Nonionic Gemini surfactant of (Octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether and its synthesis method

Abstract

The invention discloses a nonionic Gemini surfactant, (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether and its synthesis method, which nonionic Gemini surfactant has a structural formula of:

##STR00001##

and is prepared by a two-step reaction: S1, diphenyl ether 4,4-dicarboxylic acid is subjected to an acyl chlorination reaction to obtain diphenyl ether 4,4-dicarbonyl dichloride; S2, diphenyl ether 4,4-dicarbonyl dichloride is subjected to an esterification reaction with octylphenol polyoxyethylene ether (OP-10) to obtain the target product (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether. The surfactant of the present invention is expected to be applied in tertiary oil recovery as an alkali/surfactant, in polymer/surfactant binary composite flooding, in alkali/surfactant/polymer ternary composite flooding, as a microemulsion emulsifier and the like, and it can also be compounded with a common surfactant to reduce the use cost, and thus create conditions for its large-scale application.

Claims

1. A nonionic Gemini surfactant of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether, having the structural formula: ##STR00004##

2. A synthesis method for the non-ionic gemini surfactant according to claim 1, wherein the method comprises: S1, subjecting diphenyl ether 4,4-dicarboxylic acid to an acyl chlorination reaction to obtain diphenyl ether 4,4-dicarbonyl dichloride; and S2, subjecting diphenyl ether 4,4-dicarbonyl dichloride to an esterification reaction with octylphenol polyoxyethylene ether (OP-10) to obtain (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether.

3. The synthesis method according to claim 2, wherein in S1, diphenyl ether 4,4-dicarboxylic acid is subjected to an acyl chlorination reaction with thionyl chloride to obtain the diphenyl ether 4,4-dicarbonyl dichloride.

4. The synthesis method according to claim 3, wherein in S1, diphenyl ether 4,4-dicarboxylic acid and N,N-dimethylformamide are added to a solvent, thionyl chloride is added dropwise to the reaction system, then after completion of the dropwise addition the reaction is continued until the reaction completes; and the reaction system is concentrated to dryness to give diphenyl ether 4,4-dicarbonyl dichloride, which is used directly in a next reaction.

5. The synthesis method according to claim 4, wherein the molar ratio of diphenyl ether 4,4-dicarboxylic acid to N,N-dimethylformamide is 1: (0.1 to 0.2).

6. The synthesis method according to claim 4, wherein the solvent is toluene.

7. The synthesis method according to claim 4, wherein the molar ratio of diphenyl ether 4,4-dicarboxylic acid to thionyl chloride is 1: (2.1 to 2.2).

8. The synthesis method according to claim 4, wherein the reaction is carried out under a protective atmosphere comprising a protective gas, wherein the protective gas includes nitrogen and one or more inert gases.

9. The synthesis method according to claim 4, wherein upon completion of the dropwise addition of thionyl chloride, the reaction is continued at an elevated temperature.

10. The synthesis method according to claim 9, wherein the temperature is elevated to 70 C.

11. The synthesis method according to claim 2, wherein the step of S2 comprises: dissolving diphenyl ether 4,4-dicarbonyl dichloride in a first solvent to obtain a first solution; adding OP-10, N,N-dimethylformamide, triethylamine, and 2,6-di-tert-butyl-4-methylphenol as an antioxidant to a second solvent to obtain a second solution; slowly and dropwise adding the first solution to the second solution to carry out an esterification reaction; and after completion of the reaction, performing a post-treatment purification to obtain (nonylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether.

12. The synthesis method according to claim 11, wherein the first solvent is methylene chloride.

13. The synthesis method according to claim 11, wherein the second solvent is methylene chloride.

14. The synthesis method according to claim 11, wherein the molar ratio of OP-10 to diphenyl ether 4,4-dicarbonyl dichloride is (2.1 to 2.2): 1.

15. The synthesis method according to claim 11, wherein the molar ratio of N,N-dimethylformamide to diphenyl ether 4,4-dicarbonyl dichloride is (0.1 to 0.2): 1.

16. The synthesis method according to claim 11, wherein the molar ratio of triethylamine to diphenyl ether 4,4-dicarbonyl dichloride is (2.1 to 2.2): 1.

17. The synthesis method according to claim 11, wherein the molar ratio of 2,6-di-tert-butyl-4-methylphenol as antioxidant to diphenyl ether 4,4-dicarbonyl dichloride is (0.1 to 0.2): 1.

18. The synthesis method according to claim 11, wherein the post-treatment purification comprises: quenching with water; separating the liquid; recovering a organic phase, concentrating the organic phase to dryness; and performing a purification by column chromatography, to obtain the target product.

19. The synthesis method according to claim 18, wherein the developing agent in the purification by column chromatography is a system of petroleum ether and ethyl acetate.

20. The synthesis method according to claim 19, wherein the developing agent comprises a volume of petroleum ether to a volume of ethyl acetate having a ratio of 10:1.

Description

DESCRIPTION OF THE DRAWINGS

[0047] FIG. 1 is an infrared spectrum of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether prepared in the examples of the present invention.

[0048] FIG. 2 is a nuclear magnetic hydrogen spectrum of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether prepared in the examples of the present invention.

[0049] FIG. 3 is a graph of surface tension versus concentration (25 C.) of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether prepared in in the examples of the present invention.

DETAILED DESCRIPTION

[0050] In order to more clearly illustrate the present invention, the present invention will be further described in connection with preferable examples. It will be understood by those skilled in the art that the following detailed description is illustrative but not limiting, and should not be used to limit the scope of the invention.

[0051] Preparation of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether

[0052] (1) Synthesis of diphenyl ether 4,4-dicarbonyl dichloride

[0053] Into a three-necked flask placed in a constant temperature water bath and equipped with an agitator, 2 g (7.75 mmol) of diphenyl ether 4,4-dicarboxylic acid and 0.113 g (1.55 mmol) of DMF (catalyst) were added, and 50 mL of toluene as solvent was further added under the protection of nitrogen. After that, 2.03 g (17.04 mmol) of thionyl chloride was slowly added dropwise, and stirred. After completion of the dropwise addition, the temperature is raised up to 70 C., and the reaction processed for 4 h (the end point of the reaction is monitored by TLC). After completion of the reaction, the reaction was concentrated to dryness to give a brown solid intermediate, diphenyl ether 4,4-dicarbonyl dichloride which was used directly in the next reaction.

[0054] (2) Synthesis of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether

[0055] 2.7 g (9.15 mmol) of diphenyl ether 4,4-dicarbonyl dichloride is dissolved in a certain amount of methylene chloride. 13.02 g (20.13 mmol) of OP-10, 0.134 g (1.83 mmol) of DMF, 2.04 g (20.13 mmol) of TEA (triethylamine) and 0.403 g (1.83 mmol) of BHT (2,6-di-tert-butyl-4-methylphenol) as an antioxidant were added into a three-necked flask equipped with an agitator, and a certain amount of methylene chloride was added therein to dissolve the raw materials. Into the three-necked flask, the diphenyl ether 4,4-dicarbonyl dichloride in methylene chloride was slowly added dropwise, and the reaction was performed at room temperature for 4 h (the end point of the reaction is monitored by TLC). After completion of the reaction, water was added to quench, the liquid was separated, the organic phase was recovered, and concentrated to dryness, and purified by a column (at a condition of V (petroleum ether):V (ethyl acetate) EA=10:1). Thus, 8.3 g (5.49 mmol) of a brown oil-like product, (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether, was obtained.

[0056] An infrared spectrum of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether

[0057] The infrared spectrum of the obtained target product is shown in FIG. 1, and it can be seen from the analysis of the spectrum that:

[0058] 2924, 2848 are CH.sub.3, CH.sub.2 extensional vibration peaks; 1501, 1466 are vibrational peaks of the benzene ring skeleton; 872, 811 are characteristic peaks of para-substitution of benzene ring; 1728 is CO extensional vibration peak; 1105 is CO extensional vibration peak.

[0059] A nuclear magnetic hydrogen spectrum of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether

[0060] The nuclear magnetic hydrogen spectrum of the obtained target product is shown in FIG. 2, and it can be seen from the analysis of the spectrum that:

[0061] .sup.1H-NMR(400 MHz, CDCl.sub.3): : 0.71 [3H, CH.sub.3CH.sub.2], 1.25-1.33 [10H, CH.sub.3(CH.sub.2).sub.5CH.sub.2CH.sub.2], 1.69 [2H, (CH.sub.3(CH.sub.2).sub.5CH.sub.2CH.sub.2], 2.04 [2H, CH.sub.3(CH.sub.2).sub.5CH.sub.2CH.sub.2], 3.60-3.68 [16H, (CH.sub.2CH.sub.2O).sub.8CH.sub.2CH.sub.2OC], 3.70-3.73 [2H, (CH.sub.2CH.sub.2O).sub.8CH.sub.2CH.sub.2OC], 3.81-3.85 [2H, (CH.sub.2CH.sub.2O).sub.8CH.sub.2CH.sub.2OC], 4.09-4.12 [2H, COOCH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.8], 4.45-4.48 [2H, COOCH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.8], 7.04-7.28 [1H, CHCHCCOO], 8.05-8.08 [1H, CHCHCCOO].

[0062] Surface Activity Determination of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether

[0063] The ability of surfactant to reduce the surface tension of water is an important parameter to evaluate its surface activity. The surface tension of aqueous solution of target product at different concentration at 25 C. is determined by a hanging plate method, and a concentration dependent curve was made for the surface tension of an aqueous solution of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether Gemini surfactant (FIG. 3). From this curve, the surface activity parameters of the Gemini surfactant can be obtained, that is, the critical micelle concentration cmc is 0.01 wt %, and the surface tension cmc at the critical micelle concentration is 30 mN/m.

[0064] It will be apparent that the above-described examples of the present invention are merely for clearly illustration of the present invention and are not intended to limit the embodiments of the present invention. To those of ordinary skill in the art, other different forms of changes or variations may also be made on the basis of the above description. It is unable to exhaust all implementations, and the obvious changes or variations that are introduced from the technical solution of the present invention are still within the scope of the present invention.