Low-fouling and high-whiteness oxygen bleaching stabilizer, and preparation method and application thereof

Abstract

The application discloses a low-fouling and high-whiteness oxygen bleaching stabilizer, a preparation method and application thereof, and belongs to the field of textile pretreatment auxiliaries. The technical problem to be solved is that in the continuous pretreatment process, the fouling on the steaming box, guide roller and other equipment is serious, white spots and other defects appear on the fabric, and the product quality and production efficiency are low. The technical solution is that an environmentally-friendly multi-component complex component, controllable adsorption and buffer component, high-molecular dispersing and free radical capturing component, penetration and surface activity adjusting component and water are used to prepare a low-fouling, high-whiteness and high-safety stabilizer system in a scouring and bleaching one-bath process. The system guarantees the stability of hydrogen peroxide, excellent whiteness improvement effect, excellent anti-fouling property and easy cleaning of the fouling, significantly reduces the fiber strength damage, improves the safety of the process, and guarantees the product quality.

Description

Technical Field

[0001] This invention belongs to the field of textile pretreatment auxiliaries, specifically relating to an oxygen bleaching stabilizer with low scaling and high whiteness, its preparation method, and its application. Background Technology

[0002] With increasingly stringent requirements for production efficiency, energy consumption, and environmental protection in the global textile industry, technological innovation in pretreatment processes for dyeing and finishing has become a key driver of industry development. In the dyeing and finishing process of textiles, pretreatment is necessary before the dyeing step to remove components generated or added during previous processing, such as sizing agents and waxes. These components can severely affect subsequent dyeing processes, hence the necessity of pretreatment. Currently, the conventional pretreatment process includes the following steps: raw fabric preparation → singeing → desizing → washing → scouring → washing → bleaching → washing → drying. This pretreatment process is lengthy, energy-intensive, and generates a lot of wastewater. Therefore, the dyeing and finishing industry has begun to focus on researching shorter pretreatment processes, leading to the development of the "one-bath scouring and bleaching" process. The "one-bath scouring and bleaching" process, which combines the traditional scouring and bleaching processes into one, significantly shortens the process and saves water, electricity, and steam resources, thus gaining widespread application. The dyeing and finishing auxiliaries industry is a crucial link in the textile industry, and with the increasing global awareness of environmental protection and the demand for sustainable development, this industry is undergoing technological innovation and product upgrades. However, the promotion and application of this efficient process has not been smooth sailing, posing unprecedented challenges to the performance of process aids, especially oxygen bleaching stabilizers.

[0003] Furthermore, while the H2O2 bleaching method for plant fibers has unique advantages—significant whiteness increase and good whiteness stability; low bleaching cost; sulfur- and chlorine-free production, facilitating closed-loop water recycling, and being clean and environmentally friendly—most bleaching production systems achieve a high degree of enclosure, minimizing wastewater and heat discharge and conserving clean water. However, due to severe scaling during plant fiber preparation and utilization, the system must be periodically opened to maintain normal operation, wasting significant amounts of heat and water resources and causing serious environmental pollution. Simultaneously, the resulting scale is dispersed throughout the system, its dense surface resisting high-pressure water and surfactant cleaning, and exhibiting strong resistance to common acid and alkali cleaning. This significantly impacts critical components of the production system, damages valuable parts, and severely disrupts normal system operation.

[0004] Both domestically and internationally, there is a growing demand for more environmentally friendly and efficient solutions. Traditional dyeing and finishing processes are water- and electricity-intensive, resulting in large wastewater discharges, which contradicts the national "dual carbon" goals and the trend towards green and high-quality development in the dyeing and printing industry. In continuous pretreatment processes, dyeing and printing plants often experience severe scaling on steamers, guide rollers, and other equipment, particularly in continuous oxygen bleaching and one-bath scouring and bleaching processes containing silicates. This silicate scaling leads to difficulties in removing sticking from rollers, increased cleaning frequency, reduced equipment lifespan, decreased steam utilization, increased energy consumption, and defects such as white spots on fabrics, severely impacting product quality and production efficiency.

[0005] Relevant patent documents retrieved:

[0006] The document, published in China (CN109112819A) on January 1, 2019, discloses a formulation for a hydrogen peroxide stabilizer. This stabilizer is manufactured using zinc carboxylate, aminoethanol phosphate, picolinic acid, sodium silicate, and aluminum stearate as raw materials. It effectively prevents excessive chain reactions of hydrogen peroxide, allowing the stabilizer to function fully and effectively. The zinc carboxylate can form chelates with heavy metal ions, reducing or eliminating the decomposition of heavy metal ions in hydrogen peroxide.

[0007] This document, published in China (CN104262535A) on January 7, 2015, discloses a novel method for preparing a hydrogen peroxide stabilizer. It utilizes an aqueous solution of maleic anhydride-acrylamide, synthesized via polymerization under the action of an initiator. The stabilizer is simple to prepare, non-toxic, non-corrosive, and exhibits good hydrogen peroxide stability, effectively inhibiting hydrogen peroxide decomposition and preventing silica scale buildup. It also shows good resistance to Mg... 2+ Ca 2+ Fe 3+ Heavy metal ions have a significant adsorption effect.

[0008] The prior art represented by the aforementioned documents has at least the following unresolved technical problems or defects: 1. Sodium silicate readily dehydrates and condenses in high-temperature, high-pH working solutions, forming hard, dense silica scale (SiO2·xH2O), which firmly adheres to the inner walls of equipment such as steamers, guide rollers, and heat exchangers. This scaling leads to decreased heat transfer efficiency, increased energy consumption, and increased susceptibility to abrasions and white spots on fabrics during operation. Removing this silica scale requires frequent shutdowns for acid washing, severely impacting the efficiency of continuous production and the lifespan of equipment.

[0009] 2. To improve scaling issues, oxygen bleaching stabilizer systems incorporate polycarboxylic acid polymers such as polyacrylic acid and polymaleic acid as dispersants and composite stabilizers. These polymers disperse particles in the suspension through steric hindrance, thus delaying scale deposition to some extent. However, the primary function of these polymers is dispersion; their ability to capture reactive free radicals (such as -OH) that decompose hydrogen peroxide is limited, and they cannot effectively inhibit the chain decomposition reaction initiated by free radicals. Therefore, they are still insufficient in controlling the decomposition rate of hydrogen peroxide, especially in terms of decomposition stability at high temperatures, making it difficult to balance high whiteness and low strength damage.

[0010] In solving the above problems or overcoming the above defects, the present invention encountered the following difficulties and obstacles: 1. The contradiction between high efficiency and stability versus low scaling. While traditional stabilizers provide excellent hydrogen peroxide stability and whiteness, they readily form calcium / magnesium silicate scale in high-hardness water. Reducing silicate dosage in pursuit of low scaling can actually hinder the stable decomposition of hydrogen peroxide, leading to uneven whiteness and significant damage. Therefore, we introduce magnesium citrate to form a stable colloid with silicate, utilizing the complexing ability of citrate ions to inhibit scaling tendencies. Simultaneously, a strong chelating system is added to minimize the risk of scaling without compromising the stabilizing effect of hydrogen peroxide.

[0011] 2. The contradiction between high whiteness and fiber damage. High whiteness often requires efficient decomposition of hydrogen peroxide, but this process generates excessive free radicals that damage the fibers, leading to a decrease in fabric strength. Excessive inhibition of hydrogen peroxide decomposition, on the other hand, can easily result in insufficient whiteness. Therefore, we introduce a terpolymer that can bind with excess free radicals, buffering their damage to the fibers; and also provides dispersion force to prevent impurities from sticking to the fabric. Summary of the Invention

[0012] The present invention aims to overcome the shortcomings of the prior art and provide an oxygen bleaching stabilizer with high efficiency, stability, good effect, low scaling, and high whiteness. It can control heavy metal impurities, prevent scale buildup and growth, increase the solubility of scale and make it easier to clean, thereby solving the problems of serious equipment scaling, low production efficiency, and insufficient whiteness and safety of fabrics in traditional processes.

[0013] Finally, a low-scaling, high-whiteness, and high-safety stabilizer suitable for oxygen bleaching and scouring baths in the pretreatment of cotton and polyester-cotton blends was developed, possessing the following excellent properties: 1) Excellent hydrogen peroxide stabilization effect, steadily regulating the decomposition rate of hydrogen peroxide, providing a strong guarantee for the stability of the process; 2) Reduced strength loss: It can effectively inhibit the violent catalytic decomposition caused by metal ions, avoid excessive oxidation damage to fibers, significantly reduce fiber strength damage, improve process safety, and ensure product quality. 3) Excellent whiteness enhancement effect; the treated fabric has excellent whiteness. 4) Excellent anti-scaling properties: Through its excellent dispersibility, it effectively inhibits the accumulation and adhesion of scale, silica scale and various stains on the inner wall of the equipment, reducing scaling and secondary contamination of fabrics from the source. 5) Ease of cleaning scale: By reducing the aggregation of existing scale, the adhesion of scale is reduced, making cleaning easier and more thorough, thereby significantly reducing the cleaning frequency and improving production efficiency.

[0014] Terminology Explanation: Unless otherwise defined, all technical terms in this document have the same meanings as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains. Unless otherwise stated, all patents, patent inventions, and publications cited in this document are incorporated herein by reference in their entirety. If multiple definitions exist for terms in this document, the definitions in this chapter shall prevail.

[0015] It should be understood that the above brief description and the following detailed description are exemplary and for illustrative purposes only, and do not limit the subject matter of the invention in any way. In this invention, the singular is used in conjunction with the plural unless otherwise specifically stated. It should also be noted that, unless otherwise stated, the use of “or” or “or” means “and / or”. Furthermore, the use of the term “comprising” and other forms such as “including,” “containing,” and “contains” are not limiting.

[0016] Edited by Shanghai Printing and Dyeing Industry Association. Printing and Dyeing Handbook (Second Edition) [M]. Beijing: China Textile Press, 2003.

[0017] Zhou Juxian (ed.). Dictionary of Textile Dyeing and Finishing Auxiliaries [M]. Beijing: Chemical Industry Press, 2007. Unless otherwise stated, conventional methods within the scope of the art, such as hydrogen peroxide decomposition rate test, whiteness test, scouring effect test, and fabric tensile breaking strength test, shall be used.

[0018] Unless specifically defined herein, the use of all commercially available products herein employs standard techniques. For example, it may be carried out using the manufacturer's instructions for use with the kit, or in accordance with methods known in the art or the description of this invention. The techniques and methods described herein can generally be implemented according to conventional methods well known in the art, based on the descriptions in the various summary and more specific documents cited and discussed in this specification.

[0019] The terms “optional / arbitrary” or “optionally / arbitrarily” mean that the event or situation described below may or may not occur, including both the occurrence and non-occurrence of the event or situation.

[0020] The term "one-bath scouring and bleaching process" used in this article refers to a technology that combines the two separate processes of scouring (removing impurities) and bleaching (improving whiteness) in traditional textile pretreatment into a single working solution and process flow.

[0021] The term "stabilizer system" as used in this article refers to a combination of chemical additives composed of multiple functional components in a specific ratio, used to control the decomposition rate of hydrogen peroxide, prevent ineffective decomposition, and reduce side effects during the bleaching process.

[0022] The term "scaling" as used in this article refers to the hard or sticky deposits formed on the surfaces of equipment such as steamers and guide rollers by inorganic salts (such as silicates, calcium and magnesium salts) and impurities during continuous pretreatment processes.

[0023] The term "hydrogen peroxide decomposition rate" used in this article refers to the percentage of hydrogen peroxide (H2O2) decomposed under certain time and conditions relative to the initial amount, and is used to evaluate the stabilizing effect of stabilizers on hydrogen peroxide.

[0024] The term “whiteness / Wg” used in this article refers to the whiteness value of the fabric surface measured using a whiteness meter. The higher the value, the whiter the fabric.

[0025] The term "tensile strength" used in this article refers to the maximum tensile force that a fabric can withstand before breaking, as measured according to the national standard GB / T 3923.1. It is an important indicator for evaluating the degree of damage to a fabric.

[0026] The term "modulus" used in this article refers to the molar ratio of silicon dioxide (SiO2) to sodium oxide (Na2O) in sodium silicate, which is a key parameter affecting its buffering performance and scaling tendency.

[0027] The term "number-average molecular weight" used in this article refers to the average molecular weight of each molecule in a polymer compound, which is an important parameter affecting its dispersion and capture performance.

[0028] The term "EO number" used in this article refers to the number of moles of ethylene oxide (EO) added to polyoxyethylene ether surfactants, which affects their hydrophilic-lipophilic balance (HLB) and application performance.

[0029] The term "GLDA" used in this article refers to tetrasodium L-glutamate diacetate, a novel, biodegradable, and environmentally friendly chelating agent. Made from natural amino acids, it exhibits good biodegradability and excellent chelating ability, particularly under alkaline and high-temperature conditions. It is a representative of green and environmentally friendly chelating agents.

[0030] The term "HEDP" used in this article refers to hydroxyethylidene diphosphonic acid, a widely used and highly efficient organophosphonic acid scale and corrosion inhibitor and chelating agent. It possesses strong chelating ability, high chemical stability, resistance to high temperatures and alkalis, and combines scale and corrosion inhibition functions. It is a representative of traditional, highly efficient but difficult-to-biodegrade chelating agents.

[0031] In a first aspect, the present invention provides: an oxygen bleaching stabilizer with low scaling and high whiteness, characterized in that it comprises the following components by mass percentage: 20-40% environmentally friendly multi-component complexing component, 10-20% controllable adsorption and buffering component, 15-25% polymer dispersion and free radical capture component, 3-8% penetration and surface activity regulating component, and water; The environmentally friendly multi-component complex component is a mixture of GLDA and HEDP in a mass ratio of 3-5:1.

[0032] Preferably, the environmentally friendly multi-component complex component is selected from any value or range between 20% and 40% by mass percentage, specifically from: 20%, 23%, 25%, 28%, 30%, 33%, 35%, 39%, 40% or any two of these ranges.

[0033] More preferably, the environmentally friendly multi-component complex component is selected from any value or range between 20% and 40% by mass percentage, specifically from: 20%, 25%, 30%, 35%, 39% or any two of them.

[0034] More preferably, the environmentally friendly multi-component complex component is selected from any value or range between 20% and 40% by mass percentage, specifically from: 20%, 30%, 39%, 35% or any two of them.

[0035] More preferably, the environmentally friendly multi-component complex component comprises 35% by mass percentage.

[0036] Preferably, the controllable adsorption and buffering components are selected from any value or range between 10-20% by mass percentage, specifically from: 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% or any two of these ranges.

[0037] More preferably, the controllable adsorption and buffering components are selected from any value or range between 10-20% by mass percentage, specifically from: 10%, 11%, 14%, 15%, 16%, 19%, 20% or any two of them.

[0038] More preferably, the controllable adsorption and buffering components are selected from any value or range between 10-20% by mass percentage, specifically from: 10%, 15%, 16%, 20% or any two of them.

[0039] More preferably, the controllable adsorption and buffering component comprises 16% by mass.

[0040] Preferably, the polymer dispersion and free radical scavenging component is selected from any value or range between 15% and 25% by mass percentage, specifically from: 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% or any two of these ranges.

[0041] More preferably, the polymer dispersion and free radical scavenging component is selected from any value or range between 15% and 25% by mass percentage, specifically from: 15%, 16%, 19%, 20%, 21%, 22%, 23%, 24%, 25% or any two of these ranges.

[0042] More preferably, the polymer dispersion and free radical scavenging component is selected from any value or range between 15% and 25% by mass percentage, specifically from: 15%, 20%, 22%, 25% or any two of them.

[0043] More preferably, the polymer dispersion and free radical scavenging component comprises 22% by mass percentage.

[0044] Preferably, the permeation and surface activity regulating component is selected from any value or range between 3% and 8% by mass percentage, specifically from: 3%, 4%, 5%, 6%, 7%, 8% or any two of them.

[0045] More preferably, the permeation and surface activity regulating component is selected from any value or range between 3% and 8% by mass percentage, specifically from 3%, 5%, 8% or any two of them.

[0046] More preferably, the permeation and surface activity regulating component is 5% by mass percentage.

[0047] Preferably, the environmentally friendly multi-component complex component is a mixture of GLDA and HEDP in a mass ratio selected from any value or range between 3 and 5:1, specifically selected from: 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or any two of them.

[0048] More preferably, the environmentally friendly multi-component complex component is a mixture of GLDA and HEDP in any mass ratio or range between 3 and 5:1, specifically selected from 3:1, 4:1, 5:1 or any two of them.

[0049] More preferably, the environmentally friendly multi-component complex component is a mixture of GLDA and HEDP in a mass ratio of 4:1. Preferably, the controllable adsorption and buffering component is a pre-formulated colloid of sodium silicate solution and magnesium citrate.

[0050] Preferably, the SiO2 / Na2O molar ratio in the preformed colloid is selected from any value or range between 2.6 and 2.8:1.

[0051] More preferably, the SiO2 / Na2O molar ratio in the preformed colloid is selected from any value or range between 2.6-2.8 and 2.6-2.8:1, specifically from 2.6:1, 2.7:1, 2.8:1 or any two of them.

[0052] More preferably, the SiO2 / Na2O molar ratio in the preformed colloid is 2.7:1.

[0053] Preferably, the polymer dispersion and free radical scavenging component is a sodium salt of acrylic acid-maleic acid-acrylamide terpolymer.

[0054] Preferably, the molecular weight of the acrylic acid-maleic acid-acrylamide terpolymer sodium salt is selected from any value or range between 3000 and 8000.

[0055] More preferably, the molecular weight of the acrylic acid-maleic acid-acrylamide terpolymer sodium salt is selected from any value or range between 3000 and 8000, specifically from: 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000 or any two of them.

[0056] More preferably, the molecular weight of the acrylic acid-maleic acid-acrylamide terpolymer sodium salt is selected from any value or range between 3000 and 8000, specifically from: 3000, 4000, 5000, 6000, 7000, 8000 or any two of them.

[0057] More preferably, the molecular weight of the acrylic acid-maleic acid-acrylamide terpolymer sodium salt is selected from any value or range between 3000 and 8000, specifically from: 3000, 5000, 6000, 8000 or any two of them.

[0058] More preferably, the molecular weight of the acrylic acid-maleic acid-acrylamide terpolymer sodium salt is 6000.

[0059] Preferably, the penetration and surface activity regulating component is isomeric tridecyl alcohol polyoxyethylene ether.

[0060] Preferably, the amount of ethylene oxide in the isomeric tridecyl alcohol polyoxyethylene ether is selected from any value or range between 5 and 15, specifically from: 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or any two of them.

[0061] More preferably, the amount of ethylene oxide in the isomeric tridecyl alcohol polyoxyethylene ether is selected from any value or range between 9 and 11. More preferably, the amount of ethylene oxide in the isomeric tridecyl alcohol polyoxyethylene ether is 10.

[0062] As the preferred embodiment, the oxygen bleaching stabilizer system comprises the following components by mass percentage: 35% environmentally friendly multi-component complexing component, 16% controllable adsorption and buffering component, 22% polymer dispersion and free radical capture component, 5% penetration and surface activity regulating component, and 22% water.

[0063] Secondly, the present invention provides a method for preparing the above-mentioned stabilizer system, comprising the following steps: S1. Heat water, add controllable adsorption and buffer components, stir to obtain colloid A, and cool for later use; S2. Add the environmentally friendly multi-component complex to water and stir to obtain solution B; S3. Add the polymer dispersion and free radical scavenging component to solution B, stir, and obtain solution C; S4. Add colloid A to solution C, stir, then add the penetration and surface activity regulating components, stir and mix to obtain the final product.

[0064] Preferably, the heating temperature in step S1 is selected from any value or range between 50-60°C.

[0065] More preferably, the heating temperature in step S1 is selected from any value or range between 50-60℃, specifically from: 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, 60℃ or any two of them.

[0066] More preferably, the heating temperature in step S1 is selected from any value or range between 50-60°C, specifically from 50°C, 55°C, 60°C or any two of them.

[0067] More preferably, the heating temperature in step S1 is 60°C.

[0068] Preferably, step S1 specifically involves heating water, sequentially adding magnesium citrate and sodium silicate solutions, continuously stirring to form a uniform colloid A, and then cooling it for later use.

[0069] Preferably, step S3 specifically involves: slowly adding sodium salt of acrylic acid-maleic acid-acrylamide terpolymer to solution B, and continuously stirring to form a viscous solution C.

[0070] Thirdly, the present invention provides the application of the above-mentioned oxygen bleaching stabilizer in a continuous one-bath scouring and bleaching process for textiles.

[0071] Based on further solutions to the technical problems of the present invention, or simultaneous solutions to multiple technical problems, the preferred solution in the technical solution provided in the first aspect of the present invention includes: The first preferred solution is an oxygen bleaching stabilizer system. This solution not only addresses the technical problem of "severe scaling on the steamer, guide rollers, and other equipment during continuous pretreatment processes," but also further solves the technical problem of "defects such as white spots on fabrics."

[0072] The second preferred solution is an oxygen bleaching stabilizer system. This solution, in addition to addressing the technical problems of "severe scaling on the steamer, guide rollers and other equipment during continuous pretreatment processes, resulting in defects such as white spots on the fabric," further solves the technical problem of "excessively rapid hydrogen peroxide decomposition."

[0073] The third preferred solution is an oxygen bleaching stabilizer system. This solution, in addition to addressing the technical problems of "severe scaling on the steamer, guide rollers and other equipment during continuous pretreatment processes, defects such as white spots on fabrics, and excessively rapid hydrogen peroxide decomposition," further solves the technical problem of "damage to fiber strength."

[0074] The beneficial effects of this invention are as follows: The present invention has at least the following beneficial effects: 1. Excellent hydrogen peroxide stabilization effect, steadily regulating the decomposition rate of hydrogen peroxide, providing strong guarantee for process stability; 2. Reduced strength loss: It can effectively inhibit the violent catalytic decomposition caused by metal ions, avoid excessive oxidation damage to fibers, significantly reduce fiber strength damage, improve process safety, and ensure product quality. 3. Excellent whiteness enhancement effect; the treated fabric has excellent whiteness. 4. Excellent anti-scaling properties: Through its excellent dispersibility, it effectively inhibits the accumulation and adhesion of scale, silica scale and various stains on the inner wall of the equipment, reducing scaling and secondary contamination of fabrics from the source. 5. Ease of cleaning scale: By reducing the aggregation of existing scale, the adhesion of scale is reduced, making cleaning easier and more thorough, thereby significantly reducing the cleaning frequency and improving production efficiency. Detailed Implementation

[0075] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way. The following content is merely an exemplary description of the scope of protection claimed by the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, and such changes should also fall within the scope of protection claimed by the present invention.

[0076] The present invention will be further described below by way of specific embodiments. Unless otherwise specified, all instruments, devices, equipment, reagents, products, etc., used in the embodiments of the present invention are obtained through conventional commercial means.

[0077] Table 1 Materials, their manufacturers, and models

[0078] Table 2 Equipment and its manufacturers and models

[0079] Examples 1-4 Preparation of an oxygen bleaching stabilizer system The formulation of the oxygen bleaching stabilizer system is shown in Table 3 below: Table 3 Oxygen bleaching stabilizer formulation

[0080] Preparation methods of Examples 1-2: S1. Heat deionized water to 50°C, add magnesium citrate and sodium silicate solution in sequence, stir continuously to form uniform colloid A, and cool for later use; S2. Add GLDA and HEDP to water in sequence and stir until homogeneous to obtain solution B; S3. Slowly add the sodium salt of acrylic acid-maleic acid-acrylamide terpolymer to solution B and continue stirring to form a viscous solution C; S4. Add colloid A to solution C, stir until homogeneous, then add isomeric tridecyl alcohol polyoxyethylene ether, stir until homogeneous, and the product is obtained.

[0081] Preparation method of Example 3: S1. Heat deionized water to 55°C, add magnesium citrate and sodium silicate solution in sequence, stir continuously to form uniform colloid A, and cool for later use; S2. Add GLDA and HEDP to water in sequence and stir until homogeneous to obtain solution B; S3. Slowly add the sodium salt of acrylic acid-maleic acid-acrylamide terpolymer to solution B and continue stirring to form a viscous solution C; S4. Add colloid A to solution C, stir until homogeneous, then add isomeric tridecyl alcohol polyoxyethylene ether, stir until homogeneous, and the product is obtained.

[0082] Preparation method of Example 4: S1. Heat deionized water to 60°C, add magnesium citrate and sodium silicate solution in sequence, stir continuously to form uniform colloid A, and cool for later use; S2. Add GLDA and HEDP to water in sequence and stir until homogeneous to obtain solution B; S3. Slowly add the sodium salt of acrylic acid-maleic acid-acrylamide terpolymer to solution B and continue stirring to form a viscous solution C; S4. Add colloid A to solution C, stir until homogeneous, then add isomeric tridecyl alcohol polyoxyethylene ether, stir until homogeneous, and the product is obtained.

[0083] Comparative Examples 1-2 The difference from Example 4 is that the content of each component in the oxygen bleaching stabilizer system and the mass ratio of GLDA to HEDP are changed, as shown in Table 4 below: Table 4 Oxygen bleaching stabilizer formulation

[0084] The preparation method is the same as in Example 4.

[0085] Comparative Example 3 The type of oxygen bleaching stabilizer was changed, and anhydrous sodium metasilicate was used as the oxygen bleaching stabilizer.

[0086] Test Example 1: Stability of hydrogen peroxide under high temperature conditions 1. Experimental Methods: Process: Treat in a constant temperature water bath at 90℃ for 60 minutes; Working solution formula: NaOH 2g / l + H2O2 (100%) 2g / l + Fe 3+ 2.5ppm + 4g / l oxygen bleaching stabilizer; Volume: 200ml; Test method: The hydrogen peroxide content in the working solution was measured by sodium permanganate titration after 10 min, 30 min and 60 min of heat preservation at 90℃. The hydrogen peroxide decomposition rate was calculated. Evaluation Notes: The lower the hydrogen peroxide decomposition rate, the better the control over hydrogen peroxide decomposition, and the more excellent the stability of hydrogen peroxide.

[0087] 2. Experimental Results This invention, through the synergistic effect of environmentally friendly multi-component complexing components, controllable adsorption and buffering components, polymer dispersion and free radical capture components, and penetration and surface activity regulating components, can extremely effectively inhibit the decomposition of hydrogen peroxide at high temperatures, providing excellent process stability and controllability.

[0088] The oxygen bleaching stabilizers prepared in Examples 1-4 can effectively control the decomposition of hydrogen peroxide, especially by adjusting the ratio of GLDA and HEDP, which further controls the decomposition of hydrogen peroxide and improves its stability, which is crucial for high-temperature stability.

[0089] Table 5. Test results of hydrogen peroxide stability under high temperature conditions

[0090] Example 2: Effect of different amounts of oxygen bleaching stabilizer on the whiteness after treatment in a simulated long-run continuous bleaching and bleaching one-bath process. 1. Experimental Methods: Process: Padding (two dips and two nips) — Bagging — Saturated steaming (102℃) 60 min) — Hot water wash (90℃×5 min) — Cold water wash — Dry and set aside; Fabric: 100% cotton 40×40 / 133×72 greige fabric, 20×16 / 128×60 greige fabric Working solution formula: NaOH 5g / l + CP-6 (L) 5g / l + H2O2 (100%) 15g / l + Xg / l oxygen bleaching stabilizer; Test method: The whiteness of the treated fabric surface was tested using a fully automatic whiteness meter. Three different parts of the fabric were tested and the average value was calculated. Evaluation Notes: The higher the whiteness value, the better the oxygen bleaching stabilizer improves whiteness; The oxygen bleaching stabilizer is the oxygen bleaching stabilizer prepared in Examples 1-4 and Comparative Examples 1-2, and the oxygen bleaching stabilizer in Comparative Example 3; Test method: 2. Experimental Results The oxygen bleaching stabilizers prepared in Examples 1-4 can precisely control the decomposition of hydrogen peroxide during the bleaching stage, generating sufficient effective bleaching components, thereby efficiently removing pigments and improving whiteness.

[0091] Table 6. Whiteness values ​​after treatment with different amounts of oxygen bleaching stabilizer

[0092] Example 3: Effect of different amounts of oxygen bleaching stabilizer on the tensile strength of treated fabrics in a simulated long-run continuous bleaching and bleaching one-bath process. 1. Experimental Methods: Process: Padding (two dips and two nips) — Bagging — Saturated steaming (102℃) 60 min) — Hot water wash (90℃×5 min) — Cold water wash — Dry and set aside; Fabric: 100% cotton 40×40 / 133×72 greige fabric, 20×16 / 128×60 greige fabric Working solution formula: NaOH 5g / l + CP-6 (L) 5g / l + H2O2 (100%) 15g / l + Xg / l oxygen bleaching stabilizer; Test method: The tensile breaking strength of the treated fabric was tested using an electronic fabric tensile strength tester. The test was performed three times and the average value was taken. (Refer to the test method of national standard GB / T 3923.1-2013) Assessment Notes: The higher the tensile breaking strength value, the better the fabric strength, the less damage the oxygen bleaching stabilizer causes to the fabric strength, and the higher the safety. The oxygen bleaching stabilizers are the oxygen bleaching stabilizers prepared in Examples 1-4 and Comparative Examples 1-2, and the oxygen bleaching stabilizer in Comparative Example 3.

[0093] 2. Experimental Results Compared to the oxygen bleaching stabilizers prepared in Comparative Examples 1-2 and Comparative Example 3, the oxygen bleaching stabilizers prepared in Examples 1-4 effectively reduced fiber damage. This is attributed to the fact that their specific content of polymeric dispersion and free radical scavenging components effectively quenched reactive oxygen species such as hydroxyl radicals generated during the bleaching process, preventing excessive oxidative degradation of the fibers. The ratio of GLDA to HEDP also had a significant impact on the excessive oxidative degradation of the fibers. Adjusting the synergistic effect of environmentally friendly multi-component complexing components, controllable adsorption and buffering components, polymeric dispersion and free radical scavenging components, and penetration and surface activity regulating components is crucial.

[0094] Table 7. Tensile strength results of fabrics treated with different amounts of oxygen bleaching stabilizer

[0095] Test Example 4: Scaling of different oxygen bleaching stabilizers after drying at 120°C and the ease of cleaning of the scale. 1. Experimental Methods Oxygen bleaching working solution formula: CP-6(L) 12g / l + H2O2(100%) 18g / l + NaOH 4g / l + oxygen bleaching stabilizer 24g / l; Scaling degree test method: Dry in an electric constant temperature drying oven at 120℃ for 24 hours and observe the scaling condition; Scaling removal test method: Rinse the dried scale with direct water and observe the scale removal after 30 seconds; Assessment Description: The scaling degree is rated on a 5-level scale, which is evaluated based on the amount and hardness of the scale, from level 1 to level 5. The higher the level, the less scale there is and the better the anti-scaling effect of the oxygen bleaching stabilizer. The ease of cleaning is rated on a 5-level scale, which is evaluated based on how easily the scale can be cleaned. The higher the level, the easier the scale is to remove and the better the oxygen bleaching stabilizer works.

[0096] The oxygen bleaching stabilizers are the oxygen bleaching stabilizers prepared in Examples 1-4 and Comparative Examples 1-2, as well as oxygen bleaching stabilizer II in Comparative Example 3.

[0097] 2. Experimental Results The oxygen bleaching stabilizers prepared in Examples 3 and 4 showed the best performance in terms of scaling severity (level 3-4 and above) and ease of cleaning (level 5). This is mainly attributed to: 1) the sodium silicate / magnesium citrate pre-colloid improved the stability of silicates and inhibited their self-condensation scaling; 2) the GLDA / HEDP strong chelating system complexed Ca²⁺ in the water. + Mg² + Plasma prevents it from forming hard scale with silicate ions; 3) Polymer dispersants stabilize and suspend the already formed tiny scale particles, making them less prone to deposition. The oxygen bleaching stabilizers prepared in Examples 1-4 have a scale cleanability level of 3 or higher, greatly reducing the difficulty and cost of equipment maintenance.

[0098] Table 8. Whiteness values ​​after treatment with different amounts of oxygen bleaching stabilizer

[0099] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A low-scaling, high-whiteness oxygen bleaching stabilizer, characterized in that, The composition by mass percentage includes the following components: 20-40% environmentally friendly multi-component complexing component, 10-20% controllable adsorption and buffering component, 15-25% polymer dispersion and free radical capture component, 3%-8% penetration and surface activity regulating component, and water; the environmentally friendly multi-component complexing component is a mixture of GLDA and HEDP in a mass ratio of 3-5:

1.

2. The oxygen bleaching stabilizer according to claim 1, characterized in that, The environmentally friendly multi-component complex component is a mixture of GLDA and HEDP in a mass ratio of 4:

1.

3. The oxygen bleaching stabilizer according to claim 1, characterized in that, The controllable adsorption and buffering components are a sodium silicate solution and a pre-formulated colloid of magnesium citrate.

4. The oxygen bleaching stabilizer according to claim 3, characterized in that, The SiO2 / Na2O molar ratio in the preformed colloid is 2.6-2.8:

1.

5. The oxygen bleaching stabilizer according to claim 1, characterized in that, The polymer dispersion and free radical capturing component is a sodium salt of acrylic acid-maleic acid-acrylamide terpolymer with a molecular weight of 3000-8000.

6. The oxygen bleaching stabilizer according to claim 1, characterized in that, The permeation and surface activity regulating component is isomeric tridecyl alcohol polyoxyethylene ether.

7. The oxygen bleaching stabilizer according to claim 1, characterized in that, The components, by weight percentage, are as follows: 35% environmentally friendly multi-component complexing component, 16% controllable adsorption and buffering component, 22% polymer dispersion and free radical capture component, 5% penetration and surface activity regulating component, and 22% water.

8. A method for preparing the oxygen bleaching stabilizer according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Heat water, add controllable adsorption and buffer components, stir to obtain colloid A, and cool for later use; S2. Add the environmentally friendly multi-component complex to water and stir to obtain solution B; S3. Add the polymer dispersion and free radical scavenging component to solution B, stir, and obtain solution C; S4. Add colloid A to solution C, stir, then add the penetration and surface activity regulating components, stir and mix to obtain the final product.

9. The preparation method according to claim 8, characterized in that, The heating temperature described in step S1 is 50-60℃.

10. The use of the oxygen bleaching stabilizer according to any one of claims 1-7 in a continuous scouring and bleaching process for textiles.

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