CN100484617C - N-(α-aryloxy)acyl taurate surfactant and its preparation method and use - Google Patents

Abstract

The invention belongs to the field of surfactants, and particularly relates to an N- (alpha-aryloxy) acyl taurate surfactant, and a preparation method and application thereof. The hydrophilic group of the surfactant is taurate or methyl taurate, so the surfactant has the characteristics of low stimulation, low toxicity, softness and the like; the molecule has sulfonic group combined with amide group, has excellent water solubility, hard water resistance, alkali resistance and foamability, and can be well applied to industries such as washing, textile and the like. The surfactant has high activity and critical micelle concentration(CMC) is 10^-7～10^-5mol/L, the surface tension under the critical micelle concentration is 40-25 mN/m, and the interfacial tension with petroleum can reach ultra-low (10) under the condition of weak base and low mineralization degree^-3mN/m), and the surfactant pair Ca²⁺、Mg²⁺The plasma has stronger tolerance and can be applied to tertiary oil recovery. The chemical structural formula is shown as follows.

Description

N-(α-aryloxy)acyl taurate surfactant and its preparation method and use

technical field

The invention belongs to the field of high-efficiency surfactants, and in particular relates to N-(alpha-aryloxy)acyl taurate surfactants and a preparation method and application thereof.

Background technique

N-acyl methyl taurate is a surfactant present in the bile of humans and mammals. It has a structure similar to taurocholic acid. It is an anionic surfactant with high safety. Its molecule It has a sulfonic acid group combined with an amide group, and has excellent water solubility, hard water resistance, alkali resistance, and excellent foaming properties. In addition to the basic properties of emulsifying, washing, dispersing, and foaming, N-acyl methyl taurate surfactants also have properties such as low irritation, low toxicity, mildness, and good biodegradation. They are widely used in cosmetics, washing Agents, shampoos, printing and dyeing auxiliaries, dyeing dispersants, plastic emulsifiers, etc., can also be used in tertiary oil recovery, paint industry and fiber industry.

N-(α-aryloxy) acyl taurate is to introduce aryloxy group at the α position of fatty acyl group. When the alkyl chain on the aromatic ring is short, a fatty acyl group is formed as the main chain. As a branched N-acyl taurate, when the sum of the aromatic ring and its substituent chain length is similar to the aliphatic chain, a double hydrocarbon chain surfactant is formed, that is, a "Y" type surfactant.

Due to the branching of the hydrophobic group in the N-(α-aryloxy)acyl taurate molecule, the solubility of the N-(α-aryloxy)acyl taurate in water increases, while the aromatic The introduction of the radical branched chain increases the coverage of the molecule on the solution surface, so that the activity of the surfactant is greatly improved.

CN200510023559, EP0002675, US2974154, US2987526 etc. suggest the preparation method of N-acyl methyl taurate, but do not relate to N-(α-aryloxy) acyl taurate surfactant.

JP2006-63152, WO03/063812, etc. suggest that N-acyl methyl taurate surfactants are used as detergent compositions, but do not relate to N-(α-aryloxy) acyl taurate surfactants.

JP2003-327518 suggests the use of N-acylmethyl taurate surfactant as a hair dye composition, but does not relate to N-(α-aryloxy)acyl taurate surfactant.

JP11-180838 suggests the use of N-acylmethyl taurate surfactants as oral cleanser compositions, but does not relate to N-(α-aryloxy)acyl taurate surfactants.

Contents of the invention

One of the objectives of the present invention is to provide N-(α-aryloxy)acyl taurate surfactants with high surface activity.

The second object of the present invention is to provide a preparation method of N-(α-aryloxy)acyl taurate surfactant.

The third object of the present invention is to provide the use of N-(α-aryloxy)acyl taurate surfactant.

The fourth object of the present invention is to provide a kind of N-(alpha-aryloxy) acyl taurate surfactant system, so that it can form low or ultra-low interfacial tension with petroleum alone or under the effect of additives, It can be applied in the tertiary oil recovery of the oil field.

The structural formula of the N-(alpha-aryloxy group) acyl taurate surfactant synthesized by the present invention is:

Among them: n=2~28, m=0~26, and 4≤m+n≤28; R=H or CH ₃ , Ar is a benzene ring or a naphthalene ring, M is an alkali metal ion (Li ⁺ , Na ⁺ or K ⁺ ), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ or Ba ²⁺ ), ammonium ions (NH ₄ ⁺ ) or any mixture of the above ions.

N-(α-aryloxy group) acyl taurate surfactant of the present invention is characterized in that: hydrophilic group is taurine or methyl taurine; Aryloxy group is on the branched chain of hydrophobic fatty chain, Located at the α position of the carbonyl group, when the sum of the carbon numbers of the aromatic ring and its substituted alkyl is similar to that of the aliphatic chain, a double hydrocarbon chain surfactant is formed, that is, a "Y" type surfactant; the total carbon number of the hydrophobic group is 12-30.

The synthetic route of N-(α-aryloxy group) acyl taurate surfactant of the present invention comprises the following steps:

(1) Synthesis of α-aryloxy carboxylate

Wherein: n=2-28, m=0-26, and 4≤m+n≤28; R'=CH ₃ or C ₂ H ₅ , Ar is a benzene ring or a naphthalene ring.

Take a certain amount of α-bromocarboxylate, alkylphenol or alkylnaphthol (alkyl carbon number is 0-26) and alkali in the reactor, α-bromocarboxylate: alkylphenol or alkane The molar ratio of base naphthol to base is 1-1.2:1:1-2; the above mixture is dissolved in N,N'-dimethylformamide or dimethyl sulfoxide with a volume ratio of 5-1:1 In a mixed solvent of benzene or toluene (using benzene or toluene as a water separator), heat up to boiling under stirring, reflux to separate water, and wait for no more water to evaporate to indicate that the reaction is complete. After the reaction is completed, the reaction solution is cooled and filtered. The solid Wash with an appropriate amount of organic solvent, combine the washing liquid and transfer it to a separatory funnel, add an appropriate amount of organic solvent and water to extract the washing liquid, dry the organic phase with a desiccant, evaporate the organic solvent, and carry out vacuum distillation to obtain α-aryl Oxycarboxylates.

The organic solvent is ether, petroleum ether, benzene, monochloromethane, dichloromethane, 1,2-dichloroethane, chloroform or any mixture thereof.

The base is anhydrous K ₂ CO ₃ , anhydrous Na ₂ CO ₃ , anhydrous KHCO ₃ , anhydrous NaHCO ₃ , NaOH or KOH.

(2) Synthesis of α-aryloxycarboxylic acid

Wherein: n=2-28, m=0-26, and 4≤m+n≤28; R'=CH ₃ or C ₂ H ₅ , Ar is a benzene ring or a naphthalene ring.

Get the α-aryloxycarboxylate of a certain amount of step (1), sodium hydroxide or potassium hydroxide in the reactor, the mol ratio of α-aryloxycarboxylate and sodium hydroxide or potassium hydroxide is 1 : 1~2; Dissolve the above mixture in an appropriate amount of ethanol/water mixture, wherein the volume ratio of ethanol to water is 1:1~5; heat under stirring until the reaction system refluxes, the reaction liquid becomes clear, indicating that the reaction is complete, continue Stir for about one hour, stop heating, after the reaction is completed, wait for the system to cool down, add dilute hydrochloric acid or dilute sulfuric acid to it until the pH value of the reaction solution is 2-6, stir overnight, filter with suction, wash the solid with water and drain it, and use far-infrared After vacuum drying, a white solid was obtained, namely α-aryloxycarboxylic acid.

(3) Synthesis of N-(α-aryloxy)acyl taurate

method one:

Among them: n=2~28, m=0~26, and 4≤m+n≤28; R=H or CH ₃ , Ar is a benzene ring or a naphthalene ring, M is an alkali metal ion (Li ⁺ , Na ⁺ or K ⁺ ), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ or Ba ²⁺ ), ammonium ions (NH ₄ ⁺ ) or any mixture of the above ions.

Take a certain amount of α-aryloxycarboxylic acid in step (2) and a catalytic amount of catalyst in a reactor (such as a three-necked flask) and dissolve in dichloromethane or tetrahydrofuran solvent, and stir at room temperature for 2 to 6 hours to obtain the active intermediate body, filtered, and after the filtrate was evaporated to dryness, the active intermediate was dissolved in a mixed solution of tetrahydrofuran/water with a volume ratio of 1 to 5:1, and taurine or methyl taurine and alkali were added, wherein α-aryl Oxygen carboxylic acid: taurine or methyl taurine: the molar ratio of alkali is 1:1~2:1~2, stir at room temperature for 4~10 hours, after the reaction is completed, transfer the reaction solution to a separatory funnel , separate the lower layer (water layer), add 5 to 25wt% sodium chloride aqueous solution in the organic layer for extraction, the organic phase is evaporated to remove the solvent, and the resulting solid is column chromatography or ethanol, n-propanol, isopropanol, N-butanol, isobutanol, tert-butanol or any mixture thereof is recrystallized and further purified to obtain a white solid, which is vacuum-dried and stored in a desiccator to obtain N-(α-aryloxy)acyl taurate.

Method Two:

Among them: n=2~28, m=0~26, and 4≤m+n≤28; R=H or CH ₃ , Ar is a benzene ring or a naphthalene ring, M is an alkali metal ion (Li ⁺ , Na ⁺ or K ⁺ ), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ or Ba ²⁺ ), ammonium ions (NH ₄ ⁺ ) or a mixture of the above ions.

Take a certain amount of α-aryloxy carboxylic acid in step (2) in a reactor (such as a three-necked flask), add thionyl chloride dropwise, and the mol ratio of α-aryloxy carboxylic acid to thionyl chloride is 1 : 1~2, heat to 40~80°C, react for 2~6 hours, after the reaction is completed, distill off excess thionyl chloride, and add the resultant dropwise to the aqueous solution of taurine or methyl taurine and alkali , wherein the molar ratio of α-aryloxy carboxylic acid: taurine or methyl taurine: base is 1:1～2:1～2, stirred and reacted at room temperature for 4～8 hours, filtered with suction, and the obtained solid was used Column chromatography or recrystallization with ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol or any mixture thereof further purified to obtain a white solid, dried in vacuo, and the resulting white solid was N- (α-aryloxy)acyl taurate.

The catalyst is N, N'-dicyclohexyl carboximide, N, N'-diisopropyl carboximide, 4-dimethylaminopyridine, N-hydroxysuccinimide, benzo Triazole, N,N'-dimethylaniline or any mixture thereof.

The base is LiOH, Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , KHCO ₃ , Ca(OH) ₂ , Mg(OH) ₂ , Ba(OH) ₂ , Ammonia or any mixture thereof.

The desiccant is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, silica gel or molecular sieve.

The hydrophilic group of the N-(α-aryloxy)acyl taurate surfactant of the present invention is taurate or methyl taurate, which has the characteristics of low irritation, low toxicity and softness; With a sulfonic acid group combined with an amide group, it has excellent water solubility, hard water resistance, alkali resistance, and excellent foaming properties. It can be used as an emulsifier and wetting agent for pesticides, as a wetting agent and detergent for metal cleaning, as a collector and foaming agent for ore flotation, as a penetrating agent, leveling agent and antistatic agent It is used in silk dyeing and finishing, as a solubilizer and softener in leather treatment, and can also be used as one of the formulation raw materials for corrosion inhibitors, lubricants, fuel additives, foaming agents, fiber cleaning agents, antistatic agents and antirust additives .

The N-(alpha-aryloxy)acyl taurate surfactant of the invention has high surface activity and can be compounded with auxiliary agents for tertiary oil recovery. The N-(α-aryloxy) acyl taurate surfactant of the present invention has a critical micelle concentration (CMC) of 10 ^-7 ~ 10 ^-5 mol/L with high surface activity, and at the critical micelle concentration The surface tension is 40-25mN/m; under the condition of weak alkali (pH=8-12) and low salinity (1000-10000mg/L), it can form a low (10 ^-2 mN/m) Or ultra-low (10 ^-3 mN/m) interfacial tension, and this type of surfactant has strong tolerance to Ca ²⁺ or Mg ²⁺ plasma, and can be used as an effective oil displacement agent in tertiary oil recovery. In this system, the addition of an appropriate amount of Ca ²⁺ or Mg ²⁺ will not lead to a significant increase in interfacial tension.

In the above formula, the concentration of the N-(α-aryloxy)acyl taurate surfactant in the system is 100mg/L˜10000mg/L.

The auxiliary agent is alkali, anionic surfactant, nonionic surfactant, amphoteric surfactant, fatty acid, fatty alcohol, partially hydrolyzed polyacrylamide polymer, polyacrylic acid polymer, polysaccharide polymer, Hydrophobically associating copolymers, xanthan gum, chelating agents, etc. or any mixture thereof.

The base is LiOH, Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , KHCO ₃ , Ca(OH) ₂ , Mg(OH) ₂ , Ba(OH) ₂ , Ammonia or any mixture thereof.

Described anionic surfactant comprises fatty acid salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfonate, petroleum sulfonate, lignin sulfonate, alkyl sulfate, phosphoric acid ester salt or any mixture thereof.

The nonionic surfactants include fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, alkylphenol polyoxyethylene ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamides, alkyl polydextrose Glycosides or any mixture thereof.

The amphoteric surfactants include imidazoline derivatives, betaine derivatives, aminopropionic acid derivatives, taurine derivatives or any mixture thereof.

Description of drawings

Fig. 1. IR spectrogram (KBr substrate coating film) of the α-phenoxy myristate ethyl ester of the embodiment 1 of the present invention.

Fig. 2. ¹ H-NMR spectrum (deuterated chloroform) of ethyl α-phenoxytetradecanoate in Example 1 of the present invention.

Fig. 3. IR spectrogram (KBr tablet) of the 1# product of embodiment 1 of the present invention.

Fig. 4. The ¹ H-NMR spectrogram (deuterated methanol) of the 1# product of Example 1 of the present invention.

Fig. 5. 1# product aqueous solution γ-lgC curve (30 ℃ of experiment temperature) of the embodiment of the present invention 1.

Fig. 6. IR spectrogram (KBr tablet) of the 2# product of embodiment 2 of the present invention.

Fig. 7. 3# product aqueous solution γ-lgC curve (test temperature 30 ℃) of the embodiment of the present invention 3.

Fig _. 8. _The dynamic interfacial tension γ- ^lgC curve (experiment ^temperature 70°C, the oil used is Chengdong crude oil from Shengli Oilfield).

Fig. 9. The IR spectrogram (KBr tablet) of the 4# product of Example 4 of the present invention.

Fig. 10. The ¹ H-NMR spectrum (deuterated methanol) of the 5# product of Example 5 of the present invention.

Fig. 11. The IR spectrogram (KBr tablet) of the 6# product of Example 6 of the present invention.

Detailed ways

Example 1

The first step: take a certain amount of ethyl α-bromotetradecanoate, phenol and anhydrous potassium carbonate, the molar ratio of α-bromotetradecanoate: phenol: anhydrous potassium carbonate is 1:1:1.5 , dissolved in a 2:1 (v/v) mixed solvent of N,N'-dimethylformamide/benzene, heated to boiling under stirring, refluxed to separate water, and stopped heating after no more water came out. The reaction solution was cooled and filtered, the solid was washed with an appropriate amount of petroleum ether, the filtrate was combined and transferred to a separatory funnel, an appropriate amount of petroleum ether and water were added for extraction, the aqueous phase was extracted with petroleum ether until the petroleum ether layer was colorless, the organic phase was combined, After drying with anhydrous magnesium sulfate, the solvent was distilled off and distillation under reduced pressure was carried out to obtain α-phenoxy myristate. Its IR spectrum is shown in FIG. 1 , and its ¹ H-NMR spectrum is shown in FIG. 2 .

The second step: take a certain amount of synthetic α-phenoxy myristate and sodium hydroxide, the molar ratio of α-phenoxy myristate and sodium hydroxide is 1:1.5, dissolve in an appropriate amount of 1:1 ( v/v) ethanol/water, stir and heat until the reaction system refluxes, continue to stir for one hour after the reaction solution becomes clear, stop heating, add dilute hydrochloric acid dropwise to the reaction system until the pH value is 4, and stir overnight , filtered with suction, the solid was washed with water, then dried in vacuum, and dried in a far-infrared vacuum to obtain a white solid, namely α-phenoxytetradecanoic acid.

The third step: take a certain amount of synthetic α-phenoxytetradecanoic acid, N, N'-dicyclohexyl carboximide, N-hydroxysuccinimide, α-phenoxytetradecanoic acid: N , N′-dicyclohexylcarboimide:N-hydroxysuccinimide in a molar ratio of 1:1:1, and 20 mg of N,N′-dimethylaniline, dissolved in an appropriate amount of dichloromethane , stirred at room temperature for 4 hours, filtered, washed the solid with dichloromethane, combined the filtrates and evaporated the solvent, and dissolved the resultant in an appropriate amount of 2:1 (v/v) tetrahydrofuran/water mixture, added taurine and sodium carbonate, α-phenoxytetradecanoic acid: taurine: the molar ratio of sodium carbonate is 1:1.5:1.5, stirs 4 hours under room temperature, after reaction finishes, reaction solution is transferred in the separating funnel, separates lower floor (water layer), add 15wt% sodium chloride aqueous solution in the organic layer to extract and remove N-hydroxysuccinimide, the organic phase is evaporated to remove the solvent, and the gained product is purified by column chromatography to obtain a white solid, which is dried in a desiccator after vacuum drying Preserve in medium to get the 1# product N-(α-phenoxy) tetradecanoyl taurate sodium. Its IR spectrum is shown in Figure 3, its ¹ H-NMR spectrum is shown in Figure 4, and the γ-lgC curve of the 1# product aqueous solution is shown in Figure 5.

Example 2

The first step: take a certain amount of ethyl α-bromotetradecanoate, p-ethylphenol phenol and anhydrous potassium carbonate, α-bromotetradecanoic acid ethyl ester: p-ethylphenol phenol: anhydrous potassium carbonate The molar ratio is 1:1:1.5, dissolved in a 1:1 (v/v) mixed solvent of N,N'-dimethylformamide/benzene, heated to boiling under stirring, refluxed to separate water, and wait for no longer Stop heating after the water comes out, filter the reaction solution after cooling, wash the solid with an appropriate amount of petroleum ether, combine the filtrate and transfer it to a separatory funnel, add an appropriate amount of petroleum ether and water for extraction, and extract the water phase with petroleum ether to petroleum ether The layers were colorless, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was evaporated, and distillation under reduced pressure was carried out to obtain α-(4-ethylphenoxy)myristate.

The second step: get a certain amount of synthetic α-(p-ethylphenoxy) myristate and sodium hydroxide, the mol ratio of α-(p-ethylphenoxy) myristate and sodium hydroxide is 1 :1.5, dissolved in an appropriate amount of 1:1 (v/v) ethanol/water, heated under stirring until the reaction system refluxed, continued to stir for one hour after the reaction liquid became clear, stopped heating, and added dropwise to the reaction system after it became cool Dilute hydrochloric acid to a pH value of 4, stir overnight, filter with suction, wash the solid with water, dry it in vacuum, and dry it in a far-infrared vacuum to obtain a white solid, which is α-(4-ethylphenoxy)tetradecanoic acid.

The third step: take a certain amount of α-(4-ethylphenoxy)tetradecanoic acid prepared in the second step in a three-necked bottle, add thionyl chloride dropwise, α-(4-ethylphenoxy ) the molar ratio of tetradecanoic acid to thionyl chloride is 1:1.5, heated to 75°C, and reacted for 3 hours. In an aqueous solution of calcium, in which the molar ratio of α-aryloxycarboxylic acid: taurine: calcium hydroxide is 1:1.5:0.75, stir at room temperature for 4 hours, filter with suction, and dry the solid in vacuum to obtain 2# product Calcium N-(α-(4-ethylphenoxy))tetradecanoyl taurate, its infrared spectrum is shown in Figure 6.

Example 3

The first step: take a certain amount of ethyl α-bromotetradecanoate, 4-hexylphenol and anhydrous sodium carbonate, the molar ratio of α-bromotetradecanoate: 4-hexylphenol: anhydrous sodium carbonate 1.05:1:2, dissolved in a 1:1 (v/v) mixed solvent of N,N'-dimethylformamide/benzene, heated to boiling under stirring, refluxed to separate water, until there is no more moisture Stop heating after leaving, filter the reaction solution after cooling, wash the solid with an appropriate amount of petroleum ether, combine the filtrate and transfer it to a separatory funnel, add an appropriate amount of petroleum ether and water for extraction, and extract the aqueous phase with petroleum ether until the petroleum ether layer is free. The organic phases were combined, dried with anhydrous magnesium sulfate, evaporated to remove the solvent, and distilled under reduced pressure to obtain ethyl α-(4-hexylphenoxy)tetradecanoate.

The second step: get a certain amount of synthetic α-(4-hexylphenoxy) ethyl myristate and potassium hydroxide, α-(4-hexylphenoxy) ethyl myristate and potassium hydroxide mol ratio 1:1.5, dissolved in an appropriate amount of 3:1 (v/v) ethanol/water, heated under stirring until the reaction system refluxed, continued to stir for one hour after the reaction liquid became clear, stopped heating, and poured into the reaction system after cooling Add dilute hydrochloric acid dropwise until the pH value is 3, stir overnight, filter with suction, wash the solid with water, dry it in vacuum, and dry it in a far-infrared vacuum to obtain a white solid, which is α-(4-hexylphenoxy)tetradecanoic acid.

The third step: take a certain amount of synthetic α-(4-hexylphenoxy) tetradecanoic acid, N, N'-dicyclohexyl carboximide, N-hydroxysuccinimide, α-(4- Hexylphenoxy)tetradecanoic acid: N,N'-dicyclohexylcarboimide:N-hydroxysuccinimide in a molar ratio of 1:1:1, and 20 mg of N,N'-dimethyl Aniline, dissolved in an appropriate amount of dichloromethane, stirred at room temperature for 4 hours, filtered, washed the solid with dichloromethane, combined the filtrate and evaporated to dryness, the resulting product was dissolved in an appropriate amount of 2:1 (v/v) tetrahydrofuran/water, added cattle Sulfonic acid and sodium carbonate, α-phenoxytetradecanoic acid: taurine: the molar ratio of sodium carbonate is 1:1.5:1.5, stir at room temperature for 10 hours, after the reaction is completed, transfer the reaction solution to a separatory funnel , separate the lower layer (water layer), add 20wt% sodium chloride aqueous solution to the organic layer to extract and remove N-hydroxysuccinimide, evaporate the solvent from the organic phase, and recrystallize the resultant with ethanol to obtain a white solid, which is dried in vacuo Then store it in a desiccator to obtain the 3# product, sodium N-(α-(4-hexylphenoxy))tetradecanoyl taurate. See Figure 7 for the γ-lgC curve of the 3# product aqueous solution, and Figure 8 for the dynamic interfacial tension γ-lgC curve of the 3# product 1×10 ^-3 mol/L aqueous solution with Shengli crude oil in the presence of NaCl and Na ₂ CO ₃ .

Example 4

The first step: take a certain amount of α-bromododecanoic acid methyl ester, 4-hexylphenol and anhydrous potassium carbonate, the molar ratio of α-bromododecanoic acid methyl ester: 4-hexylphenol: anhydrous potassium carbonate 1.1:1:2, dissolved in 2:1 (v/v) N,N'-dimethylformamide/benzene mixed solvent, heated to boiling under stirring, refluxed to separate water, until no more moisture Stop heating after leaving, filter the reaction solution after cooling, wash the solid with an appropriate amount of petroleum ether, combine the filtrate and transfer it to a separatory funnel, add an appropriate amount of petroleum ether and water for extraction, and extract the aqueous phase with petroleum ether until the petroleum ether layer is free. The organic phases were combined, dried with anhydrous magnesium sulfate, evaporated to remove the solvent, and distilled under reduced pressure to obtain α-(4-hexylphenoxy)methyl dodecanoate.

The second step: get a certain amount of synthetic α-(4-hexylphenoxy) methyl dodecanoate and sodium hydroxide, α-(4-hexylphenoxy) methyl dodecanoate and sodium hydroxide molar ratio 1:1.5, dissolved in an appropriate amount of 2:1 (v/v) ethanol/water, heated under stirring until the reaction system refluxed, continued to stir for one hour after the reaction liquid became clear, stopped heating, and poured into the reaction system after cooling Add dilute hydrochloric acid dropwise until the pH value is 3, stir overnight, filter with suction, wash the solid with water, dry it in vacuum, and dry it in a far-infrared vacuum to obtain a white solid, which is α-(4-hexylphenoxy)dodecanoic acid.

The third step: take a certain amount of synthetic α-(4-hexylphenoxy)dodecanoic acid, N,N'-dicyclohexylcarboimide, N-hydroxysuccinimide, α-(4- Hexylphenoxy)dodecanoic acid:N,N'-dicyclohexylcarboimide:N-hydroxysuccinimide molar ratio 1:1:1, and 20mg of N,N'-dimethyl Aniline, dissolved in an appropriate amount of dichloromethane, stirred at room temperature for 4 hours, filtered, washed the solid with dichloromethane, combined the filtrate and evaporated to dryness, the resulting product was dissolved in an appropriate amount of 2:1 (v/v) tetrahydrofuran/water, added formaldehyde Base taurine and sodium carbonate, α-phenoxydodecanoic acid: methyl taurine: the molar ratio of sodium carbonate is 1:1.5:1.5, stirred at room temperature for 10 hours, after the reaction was completed, the reaction solution was transferred to In the separatory funnel, separate the lower layer (water layer), add 15wt% sodium chloride aqueous solution to the organic layer to extract and remove N-hydroxysuccinimide, evaporate the organic phase to remove the solvent, and recrystallize the resultant with isopropanol. Obtain a white solid, store it in a desiccator after vacuum drying, and obtain 4# product N-(α-(4-hexylphenoxy))sodium dodecanoyl-N-methyl taurate, and its infrared spectrum is shown in Figure 9.

Example 5

The first step: take a certain amount of ethyl α-bromotetradecanoate, 2-naphthol and anhydrous potassium carbonate, the molar ratio of α-bromotetradecanoate: 2-naphthol: anhydrous potassium carbonate 1.1:1:2, dissolved in 2:1 (v/v) N,N'-dimethylformamide/benzene mixed solvent, heated to boiling under stirring, refluxed to separate water, until no more moisture Stop heating after leaving, filter the reaction solution after cooling, wash the solid with an appropriate amount of petroleum ether, combine the filtrate and transfer it to a separatory funnel, add an appropriate amount of petroleum ether and water for extraction, and extract the aqueous phase with petroleum ether until the petroleum ether layer is free. The organic phases were combined, dried with anhydrous magnesium sulfate, evaporated to remove the solvent, and distilled under reduced pressure to obtain ethyl α-(2-naphthyloxy)tetradecanoate.

The second step: get a certain amount of synthetic α-(2-naphthyloxy) ethyl myristate and sodium hydroxide, the mol ratio of α-(2-naphthyloxy) ethyl myristate and sodium hydroxide is 1 : 2, dissolved in an appropriate amount of 1:1 (v/v) ethanol/water, heated under stirring until the reaction system refluxed, continued to stir for one hour after the reaction liquid became clear, stopped heating, and added dropwise to the reaction system after it became cool Dilute sulfuric acid to a pH value of 3, stir overnight, filter with suction, wash the solid with water, dry it in vacuum, and dry it in a far-infrared vacuum to obtain a white solid, which is α-(2-naphthyloxy)tetradecanoic acid.

The third step: take a certain amount of synthetic α-(2-naphthyloxy) tetradecanoic acid, N, N'-dicyclohexylcarboimide, N-hydroxysuccinimide, α-(2-naphthalene Oxy)tetradecanoic acid: N, N'-dicyclohexylcarboimide: N-hydroxysuccinimide molar ratio is 1:1:1, and 20 mg of N, N'-dimethylaniline, Dissolve in an appropriate amount of dichloromethane, stir at room temperature for 4 hours, filter, wash the solid with dichloromethane, combine the filtrates and evaporate the solvent to dryness, dissolve the resultant in an appropriate amount of 2:1 (v/v) tetrahydrofuran/water, add taurine And sodium carbonate, α-(2-naphthyloxy) tetradecanoic acid: taurine: the molar ratio of sodium carbonate is 1:1.5:1.5, stirred at room temperature for 8 hours, after the reaction was completed, the reaction solution was transferred to the separatory In the funnel, separate the lower layer (water layer), add 20wt% sodium chloride aqueous solution to the organic layer to extract and remove N-hydroxysuccinimide, evaporate the organic phase to remove the solvent, and recrystallize the resultant with isopropanol to obtain white The solid was vacuum-dried and stored in a desiccator to obtain the 5# product, sodium N-(α-(2-naphthyloxy))tetradecanoyl taurate, whose NMR spectrum is shown in FIG. 10 .

Example 6

The first step: take a certain amount of ethyl α-bromotetradecanoate, phenol and anhydrous potassium carbonate, the molar ratio of α-bromotetradecanoate: phenol: anhydrous potassium carbonate is 1:1:1.5 , dissolved in a 2:1 (v/v) mixed solvent of N,N'-dimethylformamide/benzene, heated to boiling under stirring, refluxed to separate water, and stopped heating after no more water came out. The reaction solution was cooled and filtered, the solid was washed with an appropriate amount of petroleum ether, the filtrate was combined and transferred to a separatory funnel, an appropriate amount of petroleum ether and water were added for extraction, the aqueous phase was extracted with petroleum ether until the petroleum ether layer was colorless, the organic phase was combined, After drying with anhydrous magnesium sulfate, the solvent was distilled off and distillation under reduced pressure was carried out to obtain α-phenoxy myristate. Its IR spectrum is shown in FIG. 1 , and its ¹ H-NMR spectrum is shown in FIG. 2 .

The second step: take a certain amount of synthetic α-phenoxy myristate and sodium hydroxide, the molar ratio of α-phenoxy myristate and sodium hydroxide is 1:1.5, dissolve in an appropriate amount of 1:1 ( v/v) ethanol/water, stir and heat until the reaction system refluxes, continue to stir for one hour after the reaction solution becomes clear, stop heating, add dilute hydrochloric acid dropwise to the reaction system until the pH value is 4, and stir overnight , filtered with suction, the solid was washed with water, then dried in vacuum, and dried in a far-infrared vacuum to obtain a white solid, namely α-phenoxytetradecanoic acid.

The third step: take a certain amount of synthetic α-phenoxytetradecanoic acid, N, N'-dicyclohexyl carboximide, N-hydroxysuccinimide, α-phenoxytetradecanoic acid: N , N′-dicyclohexylcarboimide:N-hydroxysuccinimide in a molar ratio of 1:1:1, and 20 mg of N,N′-dimethylaniline, dissolved in an appropriate amount of dichloromethane , stirred at room temperature for 4 hours, filtered, washed the solid with dichloromethane, combined the filtrate and evaporated to dryness, the resultant was dissolved in an appropriate amount of 2:1 (v/v) tetrahydrofuran/water mixture, added taurine and ammonia, α -Phenoxytetradecanoic acid: taurine: the molar ratio of ammonia water is 1:1.5:1.5, stir at room temperature for 4 hours, after the reaction is completed, transfer the reaction solution to a separatory funnel, and separate the lower layer (water layer) , adding 15wt% sodium chloride aqueous solution to the organic layer to extract and remove N-hydroxysuccinimide, the organic phase was evaporated to remove the solvent, and the resulting product was purified by column chromatography to obtain a white solid, which was stored in a desiccator after vacuum drying , That is, the 6# product N-(α-phenoxy)tetradecyl taurine amine. Its IR spectrum is shown in FIG. 11 .

Example 7

The first step: take a certain amount of ethyl α-bromotetradecanoate, 4-octylphenol and anhydrous potassium carbonate, ethyl α-bromotetradecanoate: 4-octylphenol: anhydrous potassium carbonate The molar ratio is 1.1:1:2, dissolved in 2:1 (v/v) N,N'-dimethylformamide/benzene mixed solvent, heated to boiling under stirring, refluxed to separate water, and wait for no longer Stop heating after the water comes out, filter the reaction solution after cooling, wash the solid with an appropriate amount of petroleum ether, combine the filtrate and transfer it to a separatory funnel, add an appropriate amount of petroleum ether and water for extraction, and extract the water phase with petroleum ether to petroleum ether The layers were colorless, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was evaporated, and distillation under reduced pressure was carried out to obtain ethyl α-(4-octylphenoxy)tetradecanoate.

The second step: take a certain amount of synthetic α-(4-octylphenoxy) ethyl myristate and sodium hydroxide, α-(4-octylphenoxy) ethyl myristate and sodium hydroxide The molar ratio is 1:1.5, dissolve in an appropriate amount of 2:1 (v/v) ethanol/water, heat the reaction system to reflux under stirring, continue to stir for one hour after the reaction liquid becomes clear, stop heating, and the reaction system cools down Add dilute hydrochloric acid dropwise thereto until the pH value is 3, stir overnight, filter with suction, wash the solid with water and dry it in vacuum, and dry it in a far-infrared vacuum to obtain a white solid, which is α-(4-octylphenoxy)tetradecanoic acid .

The third step: take a certain amount of synthetic α-(4-octylphenoxy) tetradecanoic acid, N, N'-dicyclohexylcarboimide, N-hydroxysuccinimide, α-(4 -octylphenoxy)tetradecanoic acid:N,N'-dicyclohexylcarboimide:N-hydroxysuccinimide molar ratio is 1:1:1, and 20mg of N,N'-dicycloimide Methylaniline was dissolved in an appropriate amount of dichloromethane, stirred at room temperature for 4 hours, filtered, the solid was washed with dichloromethane, the filtrate was combined and the solvent was evaporated to dryness, and the resulting product was dissolved in an appropriate amount of 2:1 (v/v) tetrahydrofuran/water, Add taurine and a mixture of sodium hydroxide and calcium hydroxide, the molar ratio of α-(4-octylphenoxy) tetradecanoic acid: taurine: sodium hydroxide: calcium hydroxide is 1:1.5:0.7 : 0.4, stirred at room temperature for 10 hours, after the reaction was completed, the reaction solution was transferred to the separatory funnel, and the lower floor (water layer) was separated, and the aqueous solution of sodium chloride of 15wt% was added to the organic layer to extract and remove N-hydroxysuccinyl Imine, the organic phase was evaporated to remove the solvent, and the resultant was recrystallized with isopropanol to obtain a white solid, which was dried in a vacuum and stored in a desiccator to obtain the 7# product N-(α-(4-octylphenoxy) ) a mixture of sodium myristyl taurate and calcium N-(α-(4-octylphenoxy)) myristyl taurate.

Claims (10)

1. an N-(α-aryloxy group) acyl taurate surfactant is characterized in that, the structural formula of the N-(α-aryloxy group) acyl taurate surfactant is: Among them: n=2~28, m=0~26, and 4≤m+n≤28; R=H or CH ₃ , Ar is a benzene ring or a naphthalene ring, M is Li ⁺ , Na ⁺ in alkali metal ions Or K ⁺ , Ca ²⁺ , Mg ²⁺ or Ba ²⁺ in alkaline earth metal ions, ammonium ions or any mixture of the above-mentioned ions. 2. N-(alpha-aryloxy) acyl taurate surfactant according to claim 1, is characterized in that: described N-(alpha-aryloxy) acyl taurate surfactant The critical micelle concentration of the agent is 10 ^-7 ~ 10 ^-5 mol/L, and the surface tension under the critical micelle concentration is 40 ~ 25mN/m. 3. N-(alpha-aryloxy) acyl taurate surfactant according to claim 1 and 2, is characterized in that: described N-(alpha-aryloxy) acyl taurate Surfactant can form ultra-low interfacial tension of 10 ^-2 mN/m or 10 ^-3 mN/m with petroleum under the condition of pH value of 8-12 weak base and low salinity of 1000-10000mg/L . 4. a preparation method of N-(alpha-aryloxy) acyl taurate surfactant according to any one of claims 1 to 3, characterized in that the method may further comprise the steps: (1) Synthesis of α-aryloxy carboxylate

Among them: n=2~28, m=0~26, and 4≤m+n≤28; R'=CH ₃ or C ₂ H ₅ , Ar is a benzene ring or a naphthalene ring; Take α-bromocarboxylate, alkylphenol with carbon number of 0-26 or alkylnaphthol with carbon number of 0-26 and alkali in the reactor, α-bromocarboxylate: alkylphenol or The molar ratio of alkylnaphthol:base is 1~1.2:1:1~2; dissolve the above mixture in N,N'-dimethylformamide or dimethyl sulfoxide with a volume ratio of 5~1:1 In a mixed solvent with benzene or toluene, heat up to boiling under stirring, reflux to separate water, after the reaction is completed, cool the reaction liquid and filter, wash the solid with an organic solvent, combine the washing liquid and transfer it to a separatory funnel, add organic Solvent and water extract the washing solution, the organic phase is dried with a desiccant, the organic solvent is evaporated, and the vacuum distillation is carried out to obtain α-aryloxy carboxylate; The base is anhydrous K ₂ CO ₃ , anhydrous Na ₂ CO ₃ , anhydrous KHCO ₃ , anhydrous NaHCO ₃ , NaOH or KOH; (2) Synthesis of α-aryloxycarboxylic acid

Among them: n=2~28, m=0~26, and 4≤m+n≤28; R'=CH ₃ or C ₂ H ₅ , Ar is a benzene ring or a naphthalene ring; Take the α-aryloxy carboxylate of step (1), sodium hydroxide or potassium hydroxide in the reactor, the molar ratio of α-aryloxy carboxylate to sodium hydroxide or potassium hydroxide is 1:1 ~2; Dissolve the above mixture in the mixture of ethanol/water; heat under stirring until the reaction system refluxes, the reaction liquid becomes clear, indicating that the reaction is complete, stop heating, after the reaction is complete, add dilute hydrochloric acid or dilute hydrochloric acid to the system when it cools down Sulfuric acid until the pH of the reaction solution is 2-6, stirred overnight, suction filtered, the solid was washed with water, dried in vacuum, and dried in vacuo to obtain a white solid, which is α-aryloxycarboxylic acid; (3) Synthesis of N-(α-aryloxy)acyl taurate method one:

Among them: n=2~28, m=0~26, and 4≤m+n≤28; R=H or CH ₃ , Ar is a benzene ring or a naphthalene ring, M is Li ⁺ , Na ⁺ in alkali metal ions Or K ⁺ , Ca ²⁺ , Mg ²⁺ or Ba ²⁺ in alkaline earth metal ions, ammonium ions or any mixture of the above-mentioned ions; Get the α-aryloxy carboxylic acid of step (2) and the catalyst of catalytic amount in the reactor and be dissolved in dichloromethane or tetrahydrofuran solvent, stir at room temperature, obtain active intermediate, filter, after the filtrate is evaporated to dryness solvent, active The intermediate is dissolved in a mixture of tetrahydrofuran/water, adding taurine or methyl taurine and alkali, wherein the molar ratio of α-aryloxycarboxylic acid: taurine or methyl taurine: alkali is 1 :1～2:1～2, stir at room temperature, after the reaction is completed, transfer the reaction solution to a separatory funnel, separate the water layer, add 5～25wt% sodium chloride aqueous solution to the organic layer for extraction, and evaporate the organic phase Solvent, the obtained solid is further purified by column chromatography or alcohol recrystallization to obtain a white solid, which is dried in vacuum to obtain N-(α-aryloxy)acyl taurate; or Method Two:

Among them: n=2~28, m=0~26, and 4≤m+n≤28; R=H or CH ₃ , Ar is a benzene ring or a naphthalene ring, M is Li ⁺ , Na ⁺ in alkali metal ions Or K ⁺ , Ca ²⁺ , Mg ²⁺ or Ba ²⁺ in alkaline earth metal ions, ammonium ions or any mixture of the above ions Take the α-aryloxy carboxylic acid in step (2) in the reactor, add thionyl chloride dropwise, the molar ratio of α-aryloxy carboxylic acid to thionyl chloride is 1:1~2, heat the temperature to 40～80℃, after the reaction is completed, the excess thionyl chloride is distilled off, and the resultant is added dropwise to the aqueous solution of taurine or methyl taurine and alkali, wherein α-aryloxycarboxylic acid: taurine or The molar ratio of methyl taurine: base is 1:1~2:1~2, stirring reaction at room temperature, suction filtration, the obtained solid is further purified by column chromatography or alcohol recrystallization to obtain a white solid, vacuum dried, the obtained The white solid is N-(α-aryloxy)acyl taurate; The base is LiOH, Li ₂ CO ₃ , NaOH, Na ₂ CO ₃ , NaHCO ₃ , KOH, K ₂ CO ₃ , KHCO ₃ , Ca(OH) ₂ , Mg(OH) ₂ , Ba(OH) ₂ , Ammonia or any mixture thereof. 5. the method according to claim 4 is characterized in that: described organic solvent is ether, sherwood oil, benzene, monochloromethane, methylene dichloride, 1,2-ethylene dichloride, chloroform or any of them Mixture; the alcohol in the recrystallization with alcohol is ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol or any mixture thereof. 6. The method according to claim 4, characterized in that: in the mixed solution of ethanol/water, the volume ratio of ethanol to water is 1:1-5; in the mixed solution of tetrahydrofuran/water, The volume ratio of tetrahydrofuran to water is 1-5:1. 7. The method according to claim 4, characterized in that: the catalyst is N, N'-dicyclohexylcarbimide, N, N'-diisopropylcarbimide, 4-di Aminopyridine, N-hydroxysuccinimide, benzotriazole, N,N'-dimethylaniline or any mixture thereof. 8. The method according to claim 4, characterized in that: the desiccant is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, silica gel or molecular sieves. 9. A use of the N-(alpha-aryloxy) acyl taurate surfactant according to any one of claims 1 to 3, characterized in that: the surfactant can be used as an emulsifier and wetting agent Spreading agent for pesticides, as wetting agent and detergent for metal cleaning, as collector and foaming agent for ore flotation, as penetrating agent, leveling agent and antistatic agent for silk dyeing and finishing, As a solubilizer and softener for leather treatment; and as one of the formulation raw materials for corrosion inhibitors, lubricants, fuel additives, foaming agents, fiber cleaning agents, antistatic agents and antirust additives. 10. A use of the N-(alpha-aryloxy) acyl taurate surfactant according to any one of claims 1 to 3, characterized in that: the surfactant can be used as an effective oil-displacement used in tertiary oil recovery.

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