Explosive Salt Cold Water Active Oxygen Synergistic Fragrance Adaptive Release Control Method

Abstract

This invention discloses a method for adaptive release control of active oxygen and fragrance synergistically using explosive salt in cold water. This method constructs an adaptive activation-enhancing complex composed of a binuclear manganese complex and an alkylamine phosphonate, and chemically couples it with double-walled microcapsules having a stepped pH threshold for rupture. It utilizes the dynamic change in solution pH from alkaline to neutral during the dissolution of explosive salt to synchronously regulate the active oxygen release rate and the staged release of fragrance. This invention achieves adaptive matching of active oxygen efficiency and fragrance effect through a pH-temperature linkage sensing mechanism, significantly increasing the active oxygen release rate in cold water at 10-30℃, greatly extending the fragrance retention time of clothing, and exhibiting excellent storage stability. This solves the problems of low active oxygen efficiency and fragrance waste in existing explosive salt products during cold water washing.

Description

Technical Field

[0001] This invention relates to the field of daily chemical detergent technology, and in particular to a method for adaptive release control of fragrance through synergistic effects of explosive salt, cold water, and active oxygen. Background Technology

[0002] Exploding salt is a solid detergent product with sodium percarbonate as its main active ingredient. When added to water, it decomposes to produce hydrogen peroxide, which in turn releases active oxygen, providing multiple benefits such as bleaching, stain removal, sterilization, and disinfection. To enhance the sensory experience during washing, existing explosive salt products typically add fragrance directly or utilize fragrance microencapsulation technology to release aroma during the washing process.

[0003] First, the activation efficiency of traditional activators in cold water (below 30℃) remains limited, especially under the 10-25℃ cold water washing conditions commonly used by domestic consumers. The slow decomposition rate of sodium percarbonate and insufficient release of active oxygen result in a significant decrease in stain removal and bleaching effects. Furthermore, simply increasing the amount of catalyst to improve low-temperature activity can easily lead to the rapid catalytic decomposition of hydrogen peroxide in the initial dissolution stage, causing a large instantaneous loss of active oxygen and thus reducing the overall washing effect. Second, the release of fragrances or scent microcapsules in existing explosive salts is often independent of the washing chemical process. Fragrance microcapsules often employ mechanisms such as hydration triggering, frictional rupture, or single pH threshold triggering, and their release timing during the explosive salt dissolution process lacks an intrinsic connection with the washing process. In actual use, it has been found that the fragrance is often released within the first few minutes of washing, while the scent lingers very weakly in the later stages of washing and after rinsing; or the fragrance release is too slow, resulting in no fragrance experience throughout the washing process, failing to meet consumers' dual needs for "fragrance during washing" and "lingering fragrance after washing." Third, existing technologies lack synergistic design between the low-temperature active oxygen system and the fragrance release system. The active oxygen release rate and the fragrance release timing are isolated from each other, failing to utilize the dynamic changes in the solution chemical environment (such as pH, temperature, ionic strength, etc.) during the washing process as a bridge to build an adaptive linkage mechanism. As a result, when washing with cold water, the explosive salt product either has low active oxygen efficiency or wastes fragrance, making it difficult to achieve both efficient stain removal and long-lasting fragrance at the same time.

[0004] Therefore, in response to the problems mentioned above, this invention proposes an adaptive release control method for fragrance in combination with explosive salt cold water and active oxygen. Summary of the Invention

[0005] To overcome the problem in existing technologies where the active oxygen efficiency and fragrance release of explosive salt under cold water washing conditions cannot be adaptively controlled in a coordinated manner, this invention proposes an adaptive release control method for active oxygen and fragrance in cold water using explosive salt. By constructing an adaptive activation and enhancement complex composed of a binuclear manganese complex and an alkylamine phosphonate, and chemically coupling it with a double-walled microcapsule with a stepped pH threshold for rupture, the active oxygen release rate and the staged release of fragrance are synchronously regulated by utilizing the gradient change of solution pH during the dissolution of explosive salt, thereby achieving adaptive optimization of active oxygen efficiency and fragrance effect under cold water conditions.

[0006] The technical solution of this invention is: an adaptive release control method for fragrance synergistically using explosive salt cold water and active oxygen, comprising the following steps: S1, Sodium percarbonate and anhydrous sodium carbonate are mixed at a mass ratio of (85-95):(5-15) to form an alkaline matrix; S2, an adaptive activation synergistic complex composed of a binuclear manganese complex and an alkylamine phosphonate in a mass ratio of (1-3):(1-5) is added to an alkaline matrix; S3, the fragrance is encapsulated in a double-walled microcapsule with a stepped rupture threshold, wherein the double-walled microcapsule includes an inner wall and an outer wall, the rupture pH threshold of the inner wall is 9.5-11.0, and the rupture pH threshold of the outer wall is 8.0-9.4; S4, the adaptive activation and enhancement complex and the double-walled microcapsules are progressively layered in an alkaline matrix, so that the active oxygen release rate regulation system and the fragrance release threshold regulation system are chemically coupled. When the explosive salt is added to cold water to dissolve, the adaptive activation and enhancement complex releases carbonate from the alkaline matrix and gradually activates the low-temperature decomposition of sodium percarbonate. At the same time, the double-walled microcapsules realize the staged release of fragrance according to the dynamic transition process of the solution pH from alkaline to neutral. The chemical coupling mechanism is as follows: hydrogen peroxide released during the cold water dissolution of sodium percarbonate generates reactive oxygen species under the catalytic action of the adaptive activation synergistic complex. Simultaneously, during the release process, the solution pH gradually decreases from the initial 10.5-11.0 to 8.5-9.5, and the rate of pH decrease is negatively correlated with the instantaneous generation of reactive oxygen species. When the pH decrease rate is higher than 0.5 units / minute, the instantaneous generation of reactive oxygen species decreases by 30-50%, thereby adaptively avoiding excessive concentrated release of reactive oxygen species. The fragrance release rate of the double-walled microcapsules corresponds to the rupture threshold times reached during the pH decrease process, achieving efficient time matching between fragrance release and reactive oxygen species release.

[0007] Preferably, the adaptive activation synergistic complex is non-uniformly spatially distributed in the explosive salt composition, specifically in at least one of the following two ways: In an alkaline matrix, the mass concentration of the adaptive activation synergistic complex near the outer surface of the matrix is ​​lower than that in the inner region of the matrix. The explosive salt composition is a multi-layer tablet structure consisting of an outer layer and an inner core. The outer layer thickness accounts for 15-30% of the total tablet thickness, and the inner core thickness accounts for 70-85% of the total tablet thickness. The outer layer contains sodium percarbonate, anhydrous sodium carbonate, double-walled microcapsules, and a first amount of adaptive activation and synergistic complex. The inner core contains sodium percarbonate, anhydrous sodium carbonate, and a second amount of adaptive activation and synergistic complex. The first amount is less than the second amount, and the mass concentration of the adaptive activation and synergistic complex in the outer layer is 1 / 10 to 1 / 3 of the mass concentration of the adaptive activation and synergistic complex in the inner core.

[0008] Preferably, the double-walled microcapsules adopt the following composite design: The inner wall is made of a pH-responsive polymer material selected from at least one of methacrylic acid / methyl methacrylate copolymer, polyacrylic acid, or chitosan; the outer wall is made of a protective wall material selected from at least one of melamine resin, polyurea, or gelatin-gum arabic composite. The fragrance is a complex fragrance system, comprising a wash-off fragrance component and a long-lasting fragrance component. The wash-off fragrance component accounts for 20-40% of the total fragrance mass, and the long-lasting fragrance component accounts for 60-80% of the total fragrance mass. The wash-off fragrance component is a highly volatile terpene fragrance substance, and the long-lasting fragrance component is a high molecular weight ester or macrocyclic musk fragrance substance. The average particle size of the double-walled microcapsules is 1-25 μm, of which microcapsules with a particle size of 1-10 μm account for 30-50% and microcapsules with a particle size of 10-25 μm account for 50-70%; the pH threshold for outer wall rupture of microcapsules with a particle size of 1-10 μm is set to 9.0-9.4, and the pH threshold for outer wall rupture of microcapsules with a particle size of 10-25 μm is set to 8.0-8.9.

[0009] Preferably, the composition of the explosive salt composition, by mass percentage, is as follows: 65-85% sodium percarbonate, 5-12% anhydrous sodium carbonate, 0.02-0.08% binuclear manganese complex, 0.1-0.5% alkylamine phosphonate, 0.5-3.0% double-walled microcapsules, 1-5% anionic surfactant, 0.5-3% nonionic surfactant, 0.1-1% enzyme preparation, with the balance being fillers and anti-caking agents.

[0010] Preferably, after the explosive salt is added to cold water, the current pH value is obtained through a real-time pH monitoring device. When the pH value drops to a preset fragrance release threshold, the double-walled microcapsules are triggered to rupture and release a signal. The fragrance release threshold is set according to the washing time interval as follows: first release stage threshold pH = 9.5-10.0, second release stage threshold pH = 8.8-9.4, and third release stage threshold pH = 8.0-8.7.

[0011] Preferably, the method is used to prepare explosive salt products for machine washing, hand washing, soaking, or cleaning of household surfaces; the cold water is water with a temperature in the range of 10-30℃; the working concentration of the explosive salt after being added to the cold water is 0.5-5g / L.

[0012] The beneficial effects of this invention are: 1. This invention chemically couples the pH-dependent catalytic activity of binuclear manganese complexes with the stepwise pH rupture threshold of double-walled microcapsules through the inherent dynamic change of solution pH from strongly alkaline to neutral during the dissolution of explosive salts. This constructs an adaptive linkage network integrating active oxygen release efficiency, solution pH, and fragrance rupture threshold, solving the problem of isolation and inability to coordinate control between the low-temperature active oxygen system and the fragrance release system in the prior art. It achieves adaptive matching between active oxygen release rate and fragrance release duration under cold water conditions.

[0013] 2. This invention effectively avoids the problem of ineffective decomposition of hydrogen peroxide caused by over-catalysis in the initial stage of cold water dissolution by traditional catalysts through gradient stratification distribution of adaptive activation-enhancing complex in alkaline matrix or tablet stratification structure, combined with negative feedback regulation of reactive oxygen generation by pH decrease rate.

[0014] 3. This invention uses double-walled microcapsules with inner and outer walls, and combines a composite design of fragrance during washing and fragrance during the lasting period with particle size-threshold grading matching. This allows only a small amount of fragrance to be released at the beginning of washing to provide an immediate olfactory experience, while the remaining fragrance is released in the middle and late stages of washing and during rinsing. This significantly extends the fragrance lasting time of clothes and solves the problems of rapid fragrance loss, no fragrance in the later stages of washing, and extremely short fragrance lasting time in existing explosive salt products. Attached Figure Description

[0015] Figure 1 The diagram shown is a schematic representation of the overall process of this invention. Figure 2 The diagram shown is a schematic representation of the layered structure of the explosive salt tablets of the present invention.

[0016] Figure labeling: 1. Double-walled microcapsule; 2. Adaptive activation synergistic complex. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Please see Figure 1 Example 1: S1. Weigh 8000g of sodium percarbonate and 1000g of anhydrous sodium carbonate, put them into a V-type mixer, and mix them at 15 rpm for 20 minutes to form a uniform alkaline matrix. The mass ratio of sodium percarbonate to anhydrous sodium carbonate is 88.9:11.1.

[0019] S2, weigh out 6.0 g of a binuclear manganese complex (chemical formula Mn2(μ-O)2(Me3TACN)2(PF6)2, where Me3TACN is 1,4,7-trimethyl-1,4,7-triazacyclononane) and 18 g of an alkylamine phosphonate (heptasodium diethylenetriaminepentamethylenephosphonate), with a mass ratio of 1:3. Premix and grind the binuclear manganese complex and the alkylamine phosphonate in a mortar for 5 minutes to ensure sufficient contact and the formation of an adaptive activation-enhancing complex. Then, premix this complex with a portion of the alkaline matrix (approximately 1000 g) at a mass ratio of 1:40 in a three-dimensional motion mixer for 10 minutes to obtain the complex premix. Reserve the remaining alkaline matrix for later use.

[0020] S3 is a core material made by uniformly mixing 72g of the long-lasting fragrance component (macrocyclic musk fragrance substances, musk-T) and 48g of the wash-off fragrance component (d-limonene). The inner wall material is a copolymer of methacrylic acid and methyl methacrylate, and the outer wall material is a melamine resin prepolymer.

[0021] Double-walled microcapsules were prepared using a double emulsion solvent evaporation method. The inner wall material was dissolved in dichloromethane, and the core material was added. The mixture was emulsified at 10,000 rpm for 5 minutes in a high-speed shear emulsifier to form a primary emulsion. This primary emulsion was then added to an aqueous phase containing a prepolymer of the outer wall material, and emulsification was continued at 8,000 rpm for 3 minutes to form a secondary emulsion. Finally, the temperature was raised to 55°C, and the mixture was stirred at atmospheric pressure for 4 hours to allow the solvent to evaporate completely. Simultaneously, the outer wall material underwent condensation and solidification. The double-walled microcapsules were obtained by filtration, washing, and drying.

[0022] The average particle size of the obtained microcapsules, as determined by laser particle size analyzer, was 12.5 μm, with 42% of microcapsules having a diameter of 1-10 μm and 56% having a diameter of 10-25 μm. The rupture threshold of the outer wall was controlled by adjusting the pH value during solidification: smaller microcapsules (the 1-10 μm portion obtained through sieving) were solidified in a buffer system with pH=9.2, resulting in an outer wall rupture pH threshold of 9.0-9.4; larger microcapsules (the 10-25 μm portion) were solidified in a buffer system with pH=8.5, resulting in an outer wall rupture pH threshold of 8.0-8.9. The rupture pH threshold of the inner wall was uniformly set at 10.2-10.6. A total of 120 g of double-walled microcapsules was finally obtained.

[0023] S4 uses a multi-layer tablet compressor for layered formulation. First, prepare the outer layer mixture by taking 3000g of the remaining alkaline matrix, adding 120g of the aforementioned double-walled microcapsules, and adding 93g of the first amount of adaptive activation and synergistic complex premix. Then, prepare the inner core mixture by taking 4500g of the remaining alkaline matrix and adding 931g of the second amount of adaptive activation and synergistic complex premix. Simultaneously, add 150g of anionic surfactant (sodium linear alkylbenzene sulfonate), 90g of nonionic surfactant (fatty alcohol polyoxyethylene ether), 30g of enzyme preparation (a mixture of protease and lipase), and appropriate amounts of filler (sodium sulfate) and anti-caking agent (silica) to both the outer layer and the inner core, bringing the total mass to 10000g.

[0024] Please see Figure 2 The tablets were compressed according to a ratio of 25% outer layer thickness to 75% inner core thickness, with a target tablet weight of 20g and a compression pressure of 15kN. The resulting tablets had an adaptive activating and enhancing complex concentration of approximately 0.0727% in the outer layer and approximately 0.436% in the inner core, with the outer layer concentration being approximately 1 / 6 of the inner core concentration. This yielded the explosive salt tablet product, designated as Sample 1 of Example 1.

[0025] Example 2: This embodiment is basically the same as Embodiment 1, except that the amount of adaptive activation and enhancement complex added and the ratio of the base matrix are different in step S2, and in step S4, a multi-layer tablet structure is not set, but a uniformly mixed powder is used to verify the necessity of layered arrangement.

[0026] Step S1: 8500g of sodium percarbonate and 500g of anhydrous sodium carbonate, with a mass ratio of 94.4:5.6. Step S2: 7.0g of binuclear manganese complex and 7.0g of alkylamine phosphonate, with a mass ratio of 1:1, are mixed uniformly with the entire alkaline matrix (without stratification). Step 3: Same as Example 1. Step S4: The adaptive activation synergistic complex, double-walled microcapsules, and other excipients are mixed with the entire alkaline matrix in a three-dimensional mixer for 30 minutes until completely homogeneous. Then, it is directly filled into a powder product without tableting.

[0027] Comparative Example 1: Comparative Example 1 is a commercially available conventional explosive salt product (main components: sodium percarbonate, sodium carbonate, TAED activator, and fragrance), with the fragrance being a directly added, free-state fragrance. The recommended concentration for this product in cold water (25°C) according to the product instructions is 2 g / L.

[0028] Comparative Example 2: Comparative Example 2 follows the formulation of Example 1, but omits the alkylamine phosphonate in step S2, uses only a binuclear manganese complex as a catalyst, and does not perform layered arrangement (uniform mixing). The fragrance is applied using ordinary single-walled microcapsules (wall material is gelatin-gum arabic, with a single rupture pH threshold of 8.5). The remaining components are the same as in Example 1, and the mixture is prepared into tablets.

[0029] Comparative Example 3: Comparative Example 3 follows the formulation of Example 1, but replaces the double-walled microcapsules with ordinary single-walled microcapsules (consisting of a single wall material made of methacrylic acid / methyl methacrylate copolymer, with a rupture pH threshold of 9.5), and does not have a layered arrangement (uniform mixing), otherwise it is the same as Example 1.

[0030] Furthermore, experiments were conducted on the above examples, specifically: 10g of samples from Examples 1-2 and Comparative Examples 1-3 were added to 1L of deionized water at 20℃, and the mixture was stirred at 200rpm. Samples were taken at 30 seconds, 1 minute, 2 minutes, 3 minutes, 5 minutes, 10 minutes, 15 minutes, and 20 minutes after dissolution. The concentration of hydrogen peroxide in the solution was determined by potassium permanganate titration and converted to reactive oxygen species (ROS) content (mg / L). The pH value of the solution was also recorded (continuously monitored using a pH meter). Each test was repeated three times, and the average value was taken. The results are shown in Table 1. Table 1. Changes in reactive oxygen species release from different samples in cold water at 20℃ over time (unit: mg / L)

[0031] As shown in Table 1, Example 1 exhibits a typical slow-rise and continuous release curve, with reactive oxygen species (ROS) reaching a peak of approximately 200 mg / L at around 15 minutes, and showing no significant decrease after the peak. This indicates that hydrogen peroxide is continuously catalyzed and decomposed without excessive initial release. In Example 2, due to the uniform distribution of the catalyst and the absence of pH-ROS feedback from double-walled microcapsules, the ROS release rate was significantly higher in the initial stage (30 seconds to 2 minutes) than in Example 1. However, the ROS growth slowed significantly after 5 minutes, with a peak of only 156.1 mg / L, indicating that some hydrogen peroxide was rapidly consumed in the initial stage but failed to effectively act on the stains. Comparative Example 1 showed very slow ROS release at 20°C, releasing only 84.1 mg / L in 20 minutes, indicating that the traditional TAED activator has insufficient activation efficiency at low temperatures. Comparative Example 2 contained only a binuclear manganese complex and no alkylamine phosphonate. The initial release was too rapid, but the peak was only 130.2 mg / L, and the overall release was lower than in Example 1. This indicates that the addition of alkylamine phosphonate can regulate the catalytic activity of the binuclear manganese complex, prevent excessive decomposition, and increase the total release. Comparative Example 3 used uniform mixing but retained double-walled microcapsules. Its release curve was similar to that of Example 1, but it did not show the advantage of mild initial release, indicating that layered arrangement plays an important role in achieving mild initial release.

[0032] The fragrance release of Examples 1, 1, 2, and 3 during a simulated washing process (20°C water, 10 g / L sample, 20 minutes) was measured using headspace solid-phase microextraction-gas chromatography-mass spectrometry. Samples were taken at 1, 3, 5, 10, and 20 minutes after the start of washing, and the peak area of ​​total volatile fragrance substances in the headspace was measured, expressed as the relative release rate (with the total release of Comparative Example 1 at 20 minutes as 100%). Simultaneously, the washed cotton fabric (10 cm × 10 cm) was removed after washing, without rinsing, and hung to dry at room temperature. The fragrance retention was evaluated at 1 hour, 24 hours, 48 ​​hours, and 72 hours after drying using an olfactory evaluation method (6-person olfactory evaluation group, using a 0-5 scoring system, 0 for no fragrance, 5 for strong fragrance). The test results are shown in Tables 2 and 3. Table 2. Cumulative fragrance release rate (%) of different samples during the washing process at 20℃

[0033] As shown in Table 2, the free-state fragrance of Comparative Example 1 was released at nearly 80% within 1 minute and over 90% within 3 minutes, with the fragrance almost completely depleted by the later stages of washing. The single-walled microcapsules of Comparative Example 3 also showed rapid release in the early stages of washing because the solution pH remained above 9.5 within 1 minute, causing many microcapsules to rupture prematurely. The fragrance release of Comparative Example 2 fell between the two. Example 1, however, achieved a clear phased release: only 12.3% at 1 minute, 28.5% at 3 minutes, 41.2% at 5 minutes, 62.8% at 10 minutes, and 85.6% at 20 minutes. This indicates that most of the fragrance is released in the later stages of washing, accompanying the entire washing process.

[0034] Table 3. Scent retention intensity of cotton fabric samples after washing (0-5 points, average value)

[0035] As shown in Table 3, Example 1 maintained a moderate fragrance intensity of 2.0 points after 72 hours, while Comparative Example 1 only had 0.8 points after 24 hours and was almost odorless after 48 hours. The fragrance retention of Comparative Examples 2 and 3 was significantly worse than that of Example 1. This is because most of the fragrance in Example 1 was released in the later stages of washing, and the fragrance components during the long-lasting period (macrocyclic musks, with large molecular weight and low volatility) could be effectively adsorbed onto the surface of cotton fibers and released slowly, achieving long-lasting fragrance retention.

[0036] This example prepares artificial sebum stains (containing carbon black, oleic acid, trioleic acid glycerides, etc.) and tea-stained cloths (cotton cloth soaked in black tea). The cloths were cut to 10cm x 10cm pieces and machine-washed under the following conditions: water temperature 20℃, washing time 20 minutes, explosive salt sample dosage 2g / L, washing water volume 10L, rinsing twice after the main wash, and then air-dried. The whiteness value (R457) of the cloths before and after washing was measured using a whiteness meter, and the stain removal rate was calculated using the formula: Stain removal rate (%) = (whiteness after washing - whiteness before washing) / (whiteness of original white cloth - whiteness before washing) × 100%. Three cloths were tested for each sample, and the average value was taken. Example 1, washed in 40℃ water, was used as a control (only for illustrating low-temperature performance). The test results are shown in Table 4. Table 4. Decontamination rate (%) of different samples in cold water at 20℃

[0037] Table 4 shows that in cold water at 20℃, Example 1 achieved a stain removal rate of 86.5% for sebum stains and 79.2% for tea stains. Although this is lower than the stain removal effect of Example 1 at 40℃, it is still significantly better than the 48.3% and 41.2% of Comparative Example 1. Although the catalyst in Example 4 was uniformly mixed, the stain removal rate dropped to 75.2% and 68.4% due to the initial waste of active oxygen, but it was still much higher than the comparative example. The stain removal rates of Comparative Example 2 (without alkylamine phosphonates) and Comparative Example 3 (single-walled microcapsules) were both lower than those of Example 1, indicating that the complete technical solution of the present invention has synergistic advantages in stain removal and bleaching.

[0038] Furthermore, to verify the chemical coupling mechanism of this invention, the following experiment was designed: Simulated washing solutions 1, 2, and 3 were prepared. Solution 1 was a 0.1 mol / L sodium carbonate-sodium bicarbonate buffer solution with pH=10.8, simulating the initial dissolution state of the explosive salt; Solution 2 was the same buffer solution but with pH=9.5, simulating the middle stage of dissolution; Solution 3 was with pH=8.5, simulating the later stage of dissolution. Equal amounts of the explosive salt from Example 1 (containing only sodium percarbonate and an adaptive activating synergistic complex, excluding double-walled microcapsules, and in a homogeneous mixture) were added to each of the three solutions, and the hydrogen peroxide decomposition rate constant was measured at 20°C under different pH conditions.

[0039] Specifically, samples were added to each solution system to achieve a sodium percarbonate concentration of 2 g / L. Hydrogen peroxide concentrations were measured at 0, 1, 2, 3, 5, and 10 minutes of the reaction, and the pseudo-first-order reaction rate constant k was calculated. Simultaneously, the synergistic effect under rapid pH changes was determined: the solution was linearly decreased from pH 10.8 to pH 8.5 at a rate of 0.6 units / minute (simulating a rapid pH decrease), and the instantaneous generation of reactive oxygen species was measured and compared with a system where pH was kept constant at 10.8. The results are shown in Tables 5 and 6. Table 5. Hydrogen peroxide decomposition rate constant k (min) under different constant pH conditions. -1 )

[0040] As shown in Table 5, the decomposition rate constant of hydrogen peroxide decreases significantly with decreasing pH, and the k value at pH=8.5 is only 41% of that at pH=10.8. This verifies the characteristic that the catalytic activity of the adaptive activation synergistic complex decreases with decreasing pH.

[0041] Table 6 Comparison of pH dynamic changes and cumulative release of reactive oxygen species under constant pH conditions (mg / L, 5 minutes)

[0042] As shown in Table 6, when the pH drops rapidly, the release of active oxygen within 5 minutes is reduced by 38.5% compared to when the pH is constant. This aligns with the expectation that the instantaneous generation of active oxygen will decrease by 30-50% when the pH decrease rate is higher than 0.5 units / minute. This demonstrates the effectiveness of the negative feedback regulation mechanism of this invention in actual washing processes. If the solution alkalinity is rapidly lost, the active oxygen generation rate will automatically decrease, preventing the ineffective decomposition of hydrogen peroxide under adverse conditions. Conversely, if the pH decreases slowly, active oxygen will be released efficiently and continuously, achieving adaptive optimal utilization.

[0043] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments that can be applied to other fields. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for adaptive release control of fragrance through synergistic effects of explosive salt, cold water, and activated oxygen, characterized in that... Includes the following steps: S1, Sodium percarbonate and anhydrous sodium carbonate are mixed at a mass ratio of (85-95):(5-15) to form an alkaline matrix; S2, an adaptive activation synergistic complex composed of a binuclear manganese complex and an alkylamine phosphonate in a mass ratio of (1-3):(1-5) is added to an alkaline matrix; S3, the fragrance is encapsulated in a double-walled microcapsule with a stepped rupture threshold, wherein the double-walled microcapsule includes an inner wall and an outer wall, the rupture pH threshold of the inner wall is 9.5-11.0, and the rupture pH threshold of the outer wall is 8.0-9.4; S4, the adaptive activation and enhancement complex and the double-walled microcapsules are progressively layered in an alkaline matrix, so that the active oxygen release rate regulation system and the fragrance release threshold regulation system are chemically coupled. When the explosive salt is added to cold water to dissolve, the adaptive activation and enhancement complex releases carbonate from the alkaline matrix and gradually activates the low-temperature decomposition of sodium percarbonate. At the same time, the double-walled microcapsules realize the staged release of fragrance according to the transition process of solution pH from alkaline to neutral.

2. The method for adaptive release control of explosive salt cold water active oxygen synergistic fragrance according to claim 1, characterized in that: In step S2, the adaptive activation synergistic complex is distributed in a gradient layer in the alkaline matrix, and the mass concentration of the adaptive activation synergistic complex near the outer surface of the matrix is ​​lower than that in the inner region of the matrix. When the explosive salt is added to cold water, the outer surface area dissolves first, releasing a small amount of catalyst, thus avoiding excessive catalysis in the early stage that leads to excessive decomposition of hydrogen peroxide and loss of active oxygen. The matrix dissolves later, releasing more catalyst and maintaining the continuous release of active oxygen in the middle and later stages, thus achieving full controllability of the active oxygen release rate.

3. The method for adaptive release control of fragrance through synergistic effects of explosive salt cold water and active oxygen as described in claim 1, characterized in that: The inner wall of the double-walled microcapsule is made of a pH-responsive polymer material, which is selected from at least one of methacrylic acid / methyl methacrylate copolymer, polyacrylic acid, or chitosan. The outer wall is made of a protective wall material with high mechanical strength and low swelling under alkaline conditions, the protective wall material being selected from at least one of melamine resin, polyurea, or gelatin-gum arabic composite.

4. The method for adaptive release control of explosive salt cold water activated oxygen synergistic fragrance according to claim 1, characterized in that: The fragrance encapsulated in the double-walled microcapsules is a complex fragrance system, including a wash-off fragrance component and a long-lasting fragrance component. The wash-off fragrance component accounts for 20-40% of the total fragrance mass, and the long-lasting fragrance component accounts for 60-80% of the total fragrance mass. The wash-off fragrance component is a highly volatile terpene fragrance substance, and the long-lasting fragrance component is a high molecular weight ester or macrocyclic musk fragrance substance.

5. The method for adaptive release control of fragrance through synergistic release of explosive salt cold water active oxygen as described in claim 1, characterized in that: The average particle size of the double-walled microcapsules is 1-25 μm, of which microcapsules with a particle size of 1-10 μm account for 30-50% and microcapsules with a particle size of 10-25 μm account for 50-70%; the pH threshold for outer wall rupture of microcapsules with a particle size of 1-10 μm is set to 9.0-9.4, and the pH threshold for outer wall rupture of microcapsules with a particle size of 10-25 μm is set to 8.0-8.

9.

6. The method for adaptive release control of fragrance through synergistic effects of explosive salt cold water and activated oxygen as described in claim 1, characterized in that, The chemical coupling mechanism in step S4 is as follows: hydrogen peroxide released during the cold water dissolution of sodium percarbonate generates reactive oxygen species under the catalytic action of the adaptive activation synergistic complex. Simultaneously, during the release process, the solution pH gradually decreases from the initial 10.5-11.0 to 8.5-9.

5. The rate of pH decrease is negatively correlated with the instantaneous generation of reactive oxygen species. When the pH decrease rate is higher than 0.5 units / minute, the instantaneous generation of reactive oxygen species decreases by 30-50%, thereby adaptively avoiding excessive concentrated release of reactive oxygen species. The fragrance release rate of the double-walled microcapsules corresponds to the rupture threshold times reached during the pH decrease process, achieving efficient time matching between fragrance release and reactive oxygen species release.

7. The method for adaptive release control of fragrance through synergistic effects of explosive salt cold water and activated oxygen as described in claim 1, characterized in that, The composition of the explosive salt by mass percentage is as follows: 65-85% sodium percarbonate, 5-12% anhydrous sodium carbonate, 0.02-0.08% binuclear manganese complex, 0.1-0.5% alkylamine phosphonate, 0.5-3.0% double-walled microcapsules, 1-5% anionic surfactant, 0.5-3% nonionic surfactant, 0.1-1% enzyme preparation, with the balance being fillers and anti-caking agents.

8. The method for adaptive release control of fragrance through synergistic release of explosive salt cold water active oxygen as described in claim 1, characterized in that: The explosive salt composition has a multilayer tablet structure, including an outer layer and an inner core. The outer layer thickness accounts for 15-30% of the total tablet thickness, and the inner core thickness accounts for 70-85% of the total tablet thickness. The outer layer contains sodium percarbonate, anhydrous sodium carbonate, double-walled microcapsules, and a first amount of adaptive activation and synergistic complex. The inner core contains sodium percarbonate, anhydrous sodium carbonate, and a second amount of adaptive activation and synergistic complex. The first amount is less than the second amount, and the mass concentration of the adaptive activation and synergistic complex in the outer layer is 1 / 10 to 1 / 3 of the mass concentration of the adaptive activation and synergistic complex in the inner core.

9. The method for adaptive release control of fragrance through synergistic effects of explosive salt cold water and activated oxygen as described in claim 1, characterized in that: After the explosive salt is added to cold water, the current pH value is obtained through a real-time pH monitoring device. When the pH value drops to a preset fragrance release threshold, the double-walled microcapsules are triggered to rupture and release a signal.

10. The method for adaptive release control of fragrance through synergistic effects of explosive salt cold water and activated oxygen as described in claim 9, characterized in that, The fragrance release threshold is set according to the washing time interval as follows: the first release stage threshold pH=9.5-10.0, the second release stage threshold pH=8.8-9.4, and the third release stage threshold pH=8.0-8.7.

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