Efficient environment-friendly stone bleeding cleaning agent and preparation method thereof

Abstract

The invention discloses an efficient environment-friendly stone bleeding cleaning agent and a preparation method thereof. The bleeding cleaning agent comprises the following components: a hyperbranched polyaspartic acid-molybdate hybrid, a permeation enhancer, an organic acid buffer agent, nano silicon dioxide, a biological enzyme, a fragrance agent and deionized water, wherein the hyperbranched polyaspartic acid-molybdate hybrid is prepared by loading molybdate on polyaspartic acid which is formed by carrying out condensation polymerization on L-aspartic acid. The bleeding cleaning agent has a compound chelating system, can selectively adsorb harmful metal Fe < 3 + >, and does not damage effective Ca < 2 + > / Mg < 2 + > in stone; meanwhile, a directional decomposition function and a fragrance slow release technology aiming at organic pigments are achieved, an invisible protection layer can be automatically formed after cleaning, and the maintenance period is prolonged.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of stone maintenance, and particularly relates to a high-efficiency and environment-friendly stone seepage cleaner and a preparation method thereof, which is suitable for deep stain removal and protection of porous stones such as marble, granite and sandstone. BACKGROUND

[0002] In modern home decoration, stone is widely used in kitchen countertops, tea table panels, bathroom countertops and floor decoration due to its natural texture and durability. However, the porous structure of the stone surface makes it easy to be contaminated in daily use. Liquid pollutants such as oil stains, soy sauce stains, fruit juice and food stains, colored pencil ink, red wine and coffee stains are easy to adhere to and seep into the micropores. If not removed in time, the stains will solidify inside the stone, forming stubborn stains that are difficult to remove by conventional means, seriously affecting the appearance and service life of the stone.

[0003] The mainstream stone cleaners on the current market have significant defects. Acidic solvent cleaners can decompose part of the stains, but they are easy to react with the stone, causing surface corrosion and gloss decay. Ordinary neutral cleaners have large molecular particle sizes and are difficult to penetrate into the microporous structure of the stone, so their cleaning effect on stubborn stains that have seeped into the substrate is limited. Some cleaners contain strong volatile organic compounds (VOCs) or irritating ingredients, which have a strong odor when used, affecting user experience and posing environmental and safety hazards.

[0004] Therefore, it is of great practical application value to develop a cleaner that can efficiently remove seepage stains on stone countertops without damaging the surface structure and gloss, and is environmentally friendly. SUMMARY

[0005] The present application aims to overcome the shortcomings of the prior art and provides a high-efficiency and environment-friendly stone seepage cleaner and a preparation method thereof, which solves the problems of poor cleaning effect and odor irritation of stone seepage in the background art.

[0006] The technical solution adopted by the present application to solve the technical problems is to provide a high-efficiency and environment-friendly stone seepage cleaner, which comprises an ultrabranched polyaspartic acid-molybdate hybrid, a penetration enhancer, an organic acid buffer, nano-silicon dioxide, a biological enzyme, a fragrance agent and deionized water. The ultrabranched polyaspartic acid-molybdate hybrid is prepared by loading molybdate on polyaspartic acid formed by the condensation of L-aspartic acid, and the loading amount of molybdate satisfies the molar ratio of polyaspartic acid to MoO4 2- is 1:10.

[0007] In a preferred embodiment of the present invention, the stone stain cleaner is composed of 2.5% hyperbranched polyaspartic acid-molybdate hybrid, 3-8% penetration enhancer, 1.5% organic acid buffer, 1-3% nano silica, 0.05-0.2% bio-enzyme, 0.1-0.5% fragrance, and the balance deionized water by weight percentage.

[0008] In a preferred embodiment of the present invention, the method for preparing the hyperbranched polyaspartic acid-molybdate hybrid includes the following steps:

[0009] (1) Melt polycondensation reaction and alkaline hydrolysis:

[0010] L-Aspartic acid was mixed with a catalyst and heated at 160°C for 2 hours. A protective gas was continuously introduced and the mixture was stirred at 300 rpm to generate polysuccinimide.

[0011] The polysuccinimide was cooled to room temperature, and NaOH solution was added to maintain the pH at 10.5–11.5. The mixture was stirred at 80°C for 4 hours until the polysuccinimide was completely hydrolyzed to obtain a polyaspartic acid solution.

[0012] (2) Molybdate loading: Adjust the pH to 5.5–6.5, according to hPASP:MoO4 2- Na₂MoO₄ was added to a polyaspartic acid solution at a molar ratio of 1:10, and the mixture was stirred at 60°C for 2 hours. The resulting reaction involved an ion exchange reaction to convert the MoO₄⁻ into a soluble form. 2- It binds to the carboxyl group of polyaspartic acid;

[0013] (3) Purification: Dialysis was used to remove free MoO4 from the reaction solution. 2- The solution after dialysis was freeze-dried to obtain a pale yellow solid product, which is the hyperbranched polyaspartic acid-molybdate hybrid.

[0014] In a preferred embodiment of the present invention, in step (1), the catalyst comprises phosphoric acid and the protective gas comprises nitrogen.

[0015] In a preferred embodiment of the present invention, in step (2), the reaction solution is transferred and ultrasonically treated at 20 kHz for 30 minutes.

[0016] In a preferred embodiment of the present invention, the penetration enhancer is a nonionic surfactant, including alkyl glycoside APG0810.

[0017] In a preferred embodiment of the present invention, the organic acid buffer is a mixture of citric acid and malic acid, wherein the molar ratio of citric acid to malic acid is 1.5-2:1.

[0018] In a preferred embodiment of the present invention, the bioenzyme is laccase or peroxidase.

[0019] In a preferred embodiment of the present invention, the fragrance agent is a weakly acid-resistant fragrance, including dihydromyrcene alcohol.

[0020] Another technical solution adopted by the present invention to solve its technical problem is: providing a method for preparing the above-mentioned high-efficiency and environmentally friendly stone stain cleaner, including the following steps:

[0021] 1. Heat deionized water to 40-50℃, add hyperbranched polyaspartic acid-molybdate hybrid and organic acid buffer in sequence, and stir at 300 rpm for 20 minutes until dissolved;

[0022] 2. After cooling the solution from step one to 30°C, add the penetration enhancer and biological enzyme, and mix at a low speed of 100-150 rpm for 10 minutes.

[0023] 3. Pre-disperse the fragrance agent in the penetration enhancer, add it to the solution in step 2, and stir at 200-300 rpm for 5 minutes;

[0024] 4. Add nano-silica, homogenize and emulsify, then filter and fill.

[0025] Compared with the prior art, this technical solution has the following advantages:

[0026] 1. The stone stain remover of this invention has a compound chelation system hPASP-MoO4, which can selectively adsorb harmful metal Fe. 3+ Without damaging the effective calcium in the stone 2+ / Mg 2+ ;

[0027] 2. The stone stain cleaner of this invention can achieve targeted decomposition by biological enzymes: it selects laccase for organic pigments to avoid color difference caused by bleaching with oxidants;

[0028] 3. The stone stain cleaner of this invention has nano-protective technology: it automatically forms an invisible protective layer after cleaning, extending the maintenance cycle;

[0029] 4. The preparation method of the stone stain cleaning agent of the present invention is simple and has fragrance slow-release technology: through the low-temperature addition process of APG pre-dispersant, the stable loading and controllable release of fragrance molecules in a weakly acidic system are achieved;

[0030] 5. The stone stain cleaner of this invention is easy to use. Simply spray the undiluted cleaner onto the stone surface, completely covering the stained area. Let it stand for 15 minutes, wipe with a soft cloth, rinse with water, and let it air dry to complete the cleaning. Attached Figure Description

[0031] Figure 1Images of the examples and comparative examples after 24 hours of adding contaminants;

[0032] Figure 2 Images showing traces left after rinsing with water in the examples and comparative cases;

[0033] Figure 3 Images of the examples and comparative cases after spraying the cleaning agent;

[0034] Figure 4 Images shown are of the examples and comparative cases after the cleaning agent has been removed. Detailed Implementation

[0035] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0036] Unless otherwise specified, all raw materials used in the following examples can be purchased commercially. The raw materials for preparing the hyperbranched polyaspartic acid-molybdate hybrid include L-aspartic acid (C4H7NO4), sodium molybdate (Na2MoO4·2H2O), phosphoric acid (H3PO4), citric acid (C6H8O7), sodium hydroxide (NaOH), and deionized water; the purity of L-aspartic acid is ≥99%; the sodium molybdate is analytical grade, and the MoO4... 2- The content of the substance is ≥99%; the NaOH is analytical grade and the concentration is 1 mol / L.

[0037] The preparation of hyperbranched polyaspartic acid-molybdate hybrids involves three processes: preparation of hyperbranched polyaspartic acid, molybdate loading, and purification. The specific steps are as follows:

[0038] I. Preparation of hyperbranched polyaspartic acid (hPASP)

[0039] Stage 1: Melt Polycondensation Reaction

[0040] Step 1: Add 100g of L-aspartic acid and 1g of phosphoric acid (phosphoric acid acts as a catalyst) to a three-necked flask;

[0041] Step 2: Heat the reaction at 160℃ for 2 hours, continuously purge with nitrogen for protection and stir at 300 rpm;

[0042] Step 3: The reaction produces polysuccinimide (PSI), which is a pale yellow solid.

[0043] Stage Two: Alkaline Hydrolysis

[0044] Step 1: Cool the PSI to room temperature and add 200 mL of 1 mol / L NaOH solution;

[0045] Step 2: Stir the reaction at 80°C for 4 hours until PSI is completely hydrolyzed to obtain an hPASP solution with pH maintained at around 11.

[0046] Step 3: Detect the carboxyl peak (1720 cm⁻¹) using FTIR. -1 Confirm that hydrolysis is complete.

[0047] II. Molybdate (MoO4) 2- )load

[0048] Stage 1: Ion exchange reaction

[0049] Step 1: Take 10wt% hPASP solution and adjust the pH to 6.0 with citric acid;

[0050] Step 2: Press hPASP:MoO4 2- Add Na2MoO4 at a molar ratio of 1:10

[0051] Step 3: Stir the reaction at 60℃ for 2 hours to allow MoO4 to react. 2- It binds to the carboxyl group of hPASP.

[0052] Phase Two: Ultrasonic Dispersion

[0053] The reaction solution was transferred to an ultrasonic instrument and sonicated at 20 kHz for 30 minutes to ensure the MoO4 content was within acceptable limits. 2- Uniform load.

[0054] III. Purification

[0055] Step 1: Dialysis

[0056] The reaction solution was placed in a dialysis bag (molecular weight cutoff 3.5 kDa) and dialyzed in deionized water for 48 hours (changing the water every 6 hours) to remove free MoO4. 2- .

[0057] Step 2: Freeze-drying

[0058] The dialyzed solution was pre-frozen at -80°C and then dried using a freeze dryer for 24 hours to obtain a pale yellow solid product, hPASP-MoO4.

[0059] Example 1

[0060] This embodiment describes a stone stain remover, with each 1000g of the formula comprising the following: hPASP-MoO4 15g, APG-0810 25g, citric acid 10g, malic acid 5g, nano silica 20g, laccase 1g, dihydromyrcenol 3g, and deionized water 921g.

[0061] The preparation method of the stone stain cleaner in this embodiment includes the following steps:

[0062] Step 1: Chelating agent dissolution: Heat deionized water to 45°C, add hPASP-MoO4, citric acid, and malic acid, and stir at 300 rpm for 20 minutes until a clear solution is obtained, with the pH controlled at around 5.0;

[0063] Step 2: Pre-dispersion: Dihydromyrcenol was pre-dispersed in 2% APG;

[0064] Step 3: Low-temperature mixing: Cool down to 30℃, add APG-0810 and laccase, and stir at a low speed of 120 rpm for 10 minutes;

[0065] Step 4: Fragrance dispersion: Add the pre-dispersed dihydromyrcene alcohol to the system and stir at 260 rpm for 5 min.

[0066] Step 5: Adding nanomaterials: Add nano-silica, homogenize and emulsify, then filter and fill.

[0067] Example 2

[0068] The difference between Example 2 and Example 1 is that: This example is a stone stain cleaner, and the formula of 1000g includes the following: hPASP-MoO4 25g, APG-0810 50g, citric acid 10g, malic acid 5g, nano silica 20g, laccase 1g, dihydromyrcene alcohol 3g, and deionized water 886g.

[0069] The preparation method of the stone stain cleaner in this embodiment includes the following steps:

[0070] Step 1: Chelating agent dissolution: Heat deionized water to 45°C, add hPASP-MoO4, citric acid, and malic acid, and stir at 300 rpm for 20 minutes until a clear solution is obtained, with the pH controlled at around 5.0;

[0071] Step 2: Pre-dispersion: Dihydromyrcenol was pre-dispersed in 2% APG-0810;

[0072] Step 3: Low-temperature mixing: Cool down to 30℃, add APG-0810 and laccase, and stir at a low speed of 120 rpm for 10 minutes;

[0073] Step 4: Fragrance dispersion: Add the pre-dispersed dihydromyrcene alcohol to the system and stir at 260 rpm for 5 min.

[0074] Step 5: Adding nanomaterials: Add nano-silica, homogenize and emulsify (relatively long time), then filter and fill.

[0075] Comparative Example 1

[0076] The difference between Comparative Example 1 and Example 1 is that hPASP-MoO4 is not added.

[0077] The stone stain remover of this comparative example contains the following ingredients in a 1000g formula: APG-0810 25g, citric acid 10g, malic acid 5g, nano silica 20g, laccase 1g, dihydromyrcenol 3g, and deionized water 936g.

[0078] The preparation method of this comparative stone stain-removing cleaner includes the following steps:

[0079] Step 1: Heat deionized water to 45°C, add citric acid and malic acid, and stir at 300 rpm for 20 minutes until a clear solution is obtained, with the pH controlled at around 5.0;

[0080] Step 2: Pre-dispersion: Dihydromyrcenol was pre-dispersed in 2% APG-0810;

[0081] Step 3: Low-temperature mixing: Cool down to 30℃, add APG-0810 and laccase, and stir at a low speed of 120 rpm for 10 minutes;

[0082] Step 4: Fragrance dispersion: Add the pre-dispersed dihydromyrcene alcohol to the system and stir at 260 rpm for 5 min.

[0083] Step 5: Adding nanomaterials: Add nano-silica, homogenize and emulsify, then filter and fill.

[0084] Comparative Example 2

[0085] Comparative Example 2 was the commercially available "Juqi" cleaning agent.

[0086] The stone stain removers prepared in the examples and comparative examples were subjected to performance tests:

[0087] 1. Stain removal rate test, refer to ASTM D4265 standard;

[0088] 2. Color Difference Method: Use a colorimeter to measure the color difference ΔE value (color difference) between the stone surface before and after cleaning and the uncontaminated area. Calculation formula:

[0089]

[0090] The test results are shown in the table below:

[0091] Sample Before cleaning After cleaning Stain removal Comparative Example 1 35.2 19.7 44.03％ Example 1 35.5 11.6 67.32％ Example 2 35.5 0.8 97.75％ Comparative Example 2 35.4 28.6 19.21％

[0092] 3. Stone Stain Resistance Test: Referring to JC / 908-2013 standard, gentian violet solution, blue water-soluble ink, and mercurochrome solution (2%) were respectively applied to the stone surface and left to stand for 24 hours. Figure 1 After rinsing with clean water ( Figure 2 The marks left were sprayed onto the stains.Figure 3 After soaking for 15 minutes, wipe with a dry cloth and compare the color difference on the surface. The results are as follows. Figure 4 .

[0093] The results of the above tests show that:

[0094] Comparative Examples 1 and 2 showed unsatisfactory removal effects on the three types of stains, indicating weak cleaning ability. Examples 1 and 2, however, demonstrated significant removal effects on stone stains. Example 2, with its relatively increased content of hPASP-MoO4 and APG-0810, exhibited higher permeability and more significant results. The gentian violet solution in Example 1 also achieved the expected effect after longer immersion. Based on the stain removal rate data, Example 2 showed the best value, consistent with the experimental verification of this invention.

[0095] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A highly efficient and environmentally friendly stone stain remover, characterized in that: The components include hyperbranched polyaspartic acid-molybdate hybrid, a penetration enhancer, an organic acid buffer, nano-silica, a bio-enzyme, a fragrance agent, and deionized water; wherein, the hyperbranched polyaspartic acid-molybdate hybrid is prepared by loading molybdate onto polyaspartic acid formed by the condensation polymerization of L-aspartic acid.

2. The high-efficiency and environmentally friendly stone stain cleaner according to claim 1, characterized in that: The product comprises, by weight percentage, 2.5% hyperbranched polyaspartic acid-molybdate hybrid, 3-8% penetration enhancer, 1.5% organic acid buffer, 1-3% nano-silica, 0.05-0.2% bio-enzyme, 0.1-0.5% fragrance agent, and the balance deionized water; wherein the hyperbranched polyaspartic acid-molybdate hybrid contains polyaspartic acid and MoO4. 2- The molar ratio is 1:

10.

3. The high-efficiency and environmentally friendly stone stain cleaner according to claim 1, characterized in that: The preparation method of the hyperbranched polyaspartic acid-molybdate hybrid includes the following steps: (1) Melt polycondensation reaction and alkaline hydrolysis: L-Aspartic acid was mixed with a catalyst and heated at 160°C for 2 hours. A protective gas was continuously introduced and the mixture was stirred at 300 rpm to generate polysuccinimide. The polysuccinimide was cooled to room temperature, and NaOH solution was added to maintain the pH at 10.5–11.

5. The mixture was stirred at 80°C for 4 hours until the polysuccinimide was completely hydrolyzed to obtain a polyaspartic acid solution. (2) Molybdate loading: Adjust the pH to 5.5–6.5, according to hPASP:MoO4 2- Na₂MoO₄ was added to a polyaspartic acid solution at a molar ratio of 1:10, and the mixture was stirred at 60°C for 2 hours. The resulting reaction involved an ion exchange reaction to convert the MoO₄⁻ into a soluble form. 2- It binds to the carboxyl group of polyaspartic acid; (3) Purification: Dialysis was used to remove free MoO4 from the reaction solution. 2- The solution after dialysis was freeze-dried to obtain a pale yellow solid product, which is the hyperbranched polyaspartic acid-molybdate hybrid.

4. The high-efficiency and environmentally friendly stone stain cleaner according to claim 3, characterized in that: In step (1), the catalyst includes phosphoric acid, and the protective gas includes nitrogen.

5. The high-efficiency and environmentally friendly stone stain cleaner according to claim 3, characterized in that: In step (2), the reaction solution is transferred and sonicated at 20 kHz for 30 minutes.

6. The high-efficiency and environmentally friendly stone stain cleaner according to claim 1, characterized in that: The penetration enhancer is a nonionic surfactant, including alkyl glycoside APG0810.

7. The high-efficiency and environmentally friendly stone stain cleaner according to claim 1, characterized in that: The organic acid buffer is a compound of citric acid and malic acid, wherein the molar ratio of citric acid to malic acid is 1.5-2:

1.

8. The high-efficiency and environmentally friendly stone stain cleaner according to claim 1, characterized in that: The bioenzyme is laccase or peroxidase.

9. The high-efficiency and environmentally friendly stone stain cleaner according to claim 1, characterized in that: The fragrance agent uses a mildly acid-resistant fragrance, including dihydromyrcene alcohol.

10. A method for preparing a high-efficiency and environmentally friendly stone stain cleaner as described in any one of claims 1 to 9, characterized in that: Includes the following steps:

1. Heat deionized water to 40-50℃, add hyperbranched polyaspartic acid-molybdate hybrid and organic acid buffer in sequence, and stir at 300 rpm for 20 minutes until dissolved; 2. After cooling the solution from step one to 30°C, add the penetration enhancer and biological enzyme, and mix at a low speed of 100-150 rpm for 10 minutes.

3. Pre-disperse the fragrance agent in the penetration enhancer, add it to the solution in step 2, and stir at 200-300 rpm for 5 minutes; 4. Add nano-silica, homogenize and emulsify, then filter and fill.

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