A citrate-type-lignosulfonate cationic surfactant

Abstract

The preparation method of the citric acid type-lignosulfonate cationic surfactant comprises the following steps: dissolving epichlorohydrin in a methanol solution with a certain concentration, heating and stirring to a certain temperature, adding an aniline solution with a certain concentration, and constant temperature stirring for a period of time to obtain an epichlorohydrin propyl phenyl ammonium chloride intermediate; dissolving sodium lignosulfonate into a phosphoric acid solution, heating to a certain temperature after dissolving, adding the epichlorohydrin propyl phenyl ammonium chloride intermediate, adding a NaOH solution with a certain concentration dropwise, constant temperature stirring for a certain period of time to obtain a lignin quaternary ammonium ion intermediate; dissolving citric acid into an ethanol solution, adding the lignin quaternary ammonium ion intermediate under a certain stirring speed, constant temperature stirring for a certain period of time to form the citric acid type-lignosulfonate cationic surfactant. The citric acid type-lignosulfonate cationic surfactant has the advantages of sterilization, emulsification and good washing effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of surfactant preparation, and particularly relates to a citric acid type-lignin sulfonate cationic surfactant and a preparation method thereof. BACKGROUND

[0002] Lignin sodium sulfonate is a kind of lignin sulfonate. Lignin is a natural polymer in the world, and its content is only second to cellulose and chitin. As a filler and adhesive material, it can strengthen the interaction between plant cellulose, and it is also necessary to remove the component when people extract and utilize plant cellulose on a large scale. Lignin sulfonate has good water solubility due to the introduction of sulfonic acid group in the molecule, which greatly improves its reaction capacity. Surfactant refers to a substance that can significantly reduce the surface tension of the target solution. It has a fixed hydrophilic and lipophilic group, and can be oriented on the surface of the solution. Surfactant can reduce the surface tension of water by adsorbing on the gas-liquid interface, and can also reduce the oil-water interfacial tension by adsorbing between liquid interfaces. Surfactant has a series of physical and chemical effects such as wetting or anti-sticking, emulsification or demulsification, foaming or defoaming, and solubilization, dispersion, washing, corrosion prevention, and anti-static, and corresponding practical applications, and becomes a flexible and diverse, widely used fine chemical product. Surfactant is used as a detergent in daily life. Therefore, the present application combines the characteristics of lignin sodium sulfonate and the wide application of surfactant to propose a citric acid type-lignin sulfonate cationic surfactant and a preparation method thereof. SUMMARY

[0003] To solve the problem that the emulsifying capacity of the existing surfactant gradually weakens or deactivates with the limitation of the properties of the solution and the reaction conditions during use, the present application improves these problems by preparing a citric acid type-lignin sulfonate cationic surfactant. Aniline is a stable organic compound at room temperature, and is also one of the most important intermediates in the dye industry. Therefore, the intermediate used to prepare the surfactant is relatively stable. Citric acid is widely used in detergent production, and its specificity and chelation play an active role, have good performance, and outstanding safety performance. It is easy to degrade under the action of microorganisms and heat. Therefore, the citric acid type-lignin sulfonate cationic surfactant prepared from lignin sodium sulfonate, aniline and citric acid can exert its excellent emulsifying and sterilizing properties under various environmental conditions.

[0004] The technical scheme of the present application:

[0005] A citric acid type-lignin sulfonate cationic surfactant is synthesized from aniline, lignin sodium sulfonate and citric acid as raw materials, and the manufacturing steps include:

[0006] Step 1: add epichlorohydrin to a 1%-95% methanol solution, and stop stirring after gradually heating from room temperature to 60-85°C; in the step 1, the volume ratio of methanol to epichlorohydrin is 1:1 to 1:8;

[0007] Step 2: gradually add aniline solution to the epichlorohydrin-methanol mixed solution, and obtain the epichlorohydrin propyl phenyl ammonium chloride intermediate after constant temperature heating and stirring for 1-24h; in the step 2, the volume ratio of epichlorohydrin to aniline is 1:1 to 1:10; the constant temperature is 40-85°C;

[0008] Step 3: dissolve the sodium lignosulfonate into a 5%-85% phosphoric acid solution to obtain an acidic sodium lignosulfonate solution;

[0009] Step 4: gradually add the acidic sodium lignosulfonate solution to the epichlorohydrin propyl phenyl ammonium chloride intermediate after gradually heating from room temperature to 60-85°C, and then add a 0.1 mol / L-12 mol / L NaOH solution dropwise after mixing and stirring uniformly, and obtain the lignin quaternary ammonium ion intermediate after stirring at 60-85°C for 1-24h; in the step 4, the volume ratio of the acidic sodium lignosulfonate to the epichlorohydrin propyl phenyl ammonium chloride intermediate is 1:1 to 1:6;

[0010] Step 5: dissolve the citric acid into a 5%-95% ethanol solution, and then add the lignin quaternary ammonium ion intermediate dropwise, and then carry out constant temperature heating and stirring, and then obtain the citric acid type-lignosulfonate cationic surfactant after standing for 1-24h; in the step 5, the volume ratio of the citric acid to the lignin quaternary ammonium ion intermediate is 1:1 to 1:6; the constant temperature is 40-85°C;

[0011] Step 6: separate the citric acid type-lignosulfonate cationic surfactant after standing for 3-48h.

[0012] Further, in the step 1, the heating speed is 0.5°C / min; and the stirring speed is 300 r / min.

[0013] Further, in the step 2, the solution dropwise adding speed is 5-10 drops / min; and the stirring speed is 300 r / min.

[0014] Further, in the step 4, the heating speed is 0.5°C / min; the solution dropwise adding speed is 5-10 drops / min; and the stirring speed is 300 r / min.

[0015] Further, in the step 5, the solution dropwise adding speed is 5-10 drops / min; and the stirring speed is 300 r / min.

[0016] The present application has the advantages that:

[0017] The process is simple and easy to operate, the cost of raw materials is low, the required synthesis temperature is easy to reach, the required reaction time is short, the speed is faster, the emulsifying capacity, dispersing capacity, foaming capacity, solubilizing capacity and sterilizing capacity of the prepared modified sodium lignosulfonate are obviously increased, the detergency performance is superior, the ability to promote the surface tension reduction is enhanced, and the product has great market potential. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a γ-ρ graph of Example 1.

[0019] Figure 2 is a γ-ρ graph of Example 2.

[0020] Figure 3 is a γ-ρ graph of Example 3. DETAILED DESCRIPTION

[0021] Various exemplary embodiments of the present application will now be described in detail, which should be considered to be illustrative of certain aspects, features and embodiments of the present application and are not intended to limit the present application in any manner.

[0022] Example 1:

[0023] Step 1: 20 mL of epichlorohydrin was added to a 20% methanol solution, and after gradually heating from room temperature to 65°C (heating rate of 0.5°C / min), the stirring was stopped (stirring speed of 300 rpm);

[0024] Step 2: 20 mL of aniline was added dropwise to the epichlorohydrin methanol solution (the solution was added at a rate of 5-10 drops / min), and the reaction was carried out at 76°C for 6 h with stirring (stirring speed of 300 rpm) to obtain an epoxy propyl phenyl ammonium chloride intermediate;

[0025] Step 3: 5 g of sodium lignosulfonate was dissolved in 85%, 40 mL of phosphoric acid solution to obtain an acidic sodium lignosulfonate solution;

[0026] Step 4: 20 mL of the acidic sodium lignosulfonate solution was gradually heated from room temperature to 80°C (heating rate of 0.5°C / min), and then gradually added dropwise to the epoxy propyl phenyl ammonium chloride intermediate (the solution was added at a rate of 5-10 drops / min), and after uniform mixing and stirring, a 2 mol / L NaOH solution was added dropwise (the solution was added at a rate of 5-10 drops / min), and the reaction was carried out at 80°C for 4 h with stirring to obtain a lignin quaternary ammonium ion intermediate;

[0027] Step 5: 50 mL of citric acid was dissolved into 95%, 30 mL of ethanol solution, 30 mL of citric acid mixed solution was taken and added dropwise into the lignin quaternary ammonium ion intermediate (the speed of adding solution was 5-10 drops / min), after stirring at 75℃ for 5h, it was placed for 24h;

[0028] Step 6: citric acid type-lignin sulfonate cationic surfactant was separated after standing for 24h.

[0029] The surface tension of the citric acid type-lignin sulfonate cationic surfactant obtained by the above example was determined on an XJZ-200 full-automatic interfacial tension meter; an appropriate amount of sample to be tested was weighed into a 100 mL volumetric flask, and a solution with a mass concentration (ρ) of 0.5-7.0 g·L -1 was prepared with deionized water, and the surface tension (γ) of the series of solutions was determined at 25℃ using a BZY-1 type surface tension meter to draw a γ-ρ curve, see Figure 1 . From the curve, it can be seen that the CMC value of the product is about 3.5 g / L, and γ is 30.15 mN / m; the conclusion is that the product has the ability to reduce the surface tension of the liquid at low concentration solution, and shows good surface activity. The determination of hydrophilic-lipophilic balance (HLB) value: using soybean oil and turpentine oil, standard oil samples with HLB values of 7, 8, 9, 10, 11, 12, 13, 14, and 15 were prepared in a certain proportion, and the HLB value of the target product was determined to be 10 using the standard oil sample method, indicating that the hydrophilicity of the obtained surfactant is very strong. The determination of emulsifying capacity: the sample to be tested was prepared into a 5 g·100 mL -1 aqueous solution with 0.05 mol·L -1 dilute hydrochloric acid, 30 mL of sample solution and 20 mL of turpentine oil were mixed, and the emulsion time was recorded as 186 min after vigorous shaking and standing, indicating that the emulsifying effect was good.

[0030] Example 2:

[0031] Step 1: 20 mL of epichlorohydrin was added to a 20% methanol solution, and the stirring was stopped after heating from room temperature to 65℃ at a rate of 0.5℃ / min (stirring speed was 300 r / min);

[0032] Step 2: 20 mL of aniline was added dropwise to the epichlorohydrin methanol solution (the speed of adding solution was 5-10 drops / min), and an epoxy propyl phenyl ammonium chloride intermediate was obtained by stirring at 76℃ for 6h;

[0033] Step 3: 5 g of lignin sulfonate sodium was dissolved into 85%, 40 mL of phosphoric acid solution to obtain an acidic lignin sulfonate sodium solution;

[0034] Step 4: After the 20 mL acidic lignin sulfonate sodium solution is gradually heated from room temperature to 80℃ (the heating rate is 0.5℃ / min), it is gradually added dropwise into the epoxy propyl phenyl ammonium chloride intermediate (the dropping speed of the solution is 5-10 drops / min), after the mixture is uniformly stirred, a 2 mol / L NaOH solution is added dropwise (the dropping speed of the solution is 5-10 drops / min), and after stirring at 80℃ for 4 h, a lignin quaternary ammonium ion intermediate is obtained;

[0035] Step 5: 50 mL of a citric acid solution is dissolved in 95% ethanol solution, and 30 mL of a citric acid mixed solution is gradually added dropwise into the lignin quaternary ammonium ion intermediate (the dropping speed of the solution is 5-10 drops / min), and after stirring at 75℃ for 5 h, it is left to stand for 24 h;

[0036] Step 6: After standing for 24 h, a citric acid type-lignin sulfonate cationic surfactant is obtained by separation.

[0037] The surface tension of the citric acid type-lignin sulfonate cationic surfactant obtained through the above example is determined on an XJZ-200 full-automatic interfacial tension meter; an appropriate amount of the sample to be tested is weighed into a 100 mL volumetric flask, and a deionized water solution with a mass concentration (ρ) of 0.5-7.0 g·L -1 is prepared, and the surface tension (γ) of the series of solutions is determined at 25℃ using a BZY-1 type surface tension meter to draw a γ-ρ curve, as shown in Figure 2 . From the curve, it can be seen that the CMC value of the product is about 3.5 g / L, and γ is 30.15 mN / m; it is concluded that the product has the ability to reduce the surface tension of the liquid at a low concentration solution, and exhibits good surface activity. The hydrophilic-lipophilic balance (HLB) value is determined: standard oil samples with HLB values of 7, 8, 9, 10, 11, 12, 13, 14, and 15 are prepared by mixing soybean oil and turpentine oil in a certain proportion, and the HLB value of the target product is 10, indicating that the hydrophilicity of the obtained surfactant is very strong. The emulsifying capacity is determined: the sample to be tested is prepared into a 5 g·100 mL -1 aqueous solution with 0.05 mol·L -1 dilute hydrochloric acid, and 30 mL of the sample solution and 20 mL of turpentine oil are mixed, shaken vigorously, and left to stand, and the emulsification time is recorded as 186 min, indicating that the emulsification effect is good.

[0038] Example 3:

[0039] Step 1: 20 mL of epoxy chloropropane is added to a 20% methanol solution, and after gradually heating from room temperature to 65℃ (the heating rate is 0.5℃ / min), the stirring is stopped (the stirring speed is 300 rpm);

[0040] Step 2: 20 mL of aniline was added dropwise to the epichlorohydrin methanol solution (the solution was added at a rate of 5-10 drops per minute), and the reaction was stirred at 76°C for 6h to obtain an epichlorohydrin phenyl ammonium chloride intermediate;

[0041] Step 3: 5g of sodium lignosulfonate was dissolved in 85%, 40 mL of phosphoric acid solution to obtain an acidic sodium lignosulfonate solution;

[0042] Step 4: 20 mL of the acidic sodium lignosulfonate solution was gradually heated from room temperature to 80°C (the heating rate was 0.5°C / min), and then added dropwise to the epichlorohydrin phenyl ammonium chloride intermediate (the solution was added at a rate of 5-10 drops per minute). After uniform mixing and stirring, a 2 mol / L NaOH solution was added dropwise (the solution was added at a rate of 5-10 drops per minute), and the reaction was stirred at 80°C for 4h to obtain a lignin quaternary ammonium ion intermediate;

[0043] Step 5: 50 mL of citric acid was dissolved in 95%, 30 mL of ethanol solution, and 30 mL of the citric acid mixed solution was added dropwise to the lignin quaternary ammonium ion intermediate (the solution was added at a rate of 5-10 drops per minute). After stirring at 75°C for 5h, the reaction was allowed to stand for 24h;

[0044] Step 6: After standing for 24h, a citric acid type-lignosulfonate cationic surfactant was obtained by separation.

[0045] The surface tension of the citric acid type-lignosulfonate cationic surfactant obtained by the above example was measured on an XJZ-200 full-automatic interfacial tension meter. An appropriate amount of the sample to be tested was weighed into a 100 mL volumetric flask, and deionized water was used to prepare a solution with a mass concentration (ρ) of 0.5-7.0 g·L -1 . The surface tension (γ) of the series of solutions was measured at 25°C using a BZY-1 type surface tension meter, and a γ-ρ curve was drawn, as shown in Figure 3 . From the curve, it can be seen that the CMC value of the product is about 3.5 g / L, and γ is 30.15 mN / m. The conclusion is that the product has the ability to reduce the surface tension of the liquid at low concentration, showing good surface activity. The hydrophilic-lipophilic balance (HLB) value was measured using soybean oil and turpentine oil to prepare standard oil samples with HLB values of 7, 8, 9, 10, 11, 12, 13, 14, and 15. The HLB value of the target product was 10, indicating that the hydrophilicity of the obtained surfactant is very strong. The emulsifying capacity was measured by preparing a 5g·100mL -1 solution of the sample to be tested with 0.05 mol·L -1The emulsification time of the sample solution was recorded as 186 min, indicating that the emulsification effect was good.

[0046] The above-described embodiments are merely preferred modes of the present application, and are not intended to limit the scope of the present application. Various modifications and improvements to the technical solutions of the present application made by those of ordinary skill in the art without departing from the design spirit of the present application shall fall within the scope of protection of the present application as defined by the claims.

Claims

1. A citrate-type-lignin sulfonate cationic surfactant characterized by: Synthesized from aniline, sodium lignosulfonate and citric acid as raw materials, the manufacturing steps include: Step 1: add epichlorohydrin to 1%-95% methanol solution, and stop stirring after gradually heating from room temperature to 60-85 DEG C; in the step 1, the volume ratio of methanol and epichlorohydrin is 1:1 to 1:8; Step 2: gradually add aniline solution to the epichlorohydrin methanol mixed solution, and obtain the epoxy propyl phenyl ammonium chloride intermediate after constant temperature heating and stirring reaction for 1-24h; in the step 2, the volume ratio of epichlorohydrin and aniline is 1:1 to 1:10; the constant temperature is 40-85 DEG C; Step 3: dissolve sodium lignosulfonate into 5%-85% phosphoric acid solution to obtain an acidic sodium lignosulfonate solution; Step 4: gradually add the acidic sodium lignosulfonate solution to the epoxy propyl phenyl ammonium chloride intermediate after gradually heating from room temperature to 60-85 DEG C, mix and stir uniformly, then add 0.1 mol / L-12 mol / L NaOH solution, and obtain the lignin quaternary ammonium ion intermediate after stirring reaction for 1-24h at 60-85 DEG C; in the step 4, the volume ratio of the acidic sodium lignosulfonate and the epoxy propyl phenyl ammonium chloride intermediate is 1:1 to 1:6; Step 5: dissolve citric acid into 5%-95% ethanol solution, gradually add to the lignin quaternary ammonium ion intermediate, constant temperature heating and stirring, and then stand after reaction for 1-24h; in the step 5, the volume ratio of citric acid and lignin quaternary ammonium ion intermediate is 1:1 to 1:6; the constant temperature is 40-85 DEG C; Step 6: after standing for 3-48h, the citric acid type lignosulfonate cationic surfactant is separated.

2. A citrate-type-lignosulfonate cationic surfactant according to claim 1, characterized in that: In the step 1, the heating speed is 0.5 DEG C / min; the stirring speed is 300 r / min.

3. A citrate-type-lignosulfonate cationic surfactant according to claim 1, characterized in that: In the step 2, the solution dropping speed is 5-10 drops / min; the stirring speed is 300 r / min.

4. The citrate-lignosulfonate cationic surfactant of claim 1, characterized by: In the step 4, the heating speed is 0.5 DEG C / min; the solution dropping speed is 5-10 drops / min; the stirring speed is 300 r / min.

5. The citrate-lignosulfonate cationic surfactant of claim 1, characterized in that: In the step 5, the solution dropping speed is 5-10 drops / min; the stirring speed is 300 r / min.

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