Alicyclic ethoxylated sodium bisphenol sulfonate and preparation method thereof

Abstract

The invention relates to the technical field of fine chemical engineering, in particular to the field of IPC C07C303, and more particularly relates to alicyclic ethoxylated sodium bisphenol sulfonate and a preparation method thereof. A structural general formula is shown as a formula 1: # imgabs0 #, wherein X comprises one of O, CH2 and (CH3) 2C, and R comprises an unsaturated ring. The preparation method comprises the following steps: S1, etherification reaction: adding cycloolefin, an ethoxylated bisphenol compound and an acidic catalyst into a reaction solvent, heating for reaction, and removing the solvent, the catalyst and excessive cycloolefin to obtain an alicyclic ethoxylated bisphenol intermediate; and S2, sulfonation and neutralization reaction: cooling the intermediate, dropwise adding a sulfonation reagent for reaction, and performing post-treatment to obtain the product. The preparation method is simple and mild, and has good water solubility and surface activity.

Description

Technical Field

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

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

[0003] Chinese invention patent CN101185866A discloses a type of gemini anionic surfactant and its preparation method. This type of surfactant has two synthetic routes. One is alkylation reaction, using alkyl bromide and diphenyl ether as raw materials, under the catalysis of Lewis acid AlCl3, to generate intermediate alkyl diphenyl ether; the other is phase transfer catalysis reaction, using alkyl phenol and oxyethylene ether as raw materials, under the catalysis of phase transfer catalyst hexadecyltrimethylammonium bromide, to generate alkylphenol oxyethylene ether. The generated intermediate is sulfonated and neutralized to obtain a gemini anionic surfactant. This type of surfactant has good surface activity and good synergy with other surfactants. It is expected to be widely used in tertiary oil recovery, but its adsorption capacity is strong and its dispersion force is still not high enough. 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, (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 into a first solvent, heating for reaction, and removing the solvent, the 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, the sulfonation reagent is added dropwise after cooling to react, 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 acid catalyst used is 5-30% of the mass of the cycloolefin.

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

[0017] More preferably, the acid catalyst is used in an amount of 5 to 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 6-8h.

[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 increasing the purity of the intermediate and reducing the difficulty of post-processing. This may be because the acidic protons (H+) of the etherification reaction are balanced with the oxygen atoms in the alcohol molecules to form OH bonds, thereby increasing the reaction rate of the protonated alcohol molecules and improving the stability of the protonated alcohol molecules, thereby facilitating subsequent nucleophilic attacks to form 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 route for preparing alicyclic ethoxylated sodium bisphenol sulfonate in the present application is simple and easy to operate.

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

[0032] The yield of bisphenol intermediates reaches more than 50%, while the purity of the intermediates 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 the present 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), followed by replacement with a nitrogen atmosphere, heating to 75 ° C for 6 h, and after the reaction was completed, cooling to room temperature, neutralizing with 10 wt% alkali solution, and removing the solvent and excess tricyclodecene from the upper organic phase in vacuo to obtain alicyclic ethoxylated bisphenol A intermediate 2, which can be directly used in the next sulfonation reaction.

[0042]

[0043] The intermediate 2 (7 g, 12 mmol) was dissolved in 30 mL of dichloromethane, then cooled to about 5°C, and a solution of SO3 (1.95 g, 24.5 mmol) in dichloromethane (20 mL) was added dropwise, and the reaction temperature was controlled not to exceed 10°C. The addition was completed in about 40 min, and the mixture was heated to room temperature and the reaction was continued for 1 h. The mixture was then neutralized with 8% sodium hydroxide solution (12 g) to a pH of 7, and 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 a nitrogen atmosphere, heating to 85 ° C for 8 h, and after the reaction was completed, cooling to room temperature, filtering the resin catalyst, alkali washing, 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, then cooled to about 5°C, and a solution of SO3 (2.54 g, 31.9 mmol) in dichloromethane (20 mL) was added dropwise, and the reaction temperature was controlled not to exceed 10°C. The addition was completed in about 40 min, and the mixture was heated to room temperature and the reaction was continued for 1 h. The mixture was then neutralized with 8% sodium hydroxide solution (12 g) to pH 7, and the product was dissolved in the upper aqueous phase to obtain an aqueous solution of the 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), followed by replacement with nitrogen atmosphere, heating to 80 ° C for reaction for 8 h, and after the reaction was completed, cooling to room temperature, filtering to remove the catalyst, alkali washing, and vacuum removing the solvent and excess tricyclodecene from the upper organic phase to obtain alicyclic ethoxylated bisphenol F intermediate 5, which can 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 as 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), followed by replacement with a nitrogen atmosphere, heating to 80 ° C for reaction for 8 h, and after the reaction was completed, cooling to room temperature, removing the solvent, adding 50 mL of toluene, and neutralizing with alkali solution. The solvent and excess tetracyclododecene were removed from the upper toluene phase in vacuum to obtain alicyclic ethoxylated bisphenol F intermediate 6, which can be directly used in the next sulfonation reaction.

[0059]

[0060] The intermediate 6 (5 g, 12 mmol) was dissolved in 30 mL of dichloromethane, then cooled to about 5°C, and a solution of SO3 (2.7 g, 33.9 mmol) in dichloromethane (20 mL) was added dropwise, and the reaction temperature was controlled not to exceed 10°C. The addition was completed in about 40 minutes, and the mixture was heated to room temperature and the reaction was continued for 1 hour. The mixture was then neutralized with 8% sodium hydroxide solution (12 g) to a pH of 7, and the product was dissolved in the upper aqueous phase to obtain an aqueous solution of the 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 dihydroxydiphenyl ether 7 (5 g, 17.2 mmol), tricyclodecene (6.93 g, 51.7 mmol) and methanesulfonic acid (1 g), followed by replacement with a nitrogen atmosphere, heating to 80 ° C for 8 h, and after completion of the reaction, cooling to room temperature, neutralizing with alkali solution and then separating the phases, and removing the solvent and excess tricyclodecene from the upper toluene phase in vacuo to obtain alicyclic ethoxylated dihydroxydiphenyl ether intermediate 8, which can 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 includes an unsaturated ring.

2. The alicyclic ethoxylated sodium bisphenol sulfonate according to claim 1, characterized in that: The unsaturated ring has 8 to 14 carbon atoms.

3. A method for preparing 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 into a first solvent, heating for reaction, and removing the solvent, the catalyst and excess cycloolefin to obtain an alicyclic ethoxylated bisphenol intermediate; S2, sulfonation neutralization reaction: the above intermediate is mixed with the second solvent, the sulfonation reagent is added dropwise after cooling to react, and the product is obtained after post-treatment.

4. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 3, characterized in that: 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.

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

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

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

1.

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

1.

9. The method for preparing alicyclic ethoxylated sodium bisphenol sulfonate according to claim 8, 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.

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

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