Green efficient down jacket dry cleaning agent and preparation method thereof

Abstract

The invention relates to the technical field of daily chemical cleaning agents, and particularly discloses a green and efficient down jacket dry cleaning agent which is prepared from the following raw materials in parts by mass: 50-60 parts of plant-derived isoparaffin, 5-8 parts of limonene diol, 5-10 parts of ozonized vegetable fatty acid methyl ester nano-liposome powder, 2-3 parts of sulfonated oleoyl arginine ethyl ester hydrochloride and 8-10 parts of natural camphor. According to the environment-friendly efficient down jacket dry cleaning agent, a set of all-around cleaning and protecting system is constructed through the precise matching and synergistic effect of multiple raw materials, all the components exert own characteristics and are mutually energized, the dual goals of efficient decontamination and fabric protection are achieved, plant-derived isoparaffin serves as a C8-C12 volatile component, and the environment-friendly efficient down jacket dry cleaning agent has the advantages that the environment-friendly efficient down jacket dry cleaning agent is environment-friendly and environment-friendly; by means of excellent permeability, the high-density fabric of the down jacket and down filling gaps can be rapidly penetrated, the high-density fabric can directly reach stain attachment sites, and oily dirt can be efficiently dissolved.

Description

Technical Field

[0001] This invention relates to the field of daily chemical cleaning agents, specifically to a green and efficient dry cleaning agent for down jackets and its preparation method. Background Technology

[0002] Compared to water washing, dry cleaning uses organic solvents such as chlorofluorocarbons (CFCs), tetrachloroethylene, and petroleum hydrocarbons to clean fabrics instead of water. Tetrachloroethylene, in particular, is still widely used by most dry cleaners due to its strong cleaning power, fast drying speed, and wide applicability. However, with the fast pace of modern life and increasing environmental and health awareness, especially among young people who are unwilling to spend too much time on daily chores, and with expensive down jackets often requiring conventional cleaning methods using popular online dry cleaning agents, the cleaning results are not only labor-intensive and time-consuming but also unsatisfactory. This leads to a large number of down jackets still needing to be sent to dry cleaners for centralized tetrachloroethylene dry cleaning, causing environmental pollution.

[0003] Currently, the effects of mainstream household dry cleaning agents for down jackets are not ideal. The core reason lies in the contradiction between the special characteristics of down jacket materials and the compatibility of cleaning technologies: Most down jackets have water-repellent coatings such as DWR on their surface. The high-density fabric (such as windproof nylon) and complex down filling structure can hinder the penetration of cleaning agents and their full contact with stains. Local spraying of dry cleaning agents is difficult to thoroughly remove deep stains and may even damage the coating performance. In order to balance safety and cost, household products have limited surfactant content and a single type of solvent, which is insufficient to decompose oily stains, protein and pigment stains. In the low temperature environment of winter, there are also problems such as slow solvent evaporation and difficulty in the active ingredients to play their role. In addition, some cleaning power is often sacrificed in order to reduce irritation. At the same time, dry cleaning agents are mostly designed for small stains. Large areas of dirt require repeated operation, which can easily cause uneven cleaning or residue. The mechanical force of wiping or brushing alone is insufficient to remove stains that have penetrated into the fibers. Excessive friction can also damage the fabric. In the low temperature environment, the moisture evaporates slowly, and residual moisture can easily breed odors or cause down to clump. In addition, some solvents may leave an odor after evaporation, and alkaline components in the cleaning agent may precipitate white powder if not completely wiped clean, affecting the appearance. Strong solvents may also accelerate the aging of water-repellent coatings. Coupled with users' misconceptions about the positioning of dry cleaning agents and operational errors such as not selecting products according to the type of stain, the cleaning effect is further reduced. Some existing dry cleaning agents also have obvious defects, such as repeated spot cleaning causing damage to the fabric or peeling of the coating in the same area. Some use highly penetrating surfactants as the main component, and use the friction of a wet towel to assist in the removal of stains, but sometimes the effect is not good. They can only dilute the stains or expand the stain circle, leaving residues and not removing the stains at the root. Others use oily solvents to play the role of like dissolving like, supplemented by powder absorbents, so that the oil stains are transferred to the absorbents, thereby removing the stains on the down jacket. However, powder residue is easily left embedded in the surface gaps of the down jacket, which can cause secondary pollution.

[0004] In recent years, researchers and enterprises have proposed various improvement measures to address the above problems, and related patents have also disclosed a series of technical solutions, but many pain points still exist. Chinese patent CN113234546A, "A dry cleaning agent for down jackets and its preparation method," proposes to enhance penetration and emulsification capabilities by compounding polyol ether nonionic surfactants with anionic surfactants, thereby reducing damage to the down coating. However, this solution has limited effectiveness in decomposing stubborn pigment stains and does not solve the problem of slow solvent evaporation at low temperatures. Japanese Kao patent JP2021155913A uses plant-derived saponins as the core surfactant, combined with cocamidopropyl betaine to improve the environmental friendliness of stain removal, and is suitable for protein stains. However, its activity is insufficient at low temperatures, and its emulsification and decomposition capabilities for oily stains are weak. Chinese patent CN112300877A, "Low-Temperature High-Efficiency Down Jacket Dry Cleaning Agent," adds low-temperature resistant protease and lipase to target stubborn stains such as blood and sebum. However, the enzyme preparation has poor storage stability, and its activity tends to decrease after long-term storage. Unilever's patent WO2022002532A1 uses sodium alginate microcapsules to encapsulate the protease, extending its storage stability, but this increases the complexity of the formulation and production costs. Chinese patent CN114456785A, "Photocatalytic Down Jacket Cleaner," adds nano-titanium dioxide to decompose pigment stains through natural light or ultraviolet radiation. However, the photocatalytic process depends on specific light conditions, limiting its applicability in household settings. Procter & Gamble's patent US20220169981A1 uses magnetic... While nanoparticles loaded with surfactants can directionally adsorb oil stains and reduce residue, the high cost of nanomaterials hinders large-scale deployment. 3M patent US20210371552A1 uses silicone-based solvents such as cyclopentamethoxysiloxane instead of tetrachloroethylene, which is gentler on polyester fiber coatings, but its cleaning efficiency is lower than traditional solvents. Chinese patent CN114106866A, "Supercritical Carbon Dioxide Down Cleaning Agent," utilizes high pressure... While achieving residue-free cleaning, a 5-10 MPa pressure device is required, and miniaturization for home use still faces technological bottlenecks. Chinese patent CN113621318A, "Antistatic Down Jacket Dry Cleaning Agent," adds dioctadecyl dimethyl ammonium chloride to improve fluffiness, while German Henkel patent EP3560976A1 introduces low-boiling-point modified ethanol to shorten drying time; however, neither solves the problem of white marks caused by detergent residue. Chinese patent CN114752433A, "pH-responsive Down Jacket Dry Cleaning Agent," uses a buffer system to adjust pH and activate specific components, while Korean LG Chem patent KR20220012345A uses a temperature-sensitive polymer gel to adapt to different temperature environments; however, the intelligent response mechanism requires high formulation precision, making production difficult. Japanese Lion Corporation patent JP2022087651A optimizes the formulation to reduce irritation through in vitro reconstruction of the epidermis model, but there is still room for improvement in its rapid stain removal performance.

[0005] In addition, Chinese patent CN111454782A, "A biodegradable dry cleaning agent for down jackets and its preparation method," mainly uses water-based solvents, combined with biodegradable surfactants and chelating agents. It has good green safety and certain anti-mildew properties, but its cleaning power for stubborn stains is insufficient and its drying speed is slow. Chinese patent CN111334377A, "A phase change dry cleaning agent for down jackets and its preparation method," uses phase change materials to avoid powder residue, which is highly environmentally friendly. However, the phase change process is sensitive to temperature, and its cleaning efficiency is limited at low temperatures. Chinese patent CN113604291A, "A dry cleaning agent for stains on down jackets," has excellent cleaning power and antibacterial effect, is mild and easily degradable, but it is harmful to the down fibers. Insufficient protective properties may affect the fluffiness of clothing with long-term use; Chinese patent CN116463174A, "A dry cleaning agent for down jackets and its preparation method", improves the cleaning effect by optimizing the ratio of solvent, penetrant and enzyme preparation, but the problem of low-temperature activity of enzyme preparation has not been fundamentally solved; Chinese patent CN106635466A, "A dry cleaning agent for down jackets and its preparation method", does not require rinsing and dries quickly, suitable for spot cleaning, but has poor adaptability to stains all over the body; Chinese patent CN117778114A, "An antistatic dry cleaning agent for down jackets and its preparation method", has the functions of stain removal, antibacterial and antistatic, but the residue control effect is not good, and it is easy to form hidden residues on the surface of clothing.

[0006] In summary, although existing technologies have made some progress in formula optimization, technological innovation, and environmental performance improvement, they still have pain points such as difficulty in screening natural, non-toxic, and volatile solvents, insufficient rapid stain removal, poor convenience and efficiency, high cost of nanomaterials, high requirements for application scenarios for special technologies (such as photocatalysis), and need to optimize household applicability. There is an urgent need to develop a green, environmentally friendly, easy-to-use, highly efficient stain removal agent for down jackets that leaves no residue. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides a green and efficient dry cleaning agent for down jackets and its preparation method. The dry cleaning agent is environmentally friendly, suitable for convenient home use, and can simultaneously achieve efficient stain removal, leave no residue, and effectively protect the fabric.

[0008] To achieve the above objectives, this invention discloses a green and efficient dry cleaning agent for down jackets, which is composed of the following raw materials in parts by weight: 50-60 parts of plant-derived isoalkanes, 5-8 parts of limonene glycol, 5-10 parts of ozonated plant fatty acid methyl ester nanoliposome powder, 2-3 parts of sulfonated oleyl arginine ethyl ester hydrochloride, and 8-10 parts of natural camphor.

[0009] Preferably, the plant-derived isoalkanes are obtained by acidification of plant fatty acids obtained from the byproduct of edible vegetable oil refining, soapstock, followed by methanol esterification, vacuum distillation, hydrogenation deoxygenation, isomerization, product separation and refining. The plant-derived isoalkanes are volatile isoalkanes ranging from C8 to C12.

[0010] Preferably, the hydrodeoxygenation reaction conditions are a temperature of 250-400℃, a pressure of 3-10 MPa, and a hydrogen-to-oil volume ratio of 500-1000:1, with the catalyst being nickel-molybdenum, cobalt-molybdenum, or platinum / palladium noble metals supported on a γ-alumina or silica support; the isomerization reaction conditions are a temperature of 200-350℃, a pressure of 2-5 MPa, and the catalyst being ZSM-5 type zeolite molecular sieve, SAPO-11 type silica-alumina molecular sieve, Beta type zeolite molecular sieve, or platinum / ZSM-5 type zeolite bifunctional catalyst.

[0011] Preferably, the limonene diol is prepared by epoxidation of limonene and hydrogen peroxide under acidic conditions to generate epoxidized limonene, followed by hydrolysis. The molar ratio of the epoxidation reaction is limonene: 30% hydrogen peroxide: acidic catalyst = 1: 1.2~1.5: 0.05~0.1, and the molar ratio of the hydrolysis reaction is epoxidized limonene: water: acidic catalyst = 1: 10~15: 0.05~0.1.

[0012] Preferably, the preparation of the ozonated plant fatty acid methyl ester nanoliposome powder includes: ozonating plant fatty acid methyl esters to obtain ozonated plant fatty acid methyl esters, then mixing them with phospholipids and cholesterol in a mass ratio of 3:2:1, followed by film formation, hydration, ultrasound, homogenization, and freeze drying.

[0013] Preferably, the acid value of the ozonated vegetable fatty acid methyl ester is less than 1 mg potassium hydroxide / g, and the iodine value after ozonation is lower than that of the raw material.

[0014] Preferably, the sulfonated oleylarginine ethyl ester hydrochloride is prepared by reacting oleylarginine ethyl ester hydrochloride and sodium bisulfite at a molar ratio of 1:1.2 under conditions of pH 5.0-6.0 and temperature 50-70°C for 6-12 hours.

[0015] Preferably, the natural camphor is a commercially available product with a sublimation pressure of 1.33 kPa at 25°C, and forms a eutectic system with limonene diol.

[0016] A method for preparing a green and efficient dry cleaning agent for down jackets includes the following steps: under stirring conditions, sulfonated oleyl arginine ethyl ester hydrochloride is sprinkled in batches into plant-derived isoparaffins, heated to 45-50°C and stirred for at least 2 hours until transparent; limonene diol is added, and stirring is continued for at least 1 hour until transparent; the temperature is lowered to below 38°C, and natural camphor is sprinkled in batches and stirred evenly; a high-speed homogenizer is started, and homogenization is performed at a speed of 12,000 rpm for at least 10 minutes; the speed is reduced to 1,000 rpm, and ozonated plant fatty acid methyl ester nanoliposome powder is added in batches, and stirred for at least 1 hour until a stable homogeneous state is achieved.

[0017] Preferably, the stable and homogeneous dry cleaning agent does not separate or gel after standing for more than 200 days.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] This invention's green and efficient down jacket dry cleaning agent constructs a comprehensive cleaning and protection system through the precise ratio and synergistic effect of multiple raw materials. Each component exerts its own characteristics and empowers each other to achieve the dual goals of efficient stain removal and fabric protection. Plant-derived isoalkanes, as volatile components with C8 to C12 content, have excellent permeability and can quickly penetrate the high-density fabric and down filling gaps of down jackets, reaching the stain adhesion site and efficiently dissolving oily dirt. Ozone-oxidized plant fatty acid methyl ester nanoliposome powder releases active oxygen upon contact with stains, specifically breaking down stubborn protein and pigment stains. Its acid value is less than 1 mg potassium hydroxide / g, avoiding corrosion to the fabric. Sulfonated oleyl arginine ethyl ester hydrochloride, as an amphoteric surfactant, can capture dirt particles with different charge types, preventing stains from re-adhering during the cleaning process and ensuring thorough cleaning.

[0020] Limonene glycol not only helps remove polar dirt through volatilization, but also forms a eutectic system with natural camphor. The synergistic effect of the two, combined with the stepwise volatilization characteristics of plant-derived isoalkanes, creates a rapid drying system. The volatilization rate can reach over 85% in the first 30 minutes, achieving surface drying within 15 minutes. The phase change effect brought about by the eutectic system allows any remaining residue to automatically pulverize and fall off, completely avoiding the white residue problem common in traditional dry cleaning agents. At the same time, the complementary properties of each raw material make the cleaning process gentler. The surface tension of the formula is controlled within an appropriate range, and the breaking strength loss of down fibers is less than 3%. This maintains the water-repellent properties of the fabric while preventing down from clumping. After cleaning, the garment's softness reaches 4.8 and its loft reaches 4.9. Long-term use can still maintain the warmth and appearance of the down jacket.

[0021] All raw materials are selected from natural sources or green synthetic products. The plant-derived isoalkanes are derived from by-products of edible vegetable oil refining, and the remaining components are prepared through environmentally friendly processes. The biodegradability rate reaches 92% after 28 days, and the biosafety is far superior to traditional dry cleaning solvents. It is non-irritating to the skin. The sublimation pressure of natural camphor is 1.33 kPa at 25°C, forming a dynamic gas phase barrier, so that no preservatives need to be added to the product. The total number of microorganisms remains at a low level within 12 months after opening, and it can still maintain a homogeneous state after standing for more than 200 days without layering or gelling.

[0022] Furthermore, this dry cleaning agent does not require special equipment such as ultraviolet light or high pressure, making it suitable for everyday household cleaning. Cleaning can be completed simply by spraying and wiping, making it convenient and energy-efficient. Actual testing showed that it achieves a 99.7% removal efficiency for mixed stains such as soy sauce, soybean oil, and fruit juice. Cleaned fabrics remained mold-free even after 7 days in a high-temperature, high-humidity environment, demonstrating its long-lasting and stable effectiveness. Multiple uses will not damage the coating or down fibers of down jackets, truly achieving multiple advantages: environmentally friendly, highly efficient stain removal, no residue, and fabric protection. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0024] Example 1:

[0025] A green and efficient dry cleaning agent for down jackets is composed of the following raw materials in parts by weight: 50-60 parts of plant-derived isoalkanes, 5-8 parts of limonene glycol, 5-10 parts of ozonated plant fatty acid methyl ester nanoliposome powder, 2-3 parts of sulfonated oleyl arginine ethyl ester hydrochloride, and 8-10 parts of natural camphor.

[0026] Plant-derived isoalkanes are obtained by acidifying the soapstock, a byproduct of edible vegetable oil refining, with plant fatty acids, followed by methanol esterification, vacuum distillation, hydrogenation deoxygenation, isomerization, product separation, and purification. The plant-derived isoalkanes are volatile isoalkanes ranging from C8 to C12. The preparation process for plant-derived isoalkanes is as follows:

[0027] Raw material pretreatment: Moisture in plant fatty acids is removed by vacuum distillation or molecular sieve adsorption, free fatty acids are neutralized by alkaline adsorbents (such as silica gel and activated alumina), and solid particles are removed by microporous filtration to avoid catalyst poisoning in subsequent reactions;

[0028] Hydrodeoxygenation reaction: Under a hydrogen atmosphere, oxygen in fatty acid methyl esters is removed in the form of water and carbon dioxide to generate straight-chain alkanes. The reaction conditions are a temperature of 250-400℃, a pressure of 3-10 MPa, and a hydrogen to oil volume ratio of 500-1000:1. The catalyst is a nickel-molybdenum, cobalt-molybdenum or platinum-palladium noble metal supported on a γ-alumina or silica support. Sulfide catalysts need to be pre-sulfurized to improve stability.

[0029] Isomerization reaction: converting straight-chain alkanes into branched isomers, lowering the freezing point and increasing volatility; the reaction conditions are a temperature of 200-350℃ and a pressure of 2-5 MPa (hydrogen atmosphere), and the catalyst is ZSM-5 type zeolite molecular sieve, SAPO-11 type silica-alumina phosphate molecular sieve, Beta type zeolite molecular sieve or platinum / ZSM-5 type zeolite bifunctional catalyst, and the cracking side reactions are suppressed by controlling the temperature and space velocity;

[0030] Product separation and purification: Based on the difference in boiling point, isoalkanes of different carbon chain lengths are separated by fractional distillation, and light components (volatile isoalkanes) from C8 to C12 are collected. Heavy components can be recycled back to the isoalkanes chemical section or used as fuel components. Residual impurities are removed by desulfurization and denitrification through activated carbon or molecular sieve adsorption, and unreacted hydrogen is recovered by membrane separation or pressure swing adsorption.

[0031] Natural camphor is a commercially available product with a sublimation pressure of 1.33 kPa at 25°C. It forms a eutectic system with limonene diol.

[0032] Before starting, prepare the equipment as follows: Use a 5-liter glass autoclave with a vacuum of ≤10 mbar, a heating temperature of ≤80℃, and a dehydration efficiency of ≥95%; use a 10×50 cm diameter glass adsorption column filled with 100-200 mesh silica gel or 5 Å pore size activated alumina; use a 0.45 micron PTFE membrane precision filter; use a 500 ml Hastelloy high-pressure reactor with a pressure resistance of 15 MPa and a temperature resistance of 450℃, equipped with a magnetic stirrer at 0-1200 rpm; use a hydrogen pressure reducing valve with a hydrogen cylinder of ≥99.99% purity; use a 2.5×30 cm diameter reaction tube in a fixed-bed reactor; use a molecular distillation apparatus with an evaporation area of ​​0.05 m² and a vacuum of ≤0.1 mbar; and use a 5×30 cm diameter laboratory-grade activated carbon adsorption column that can be filled with activated carbon.

[0033] Hydrodeoxygenation catalyst is The catalyst has a particle size of 0.5-1 mm, and the isomerization catalyst is a Pt / ZSM-5 bifunctional catalyst with a platinum loading of 0.5%.

[0034] Purchase 5 kg of commercially available methyl soybean oil for raw material pretreatment:

[0035] 1. Rotary evaporator dehydration operation: Process 5 kg of raw material in 3 batches, 2 kg each time, and 1 kg in the last batch. Set the vacuum pump vacuum degree to ≤10 mbar, the water bath temperature to ≤80℃ to avoid thermal decomposition of methyl ester, the rotation speed to 50 rpm, and dehydrate each batch for 2 hours. The moisture content after dehydration is ≤0.1%, which can be detected by Karl Fischer method.

[0036] 2. Deacidification adsorption column operation: Fill a 10×50 cm diameter glass column with 100 g of silica gel, place glass wool at the bottom, and inject the dehydrated methyl soybean oil into the column at a flow rate of 10 mL / min using a constant flow pump. Collect the effluent and test the acid value to be ≤0.1 mg potassium hydroxide / g.

[0037] 3. Precision filtration: Using a 0.45-micron PTFE membrane filter, gravity filtration or low-pressure nitrogen filtration ≤0.1 MPa is used to obtain 4.8 kg of filtrate.

[0038] Hydrodeoxygenation (HDO) reaction treatment:

[0039] 1. Feeding and sealing of the high-pressure reactor: Inject 4.8 kg of pretreated methyl soybean oil into the high-pressure reactor, and add 240 g of... The catalyst accounts for 5 wt% of the raw materials. Gently stir with a glass rod to suspend the catalyst, install the sealing cap, and tighten the bolts in a diagonal sequence.

[0040] 2. Heating and hydrogen pressure control: A jacketed oil bath can be used with silicone oil. The heating rate can be set from 3℃ / minute to 320℃, and the temperature control accuracy is within ±2℃. Hydrogen is charged to 6 MPa at a flow rate of 500 liters / hour through the hydrogen pressure reducing valve. Then, a magnetic stirrer is started at 800 rpm. If the pressure is >6.2 MPa, the excess hydrogen is released through the back pressure valve.

[0041] 3. Reaction control: Liquid hourly space velocity (LHSV) ≈ 5.7 hours After reacting for 4 hours, 4.2 kg of straight-chain alkanes were obtained.

[0042] Isomerization reaction treatment:

[0043] 1. Feeding and Process Setting: Pump 4.0 kg of HDO product (n-alkane) into the feed tank of the fixed-bed reactor, add 20 g of Pt / ZSM-5 catalyst, and set the reaction temperature to 280℃, hydrogen pressure to 3 MPa, and liquid hourly space velocity to 2 h⁻¹. Hydrogen flow rate: 300 liters / hour;

[0044] 2. Gas hourly space velocity (GHSV): 15,000 hours The reaction yielded 3.4 kg of isoparaffins.

[0045] Fractionation and refining process

[0046] 1. Short-path distillation: Under a vacuum of 0.1 mbar, the fraction distilled at 150-250℃ is cut to obtain 2.9 kg of C8 to C12 components;

[0047] 2. Adsorption desulfurization: Add 290 grams of activated carbon (approximately 10% of the feed amount) for adsorption desulfurization to obtain 2.8 kg of plant-derived isoalkanes (the plant-derived isoalkanes can also be commercially available C8 to C12 volatile plant-derived isoalkanes).

[0048] Example 2, Preparation of limonene diol:

[0049] Limonene diol is prepared by epoxidation of limonene with hydrogen peroxide under acidic conditions to form epoxidized limonene, followed by hydrolysis. The molar ratio of the epoxidation reaction is limonene: 30% hydrogen peroxide: acidic catalyst = 1:1.2~1.5:0.05~0.1, and the molar ratio of the hydrolysis reaction is epoxidized limonene: water: acidic catalyst = 1:10~15:0.05~0.1. The preparation process of limonene diol is as follows:

[0050] Epoxidation reaction: Limonene and an acidic catalyst (such as sulfuric acid) are added to the reaction apparatus, and stirring is started at a speed of 300-500 rpm. The temperature is raised to 50-60°C, and 30% hydrogen peroxide solution is slowly added dropwise through a constant pressure funnel. The dropping rate is controlled to avoid violent exothermic reactions, and the temperature is maintained for 4-6 hours. During the reaction, the epoxidation process is monitored by TLC or GC. After the epoxidation group is formed, the limonene peak decreases. After the reaction is completed, the mixture is cooled to room temperature and neutralized with saturated sodium carbonate solution. The organic phase of epoxidized limonene is collected in layers using a separatory funnel, washed with water until neutral, dried with anhydrous sodium sulfate, and purified by vacuum distillation to obtain the fraction with a boiling point of 180-200°C.

[0051] Hydrolysis reaction: Epoxy limonene is mixed with 5%~10% dilute sulfuric acid and heated to 70~80℃ with stirring for 2~4 hours for hydrolysis reaction. The ring opening of the epoxy group is monitored by TLC or GC, and the epoxy peak disappears and the diol peak appears. After cooling, it is neutralized to neutral with sodium hydroxide solution, and the water is removed by vacuum distillation to obtain crude product. It is further purified by recrystallization with ethanol / water mixed solvent or by silica gel-ethyl acetate / petroleum ether column chromatography to obtain high-purity limonene diol.

[0052] Before proceeding with equipment preparation, the equipment includes a 100-liter glass-lined reactor with a working pressure of 0.4 MPa, a tubular condenser with a heat transfer area of ​​2 square meters and made of stainless steel, a vacuum distillation system with a vacuum degree of ≤10 mmHg, a centrifuge with a drum diameter of 450 mm, a 200-liter stainless steel jacketed tank, and a recrystallization tank with temperature control and stirring functions.

[0053] Epoxidation treatment from limonene to epoxidized limonene:

[0054] 1. Feeding amounts per batch: 25 kg limonene (approximately 183.8 mol, density 0.84 kg / L, volume 29.76 L), 27.1 kg 30% hydrogen peroxide solution (approximately 24.43 L, containing 8.13 kg hydrogen peroxide, 239 mol, molar ratio 1.3:1), 1.875 kg concentrated sulfuric acid (volume 1.02 L, diluted to 25.5 L of dilute sulfuric acid, pH 2~3);

[0055] 2. Operating procedures:

[0056] Equipment preparation: The 100-liter glass-lined reactor is equipped with an anchor-type stirrer with a speed of 50-150 rpm, a temperature sensor, a constant pressure dripping system, a reflux condenser, and a jacketed oil bath temperature control with a temperature control accuracy of ±2℃.

[0057] Reaction process: 25 kg of limonene and 25.5 L of diluted sulfuric acid were added to the reactor, and the mixture was stirred at 100 rpm and heated to 55 ± 5 °C. 27.1 kg of 30% hydrogen peroxide solution was slowly added dropwise at a rate of approximately 0.4 L / min, while maintaining the temperature at ≤60 °C. After the addition was complete, the reaction was maintained at 55 °C for 5 hours. The conversion rate of limonene was monitored by online GC, with a target of >95%.

[0058] Post-processing: Cool to 25°C, add saturated sodium carbonate solution to neutralize to pH 7; allow to stand and separate into layers, separate the organic phase epoxide limonene, wash twice with water until neutral; dry the organic phase with molecular sieve, and then distill under reduced pressure to obtain epoxide limonene with a yield of 90% and a weight of 22.5 kg.

[0059] Hydrolysis treatment of epoxidized limonene to limonene diol:

[0060] 1. Feeding amount per batch: 22.5 kg of epoxidized limonene (148.03 mol, density 0.84 kg / L, volume 26.79 L), 26.65 kg of deionized water (volume 26.65 L, molar ratio 10:1), and 1.125 kg of concentrated sulfuric acid (volume 0.61 L, diluted to 12.2 L of dilute sulfuric acid, concentration 5%).

[0061] 2. Operating procedures:

[0062] Using the same 100-liter reactor, switch to atmospheric pressure stirring mode, mix 22.5 kg of epoxidized limonene with 12.2 liters of dilute sulfuric acid, and add 26.65 kg of deionized water; heat to 75±5℃, stir and react for 3 hours, monitor the disappearance of epoxy groups by TLC, and use ethyl acetate / petroleum ether as the developing solvent: 1:3;

[0063] Then, post-processing was performed, cooling to 30°C, and neutralizing to pH 7 with 10% sodium hydroxide solution; the product was concentrated under reduced pressure at 60°C / 20 mmHg to remove water, yielding a crude product; the crude product was recrystallized from ethanol / water (1:1) to obtain white crystalline limonene diol with a yield of 85% and a final yield of 21.6 kg, with a total yield of 76.5% (based on limonene), and a single batch capacity of 21.6 kg of limonene diol.

[0064] Example 3, Preparation of ozonated plant fatty acid methyl ester nanoliposome powder:

[0065] The preparation of ozonated plant fatty acid methyl ester nanoliposome powder includes: ozonating plant fatty acid methyl esters to obtain ozonated plant fatty acid methyl esters, then mixing them with phospholipids and cholesterol in a mass ratio of 3:2:1, followed by film formation, hydration, ultrasonication, homogenization, and freeze-drying. The specific preparation process is as follows:

[0066] Preparation of ozonated plant fatty acid methyl esters:

[0067] Raw material preparation: Select highly unsaturated vegetable oils, such as soybean oil, sunflower oil, and flaxseed oil, as they contain more double bonds such as linoleic acid and methyl linolenic acid, which are beneficial for subsequent ozone addition; react the vegetable oils with methanol in an alkaline catalyst, with a molar ratio of vegetable oil to methanol of 1:6~10. The alkaline catalyst can be NaOH or KOH, with a dosage of 0.5%~1.5% w / w, and the reaction temperature is 60~70℃ for 1~2 hours; separate the glycerol byproduct, wash to remove residual catalyst, and dry to obtain high-purity fatty acid methyl ester (FAME).

[0068] Ozone oxidation reaction: Ozone is prepared by corona discharge or ultraviolet photolysis at a concentration of 5-10% w / w, or qualified ozone cylinders can be purchased directly. The reactor is made of glass or corrosion-resistant material, such as PTFE or 316 stainless steel, and is equipped with a gas distributor, cooling jacket, stirrer, and tail gas treatment device. Fatty acid methyl ester is added to the reactor and pre-cooled to 0-5°C to reduce side reactions. The reaction liquid is introduced at a constant flow rate of 0.1-0.5 L / min, and then an ozone-oxygen mixture is introduced. The reaction time is 2-6 hours (adjusted according to the double bond content). The consumption of double bonds is monitored by iodometric method or online infrared method. Vigorous stirring is maintained to ensure sufficient gas-liquid contact. The stirring speed can be 500-1000 rpm. Ozone undergoes 1,3-dipolar cycloaddition with the double bond to generate an ozonooxide intermediate, which then decomposes into peroxides or undergoes further rearrangement.

[0069] Post-treatment and purification: After stopping ozone flow, continue stirring for 30 minutes to deplete residual ozone. Purge with nitrogen or inert gas to remove unreacted ozone. Add reducing agents such as sodium bisulfite or sodium thiosulfate to decompose residual peroxides and prevent oxidative degradation during storage. Wash with water to remove water-soluble impurities, and take the organic phase after separation. Add anhydrous sodium sulfate or molecular sieves for dehydration and drying, and then remove low-boiling-point impurities by vacuum distillation at a temperature <80℃ and a vacuum degree <10 mmHg.

[0070] Key indicators include peroxide value (POV) controlled between 100 and 500 meq / kg, significant reduction in iodine value after ozonation, and acid value below 1 mg potassium hydroxide / g. Once these indicators are met, the ozonated vegetable fatty acid methyl ester is considered to meet the requirements.

[0071] Preparation of nanoliposome powder:

[0072] Formula optimization: The lipid mass ratio is ozonated vegetable fatty acid methyl ester: phospholipid: cholesterol = 3:2:1, and 0.1%-0.5% of Tween 80 is added at 5%-10% of the total lipid mass to prevent aggregation;

[0073] Preparation steps: Ozone-oxidized plant fatty acid methyl esters, phospholipids, and cholesterol were dissolved in a chloroform-ethanol (2:1, v / v) mixture and vortexed until completely dissolved. The solvent was removed using a rotary evaporator at 40°C under reduced pressure to form a uniform lipid film. The film was then vacuum-dried for at least 2 hours to remove residual solvent. Preheated PBS buffer (containing 0.3% Tween 80) to 55°C was added, and the mixture was vortexed for 30 minutes to form multilayer liposomes (MLVs). The solution was sonicated under ice bath until clear. The mixture was cycled 3-5 times to further reduce the particle size to 100-200 nm. Unencapsulated material was removed by ultracentrifugation or dialysis (MWCO 10 kDa, 24 hours).

[0074] Powder preparation (lyophilization method): Add a lyophilization protectant, such as 5%-10% (w / v) mannitol, trehalose, or sucrose (trehalose preferred), or 2%-5% glycerol, to the aqueous phase of the liposome suspension. This prevents ice crystal formation from damaging the liposome membrane and maintains the porous structure after lyophilization. Dispense the liposome suspension into lyophilization bottles and rapidly freeze them in a -80°C freezer or liquid nitrogen to avoid slow freezing which could cause large ice crystals to damage the liposomes. Pre-cool the freeze dryer to -50°C, evacuate to 0.1-0.01 mbar, and slowly raise the temperature to -30°C, maintaining this temperature for 12-24 hours as the primary drying and sublimation stage, allowing the ice crystals to sublimate and remove free water. Then raise the temperature to 20-25°C and maintain a vacuum of 0.001-0.01 mbar for 6-12 hours as the secondary drying and desorption stage, removing bound water. The endpoint is determined when the sample temperature matches the shelf temperature or when there is no significant change in pressure.

[0075] The acid value of ozonated vegetable fatty acid methyl esters is less than 1 mg potassium hydroxide / g, and the iodine value after ozonation is lower than that of the raw material.

[0076] Before proceeding, prepare the following equipment: a 1000-liter glass-lined reactor, a horizontal centrifuge, a 500-liter glass-lined reactor, an ozone generator, a rotary evaporator, a high-pressure homogenizer, and a freeze dryer.

[0077] Preparation of plant fatty acid methyl esters (FAME):

[0078] 1. Single batch feed amount: 125 kg soybean oil, 453.75 kg methanol (molar ratio 8:1), 1.25 kg potassium hydroxide catalyst (1% w / w);

[0079] 2. Operating steps:

[0080] Add 125 kg of soybean oil to the reactor and start stirring at 200 rpm; slowly add 453.75 kg of methanol, keeping the temperature ≤40℃ with jacket cooling water circulation; add 1.25 kg of potassium hydroxide in batches to avoid local overheating;

[0081] Heat to 65±5℃, increase stirring speed to 400 rpm, and react for 2 hours; endpoint detection: take a sample of the reaction solution and let it stand to separate into layers. If the lower glycerol phase has a stable volume of about 10% of the total volume, the reaction is considered complete.

[0082] The reaction solution was transferred to a horizontal centrifuge and centrifuged at 3000 rpm for 30 minutes to separate the glycerol byproduct. The crude FAME was washed three times with deionized water, each time with 20% of the crude product volume, until the pH was neutral. 5 kg of anhydrous sodium sulfate was added, and the mixture was stirred for 30 minutes to dehydrate. After filtration, purified FAME with a purity ≥98% was obtained.

[0083] Preparation of FAME by ozonation:

[0084] 1. Single batch feed amount: 119 kg of FAME, ozone-oxygen mixture concentration of 8% w / w, flow rate of 0.3 L / (min·L of reaction liquid);

[0085] 2. Operating steps:

[0086] Add 119 kg of FAME to the reactor, start the jacketed cooling system to circulate ethylene glycol, and cool down to 0-5°C; start high-speed stirring at 1000 rpm to ensure uniform liquid flow;

[0087] Ozone introduction: Start the ozone generator, set the ozone concentration to 8% w / w, and the gas flow rate to 0.3 L / (min·L of reaction liquid); continue to introduce ozone for 4 hours, and monitor the double bond consumption rate online with infrared technology to ensure the target: iodine value reduction ≥90%; then perform exhaust gas treatment, the reaction exhaust gas is processed by the catalytic decomposition unit containing... Catalyst converted to Rear exhaust;

[0088] Post-treatment: Stop ozone supply, continue stirring for 30 minutes, purge with nitrogen for 10 minutes to remove residual ozone; add 50 liters of 10% sodium bisulfite solution (1:2 volume ratio with FAME), stir for 1 hour to decompose peroxides; wash with water until free of ozone. The residue was negative in the starch-potassium iodide test paper. After separation, the organic phase was taken. Low-boiling substances were removed by vacuum distillation, and the peroxide value of ozonated FAME was 300±50 meq / kg.

[0089] Preparation of nanoliposome powder

[0090] 1. Single batch feed amount: ozonated FAME 107.14 kg, soybean lecithin 71.43 kg, cholesterol 35.71 kg, Tween 80 10.71 kg, trehalose (lyophilization protectant) 25 kg;

[0091] 2. Operating steps:

[0092] Ozoned FAME, phospholipids, and cholesterol were added to a chloroform-ethanol (2:1 v / v) mixed solvent in a ratio of 3:2:1, totaling 500 liters. The mixture was vortexed until completely dissolved, then transferred to a rotary evaporator and evaporated under reduced pressure at 40°C until a uniform lipid film was formed with a vacuum degree of <10 mbar.

[0093] Hydration and particle size control: PBS buffer (preheated to 55°C with 0.3% Tween 8) was added to the membrane, with a total volume of 625 L; high-speed shear pre-dispersion for 10 minutes to form multilayer liposomes (MLVs); high-pressure homogenizer was used for 5 cycles to control the particle size at 100~200 nm, with real-time monitoring by DLS;

[0094] Preparation of lyophilized powder: Add 25 kg of trehalose to the liposome suspension, stir to dissolve, and then pre-freeze: flash freeze in liquid nitrogen to -80℃ and maintain for 4 hours to form a glassy state; lyophilization program: primary drying (-50℃→-30℃, 24 hours, vacuum degree 0.01 mbar), secondary drying (25℃, 24 hours, vacuum degree 0.001 mbar); reconstitution test: after reconstitution, the particle size PDI < 0.25, moisture ≤ 3%, and encapsulation rate ≥ 90%.

[0095] Example 4, Preparation of sulfonated oleylarginine ethyl ester hydrochloride:

[0096] Sulfonated oleylarginine ethyl ester hydrochloride is prepared by reacting oleylarginine ethyl ester hydrochloride with sodium bisulfite at a molar ratio of 1:1.2 under conditions of pH 5.0-6.0 and temperature 50-70℃ for 6-12 hours. The preparation method is as follows:

[0097] Dissolve oleoylarginine ethyl ester hydrochloride in water or a water / ethanol (1:1) mixture and stir until completely dissolved. Slowly add sodium bisulfite, a sulfonating agent, at a molar ratio of 1.2 equivalents and stir until homogeneous. Adjust the pH of the reaction solution to 5.0-6.0 with dilute hydrochloric acid to maintain a weakly acidic environment and prevent ester hydrolysis. Then heat to 58-62℃ and stir at a constant temperature for at least 8 hours. Monitor the reaction progress by detecting double bond conversion using TLC or HPLC. Cool to room temperature and adjust the pH to neutral (7.0) with sodium hydroxide solution to prevent sulfonic acid matrix protonation. Remove excess sulfite by dialysis or ion exchange resin. Remove the solvent by vacuum distillation and vacuum dry to obtain the crude product. Recrystallize with ethanol or purify by column chromatography to obtain an amphoteric surfactant with both anionic and cationic properties.

[0098] Equipment preparation before preparation includes a 2000-liter jacketed heating main reaction vessel and an acid and alkali resistant glass-lined reactor; an anchor-type stirring system with a speed of 0-200 rpm to ensure uniform mixing of materials; an online pH monitor that can monitor the pH of the reaction solution in real time; a stainless steel plate condenser with a heat exchange area of ​​5 square meters and solvent reflux control; a 1000-liter vacuum drying oven with a vacuum degree of ≤-0.1 MPa that can recover solvent and dry the product; a horizontal centrifuge capable of separating and purifying the product; and an ion exchange column with a diameter of 30 cm and a height of 2 meters capable of removing excess sulfite.

[0099] Raw material preparation before preparation: 220 kg of oleoylarginine ethyl hydrochloride with a purity ≥98% and containing a cis-9-octadecene structure; 52 kg of sodium bisulfite with a purity ≥99%, which is 1.2 equivalents required for the reaction; 600 L of deionized water with a conductivity ≤5 μS / cm as the main solvent for the reaction; 200 L of anhydrous ethanol with a purity ≥99.7%, which is used as a co-solvent and mixed with deionized water at a volume ratio of 3:1; at the same time, appropriate amounts of industrial-grade 1M dilute hydrochloric acid and industrial-grade 1M sodium hydroxide solution are prepared to adjust the pH value of the reaction system and the subsequent neutralization process, respectively.

[0100] Preparation process:

[0101] 1. Pretreatment and feeding: Solvent preparation: Add 600 liters of deionized water and 200 liters of ethanol to the reactor and start stirring; Dissolve the main raw material: Slowly add 220 kg of oleoyl arginine ethyl ester hydrochloride and heat to 40℃ to accelerate dissolution for about 1 hour;

[0102] 2. Sulfonation reaction: Add 52 kg of sodium bisulfite in batches to the reaction vessel, 10 kg every 10 minutes, to avoid excessive local concentration; pH adjustment: Adjust the pH to 5.5 ± 0.2 with 1M dilute hydrochloric acid, with a control accuracy of ± 0.1; Heating reaction: Increase the temperature to 60℃ at 2℃ / min, stir at a constant temperature for 8 hours, and reflux to prevent solvent evaporation;

[0103] 3. Reaction monitoring: TLC detection: take samples every 2 hours, develop solvent: chloroform: methanol = 8:2, and observe the change in Rf value when double bonds disappear under UV light; HPLC assistance: if the conversion rate is <95%, extend the reaction time to 12 hours;

[0104] 4. Post-treatment: Neutralization: Cool to 30℃, add 1M NaOH solution dropwise to pH 7.0 to form sodium salt; Purification: Ion exchange: Pass the reaction solution through anion exchange resin at a flow rate of 10 L / min to remove unreacted sulfite; Concentration: Distill under reduced pressure at 60℃ and -0.08 MPa to 1 / 3 of the original volume; Drying: Spray dry at inlet temperature 180℃ and outlet temperature 80℃ to obtain a white powder;

[0105] 5. Quality inspection: Sulfonic acid group content: detected by ion chromatography, with the standard of ≥95% conversion rate; surface tension: measured by platinum plate method, ≤30 mN / m is qualified.

[0106] Example 5, Preparation of the finished product of a green and efficient dry cleaner for down jackets:

[0107] A preparation method of a green and efficient dry cleaner for down jackets, comprising the following steps:

[0108] S1. Under stirring conditions, batchwise sprinkle sulfonated ethyl oleoyl arginine hydrochloride into the plant-derived isoparaffin, and heat up to 45 - 50 °C and stir for at least 2 hours until transparent;

[0109] S2. Add limonene diol and continue to stir for at least 1 hour until transparent;

[0110] S3. Cool down to below 38 °C, batchwise sprinkle natural camphor and stir evenly;

[0111] S4. Start the high-speed homogenizer and homogenize at a speed of 12,000 revolutions per minute for at least 10 minutes;

[0112] S5. Reduce the speed to 1,000 revolutions per minute, batchwise add the ozone-oxidized plant fatty acid methyl ester nanoliposome powder, and stir for at least 1 hour until a stable homogeneous state.

[0113] The dry cleaner in the stable homogeneous state does not stratify or gelify after standing for more than 200 days.

[0114] The single-batch feeding formula and related remarks for preparing the green and efficient dry cleaner for down jackets in this example are as follows: 55.0 kg of plant-derived isoparaffin, which can be the product prepared in Example 1 or commercially available C8 - C12 volatile plant-derived isoparaffin; 6.5 kg of limonene diol, which is the synthetic product of Example 2; 8.0 kg of ozone-oxidized plant fatty acid methyl ester nanoliposome powder, which is the synthetic product of Example 3; 2.5 kg of sulfonated ethyl oleoyl arginine hydrochloride, which is the synthetic product of Example 4; 9.0 kg of natural camphor, which is a commercially available product. The total feeding amount of the above raw materials is 81.0 kg. If the total feeding amount is less than 100 kg, just add plant-derived isoparaffin to the target feeding amount.

[0115] Procedure: Add 55.0 kg of plant-derived isoalkanes to a 200 L stirred stainless steel reactor. Start stirring at 500 rpm. Gradually add 2.5 kg of sulfonated oleyl arginine ethyl ester hydrochloride, controlling the addition speed to prevent clumping. Then heat to 45–50 °C and maintain stirring for 3 hours until the system is transparent and free of particles. Maintain the temperature at 45–50 °C and slowly add 6.5 kg of limonene diol, continuing stirring for 1 hour. Observe until the solution is completely transparent, then cool it with a jacketed water cooler. The temperature was circulated and cooled to below 38°C. 9.0 kg of natural camphor was added in five batches and stirred for 30 minutes until completely dissolved. A high-speed homogenizer was started, and the speed was adjusted to 12,000 rpm. Homogenization was carried out for 10 minutes until the system was nearly transparent. The speed was then reduced to 1,000 rpm. 8.0 kg of nano-liposome powder was slowly added in batches to avoid dust. The mixture was stirred for 1 hour until the system was stable and homogeneous, without stratification or precipitation. Finally, the mixture was filtered through a 200-mesh filter, filled into spray bottles, and labeled and sealed.

[0116] Performance testing

[0117] Test material: A 10cm x 10cm cut piece of a regular down jacket, with a white nylon outer layer and duck down lining;

[0118] Treatment method: Apply a mixture of soy sauce, soybean oil, and fruit juice in a mass ratio of 0.1:0.05:1 evenly to the surface of a cut piece of down jacket, with a coating size of 2 cm × 2 cm. Allow it to air dry for 8 hours. Then, clean it with the dry cleaning agent of this invention. Specifically, spray the agent directly onto the stain, wait 3-5 seconds, then spread the dry cleaning agent evenly with a wet wipe until it covers the stain. After 6-8 seconds, wipe off any excess dry cleaning agent with a wet wipe.

[0119] Evaluation 1, Stain Removal Power Test Method: Whiteness test according to AATCC Test Method 110-2005 standard, using a whiteness meter to measure the whiteness of the down jacket cut surface. The stain removal efficiency is (whiteness after stain removal - whiteness before stain removal) / (original whiteness - whiteness before stain removal) × 100%. Test results show that the high-efficiency down jacket dry cleaning agent prepared in Example 5 of this invention is uniform and stable, does not separate or gel after standing for more than 200 days, and the stain removal efficiency can reach 99.7%.

[0120] Evaluation 2, Anti-mold effect test method: The cleaned down jacket was cut into pieces and placed in an environment with 80% relative humidity and 35°C. After 7 days, the surface of the pieces, especially the original stains, was checked for mold spots. If no mold spots appeared, the anti-mold effect was very good. If 1 to 2 spots appeared, it was better. If 3 or more spots appeared, it was average. The test results showed that the high-efficiency down jacket dry cleaning agent prepared in Example 5 of this invention had a very good anti-mold effect.

[0121] Evaluation 3, Softness and Loft Testing Method: An evaluation team of five or more people conducts a touch assessment, with 5 being the best and 1 the worst. First, the down jackets that have been cleaned and naturally dried for 2 hours are cut into pieces and placed together for initial selection. The worst ones are excluded and rated as 1. After the initial selection, another round of selection is conducted and rated as 2. The remaining down jackets are ranked in order of feel to obtain 3 to 5 levels. Finally, the average value is calculated. The test results show that the high-efficiency down jacket dry cleaning agent prepared in Example 5 of this invention can achieve a softness level of 4.8 and a loft level of 4.9.

[0122] Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A green and efficient dry cleaning agent for down jackets, characterized in that, It is composed of the following raw materials in parts by weight: 50-60 parts of plant-derived isoalkanes, 5-8 parts of limonene glycol, 5-10 parts of ozonated plant fatty acid methyl ester nanoliposome powder, 2-3 parts of sulfonated oleyl arginine ethyl ester hydrochloride, and 8-10 parts of natural camphor.

2. The green and efficient dry cleaning agent for down jackets according to claim 1, characterized in that, The plant-derived isoalkanes are obtained by acidification of plant fatty acids obtained from the byproduct of edible vegetable oil refining, soapstock, followed by methanol esterification, vacuum distillation, hydrogenation deoxygenation, isomerization, product separation and refining. The plant-derived isoalkanes are volatile isoalkanes ranging from C8 to C12.

3. The green and efficient dry cleaning agent for down jackets according to claim 2, characterized in that, The hydrodeoxygenation reaction conditions are a temperature of 250-400℃, a pressure of 3-10 MPa, and a hydrogen-to-oil volume ratio of 500-1000:

1. The catalyst is a nickel-molybdenum, cobalt-molybdenum, or platinum / palladium noble metal supported on a γ-alumina or silica support. The isomerization reaction conditions are a temperature of 200-350℃ and a pressure of 2-5 MPa. The catalyst is a ZSM-5 type zeolite molecular sieve, a SAPO-11 type silica-alumina molecular sieve, a Beta type zeolite molecular sieve, or a platinum / ZSM-5 type zeolite bifunctional catalyst.

4. The green and efficient dry cleaning agent for down jackets according to claim 1, characterized in that, The limonene diol is prepared by epoxidation of limonene and hydrogen peroxide under acidic conditions to generate epoxidized limonene, followed by hydrolysis. The molar ratio of the epoxidation reaction is limonene: 30% hydrogen peroxide: acidic catalyst = 1: 1.2~1.5: 0.05~0.1, and the molar ratio of the hydrolysis reaction is epoxidized limonene: water: acidic catalyst = 1: 10~15: 0.05~0.

1.

5. The green and efficient dry cleaning agent for down jackets according to claim 1, characterized in that, The preparation of the ozonated plant fatty acid methyl ester nanoliposome powder includes: ozonated plant fatty acid methyl ester is obtained by ozonation reaction of plant fatty acid methyl ester, and then mixed with phospholipids and cholesterol in a mass ratio of 3:2:1, followed by film formation, hydration, ultrasound, homogenization and freeze drying.

6. The green and efficient dry cleaning agent for down jackets according to claim 5, characterized in that, The acid value of the ozonated plant fatty acid methyl ester is less than 1 mg potassium hydroxide / g, and the iodine value after ozonation is lower than that of the raw material.

7. The green and efficient dry cleaning agent for down jackets according to claim 1, characterized in that, The sulfonated oleylarginine ethyl ester hydrochloride is prepared by reacting oleylarginine ethyl ester hydrochloride with sodium bisulfite at a molar ratio of 1:1.2 under conditions of pH 5.0-6.0 and temperature 50-70℃ for 6-12 hours.

8. The green and efficient dry cleaning agent for down jackets according to claim 1, characterized in that, The natural camphor is a commercially available product with a sublimation pressure of 1.33 kPa at 25°C, and forms a eutectic system with limonene glycol.

9. A method for preparing a green and efficient dry cleaning agent for down jackets according to any one of claims 1-8, characterized in that, The process includes the following steps: Under stirring conditions, sulfonated oleyl arginine ethyl ester hydrochloride is added in batches to plant-derived isoalkanes, and the mixture is heated to 45-50°C and stirred for at least 2 hours until transparent; limonene diol is added, and stirring is continued for at least 1 hour until transparent; the mixture is cooled to below 38°C, and natural camphor is added in batches and stirred evenly; a high-speed homogenizer is started and homogenized at 12,000 rpm for at least 10 minutes; the speed is reduced to 1,000 rpm, and ozonated plant fatty acid methyl ester nanoliposome powder is added in batches and stirred for at least 1 hour until a stable homogenized state is achieved.

10. The preparation method according to claim 9, characterized in that, The stable and homogeneous dry cleaning agent does not separate or gel after standing for more than 200 days.