Low-foam high-activity environment-friendly detergent and preparation method thereof

Abstract

The invention discloses a low-foam high-activity environment-friendly detergent and a preparation method thereof, and relates to the technical field of detergents. The preparation method comprises the following steps: reacting castor oil with lactic acid to generate a lactic ricinoleate copolymer, and introducing an easily degradable group to improve the biodegradability of the copolymer; and then hydroxyl in the lactic acid ricinoleate copolymer reacts with carboxyl of lauric acid to generate lactic acid castor oil laurate, so that oil stains are more effectively emulsified and dispersed, and the decontamination capability of the detergent is improved. And secondly, tetradecanoic acid containing a hydrophobic structure and an unsaturated ester compound are polymerized with double-bond free radicals to form tetradecanoic acid grafted polyester, so that the stability of the polyester is enhanced. Finally, aminated silicon dioxide and ester groups of tetradecanoic acid grafted polyester are subjected to an addition reaction to generate a polyester-silicon dioxide compound, the defoaming performance of the filler is improved, the filler stably plays a role in the detergent, and the dirt-removing power of the detergent is further improved in cooperation with lactic castor oil laurate.

Description

Technical Field

[0001] The present invention relates to the technical field of detergents, and specifically to a low-foaming and highly active environmentally friendly detergent and a preparation method thereof. Background Art

[0002] With the rapid economic development of developing countries and the improvement of residents' living standards, the demand for detergents is also continuously increasing. Detergents play an extremely important role in personal hygiene, household cleaning, industrial production, environmental protection, etc. Detergents can improve the quality of life and have become an indispensable part of modern life.

[0003] The surfactants in some highly active detergents have poor biodegradability and are likely to accumulate in the environment, leading to eutrophication of water bodies and ecological damage. Moreover, they may cause irritation to the skin, especially allergic reactions in sensitive skin, posing potential hazards to human health and the environment. In addition, if a large amount of foam is generated during the use of detergents, it is necessary to increase the water consumption and washing time, resulting in a waste of water resources. Therefore, it is particularly important to develop an environmentally friendly detergent with both low-foaming and highly active properties. Summary of the Invention

[0004] The purpose of the present invention is to provide a low-foaming and highly active environmentally friendly detergent and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A preparation method of a low-foaming and highly active environmentally friendly detergent, including the following preparation steps:

[0006] S1. Castor oil and lactic acid are added to a reaction kettle, and then an ethanol aqueous solution is added and mixed evenly. It is heated to 40°C - 60°C, and lipase is slowly added. Stir at a speed of 100 - 300 rpm for 12 - 24 h. After cooling to room temperature, the solid is taken and washed 3 - 5 times with deionized water, and dried at 60°C for 3 - 5 h to obtain a lactic acid castor oil acid ester copolymer.

[0007] S2. The lactic acid castor oil acid ester copolymer obtained in S1 and lauric acid are taken in a reaction kettle. After adding an ethanol aqueous solution and mixing evenly, lipase is added. Stir at 40°C - 60°C at a speed of 100 - 300 rpm for 12 - 24 h. After cooling to room temperature, the solid is taken and washed 3 - 5 times with deionized water, and dried at 60°C for 3 - 5 h to obtain a lactic acid castor oil laurate.

[0008] S3. Mix tetradecanoic acid, unsaturated ester compounds and anhydrous toluene in a three-necked flask, then add benzoyl peroxide, heat to 120 - 140 °C under nitrogen protection, stir at a speed of 100 - 300 rpm for 6 - 8 h, after cooling to room temperature, filter to collect the solid, wash it with ethanol 3 - 5 times, and dry it at 60 °C for 12 - 24 h to obtain tetradecanoic acid grafted polyester;

[0009] S4. Dissolve the tetradecanoic acid grafted polyester obtained in S3 and modified SiO₂ in anhydrous toluene, after mixing evenly, add tetrabutyl titanate, heat to 80 - 100 °C under nitrogen protection, stir at a speed of 200 - 400 rpm for 6 - 12 h, then centrifuge at a speed of 7000 - 8000 rpm for 10 - 30 min, take the precipitate, wash it with ethanol 3 - 5 times, and dry it at 60 °C for 12 - 24 h to obtain polyester-silica composite;

[0010] S5. Add deionized water to the reaction kettle, under the condition of 60 °C - 70 °C, add the surfactant obtained in S2 and the defoamer obtained in S4, stir at a speed of 100 - 300 rpm for 20 - 30 min, successively add builder, preservative and fragrance, and stir at a speed of 100 - 300 rpm for 10 - 20 min to obtain a low-foam and highly active environmental protection detergent.

[0011] Further, the ethanol aqueous solution described in S1 is composed of ethanol and deionized water mixed in a mass ratio of 9:1.

[0012] Further, the mass ratio of lipase, castor oil, lactic acid and ethanol aqueous solution in S1 is 0.01:3:1:10 - 0.1:4:1:10.

[0013] Further, the mass ratio of lipase, lactic acid castor oil laurate copolymer, lauric acid and ethanol aqueous solution in S2 is 0.01:4:1:10 - 0.1:6:1:10.

[0014] Further, the preparation method of the unsaturated ester compounds described in S3: Mix itaconic acid, 1,6-hexanediol and toluene in a three-necked flask in a mass ratio of 1:1.5:5 - 1:2.5:5, add sulfuric acid 0.01 - 0.03 times the mass of itaconic acid at a stirring speed of 100 - 300 rpm, slowly heat to 120 - 140 °C and stir for 4 - 6 h, after cooling to room temperature, take the solid, wash it with ethanol 3 - 5 times, and dry it at 60 °C for 6 - 8 h to obtain unsaturated ester compounds.

[0015] Further, the mass ratio of tetradecanoic acid, unsaturated ester compounds, benzoyl peroxide and anhydrous toluene in S3 is 2:1:0.02:5 - 4:1:0.1:5.

[0016] Further, the preparation method of the modified SiO2 in S4: Mix the silane coupling agent and the ethanol aqueous solution in a mass ratio of 1:100 in a beaker, add sulfuric acid at room temperature to adjust the solution pH to 4-5, stir at a speed of 300-500 rpm for 20-40 min, then add silica particles 5-15 times the mass of the silane coupling agent, stir at a speed of 500-1000 rpm at 60°C - 80°C for 2-4 h. After cooling to room temperature, take the solid and wash it once with ethanol, and dry it at 60°C for 12-24 h to obtain amino-functionalized SiO2.

[0017] Further, the silane coupling agent is aminopropyltriethoxysilane KH550.

[0018] Further, the mass ratio of the myristic acid-grafted polyester, modified SiO2, tetrabutyl titanate, and anhydrous toluene in S4 is 1:1:0.02:5 - 5:1:0.2:5.

[0019] Further, the low-foam and high-activity environmentally friendly detergent in S5 comprises the following preparation raw materials: 15-25 parts of surfactant, 2-4 parts of defoamer, 3-5 parts of sodium citrate, 0.1-0.3 parts of potassium sorbate, 0.1-0.3 parts of lemon essence, and 70-80 parts of water.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0021] The present invention uses surfactant, defoamer, builder, preservative, fragrance, and water as raw materials to prepare a low-foam and high-activity environmentally friendly detergent, which has excellent detergency and low foaming property, and solves the problems of traditional detergents such as excessive foam, difficult rinsing, and poor environmental performance.

[0022] First, castor oil and lactic acid are subjected to an esterification reaction under the catalysis of lipase to generate a lactic acid ricinoleate copolymer, introducing easily degradable groups, which not only retains the surface activity of castor oil but also improves the biodegradability of the copolymer, reducing environmental pollution during the use of the detergent. Then, the hydroxyl group in the lactic acid ricinoleate copolymer reacts with the carboxyl group of lauric acid to prepare lactic acid ricinoleate laurate, connecting the hydrophobic chain of lauric acid to the copolymer, which can more effectively form a stable emulsion system with oil stains and further improve the detergency of the detergent.

[0023] Secondly, it uses itaconic acid to react with 1,6 - hexanediol to generate unsaturated ester compounds, and then combines with tetradecanoic acid containing a hydrophobic structure. The hydrophobic chain of tetradecanoic acid is grafted onto the polyester through free radical polymerization with double bonds, improving the stability of the polyester. Meanwhile, the hydrophobic chain further enhances the hydrophobic performance of the subsequent composite filler, thereby strengthening the defoaming effect of silica. Then, silane coupling agent is used to modify silica, introducing organic groups on the surface of silica, and making it react with the ester group of the tetradecanoic acid - grafted polyester through an addition reaction to form a polyester - silica composite, significantly improving the dispersibility of silica to form a stable suspension system. Through the dual combination of chemical bonding and physical adsorption, the overall performance of the filler is further improved, enabling it to play a stable role in detergents.

[0024] Finally, the polyester - silica composite, as a filler, synergistically combines with ricinoleic acid laurate to further improve the detergency of the detergent, helping to remove stubborn dirt attached to clothes or hard surfaces and preventing stain redeposition, conforming to the trend of green washing and meeting the environmental protection requirements. Specific embodiments

[0025] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0026] In order to more clearly illustrate the method provided by the present invention, the following examples are used for detailed description. The test methods for each index of a low - foam and highly active environmentally friendly detergent prepared in the following examples are as follows:

[0027] Detergency performance: Select standard - compliant cotton cloth, evenly apply stains and dry it. Immerse the stained cloth in the detergent, take it out and stir with a stain tester for 20 min, and measure the reflectance with a whiteness meter to calculate the detergency rate.

[0028] Biodegradability performance: Dissolve the detergent in a culture medium inoculated with microorganisms, and cultivate it at a constant temperature (25 °C) in the dark for 28 days. Calculate the biodegradation rate of the detergent by detecting the amount of CO2 generated during the reaction process.

[0029] Defoaming performance: Prepare 1% detergent, pour 200 mL of the test solution from a height of 90 cm into a graduated cylinder, and record the residual foam height after 5 minutes.

[0030] Example 1

[0031] (1) Castor oil, lactic acid and an aqueous ethanol solution with a mass fraction of 90% were added to a reaction kettle in a mass ratio of 3:1:10, heated to 40 °C, and lipase 0.01 times the mass of lactic acid was added at a rate of 0.1 mL / min. Stir at a speed of 100 rpm for 12 h. After cooling to room temperature, the solid was taken and washed 3 times with deionized water and dried at 60 °C for 3 h to obtain a lactic acid ricinoleic acid ester copolymer;

[0032] (2) The lactic acid ricinoleic acid ester copolymer obtained in step (1), lauric acid and an aqueous ethanol solution with a mass fraction of 90% were mixed in a reaction kettle in a mass ratio of 4:1:10. Lipase 0.01 times the mass of lauric acid was added at a rate of 0.1 mL / min. Stir at 40 °C and a speed of 100 rpm for 12 h. After cooling to room temperature, the solid was taken and washed 3 times with deionized water and dried at 60 °C for 3 h to obtain lactic acid ricinoleic acid laurate;

[0033] (3) Itaconic acid, 1,6 - hexanediol and toluene were mixed in a mass ratio of 1:1.5:5. Concentrated sulfuric acid 0.01 times the mass of itaconic acid was added under a stirring speed of 100 rpm, and the temperature was raised to 120 °C and stirred for 4 h. After cooling to room temperature, the solid was taken and washed 3 times with ethanol and dried at 60 °C for 6 h to obtain an unsaturated ester compound;

[0034] (4) Myristic acid, the unsaturated ester compound obtained in step (3) and anhydrous toluene were mixed in a reaction kettle in a mass ratio of 2:1:5. Then benzoyl peroxide 0.02 times the mass of the unsaturated ester compound was added. Under nitrogen protection, the temperature was raised to 120 °C and stirred at a speed of 100 rpm for 6 h. After cooling to room temperature, the solid was filtered and collected, washed 3 times with ethanol and dried at 60 °C for 12 h to obtain a myristic acid - grafted polyester;

[0035] (5) KH550 and an aqueous ethanol solution with a mass fraction of 90% were mixed in a reaction kettle in a mass ratio of 1:100. Concentrated sulfuric acid was added at room temperature to adjust the solution pH = 4 and stirred at a speed of 300 rpm for 20 min. Then silicon dioxide particles with a particle size of 20 - 50 nm and 5 times the mass of KH550 were added. Stir at 60 °C and a speed of 500 rpm for 2 h. After cooling to room temperature, the solid was taken and washed 1 time with ethanol and dried at 60 °C for 12 h to obtain amino - functionalized SiO₂;

[0036] (6) The myristic acid - grafted polyester obtained in step (4), the modified SiO₂ obtained in step (5) and anhydrous toluene were mixed in a reaction kettle in a mass ratio of 1:1:5. After mixing evenly, tetrabutyl titanate 0.02 times the mass of the modified SiO₂ was added. Under nitrogen protection, the temperature was raised to 80 °C and stirred at a speed of 200 rpm for 6 h. Then centrifuged at a speed of 7000 rpm for 10 min. The precipitate was taken and washed 3 times with ethanol and dried at 60 °C for 12 h to obtain a polyester - silicon dioxide composite;

[0037] (7) Add 80 parts by mass of deionized water into a reaction kettle. Under the condition of 60 °C, add 15 parts by mass of the lactic acid castor oil laurate obtained in step (2) and 2 parts by mass of the polyester-silica composite obtained in step (6). Stir at a speed of 100 rpm for 20 min, then sequentially add 3 parts by mass of sodium citrate, 0.1 part by mass of potassium sorbate and 0.1 part by mass of lemon essence, and stir at a speed of 100 rpm for 10 min to obtain a low-foam and highly active environmental protection detergent.

[0038] Example 2

[0039] (1) Add castor oil, lactic acid and 90% aqueous ethanol solution into a reaction kettle according to a mass ratio of 3.5:1:10. Heat to 50 °C, add lipase at a rate of 0.05 times the mass of lactic acid at a speed of 0.1 mL / min, and stir at a speed of 200 rpm for 18 h. After cooling to room temperature, take the solid and wash it 4 times with deionized water, and dry it at 60 °C for 4 h to obtain a lactic acid castor oil fatty acid ester copolymer.

[0040] (2) Mix the lactic acid castor oil fatty acid ester copolymer obtained in step (1), lauric acid and 90% aqueous ethanol solution in a reaction kettle according to a mass ratio of 5:1:10. Add lipase at a rate of 0.05 times the mass of lauric acid at a speed of 0.1 mL / min, stir at 50 °C at a speed of 200 rpm for 18 h. After cooling to room temperature, take the solid and wash it 4 times with deionized water, and dry it at 60 °C for 4 h to obtain lactic acid castor oil laurate.

[0041] (3) Mix itaconic acid, 1,6-hexanediol and toluene according to a mass ratio of 1:2:5. Add concentrated sulfuric acid at a rate of 0.02 times the mass of itaconic acid at a stirring speed of 200 rpm, heat up to 130 °C and stir for 5 h. After cooling to room temperature, take the solid and wash it 4 times with ethanol, and dry it at 60 °C for 7 h to obtain an unsaturated ester compound.

[0042] (4) Mix tetradecanoic acid, the unsaturated ester compound obtained in step (3) and anhydrous toluene in a reaction kettle according to a mass ratio of 3:1:5, then add benzoyl peroxide at a rate of 0.06 times the mass of the unsaturated ester compound, heat up to 130 °C under nitrogen protection, stir at a speed of 200 rpm for 7 h. After cooling to room temperature, filter and collect the solid, wash it 4 times with ethanol, and dry it at 60 °C for 18 h to obtain tetradecanoic acid grafted polyester.

[0043] (5) Mix KH550 with an aqueous ethanol solution with a mass fraction of 90% at a mass ratio of 1:100 in a reaction kettle. Add concentrated sulfuric acid at room temperature to adjust the solution pH to 4.5, stir at a speed of 400 rpm for 30 min, then add silica particles with a size of 20 - 50 nm and 10 times the mass of KH550. Stir at a speed of 750 rpm at 70 °C for 3 h. After cooling to room temperature, take the solid and wash it once with ethanol, and dry it at 60 °C for 18 h to obtain amino-functionalized SiO₂;

[0044] (6) Mix the tetradecanoic acid-grafted polyester obtained in step (4), the modified SiO₂ obtained in step (5), and anhydrous toluene at a mass ratio of 3:1:5 in a reaction kettle. After mixing evenly, add tetrabutyl titanate at 0.1 times the mass of the modified SiO₂. Under nitrogen protection, heat up to 90 °C, stir at a speed of 300 rpm for 9 h, then centrifuge at a speed of 7500 rpm for 20 min. Take the precipitate and wash it 4 times with ethanol, and dry it at 60 °C for 18 h to obtain a polyester-silica composite;

[0045] (7) Add 75 parts by mass of deionized water to a reaction kettle. Under the condition of 65 °C, add 20 parts by mass of the lactic acid castor oil laurate obtained in step (2) and 3 parts by mass of the polyester-silica composite obtained in step (6). Stir at a speed of 200 rpm for 25 min, and successively add 4 parts by mass of sodium citrate, 0.2 parts by mass of potassium sorbate, and 0.2 parts by mass of lemon essence. Stir at a speed of 200 rpm for 15 min to obtain a low-foam and highly active environmentally friendly detergent.

[0046] Example 3

[0047] (1) Add castor oil, lactic acid, and an aqueous ethanol solution with a mass fraction of 90% to a reaction kettle at a mass ratio of 4:1:10. Heat to 60 °C, add lipase at 0.1 times the mass of lactic acid at a speed of 0.1 mL / min, stir at a speed of 300 rpm for 24 h. After cooling to room temperature, take the solid and wash it 5 times with deionized water, and dry it at 60 °C for 5 h to obtain a lactic acid castor oil acid ester copolymer;

[0048] (2) Mix the lactic acid castor oil acid ester copolymer obtained in step (1), lauric acid, and an aqueous ethanol solution with a mass fraction of 90% in a reaction kettle at a mass ratio of 6:1:10. Add lipase at 0.1 times the mass of lauric acid at a speed of 0.1 mL / min. At 60 °C, stir at a speed of 300 rpm for 24 h. After cooling to room temperature, take the solid and wash it 5 times with deionized water, and dry it at 60 °C for 5 h to obtain lactic acid castor oil laurate;

[0049] (3) Mix itaconic acid, 1,6 - hexanediol, and toluene in a mass ratio of 1:2.5:5. Add concentrated sulfuric acid at 0.03 times the mass of itaconic acid under a stirring speed of 300 rpm. Heat up to 140 °C and stir for 6 h. After cooling to room temperature, take the solid and wash it with ethanol 5 times, then dry it at 60 °C for 8 h to obtain an unsaturated ester compound;

[0050] (4) Mix myristic acid, the unsaturated ester compound obtained in step (3), and anhydrous toluene in a mass ratio of 4:1:5 in a reaction kettle. Then add benzoyl peroxide at 0.1 times the mass of the unsaturated ester compound. Under nitrogen protection, heat up to 140 °C and stir at a speed of 300 rpm for 8 h. After cooling to room temperature, filter to collect the solid, wash it with ethanol 5 times, and dry it at 60 °C for 24 h to obtain myristic acid - grafted polyester;

[0051] (5) Mix KH550 and an ethanol - aqueous solution with a mass fraction of 90% in a reaction kettle in a mass ratio of 1:100. Add concentrated sulfuric acid at room temperature to adjust the solution pH to 5, and stir at a speed of 500 rpm for 40 min. Then add silicon dioxide particles with a particle size of 20 - 50 nm at 15 times the mass of KH550. Stir at 80 °C at a speed of 1000 rpm for 4 h. After cooling to room temperature, take the solid and wash it with ethanol 1 time, and dry it at 60 °C for 24 h to obtain amino - functionalized SiO₂;

[0052] (6) Mix the myristic acid - grafted polyester obtained in step (4), the modified SiO₂ obtained in step (5), and anhydrous toluene in a mass ratio of 5:1:5 in a reaction kettle. After mixing evenly, add tetrabutyl titanate at 0.2 times the mass of the modified SiO₂. Under nitrogen protection, heat up to 100 °C and stir at a speed of 400 rpm for 12 h. Then centrifuge at a speed of 8000 rpm for 30 min. Take the precipitate and wash it with ethanol 5 times, and dry it at 60 °C for 24 h to obtain a polyester - silicon dioxide composite;

[0053] (7) Add 70 parts by mass of deionized water to the reaction kettle. Under the condition of 70 °C, add 25 parts by mass of the lactic acid castor oil laurate obtained in step (2) and 4 parts by mass of the polyester - silicon dioxide composite obtained in step (6). Stir at a speed of 300 rpm for 30 min. Sequentially add 5 parts by mass of sodium citrate, 0.3 parts by mass of potassium sorbate, and 0.3 parts by mass of lemon essence, and stir at a speed of 300 rpm for 20 min to obtain a low - foam and highly active environmental protection detergent.

[0054] Comparative Example 1

[0055] The difference between Comparative Example 1 and Example 2 lies in step (1). Modify step (1) as follows: Add castor oil, lactic acid, and a 90% ethanol aqueous solution to the reaction kettle at a mass ratio of 5:1:10, heat to 50°C, add lipase at a rate of 0.1 mL / min in an amount 0.05 times the mass of lactic acid, stir at a speed of 200 rpm for 18 h. After cooling to room temperature, take the solid and wash it 4 times with deionized water, and dry it at 60°C for 4 h to obtain the lactic acid castor oil acid ester copolymer.

[0056] Comparative Example 2

[0057] The difference between Comparative Example 2 and Example 2 lies in step (2). Modify step (2) as follows: Mix the lactic acid castor oil acid ester copolymer obtained in step (1), lauric acid, and a 90% ethanol aqueous solution in the reaction kettle at a mass ratio of 4:1:10, add lipase at a rate of 0.1 mL / min in an amount 0.05 times the mass of lauric acid, stir at 50°C and a speed of 200 rpm for 18 h. After cooling to room temperature, take the solid and wash it 4 times with deionized water, and dry it at 60°C for 4 h to obtain the lactic acid castor oil laurate.

[0058] Comparative Example 3

[0059] The difference between Comparative Example 3 and Example 2 lies in step (3). Modify step (3) as follows: Mix itaconic acid, 1,6 - hexanediol, and toluene at a mass ratio of 1:1.5:5, add concentrated sulfuric acid at a rate of 0.02 times the mass of itaconic acid under a stirring speed of 200 rpm, raise the temperature to 130°C and stir for 5 h. After cooling to room temperature, take the solid and wash it 4 times with ethanol, and dry it at 60°C for 7 h to obtain the unsaturated ester compound.

[0060] Comparative Example 4

[0061] The difference between Comparative Example 4 and Example 2 lies in step (4). Modify step (4) as follows: Mix myristic acid, the unsaturated ester compound obtained in step (3), and anhydrous toluene in the reaction kettle at a mass ratio of 2:1:5, then add benzoyl peroxide at a rate of 0.06 times the mass of the unsaturated ester compound, heat to 130°C under nitrogen protection, stir at a speed of 200 rpm for 7 h. After cooling to room temperature, filter and collect the solid, wash it 4 times with ethanol, and dry it at 60°C for 18 h to obtain the myristic acid - grafted polyester.

[0062] Comparative Example 5

[0063] The difference between Comparative Example 5 and Example 2 lies in step (5). Step (5) is changed to: Mix KH550 with an aqueous ethanol solution with a mass fraction of 90% at a mass ratio of 1:100 in a reaction kettle. Add concentrated sulfuric acid at room temperature to adjust the pH of the solution to 4.5, stir at a speed of 400 rpm for 30 min, then add silicon dioxide particles with a particle size of 20 - 50 nm and 5 times the mass of KH550, stir at a speed of 750 rpm at 70 °C for 3 h. After cooling to room temperature, take the solid and wash it once with ethanol, and dry it at 60 °C for 18 h to obtain amino-functionalized SiO2.

[0064] Comparative Example 6

[0065] The difference between Comparative Example 6 and Example 2 lies in step (6). Step (6) is changed to: Mix the tetradecanoic acid-grafted polyester obtained in step (4), the modified SiO2 obtained in step (5), and anhydrous toluene at a mass ratio of 1:1:5 in a reaction kettle. After mixing evenly, add tetrabutyl titanate with 0.1 times the mass of the modified SiO2, heat to 90 °C under nitrogen protection, stir at a speed of 300 rpm for 9 h, then centrifuge at a speed of 7500 rpm for 20 min. Take the precipitate and wash it 4 times with ethanol, and dry it at 60 °C for 18 h to obtain a polyester-silica composite.

[0066] Comparative Example 7

[0067] The difference between Comparative Example 7 and Example 2 lies in step (7). Step (7) is changed to: Add 80 parts by mass of deionized water to a reaction kettle. Under the condition of 65 °C, add 15 parts by mass of the lactic acid castor oil laurate obtained in step (2) and 2 parts by mass of the polyester-silica composite obtained in step (6), stir at a speed of 200 rpm for 25 min, sequentially add 3 parts by mass of sodium citrate, 0.1 part by mass of potassium sorbate, and 0.1 part by mass of lemon essence, and stir at a speed of 200 rpm for 15 min to obtain a low-foam and highly active environmentally friendly detergent.

[0068] Effect Example

[0069] Table 1 below gives the performance analysis results of the low-foam and highly active environmentally friendly detergents using Examples 1 to 3 and Comparative Examples 1 to 7 of the present invention.

[0070] Table 1

[0071]

[0072]

[0073] From the comparison of the experimental data on the detergency of the examples and the comparative examples, it can be found that after using castor oil and lactic acid to generate ricinoleic acid ester copolymer in this product, and then connecting the hydrophobic chain of lauric acid to this copolymer, the ability of the detergent to emulsify and disperse oil stains is greatly improved, the detergency of the detergent is improved. At the same time, the polyester-silica composite can synergistically improve the detergency of the detergent with lauryl ricinoleate; from the comparison of the experimental data on the biodegradation rate, it can be found that the addition of lactic acid introduces easily degradable groups, improving the biodegradability of the detergent, thereby reducing the environmental pollution caused by the detergent during use; from the comparison of the experimental data on the foam height, it can be found that the hydrophobic structure of myristic acid grafted polyester improves the hydrophobicity and stability of the composite filler, and the combination of polyester significantly improves the dispersibility of silica, enabling the filler to play a stable role in the detergent, thus strengthening the defoaming effect of the polyester-silica composite.

[0074] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be construed as limiting the claims involved.

Claims

1. A preparation method of a low-foam and highly active environmentally friendly detergent, characterized in that, It includes the following preparation steps: S1. Castor oil and lactic acid are added into a reaction kettle, then an ethanol aqueous solution is added and mixed evenly. It is heated to 40°C - 60°C, and lipase is slowly added. Stir at a speed of 100 - 300 rpm for 12 - 24 h. After cooling to room temperature, the solid is taken and washed 3 - 5 times with deionized water, and dried at 60°C for 3 - 5 h to obtain a lactic acid ricinoleate copolymer; S2. The lactic acid ricinoleate copolymer obtained in S1 and lauric acid are taken into a reaction kettle. After adding an ethanol aqueous solution and mixing evenly, lipase is added. Stir at 40°C - 60°C at a speed of 100 - 300 rpm for 12 - 24 h. After cooling to room temperature, the solid is taken and washed 3 - 5 times with deionized water, and dried at 60°C for 3 - 5 h to obtain lactic acid ricinoleate laurate; S3. Myristic acid, unsaturated ester compounds and anhydrous toluene are mixed in a three-necked flask, and then benzoyl peroxide is added. Under nitrogen protection, the temperature is raised to 120 - 140°C, and stirred at a speed of 100 - 300 rpm for 6 - 8 h. After cooling to room temperature, the solid is collected by filtration, washed 3 - 5 times with ethanol, and dried at 60°C for 12 - 24 h to obtain myristic acid-grafted polyester; S4. The myristic acid-grafted polyester obtained in S3 and modified SiO₂ are dissolved in anhydrous toluene. After mixing evenly, tetrabutyl titanate is added. Under nitrogen protection, the temperature is raised to 80 - 100°C, and stirred at a speed of 200 - 400 rpm for 6 - 12 h. Then centrifuge at a speed of 7000 - 8000 rpm for 10 - 30 min. The precipitate is taken and washed 3 - 5 times with ethanol, and dried at 60°C for 12 - 24 h to obtain a polyester-silica composite; S5. Deionized water is added into a reaction kettle. Under the condition of 60°C - 70°C, the surfactant obtained in S2 and the defoamer obtained in S4 are added. Stir at a speed of 100 - 300 rpm for 20 - 30 min. A builder, a preservative and a fragrance are added in sequence, and stirred at a speed of 100 - 300 rpm for 10 - 20 min to obtain a low-foam and high-activity environmentally friendly detergent.

2. The preparation method of a low-foaming and highly active environmental protection detergent according to claim 1, characterized in that, The ethanol aqueous solution described in S1 is composed of ethanol and deionized water mixed in a mass ratio of 9:

1.

3. The preparation method of a low-foam and highly active environmentally friendly detergent according to claim 1, characterized in that, In S1, the mass ratio of lipase, castor oil, lactic acid and ethanol aqueous solution is 0.01:3:1:10 - 0.1:4:1:

10.

4. The preparation method of a low-foam and highly active environmental protection detergent according to claim 1, wherein, In S2, the mass ratio of lipase, lactic acid ricinoleate laurate copolymer, lauric acid and ethanol aqueous solution is 0.01:4:1:10 - 0.1:6:1:

10.

5. The preparation method of a low-foam and highly active environmental protection detergent according to claim 1, characterized in that, The preparation method of the unsaturated ester compounds described in S3: Itaconic acid, 1,6-hexanediol and toluene are mixed in a three-necked flask in a mass ratio of 1:1.5:5 - 1:2.5:

5. Sulfuric acid 0.01 - 0.03 times the mass of itaconic acid is added under a stirring speed of 100 - 300 rpm. Slowly raise the temperature to 120 - 140°C and stir for 4 - 6 h. After cooling to room temperature, the solid is taken and washed 3 - 5 times with ethanol, and dried at 60°C for 6 - 8 h to obtain unsaturated ester compounds.

6. The preparation method of a low-foam and high-activity environmentally friendly detergent according to claim 1, characterized in that, In S3, the mass ratio of myristic acid, unsaturated ester compounds, benzoyl peroxide and anhydrous toluene is 2:1:0.02:5 - 4:1:0.1:

5.

7. The preparation method of a low-foam and highly active environmental protection detergent according to claim 1, characterized in that, Preparation method of the modified SiO2 described in S4: Mix a silane coupling agent and an ethanol aqueous solution at a mass ratio of 1:100 in a beaker. Add sulfuric acid at room temperature to adjust the pH of the solution to 4-5, stir at a speed of 300-500 rpm for 20-40 min, then add silica particles 5-15 times the mass of the silane coupling agent, stir at a speed of 500-1000 rpm at 60°C-80°C for 2-4 h. After cooling to room temperature, take the solid and wash it once with ethanol, and dry it at 60°C for 12-24 h to obtain amino-functionalized SiO2.

8. The preparation method of a low-foam and highly active environmentally friendly detergent according to claim 6, characterized in that, The silane coupling agent is 3-aminopropyltriethoxysilane KH550.

9. The preparation method of a low-foam and highly active environmental protection detergent according to claim 1, characterized in that, The mass ratio of the tetradecanoic acid grafted polyester, modified SiO2, tetrabutyl titanate and anhydrous toluene described in S4 is 1:1:0.02:5 - 5:1:0.2:

5.

10. The preparation method of a low-foam and highly active environmental protection detergent according to claim 1, characterized in that, The low-foaming and highly active environmentally friendly detergent in S5 comprises the following preparation raw materials: 15-25 parts of surfactant, 2-4 parts of defoamer, 3-5 parts of sodium citrate, 0.1-0.3 parts of potassium sorbate, 0.1-0.3 parts of lemon essence, and 70-80 parts of water.

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