclic ethoxylated bisphenol intermediate is (2-4):1, which can further increase the yield of the alicyclic ethoxylated bisphenol intermediate to more than 70%.

[0034] 4. The alicyclic ethoxylated sodium bisphenol sulfonate prepared in this application has good surface activity and a critical micelle concentration of 110-130 mg / L.

[0035] 5. The surface tension of the alicyclic ethoxylated sodium bisphenol sulfonate prepared in the present application is 65-75 mN / m in a 0.001 wt% aqueous solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the infrared spectrum of the alicyclic ethoxylated sodium bisphenol sulfonate prepared in Example 2. DETAILED DESCRIPTION

[0037] Example 1

[0038] An alicyclic ethoxylated sodium bisphenol sulfonate, the structure of which is shown in Formula 9:

[0039]

[0040] A method for preparing alicyclic ethoxylated sodium bisphenol sulfonate comprises the following steps:

[0041] As shown in the following formula, 30 mL of anhydrous toluene (water content <100 ppm) was added to a 250 mL three-necked flask, followed by the addition of ethoxylated bisphenol A1 (5 g, 15.8 mmol), tricyclodecene (5.3 g, 39.6 mmol) and concentrated sulfuric acid (0.4 g). The atmosphere was then replaced with nitrogen and heated to 75° C. for 6 h. After the reaction was completed, the mixture was cooled to room temperature and neutralized with 10 wt % alkali solution. The solvent and excess tricyclodecene were removed from the upper organic phase under vacuum to obtain the alicyclic ethoxylated bisphenol A intermediate 2, which could be directly used in the next sulfonation reaction.

[0042]

[0043] Intermediate 2 (7 g, 12 mmol) was dissolved in 30 mL of dichloromethane, and then the temperature was lowered to about 5 ° C. SO3 (1.95 g, 24.5 mmol) dichloromethane (20 mL) solution was added dropwise, and the reaction temperature was controlled not to exceed 10 ° C. The addition was completed in about 40 minutes. The temperature was raised to room temperature and the reaction was continued for 1 hour. Then, it was neutralized with 8% sodium hydroxide solution (12 g) to pH 7. The product was dissolved in the upper aqueous phase to obtain an aqueous solution of product 9 with a content of about 45%.

[0044] Example 2

[0045] An alicyclic ethoxylated sodium bisphenol sulfonate, the structure of which is shown in Formula 10:

[0046]

[0047] A method for preparing alicyclic ethoxylated sodium bisphenol sulfonate comprises the following steps:

[0048] As shown in the following formula, 30 mL of anhydrous xylene (water content <100 ppm) was added to a 250 mL three-necked flask, followed by the addition of ethoxylated bisphenol A1 (5 g, 15.8 mmol), tetracyclododecene (7.6 g, 47.5 mmol) and perfluorosulfonic acid resin (1 g), followed by replacement with nitrogen atmosphere, heating to 85 ° C for 8 h, and after completion of the reaction, cooling to room temperature, filtering the resin catalyst, alkali washing, and vacuum removal of the solvent and excess tetracyclododecene to obtain alicyclic ethoxylated bisphenol A intermediate 3, the infrared spectrum of which is shown in FIG. Figure 1 As shown, it can be directly used in the next sulfonation reaction.

[0049]

[0050] The intermediate 3 (5 g, 12 mmol) was dissolved in 30 mL of dichloromethane, and then the temperature was lowered to about 5 ° C. SO3 (2.54 g, 31.9 mmol) dichloromethane (20 mL) solution was added dropwise, and the reaction temperature was controlled not to exceed 10 ° C. The addition was completed in about 40 minutes. The temperature was raised to room temperature and the reaction was continued for 1 hour. Then, it was neutralized with 8% sodium hydroxide solution (12 g) to pH 7. The product was dissolved in the upper aqueous phase to obtain an aqueous solution of product 10 with a content of about 45%.

[0051] A method for preparing an alicyclic ethoxylated bisphenol intermediate comprises the following steps:

[0052] As shown in the following formula, 30 mL of anhydrous toluene (water content <100 ppm) was added to a 250 mL three-necked flask, followed by the addition of ethoxylated bisphenol F 4 (5 g, 17.4 mmol), tricyclodecene (7 g, 52 mmol) and perfluorosulfonic acid resin (1 g). The flask was then replaced with a nitrogen atmosphere and heated to 80° C. for 8 h. After the reaction was completed, the flask was cooled to room temperature, the catalyst was filtered out, and the flask was washed with alkali. The solvent and excess tricyclodecene were removed from the upper organic phase under vacuum to obtain the alicyclic ethoxylated bisphenol F intermediate 5, which could be directly used in the next sulfonation reaction.

[0053]

[0054] Example 4

[0055] An alicyclic ethoxylated sodium bisphenol sulfonate, characterized in that the structure is shown in Formula 11:

[0056]

[0057] A method for preparing alicyclic ethoxylated sodium bisphenol sulfonate comprises the following steps:

[0058] As shown in the following formula, 50 mL of anhydrous THF (water content <100 ppm) was added to a 250 mL three-necked flask, followed by the addition of ethoxylated bisphenol F 4 (5 g, 17.4 mmol), tetracyclododecene (7.8 g, 48.6 mmol) and trifluoromethanesulfonic acid (0.3 g). The mixture was then replaced with a nitrogen atmosphere and heated to 80° C. for 8 h. After the reaction was completed, the mixture was cooled to room temperature and the solvent was removed. 50 mL of toluene was added, and after neutralization with alkali solution, the solvent and excess tetracyclododecene were removed from the upper toluene phase under vacuum to obtain alicyclic ethoxylated bisphenol F intermediate 6, which could be directly used in the next sulfonation reaction.

[0059]

[0060] Intermediate 6 (5 g, 12 mmol) was dissolved in 30 mL of dichloromethane, and then the temperature was lowered to about 5 ° C. SO3 (2.7 g, 33.9 mmol) dichloromethane (20 mL) solution was added dropwise, and the reaction temperature was controlled not to exceed 10 ° C. The addition was completed in about 40 minutes. The temperature was raised to room temperature and the reaction was continued for 1 hour. Then, it was neutralized with 8% sodium hydroxide solution (12 g) to pH 7. The product was dissolved in the upper aqueous phase to obtain an aqueous solution of product 11 with a content of about 45%.

[0061] Example 5

[0062] A method for preparing alicyclic ethoxylated sodium bisphenol sulfonate comprises the following steps:

[0063] As shown in the following formula, 30 mL of anhydrous xylene (water content <100 ppm) was added to a 250 mL three-necked flask, followed by the addition of ethoxylated dihydroxy diphenyl ether 7 (5 g, 17.2 mmol), tricyclodecene (6.93 g, 51.7 mmol) and methanesulfonic acid (1 g). The mixture was then replaced with a nitrogen atmosphere and heated to 80° C. for 8 h. After the reaction was completed, the mixture was cooled to room temperature, neutralized with alkali solution, and then phases were separated. The solvent and excess tricyclodecene were removed from the upper toluene phase under vacuum to obtain the alicyclic ethoxylated dihydroxy diphenyl ether intermediate 8, which could be directly used in the next sulfonation reaction.

[0064]

[0065] Performance testing methods

[0066] The yields of the intermediates in the examples were calculated and the test data are listed in Table 1.

[0067] The alicyclic ethoxylated sodium bisphenol sulfonate prepared in Examples 1, 2, and 4 was tested for wettability, critical micelle concentration, and surface tension. The test data are listed in Table 2.

[0068] Performance test data

[0069] Table 1

[0070] Intermediate yield% Example 1 65 Example 2 93 Example 3 94 Example 4 72 Example 5 52

[0071] Table 2

[0072]

Claims

1. An alicyclic ethoxylated sodium bisphenol sulfonate, characterized in that: The general structural formula is shown in Formula 1: , 1; wherein X includes one of O, CH2, (CH3)2C, and R is one of Formula 2 and Formula 3; 2; 3.

2. A method for preparing the alicyclic ethoxylated sodium bisphenol sulfonate according to claim 1, characterized in that: The following steps are involved: S1, etherification reaction: adding a cycloolefin, an ethoxylated bisphenol compound, and an acidic catalyst to a first solvent, heating for reaction, and removing the solvent, catalyst, and excess cycloolefin to obtain an alicyclic ethoxylated bisphenol intermediate; S2, sulfonation neutralization reaction: the above intermediate is mixed with the second solvent, cooled and then dropwise added with a sulfonation reagent for reaction, and the product is obtained after post-treatment.

3. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 2, wherein: The acidic catalyst includes at least one of concentrated sulfuric acid, anhydrous hydrofluoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, macroporous sulfonic acid resin, and perfluorosulfonic acid resin.

4. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 3, wherein: The amount of the acidic catalyst used is 5-30% of the mass of the cycloolefin.

5. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 4, wherein: The reaction temperature in S1 is 30-120° C. and the reaction time is 6-24 h.

6. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 5, characterized in that: The molar ratio of the cycloolefin to the ethoxylated bisphenol compound is (2-5):

1.

7. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 6, characterized in that: The molar ratio of the sulfonating agent to the alicyclic ethoxylated bisphenol intermediate is (2-4):

1.

8. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 7, characterized in that: The first solvent includes at least one of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetonitrile, toluene, and xylene.

9. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 8, characterized in that: The second solvent includes at least one of dichloromethane, chloroform, dichloroethane, tetrachloroethane, nitromethane, and nitroethane.

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