A highly active detergent composition containing succinic anhydride and its preparation method

Abstract

This invention relates to the field of detergent technology, specifically disclosing a highly active detergent composition containing succinic anhydride and its preparation method. The invention prepares the highly active detergent composition by hydrolyzing a small amount of alkenyl succinic anhydride to obtain succinic acid. The invention also provides a lignin-based surfactant to work in conjunction with the composition, effectively preventing the redeposition of dirt washed off the fabric, thus ensuring washing performance. The composition prepared by this invention can prevent the aggregation and precipitation of dirt particles during washing, ensuring the formula remains stable and does not separate throughout its shelf life and during washing, while improving detergency.

Description

Technical Field

[0001] This invention relates to the field of detergent technology, and in particular to a highly active detergent composition containing succinic anhydride and its preparation method. Background Technology

[0002] High-activity detergent compositions are a type of modern detergent formulation characterized by high-efficiency stain removal, low dosage, and strong adaptability. Their core advantage lies in optimizing the proportion of active ingredients, scientifically compounding functional additives, and innovative formulation design. This allows for the rapid removal of various stubborn stains such as grease, protein, starch, and pigment stains while reducing dosage. They are widely used in laundry, dishwashing, and industrial heavy oil stain removal. The high activity of these compositions is not due to the potency of a single component, but rather to the enhanced systemic efficiency resulting from the synergistic effect of multiple components. The core technology is reflected in three dimensions: a high proportion and precise selection of active ingredients, synergistic effects of functional additives, and strong adaptability to complex washing environments.

[0003] From the perspective of active ingredients, high-activity detergent compositions typically feature high levels of surfactants as their core, often employing a compound system. Compared to traditional detergents, high-activity compositions generally have a higher total active ingredient content and contain very few fillers. Therefore, only a small amount is needed to achieve the same detergency as traditional products, reducing resource consumption and the risk of rinsing residue. In terms of synergistic design of functional additives, high-activity detergent compositions further enhance detergency and user experience by adding highly efficient enzymes, chelating agents, and anti-redeposition agents. Enzymes are key synergistic ingredients, typically compounded with alkaline proteases, lipases, amylases, and cellulases. The activity units of these enzymes are far higher than those in ordinary detergents, allowing them to function rapidly at room temperature. Furthermore, some high-activity compositions also add low-temperature activators to improve detergency at low temperatures, or add antibacterial agents to achieve both cleaning and antibacterial effects.

[0004] CN1078998A discloses a method for manufacturing a concentrated liquid detergent composition, comprising the following steps: i) mixing succinic anhydride, water, and an alkaline catalyst, wherein the ratio of succinic anhydride to water is not less than 4:1; ii) carrying out an exothermic hydrolysis reaction in a buffer tank; iii) mixing highly active, partially neutralized succinic acid and other detergent components.

[0005] CN113930298A relates to the field of daily chemical product technology, specifically to a high-surfactant-content and stable concentrated liquid detergent composition and its preparation method. The formulation, by weight, consists of 0.1%–16% of an alkaline neutralizing agent, 50%–96% of total surfactant, 0.1%–5% of organic polycarboxylic acids and their salts, 0.2%–3.5% of an enzyme preparation, 0%–5% of auxiliary agents, and the balance being a solvent. The total water content in the composition is less than 10%. This concentrated liquid detergent composition achieves a good balance among surfactants (content above 50%), organic polycarboxylic acids and their salts, and enzyme preparations, exhibiting excellent detergency while ensuring enzyme activity and maintaining strong stability throughout the entire composition system.

[0006] Alkyl / alkenyl succinic acid, due to its hydrophilic dicarboxylic acid head group and long hydrophobic tail chain, can be used as a highly effective anionic surfactant for removing oil stains. Its dicarboxylic acid structure not only binds calcium and magnesium ions to prevent soap scum formation, but its chelating ability is also enhanced by its unique molecular structure. Alkyl / alkenyl succinic acid is usually a solid or a very viscous semi-solid at room temperature, making it extremely difficult to handle. To add it to liquid detergents, it usually needs to be dissolved in a large amount of water to prepare a low-concentration solution. However, high-activity detergents have a high surfactant content and very low water content, so it is necessary to minimize the use of water. Summary of the Invention

[0007] In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a highly active detergent composition containing succinic anhydride and a method for preparing the same.

[0008] Succinic anhydride has a highly reactive cyclic anhydride molecular structure, readily undergoing ring-opening hydrolysis with water to produce the corresponding succinic acid. The hydrolysis of anhydrides is quantitative; for example, approximately 4.4 parts by weight of dodecenylsuccinic anhydride can be hydrolyzed by 1 part by weight of water. This means that the reaction can be completed with a very small amount of water, producing a high-concentration succinic acid solution. Therefore, using succinic anhydride for hydrolysis can achieve high-content, highly active detergent compositions.

[0009] This invention prepares a highly active detergent composition by hydrolyzing a small amount of alkenyl succinic anhydride to obtain succinic acid. This method not only minimizes the use of succinic anhydride but also features a low concentration and high content. However, the carboxylate group of the hydrolyzed succinic acid has a strong binding ability with calcium and magnesium ions in water, resulting in poor hard water resistance and easy formation of soap scum. This can lead to stiff and yellowing fabrics after washing and may also cause precipitation and stratification of the composition. Therefore, this invention provides a lignin-based surfactant to work in conjunction with the lignin. The inherently large and rigid aromatic skeleton of lignin acts as a network barrier suspended in the detergent solution, effectively preventing dirt washed off the fabric from redepositing onto the fabric, thus ensuring the washing effect. The large molecular structure of lignin provides a strong steric hindrance effect. It adsorbs onto the surface of dirt particles or oil droplets, physically preventing particles from approaching and agglomerating due to its large volume, thereby maintaining the stability of the system. It also prevents dirt particles in the detergent solution from agglomerating and settling, ensuring the formula remains stable and does not stratify throughout its shelf life and during washing, while improving the detergency effect.

[0010] To achieve the above objectives, the present invention provides a method for preparing a highly active detergent composition containing succinic anhydride, comprising the following steps, in parts by weight: S1. Hydrolyze a mixture of dodecenyl succinic anhydride, water and alkaline solution to obtain a hydrolysate. S2. Add 2-4 parts of chelating agent and 6-10 parts of 1,2-propanediol to 50-60 parts of water at 30-40℃. Add 20wt% sodium hydroxide aqueous solution to adjust the pH to 10-11, then add 10-20 parts of the hydrolysate from step S1. Stir evenly and cool to room temperature. Add 0.1-0.3 parts of preservative, 0.5-2 parts of alkaline protease and 15-20 parts of lignin-based surfactant. Mix evenly and defoam. Let stand in the dark for 20-30 hours to mature before discharging.

[0011] The method for preparing the lignin-based surfactant includes the following steps: Alkaline lignin was dispersed in water, the pH was adjusted to alkaline, and sodium 3-chloro-2-hydroxypropane sulfate was added. The mixture was heated and stirred. After the reaction was completed, the mixture was dialyzed and freeze-dried to obtain a lignin-based surfactant.

[0012] Furthermore, the mass ratio of the dodecenyl succinic anhydride, water, and alkaline solution is 4~5:1:0.05~1.

[0013] Furthermore, the chelating agent is methylglycine diacetic acid.

[0014] Furthermore, the preservative is sodium benzoate.

[0015] Furthermore, the mass ratio of the alkaline lignin to water and sodium 3-chloro-2-hydroxypropane sulfate is 1:15~25:1~1.5.

[0016] Furthermore, the pH adjustment range is 10~12.

[0017] Furthermore, the temperature range for the heating is 75~85℃.

[0018] Furthermore, the heating and stirring time is 6-8 hours.

[0019] Preferably, the method for preparing the lignin-based surfactant includes the following steps: Basic lignin and allyl glycidyl ether were added to a water / acetone mixture, followed by the addition of tetrabutylammonium bromide. The mixture was then heated to 50-60°C and stirred for 4-8 hours. Diethylenetriamine was then added and stirring continued for 10-14 hours. After concentration to remove the solvent, the mixture was dialyzed and freeze-dried to obtain a lignin-based surfactant. The mass ratio of basic lignin to allyl glycidyl ether, water / acetone mixture, tetrabutylammonium bromide, and diethylenetriamine was 1:1-2:15-25:0.01-0.05:0.3-1.

[0020] More preferably, the method for preparing the lignin-based surfactant includes the following steps: Alkaline lignin was dispersed in water, and the pH was adjusted to 10-12. Then, 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, and the mixture was heated to 60-80°C and stirred for 4-6 hours. Sodium bisulfite was then added, and the mixture was heated to 75-85°C and stirred for 3-5 hours. After cooling to room temperature, the mixture was dialyzed and freeze-dried to obtain a lignin-based surfactant. The mass ratio of alkaline lignin to water, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and sodium bisulfite was 1:15-25:0.5-1:0.1-0.5.

[0021] The present invention also provides a highly active detergent composition containing succinic anhydride, which is prepared by the above method.

[0022] The beneficial effects of this invention are: This invention prepares a highly active detergent composition by hydrolyzing a small amount of alkenyl succinic anhydride to obtain succinic acid. This not only minimizes the use of succinic anhydride but also features a low concentration and high content. This invention provides a lignin-based surfactant that, in conjunction with the composition, effectively prevents the redeposition of dirt already washed off the fabric, ensuring effective washing. The macromolecular structure of lignin provides a strong steric hindrance effect, maintaining system stability and preventing the aggregation and precipitation of dirt particles in the detergent solution. This ensures the formulation remains stable and does not separate throughout its shelf life and during washing, while also enhancing detergency. Detailed Implementation

[0023] Alkaline lignin, CAS No.: 9005-53-2.

[0024] Alkaline protease, model: APL4000, enzyme activity ≥400,000 u / mL, sourced from Cangzhou Xiasheng Enzyme Biotechnology Co., Ltd.

[0025] Example 1 A method for preparing a highly active detergent composition containing succinic anhydride includes the following steps, in parts by weight: S1. Mix 18 parts of dodecenyl succinic anhydride, 4 parts of water and 0.2 parts of 50wt% sodium hydroxide aqueous solution and then hydrolyze to obtain hydrolysate; S2. Add 3 parts of methylglycine diacetic acid and 8 parts of 1,2-propanediol to 50 parts of water at 35°C. Adjust the pH to 11 by adding 20wt% sodium hydroxide aqueous solution. Then add 15 parts of the hydrolysate from step S1. Stir well and cool to room temperature. Add 0.2 parts of sodium benzoate, 0.8 parts of alkaline protease and 15 parts of lignin-based surfactant. Mix well and defoam. Let stand in the dark for 24 hours to mature before discharging.

[0026] The method for preparing the lignin-based surfactant includes the following steps: Alkaline lignin was dispersed in water, and sodium hydroxide was added to adjust the pH to 11. Then, sodium 3-chloro-2-hydroxypropane sulfate was added, and the mixture was heated to 80°C and stirred for 7 hours. After the reaction was completed, the mixture was dialyzed and freeze-dried to obtain a lignin-based surfactant. The mass ratio of alkaline lignin to water and sodium 3-chloro-2-hydroxypropane sulfate was 1:20:1.25.

[0027] Example 2 It is basically the same as Example 1, except that the lignin-based surfactant is different; The method for preparing the lignin-based surfactant includes the following steps: Basic lignin and allyl glycidyl ether were added to a 50wt% water / acetone mixture, followed by the addition of tetrabutylammonium bromide. The mixture was then heated to 55℃ and stirred for 6 hours. Diethylenetriamine was then added and stirring continued for 12 hours. After concentration to remove the solvent, the mixture was dialyzed and freeze-dried to obtain a lignin-based surfactant. The mass ratio of basic lignin to allyl glycidyl ether, water / acetone mixture, tetrabutylammonium bromide, and diethylenetriamine was 1:1.5:20:0.02:0.6.

[0028] Example 3 It is basically the same as Example 1, except that the lignin-based surfactant is different; The method for preparing the lignin-based surfactant includes the following steps: Alkaline lignin was dispersed in water, and sodium hydroxide was added to adjust the pH to 11. Then 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, and the mixture was heated to 70°C and stirred for 5 hours. Sodium bisulfite was then added, and the mixture was heated to 80°C and stirred for 4 hours. After cooling to room temperature, the mixture was dialyzed and freeze-dried to obtain a lignin-based surfactant. The mass ratio of alkaline lignin to water, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and sodium bisulfite was 1:20:0.75:0.3.

[0029] Compare with Example 1 A method for preparing a highly active detergent composition containing succinic anhydride includes the following steps, in parts by weight: S1. A mixture of 18 parts dodecenyl succinic anhydride, 4 parts water, and 0.2 parts 50 wt% sodium hydroxide aqueous solution was hydrolyzed to obtain a hydrolysate. S2. Add 3 parts of methylglycine diacetic acid and 8 parts of 1,2-propanediol to 50 parts of water at 35℃. Add 20wt% sodium hydroxide aqueous solution to adjust the pH to 11, then add 15 parts of the hydrolysate from step S1. Stir well and cool to room temperature. Add 0.2 parts of sodium benzoate and 0.8 parts of alkaline protease. Mix well and defoam. Let stand in the dark for 24 hours to mature before discharging.

[0030] Compare with Example 2 A method for preparing a highly active detergent composition containing succinic anhydride includes the following steps, in parts by weight: S1. Mix 18 parts of dodecenyl succinic anhydride, 4 parts of water and 0.2 parts of 50wt% sodium hydroxide aqueous solution and then hydrolyze to obtain hydrolysate; S2. Add 3 parts of methylglycine diacetic acid and 8 parts of 1,2-propanediol to 50 parts of water at 35°C. Adjust the pH to 11 by adding 20wt% sodium hydroxide aqueous solution. Then add 15 parts of the hydrolysate from step S1. Stir well and cool to room temperature. Add 0.2 parts of sodium benzoate, 0.8 parts of alkaline protease and 15 parts of sodium lignosulfonate. Mix well and defoam. Let stand in the dark for 24 hours to mature before discharging.

[0031] Test Example 1 The highly active detergent compositions prepared in the examples and control examples were subjected to stain removal tests, referring to GB / T13174-2008 "Determination of Stain Removal Power and Recycled Washing Performance of Detergents for Clothing". The detergent's stain removal performance was tested by preparing a washing solution with 150 ppm hard water at a concentration of 2 g / L. The solution was then placed in a vertical stain remover and washed for 20 minutes at 30±1℃ on JB-01 carbon black oil-stained cloth, JB-02 protein-stained cloth, and JB-03 sebum-stained cloth cut to 6cm×6cm. The difference in whiteness between the cloth before and after washing was measured using a whiteness meter under 457nm blue light irradiation. The stain removal value R of the cloth was determined. i =∑(F2i -F 1i ) / n, where i refers to the i-th test piece; F 1i F refers to the spectral reflectance (%) of the i-th sample before washing. 2i The spectral reflectance (%) of the i-th sample after washing is indicated; n is the effective number of samples in each group.

[0032] To ensure the stability of experimental data, relative detergency is typically used to evaluate the detergency of detergents. Relative detergency is the ratio of the detergency value of a test sample washed with the desired detergent formulation to that of a standard laundry detergent under the same washing conditions, expressed as P. i =R / R0, where R0 is the detergency value of the standard detergent powder; R is the detergency value of the tested detergent. When P i When P ≥ 1.0, the detergency is considered acceptable; when P i If the value is less than 1.0, the detergency is not up to standard.

[0033] Table 1

[0034] As shown in Table 1, the detergency of the examples is significantly better than that of the control examples. Control Example 1 uses a small amount of alkenyl succinic anhydride hydrolyzed to obtain succinic acid, thus preparing a highly active detergent composition. This not only minimizes the use of succinic anhydride but also features a low concentration and high content. However, the carboxyl group of the hydrolyzed succinic acid has a strong binding ability with calcium and magnesium ions in water, resulting in poor hard water resistance and easy formation of soap scum. This not only causes the washed fabrics to become stiff and yellow but may also lead to precipitation and stratification of the composition, thus making its detergency inferior to that of the examples. In contrast, sodium lignin sulfonate in Control Example 2 is also an anionic surfactant. The sulfonate group gives the dirt and fibers a negative charge, causing them to repel each other. In hard water, The neutralization of charges significantly weakens this effect, resulting in a cleaning effect that is also inferior to that of Example 1.

[0035] In this embodiment, the prepared lignin-based surfactant is combined with the hydrolysate of alkenyl succinic anhydride. The inherently large and rigid aromatic skeleton of lignin acts as a network barrier suspended in the washing liquid, effectively preventing dirt already washed off the fabric from redepositing onto the fabric, thus ensuring washing performance. The large molecular structure of lignin provides a strong steric hindrance effect. It adsorbs onto the surface of dirt particles or oil droplets, physically preventing particles from approaching and agglomerating due to its large volume, thereby maintaining system stability. It also prevents dirt particles in the washing liquid from agglomerating and settling, ensuring the formulation remains stable and does not separate throughout its shelf life and during washing, while improving detergency.

[0036] In Example 1, an surfactant with a unique twin structure was obtained by alkaline lignin etherification and sulfonate linkage. It has a high effect of reducing surface tension, forming micelles and solubilizing oil stains. Through the dual mechanism of electrostatic repulsion and steric hindrance, it provides stronger and more reliable anti-redeposition protection than sodium lignin sulfonate relying solely on electrostatic repulsion.

[0037] Example 2 yielded a lignin-based surfactant with a polyether chain through epoxy ring-opening and addition. The polyether chain is also unaffected by hardness, thus exhibiting good detergency even in hard water.

[0038] Example 3 describes the preparation of an amphoteric surfactant by quaternization and sulfonation of alkaline lignin. The amphoteric properties not only do not restrict hard water systems, but also provide protection for the entire composition system, thus exhibiting the strongest detergency.

[0039] Test Example 2 Anti-deposition tests were conducted on the highly active detergent compositions prepared in the examples and control examples. Standard cotton cloth was circulated and washed in detergent solution containing dirt. The ability to retain whiteness was used to indicate the color fading of white fabric, which is a measure of the detergent's ability to suspend dirt and is an indicator of the detergent's anti-redeposition performance.

[0040] T(times) = ∑F k 2 / ∑F1×100%, where ∑F1 is the spectral reflectance (%) of the same group of standard cotton fabrics before washing; ∑F k 2 represents the spectral reflectance (%) of the same group of standard cotton fabrics after k cycles of washing; k is the number of cycles of washing, with a value of 25.

[0041] Table 2

[0042] As shown in Table 2, the washing compositions in the examples exhibit superior anti-deposition properties. This demonstrates that the lignin-based surfactant prepared in this invention, when used in conjunction with the composition, effectively prevents dirt washed off the fabric from redepositing onto the fabric. In Example 3, the lignin-based surfactant, under alkaline conditions during washing, exhibits predominantly negatively charged sulfonate groups, functioning through electrostatic repulsion. Its zwitterionic structure possesses extremely strong hydration capabilities, forming a stable hydration protective layer on the surface of dirt and fibers. This water film provides excellent steric hindrance, effectively isolating dirt. Its anti-deposition performance is almost entirely unaffected by hard water, as steric hindrance is the primary mechanism, and this mechanism is insensitive to water hardness. This is a significant advantage over anionic surfactants, resulting in superior anti-deposition performance. In Example 1, the performance is limited by weakened electrostatic repulsion, and the polyether segment in Example 2 may pose a deposition risk due to residue; therefore, their performance is inferior to Example 3.

[0043] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A method for preparing a highly active detergent composition containing succinic anhydride, characterized in that, The steps are as follows, in parts by weight: S1. Hydrolyze a mixture of dodecenyl succinic anhydride, water and alkaline solution to obtain a hydrolysate. The mass ratio of dodecenyl succinic anhydride, water and alkaline solution is 4~5:1:0.05~1. S2. Add 2-4 parts of chelating agent and 6-10 parts of 1,2-propanediol to 50-60 parts of water at 30-40℃. Add 20wt% sodium hydroxide aqueous solution to adjust the pH to 10-11, then add 10-20 parts of the hydrolysate from step S1. Stir evenly and cool to room temperature. Add 0.1-0.3 parts of preservative, 0.5-2 parts of alkaline protease and 15-20 parts of lignin-based surfactant. Mix evenly and defoam. Let stand in the dark for 20-30 hours to mature before discharging. The preparation method of the lignin-based surfactant comprises the following steps: Alkaline lignin was dispersed in water, and the pH was adjusted to 10-12. Then, 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, and the mixture was heated to 60-80°C and stirred for 4-6 hours. Sodium bisulfite was then added, and the mixture was heated to 75-85°C and stirred for 3-5 hours. After cooling to room temperature, the mixture was dialyzed and freeze-dried to obtain a lignin-based surfactant. The mass ratio of alkaline lignin to water, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and sodium bisulfite was 1:15-25:0.5-1:0.1-0.

5.

2. The method for preparing the highly active detergent composition containing succinic anhydride as described in claim 1, characterized in that, The chelating agent is methylglycine diacetic acid.

3. The method for preparing the highly active detergent composition containing succinic anhydride as described in claim 1, characterized in that, The preservative is sodium benzoate.

4. A highly active detergent composition containing succinic anhydride, characterized in that, Prepared by the method described in any one of claims 1 to 3.

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