Hydrophobic modified dispersant and preparation method thereof, high-efficiency detergent composition containing hydrophobic modified dispersant and preparation method and application of high-efficiency detergent composition

Abstract

The invention provides a hydrophobic modified dispersant containing unsaturated fatty acid, a preparation method of the hydrophobic modified dispersant, an efficient detergent composition containing the hydrophobic modified dispersant, and a preparation method and application of the efficient detergent composition. The hydrophobic modified dispersant containing unsaturated fatty acid in the composition is modified by grafting a long-carbon-chain unsaturated fatty acid chain to a traditional dispersant chain segment, and meanwhile, a shorter saturated fatty acid chain is added to prepare a core-shell structure, so that the unsaturated fatty acid chain is in a micelle, and is not easy to oxidize and discolor in a storage process. In the cleaning process, unsaturated fatty acid chains in the dispersing agent are released from micelles and combined with unsaturated fatty acid in human body sweat stains on fabric, the sebum removal capacity of a system can be effectively improved, the dispersing agent and a surface active agent in the system can achieve synergistic decontamination, and the usage amount can be reduced under the condition that the same decontamination effect is achieved.

Description

Technical Field

[0001] This invention belongs to the field of civilian or industrial detergent technology, and specifically relates to a high-efficiency detergent composition containing an unsaturated fatty acid hydrophobic modified dispersant, its preparation method, and its application. Background Technology

[0002] Acrylic dispersants are a common type of dispersant used in detergents. Traditional dispersants mainly function to change the interfacial tension of dirt on fabrics, making it easier to remove. They can also effectively disperse stains in the washing liquid, preventing them from redepositing on clothing. In addition, they can chelate metal ions in water, making them less likely to combine with detergent and deposit on fabrics.

[0003] As people's living standards improve, their demands for detergents are also increasing. However, problems such as clothes yellowing after repeated washing still exist. The main factors contributing to yellowing include human sweat stains, staining from dark-colored clothing, poor water quality leading to metal ion deposition, and microbial growth. Human sweat stains are one of the more difficult problems to solve. Because the human body mainly secretes unsaturated fatty acid esters, which are easily oxidized and turn yellow, conventional detergents primarily use products with saturated fatty acid esters at their hydrophobic ends. Therefore, these products have limited effectiveness in removing human sebum, making it difficult to resolve the yellowing problem caused by sweat stains.

[0004] Chinese patent CN101407750B discloses an oligomeric dirt dispersant, which is a condensation product of formaldehyde and one or more aryl sulfonates. When this dispersant is applied to laundry detergent, it can work synergistically with surfactants to remove dirt, especially effectively suspending oily dirt. It is also compatible with various liquid laundry detergents. However, its hydrophobically modified monomer does not contain unsaturated fatty acid segments, so its synergistic removal ability for human sebum dirt is limited.

[0005] Chinese patent CN1173024C discloses a laundry composition containing an alkoxylated polyalkylene imide dispersant, mainly to improve the compatibility between the dispersant and the bleach, so that the dispersant and the bleach will not consume each other and affect the bleaching performance. It does not mention the improvement of the system's final degreasing ability. The final improvement in the stain removal effect on the fabric mainly depends on the role of the bleach.

[0006] Chinese patent CN1224453A discloses a detergent composition containing specific lipase and calcium soap dispersant. This composition can improve the overall washing performance of the system, reduce the redeposition of grease / oily substances on fabrics, tableware and hard surfaces, thereby improving whiteness retention, etc. The main improving effect is the added lipase and dispersant composition. However, the lipase is relatively easy to be deactivated in the system and lose its actual degreasing effect.

[0007] In response to the problems existing in detergents on the market, there is a need to provide a high-efficiency detergent composition that can effectively enhance the degreasing ability of the system during the washing process, and can also work synergistically with surfactants in the system to remove dirt, achieving the same cleaning effect while reducing the amount of surfactant used. Summary of the Invention

[0008] One objective of this invention is to provide a hydrophobically modified dispersant containing unsaturated fatty acids and its preparation method. This method modifies traditional dispersants by incorporating long carbon chains of unsaturated fatty acids into the dispersant chain segments, while simultaneously adding shorter saturated fatty acid chains to create a core-shell structure. This makes the unsaturated fatty acid segments more easily aggregate within the micelles, reducing their susceptibility to oxidation and discoloration during storage. During the washing process, the unsaturated fatty acid chains of the dispersant in this invention are released from within the micelles and combine with the unsaturated fatty acids in human sweat stains on the fabric. This effectively enhances the system's degreasing ability and can also synergistically work with surfactants in the system to remove dirt, achieving the same cleaning effect while reducing the amount of surfactant required.

[0009] Another object of the present invention is to provide a highly efficient detergent composition containing such a hydrophobically modified dispersant containing unsaturated fatty acids, a method for preparing the composition, and its application.

[0010] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0011] A hydrophobically modified dispersant containing unsaturated fatty acids has a core-shell structure consisting of an inner layer containing unsaturated fatty acids and an outer layer containing saturated fatty acids and a hydrophobically modified dispersant.

[0012] Preferably, the molecular weight of the hydrophobic modified dispersant containing unsaturated fatty acids is 500-5000, such as 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, etc., and more preferably 1000-3000.

[0013] On the other hand, the aforementioned method for preparing a hydrophobically modified dispersant containing unsaturated fatty acids involves reacting raw materials comprising an inner layer component and an outer layer component with a free radical initiator: wherein...

[0014] a) The inner layer components, based on their total mass, comprise:

[0015] a1) 20-60%, for example, 20%, 30%, 40%, 50% or 60%, of at least one C18-C22 unsaturated carboxylic acid containing two or more carbon-carbon unsaturated double bonds, wherein at least one of them is a polymerizable carbon-carbon double bond and a carboxyl group;

[0016] a2) 40-80%, for example, 40%, 50%, 60%, 70% or 80%, of at least one functional monomer containing a polymerizable carbon-carbon double bond;

[0017] b) The outer layer components, based on the total mass of the outer layer components, comprise:

[0018] b1) 50-80%, for example, 50%, 60%, 70% or 80%, of at least one C12-C16 unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and wherein at least one polymerizable carbon-carbon double bond and a carboxyl group;

[0019] b2) 20-50%, for example, 20%, 30%, 40%, 50%, of at least one functional monomer containing a polymerizable carbon-carbon double bond;

[0020] The inner layer component accounts for 20-40% of the total mass of the inner and outer layers, for example, 20%, 30%, 40%, etc., and the outer layer component accounts for 60-80% of the total mass, for example, 60%, 70%, 80%, etc.

[0021] In some specific embodiments, the hydrophobically modified dispersant containing unsaturated fatty acids is obtained by reacting raw materials comprising the following inner and outer layer components with a free radical initiator, wherein the free radical initiator accounts for 0.1-1% of the total monomer mass, for example 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, and the specific inner and outer layer components are as follows:

[0022] a) The inner layer component is obtained by a reaction system containing a second solvent and comprising the following reaction components, initiated by a free radical initiator;

[0023] a1) Based on the total mass of the inner layer components, 20-60% (e.g., 20%, 30%, 40%, 50% or 60%) of at least one C18-C22 unsaturated carboxylic acid containing two or more carbon-carbon unsaturated double bonds, wherein at least one of the carbon-carbon double bonds is polymerizable and a carboxyl group;

[0024] a2) Based on the total mass of the inner layer components, 40-80%, for example 40%, 50%, 60%, 70%, 80%, of at least one functional monomer containing a polymerizable carbon-carbon double bond;

[0025] b) The outer layer component, which is obtained by reacting a system containing a first solvent and comprising the following components:

[0026] b1) Based on the total mass of the outer layer components, 50-80%, for example 50%, 60%, 70%, 80%, of at least one C12-C16 unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and wherein at least one polymerizable carbon-carbon double bond and a carboxyl group;

[0027] b2) Based on the total mass of the outer layer components, 20-50%, for example 20%, 30%, 40%, 50%, of at least one functional monomer containing a polymerizable carbon-carbon double bond;

[0028] Wherein, based on the total mass of the product, the mass fraction of the inner layer component is 20-40%, for example 20%, 30%, or 40%, and the mass fraction of the outer layer component is 60-80%, for example 60%, 70%, or 80%.

[0029] In a preferred embodiment, the method for preparing the hydrophobically modified dispersant containing unsaturated fatty acids includes the following steps:

[0030] 1) Add the reaction components for preparing the inner layer to the second solvent in proportion and mix;

[0031] 2) Heat the reaction system obtained in step 1) to 50-80℃, add the free radical initiator, and carry out the polymerization reaction to obtain the inner layer component;

[0032] 3) In the first solvent, the free radical initiator and the outer layer component are mixed with the inner layer component obtained in step 2) at 50-80°C to carry out a polymerization reaction. After the reaction, the mixture is cooled to obtain the hydrophobic modified dispersant containing unsaturated fatty acids.

[0033] In some specific embodiments, the C18-C22 unsaturated carboxylic acid containing two or more carbon-carbon unsaturated double bonds, of which at least one is polymerizable, and a carboxyl group, as described in component a1, is selected from one or more of linoleic acid, linolenic acid, octadecanoic acid, nonadecanodienoic acid, eicosadienoic acid, eicostrienoic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid, docosahexaenoic acid (DHA), docosahexaenoic acid, docosatrienoic acid, docosatraenoic acid, and docosapentaenoic acid (DPA), preferably one or a combination of two of linoleic acid, linolenic acid, or arachidonic acid.

[0034] In some specific embodiments, the functional monomer containing a polymerizable carbon-carbon double bond described in component a2 is selected from one or more of maleic acid, maleic anhydride, itaconic acid, itacate, crotonic acid, crotonate, medaconic acid, medacate, acrylic acid, acrylate, methacrylic acid, methacrylate, fumaric acid, fumarate, citraconic acid, citracate, aconitic acid, or aconitate, preferably one or a combination of two of acrylic acid or methacrylic acid.

[0035] In some specific embodiments, the C12-C16 unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and at least one polymerizable carbon-carbon double bond and a carboxyl group described in component b1 is selected from one or more of 2-dodecenoic acid, 11-dodecenoic acid, 2-tridecenoic acid, 2-tetradecenoic acid, myristenoic acid, pentadecenoic acid, and hexadecenoic acid, preferably one or a combination of two of myristenoic acid, 2-tetradecenoic acid, or hexadecenoic acid.

[0036] In some specific implementations, the functional monomeric acid containing polymerizable carbon-carbon double bonds described in component b2 is preferably one or more of maleic acid, maleic anhydride, itaconic acid, itacate, crotonic acid, crotonate, medaconic acid, medacate, acrylic acid, acrylate, methacrylic acid, methacrylate, fumaric acid, fumarate, citraconic acid, citracate, aconitic acid, or aconitate, preferably one or a combination of two of acrylic acid or methacrylic acid.

[0037] In some specific embodiments, the free radical initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, dodecyl peroxide, ammonium persulfate, sodium persulfate, or hydrogen peroxide, preferably ammonium persulfate.

[0038] In another aspect of the present invention, a high-efficiency detergent composition comprises the following components:

[0039]

[0040] The hydrophobic dispersant containing unsaturated fatty acids is either the aforementioned hydrophobic dispersant containing unsaturated fatty acids or the hydrophobic dispersant containing unsaturated fatty acids prepared by the aforementioned method.

[0041] In a preferred embodiment, the high-efficiency detergent composition is in liquid form, wherein the mass percentage of component 1) containing an unsaturated fatty acid hydrophobic modified dispersant is preferably 2-8%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, etc., based on the total mass of the composition.

[0042] In some specific embodiments, the surfactant is selected from anionic, nonionic, amphoteric, and cationic surfactants and combinations thereof, specifically from one or more of sodium alkylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, isomeric alcohol ethers, capped polyethers, sodium α-alkenyl sulfonate, sodium fatty acid methyl ester sulfonate, fatty alcohol polyoxyethylene ether, sodium fatty alcohol ether carboxylate, isomeric C10 ethoxylates, C12-C16 alkyl glycosides, coconut oil fatty acid diethanolamine, fatty acid polyoxyethylene esters, alkylphenol polyoxyethylene ethers, dodecyl dimethyl betaine, lauryl amphoteric propyl sulfonate, rhamnolipid, sophorolipid, carboxylate imidazoline, or ester-based quaternary ammonium salts; preferably, one or more of a combination of sodium dodecylbenzene sulfonate, AEO9, and rhamnolipid.

[0043] In a preferred embodiment, the surfactant content of component 2) is preferably 10-20% by mass, for example, 10%, 15%, 20%, etc., based on the total mass of the composition.

[0044] In some specific implementation schemes, the functional active ingredient is selected from at least one of enzymes, enzyme stabilizers, color-protecting agents, bleaching / color bleaching agents, anti-pilling agents, softening antistatic bactericides, etc.

[0045] The enzyme is selected from at least one of protease, amylase, lipase, cellulase, etc.

[0046] The enzyme stabilizer is selected from any one of calcium cations, borates, polyol solvents, etc.

[0047] The color-protecting agent is selected from at least one of the following: polyurethane color-protecting agents, nonionic fluorocarbons, nonionic hydroquinone epoxy ethers, polyvinylpyrrolidone, polyamine polymers, cationic oxidized starch-derived polymers, polydimethyldiallyl ammonium chloride, and fluorescent whitening agents.

[0048] The bleaching / color bleaching agent is selected from at least one of sodium hypochlorite, hydrogen peroxide, sodium peroxide, benzoyl peroxide, calcium hypochlorite, sodium persulfate, chloroform, etc.

[0049] The anti-pilling agent is selected from at least one of polyvinylpyrrolidone, polyurethane, polyacrylic acid, polyurea and polycarboxylic acid polymers;

[0050] The soft antistatic bactericide is selected from at least one of the following cationic bactericides: dodecyl dimethyl benzyl ammonium chloride (1227), hexadecyl trimethyl ammonium chloride (1631), octadecyl trimethyl ammonium chloride (1831), methyl ditauroyl ethyl-2-hydroxyethyl ammonium sulfate, N-methyl-N-oroxyamidoethyl-2-tauroyl imidazoline methyl sulfate, and cationic guar gum.

[0051] In a preferred embodiment, the functional active ingredient is preferably a combination of a protease and a polyurethane color-protecting agent, and the mass percentage of the functional active ingredient in component 3) is preferably 0.5-1.5% by weight of the total mass of the composition, for example, 0.5%, 1%, 1.5%, etc.

[0052] In some specific embodiments, the aqueous carrier is a composition of water and an additive, wherein the mass percentage of the additive in the aqueous carrier is 1-10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0053] The additives are selected from any one or more of thickeners, pH adjusters, preservatives, fragrances, pigments, or chelating agents.

[0054] Preferably, the thickener is selected from any one or more of associative polyurethane thickeners, xanthan gum, cellulose, polyoxyethylene, polyacrylic acid, gellan gum, guar gum, alginate and its salts, carrageenan and its modified forms, acrylic copolymers, sodium chloride, polyacrylamide, or polyvinylpyrrolidone; preferably sodium chloride.

[0055] The pH adjuster is selected from any one or more of hydrochloric acid, phosphoric acid, citric acid, sodium hydroxide, potassium hydroxide, triethanolamine, aminoethylaminopropyltrimethoxy, or ethylenediamine; preferably citric acid and aminoethylaminopropyltrimethoxy.

[0056] The preservative is selected from any one or more of Kathon, parabens, sodium benzoate, salicylic acid, 1,3-dihydroxymethyl-5,5-dimethylhydantoin, phenoxyethanol, ethylhexylglycerin, or succinate; preferably phenoxyethanol.

[0057] The fragrance is selected from any one or more of artificial and natural fragrances; or it contains no fragrance, preferably no fragrance.

[0058] The pigment is selected from any one or more of water-soluble synthetic pigments and natural pigments; or it may be pigment-free, preferably pigment-free.

[0059] The chelating agent is selected from sodium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid, nitrogen-tritium triacetic acid, nitrogen-tritium triacetic acid, ethylenediaminetetrapropionic acid, sodium ethylenediaminetetrapropionate, preferably one or more of sodium ethylenediaminetetraacetate, sodium citrate, and sodium gluconate, and more preferably sodium ethylenediaminetetraacetate.

[0060] In another aspect of the present invention, the aforementioned method for preparing the high-efficiency detergent composition includes the step of stirring and mixing a liquid composition containing an unsaturated fatty acid hydrophobic modified dispersant, a surfactant, a functional active ingredient, and an aqueous carrier component in a certain proportion until a homogeneous state is obtained.

[0061] In another aspect of the present invention, the application of the aforementioned high-efficiency detergent composition or the high-efficiency detergent composition prepared by the aforementioned method in detergents.

[0062] Compared with the prior art, the present invention has the following beneficial effects:

[0063] 1) The dispersant in the composition of the present invention is prepared by adding long carbon unsaturated fatty acid chains to the chain segments of traditional dispersants and adding shorter saturated fatty acid chains to form a core-shell structure, which makes it easier for the unsaturated fatty acid chain segments to aggregate inside the micelles and be surrounded by saturated fatty acids and hydrophilic groups on the outside, so that it is not easily oxidized and discolored during storage.

[0064] 2) When the composition of the present invention is used, the formulation contains a large amount of surfactant, which can solubilize the dispersant and form more surfactant cavities. It can also encapsulate the dispersant inside the micelles, so that the unsaturated fatty acids therein can be well protected, effectively preventing the formulation from being deactivated.

[0065] 3) During the washing process, the composition of the present invention is diluted with a large amount of water, and the unsaturated fatty acid chains of the dispersant in the present invention can be released from the micelles and combine with the unsaturated fatty acids in human sweat stains on the fabric. This can effectively improve the system's ability to remove sebum and can also work synergistically with the surfactants in the system to remove dirt. When achieving the same dirt removal effect, the amount of surfactant can be reduced.

[0066] 4) The dispersant in the composition of the present invention contains a large number of hydrophilic and hydrophobic groups, so it is well compatible with and penetrates different fabrics, effectively combining with the stubborn unsaturated sebum inside the fabric, avoiding the problem of stubborn sebum remaining on the fabric surface and causing the fabric to yellow or discolor due to microbial growth. Detailed Implementation

[0067] The present invention will be further described below with reference to the embodiments. However, the present invention is not limited to the listed embodiments, but should also include equivalent improvements and modifications of the technical solutions defined in the appended claims of the present invention.

[0068] The main raw materials used in the examples and comparative examples are:

[0069] AA (Acrylic acid, Wanhua Chemical Group Co., Ltd.)

[0070] MAA (Methacrylic Acid, Wanhua Chemical Group Co., Ltd.)

[0071] LA (Linoleic acid, Zhengzhou Yuhe Food Additives Co., Ltd.)

[0072] Alpha-linolenic acid (Chengdu Manster Biotechnology Co., Ltd.)

[0073] Arachidonic acid (Shanghai Yuanye Biotechnology Co., Ltd.)

[0074] Myristenoic acid (Hubei Dahao Chemical Co., Ltd.)

[0075] 2-Tetradecenoic acid (Wuhan Shuer Biotechnology Co., Ltd.)

[0076] 9-Hexadecenoic acid (Wuhan Jiyesheng Chemical Co., Ltd.)

[0077] Propylene glycol (solvent, Dow Chemical Company, USA)

[0078] APS (Ammonium persulfate, Jinan Fengle Chemical Co., Ltd.)

[0079] SDS (Sodium dodecyl sulfate, Shanghai Youyang Industrial Co., Ltd.)

[0080] AEO9 (fatty alcohol polyoxyethylene ether, Wanhua Chemical Group Co., Ltd.)

[0081] RL (Rhamnose glycolipid, Wanhua Chemical Group Co., Ltd.)

[0082] Protease (Novozymes Enzyme Company)

[0083] Polyurethane color-protecting agent (Carfil 9235NP, Wanhua Chemical Group Co., Ltd.)

[0084] Citric acid (pH adjuster, Guangzhou Huazhiwang Chemical Co., Ltd.)

[0085] AMP-95 (pH adjuster, Dow Chemical Company, USA)

[0086] Disodium EDTA (chelating agent, AkzoNobel, USA)

[0087] Phenoxyethanol (preservative, Dow Chemical, USA)

[0088] Sodium chloride (Qingdao Yufengda Fine Chemical Co., Ltd.)

[0089] Preparation of dispersants:

[0090] Acrylic dispersant 1:

[0091] 1) Add 150g of propylene glycol and 150g of water to a 1500ml four-necked flask (reactor 1) equipped with a mechanical stirrer and a nitrogen inlet, mix well, and purge with nitrogen for more than 30 minutes to replace the oxygen content in the system to below 1*10^7mg / L.

[0092] 2) Add 40g of linoleic acid and 160g of acrylic acid to a four-necked flask, mix well, and continuously purge with nitrogen to replace oxygen.

[0093] 3) Raise the reaction temperature to 50°C, add 0.2g of ammonium persulfate to the four-necked flask, and start the polymerization reaction. React for 7 hours until the reaction is complete, then cool to room temperature.

[0094] 4) Add 400g myristic acid, 400g methacrylic acid, 860g water and 580g propylene glycol to a 1000ml three-necked flask (reactor 2), and mix well under a nitrogen atmosphere for later use.

[0095] 5) Add 8g of ammonium persulfate, 100g of water and 60g of propylene glycol to a 250ml three-necked flask (reactor 3), and mix well under a nitrogen atmosphere for later use.

[0096] 6) After raising the temperature of reactor 1 to 80°C, add monomers and initiators from reactors 2 and 3 simultaneously. The metered addition time is 4 hours to start the polymerization reaction. After the addition is completed, keep the temperature for 2 hours until the reaction ends. After cooling, the desired dispersant is obtained.

[0097] Acrylic dispersant 2

[0098] 1) Add 175g of propylene glycol and 350g of water to a 1500ml four-necked flask (reactor 1) equipped with a mechanical stirrer and a nitrogen inlet, mix well, and purge with nitrogen for more than 30 minutes to replace the oxygen content in the system to below 1*10^7mg / L.

[0099] 2) Add 150g of linolenic acid and 150g of acrylic acid to a four-necked flask, mix well, and continuously purge with nitrogen to replace oxygen.

[0100] 3) Raise the reaction temperature to 50°C, add 2.1g of ammonium persulfate to the four-necked flask, and start the polymerization reaction. React for 7 hours until the reaction is complete, then cool to room temperature.

[0101] 4) Add 455g of 2-dodecenoic acid, 245g of methacrylic acid, 552.5g of water and 572.5g of propylene glycol to a 1000ml three-necked flask (reactor 2), and mix well under a nitrogen atmosphere for later use.

[0102] 5) Add 4.9g ammonium persulfate, 60g water and 40g propylene glycol to a 250ml three-necked flask (reactor 3), and mix well under a nitrogen atmosphere for later use;

[0103] 6) After raising the temperature of reactor 1 to 80°C, add monomers and initiators from reactors 2 and 3 simultaneously. The metered addition time is 4 hours to start the polymerization reaction. After the addition is completed, keep the temperature for 2 hours until the reaction ends. After cooling, the desired dispersant is obtained.

[0104] Acrylic dispersant 3

[0105] 1) Add 300g of propylene glycol and 500g of water to a 1500ml four-necked flask (reactor 1) equipped with a mechanical stirrer and a nitrogen inlet, mix well, and purge with nitrogen for more than 30 minutes to replace the oxygen content in the system to below 1*10^7mg / L.

[0106] 2) Add 240g of arachidonic acid and 160g of acrylic acid to a four-necked flask, mix well, and continuously purge with nitrogen to replace oxygen.

[0107] 3) Raise the reaction temperature to 50°C, add 4g of ammonium persulfate to the four-necked flask, start the polymerization reaction, react for 7 hours until the reaction is complete, and then cool to room temperature;

[0108] 4) Add 480g hexadecenoic acid, 120g methacrylic acid, 280g water and 570g propylene glycol to a 1000ml three-necked flask (reactor 2), mix well under a nitrogen atmosphere and set aside.

[0109] 5) Add 0.6g ammonium persulfate, 20g water and 30g propylene glycol to a 250ml three-necked flask (reactor 3), and mix well under a nitrogen atmosphere for later use;

[0110] 6) After raising the temperature of reactor 1 to 80°C, add monomers and initiators from reactors 2 and 3 simultaneously. The metered addition time is 4 hours to start the polymerization reaction. After the addition is completed, keep the temperature for 2 hours until the reaction ends. After cooling, the desired dispersant is obtained.

[0111] Acrylic dispersant 4

[0112] 1) Add 150g of propylene glycol and 150g of water to a 1500ml four-necked flask (reactor 1) equipped with a mechanical stirrer and a nitrogen inlet, mix well, and purge with nitrogen for more than 30 minutes to replace the oxygen content in the system to below 1*10^7mg / L.

[0113] 2) Add 200g of acrylic acid to a four-necked flask, mix well, and continuously purge with nitrogen to replace oxygen;

[0114] 3) Raise the reaction temperature to 50°C, add 0.2g of ammonium persulfate to the four-necked flask, and start the polymerization reaction. React for 7 hours until the reaction is complete, then cool to room temperature.

[0115] 4) Add 400g myristic acid, 400g methacrylic acid, 860g water and 580g propylene glycol to a 1000ml three-necked flask (reactor 2), and mix well under a nitrogen atmosphere for later use.

[0116] 5) Add 8g of ammonium persulfate, 100g of water and 60g of propylene glycol to a 250ml three-necked flask (reactor 3), and mix well under a nitrogen atmosphere for later use.

[0117] 6) After raising the temperature of reactor 1 to 80°C, add monomers and initiators from reactors 2 and 3 simultaneously. The metered addition time is 4 hours to start the polymerization reaction. After the addition is completed, keep the temperature for 2 hours until the reaction ends. After cooling, the desired dispersant is obtained.

[0118] Acrylic dispersant 5

[0119] 1) Add 150g of propylene glycol and 150g of water to a 1500ml four-necked flask (reactor 1) equipped with a mechanical stirrer and a nitrogen inlet, mix well, and purge with nitrogen for more than 30 minutes to replace the oxygen content in the system to below 1*10^7mg / L.

[0120] 2) Add 40g of linoleic acid and 160g of acrylic acid to a four-necked flask, mix well, and continuously purge with nitrogen to replace oxygen.

[0121] 3) Raise the reaction temperature to 50°C, add 0.2g of ammonium persulfate to the four-necked flask, and start the polymerization reaction. React for 7 hours until the reaction is complete, then cool to room temperature.

[0122] 4) Add 800g of methacrylic acid, 860g of water and 580g of propylene glycol to a 1000ml three-necked flask (reactor 2), and mix well under a nitrogen atmosphere for later use.

[0123] 5) Add 8g of ammonium persulfate, 100g of water and 60g of propylene glycol to a 250ml three-necked flask (reactor 3), and mix well under a nitrogen atmosphere for later use.

[0124] 6) After raising the temperature of reactor 1 to 80°C, add monomers and initiators from reactors 2 and 3 simultaneously. The metered addition time is 4 hours to start the polymerization reaction. After the addition is completed, keep the temperature for 2 hours until the reaction ends. After cooling, the desired dispersant is obtained.

[0125] Acrylic dispersant 6

[0126] 1) Add 150g of propylene glycol and 150g of water to a 1500ml four-necked flask (reactor 1) equipped with a mechanical stirrer and a nitrogen inlet, mix well, and purge with nitrogen for more than 30 minutes to replace the oxygen content in the system to below 1*10^7mg / L.

[0127] 2) Add 200g of acrylic acid to a four-necked flask, mix well, and continuously purge with nitrogen to replace oxygen;

[0128] 3) Raise the reaction temperature to 50°C, add 0.2g of ammonium persulfate to the four-necked flask, and start the polymerization reaction. React for 7 hours until the reaction is complete, then cool to room temperature.

[0129] 4) Add 800g of methacrylic acid, 860g of water and 580g of propylene glycol to a 1000ml three-necked flask (reactor 2), and mix well under a nitrogen atmosphere for later use.

[0130] 5) Add 8g of ammonium persulfate, 100g of water and 60g of propylene glycol to a 250ml three-necked flask (reactor 3), and mix well under a nitrogen atmosphere for later use.

[0131] 6) After raising the temperature of reactor 1 to 80°C, add monomers and initiators from reactors 2 and 3 simultaneously. The metered addition time is 4 hours to start the polymerization reaction. After the addition is completed, keep the temperature for 2 hours until the reaction ends. After cooling, the desired dispersant is obtained.

[0132] The components were mixed according to the proportions shown in Table 1 until a homogeneous liquid composition was obtained. Water was added to bring the volume to 100 to prepare the detergent compositions of Examples 1-8 and Comparative Examples 1-4. The specific formulations are shown in the table below (parts by weight):

[0133] Table 1: Formulation Composition

[0134]

[0135]

[0136] Performance testing methods:

[0137] A. Appearance and stability testing

[0138] Visually inspect the hard surface cleaning agent system; it should appear uniform and without stratification. Place the product in a refrigerator at -5℃±2℃ for 24 hours, then remove and allow it to return to room temperature for observation. Alternatively, place it in an oven at 40℃±2℃ for 24 hours, then remove and allow it to return to room temperature for observation. Liquid products should show no stratification, crystallization, precipitation, or discoloration, while transparent products should remain clear and uncolored, indicating good stability.

[0139] B. Sebum removal ability test

[0140] According to the test method described in GBT13174-2008 "Test Methods for Laundry Detergents", the cleaning ability of different formulas on grease-stained cloths is judged by testing the stain removal ratio of different formulas and standard laundry detergents on grease-stained cloths.

[0141] Table 3: Evaluation Results

[0142]

[0143]

[0144] The evaluation results show that the hydrophobically modified dispersant containing unsaturated fatty acids of the present invention has a good synergistic ability to remove sebum and dirt. As can be seen from Examples 1-8 and Comparative Examples 1-4, the addition of this dispersant can significantly improve the removal rate of sebum. Due to its special core-shell structure, it can remain stable and colorless in the system. Moreover, even with a decrease in surfactant content, the removal of sebum and dirt can be improved by adding more of this dispersant. In addition, comparing Example 7 and Comparative Example 2, it was found that if no protective oil is added to the outer layer of the dispersant, the dispersant will change color, causing discoloration of the product appearance. Comparing Example 7 and Comparative Example 1, it was found that if the inner layer of the dispersant contains unsaturated oil, the synergistic detergency of the system is significantly improved. Comparing Example 7 and Comparative Example 3, it was found that after simultaneously increasing the modification of both the inner and outer layers with more oils, the synergistic detergency of the dispersant on the system is significantly improved.

[0145] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A hydrophobically modified dispersant containing unsaturated fatty acids, characterized in that, The hydrophobically modified dispersant containing unsaturated fatty acids has a core-shell structure consisting of an inner layer containing unsaturated fatty acids and an outer layer containing saturated fatty acids and a hydrophobically modified dispersant. Preferably, the molecular weight of the hydrophobic modified dispersant containing unsaturated fatty acids is 500-5000, and more preferably 1000-3000.

2. The preparation method of the hydrophobically modified dispersant containing unsaturated fatty acids according to claim 1, characterized in that, It is obtained by reacting raw materials, including inner and outer components, with a free radical initiator. a) The inner layer components, based on their total mass, comprise: a1) 20-60% of at least one C18-C22 unsaturated carboxylic acid containing two or more carbon-carbon unsaturated double bonds, wherein at least one of them is a polymerizable carbon-carbon double bond and a carboxyl group; a2) 40-80% of at least one functional monomer containing a polymerizable carbon-carbon double bond; b) The outer layer components, based on the total mass of the outer layer components, comprise: b1) 50-80% of at least one C12-C16 unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and at least one polymerizable carbon-carbon double bond and a carboxyl group; b2) 20-50% of at least one functional monomer containing a polymerizable carbon-carbon double bond; In this case, based on the total mass of the inner and outer components, the mass fraction of the inner component is 20-40%, and the mass fraction of the outer component is 60-80%. Preferably, the preparation method of the hydrophobically modified dispersant containing unsaturated fatty acids includes the following steps: 1) Add the reaction components for preparing the inner layer to the second solvent in proportion and mix; 2) Heat the reaction system obtained in step 1) to 50-80℃, add the free radical initiator, and carry out the polymerization reaction to obtain the inner layer component; 3) In the first solvent, the free radical initiator and the outer layer component are mixed with the inner layer component obtained in step 2) at 50-80°C to carry out a polymerization reaction. After the reaction, the mixture is cooled to obtain the hydrophobic modified dispersant containing unsaturated fatty acids.

3. The preparation method according to claim 2, characterized in that, The C18-C22 unsaturated carboxylic acid containing two or more carbon-carbon unsaturated double bonds, of which at least one is polymerizable, and a carboxyl group, as described in component a1, is selected from one or more of linoleic acid, linolenic acid, octadecanoic acid, nonadecanodienoic acid, eicosadienoic acid, eicostrienoic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid, docosahexaenoic acid (DHA), docosadienoic acid, docosatrienoic acid, docosatraenoic acid, and docosapentaenoic acid (DPA), preferably one or a combination of two of linoleic acid, linolenic acid, or arachidonic acid; and / or The polymerizable carbon-carbon double bond-containing functional monomers described in components a2 and b2 are selected from one or more of maleic acid, maleic anhydride, itaconic acid, itaconic acid salt, crotonic acid salt, medaconic acid salt, medaconic acid salt, acrylic acid, acrylate, methacrylic acid, methacrylate, fumaric acid, fumarate, citraconic acid, citraconic acid salt, aconitic acid, or aconitate, preferably one or a combination of two of acrylic acid or methacrylic acid; and / or The C12-C16 unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and at least one polymerizable carbon-carbon double bond and a carboxyl group described in component b1 is selected from one or more of 2-dodecenoic acid, 11-dodecenoic acid, 2-tridecenoic acid, 2-tetradecenoic acid, myristenoic acid, pentadecenoic acid, and hexadecenoic acid, preferably one or a combination of two of myristenoic acid, 2-tetradecenoic acid, or hexadecenoic acid.

4. The preparation method according to claim 2 or 3, characterized in that, The free radical initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, dodecyl peroxide, ammonium persulfate, sodium persulfate, or hydrogen peroxide; and / or The first solvent and the second solvent are a mixture of water and propylene glycol; Preferably, the first solvent and the second solvent are a mixture of water and propylene glycol in a mass ratio of 2:1 to 1:3, and more preferably a mixture of water and propylene glycol in a mass ratio of 1:1 to 1:

2. More preferably, the total proportion of the first solvent and the second solvent is 1.2-5 times the total mass of the monomer, preferably 1.5-2 times.

5. A high-efficiency detergent composition, characterized in that, The dispersant containing unsaturated fatty acids as described in claim 1 or the dispersant containing unsaturated fatty acids prepared by any one of the preparation methods described in claims 2-4; Preferably, the components comprise the following parts by weight:

6. The high-efficiency washing composition according to claim 5, characterized in that, The surfactant is selected from one or more of the following: sodium alkylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, isomeric alcohol ether, capped polyether, sodium α-alkenyl sulfonate, sodium fatty acid methyl ester sulfonate, fatty alcohol polyoxyethylene ether, sodium fatty alcohol ether carboxylate, isomeric C10 ethoxylate, C12-C16 alkyl glycoside, coconut oil fatty acid diethanolamine, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene ether, dodecyl dimethyl betaine, lauryl amphoteric propyl sulfonate, rhamnolipid, sophorolipid, carboxylate imidazoline, or ester quaternary ammonium salt.

7. The high-efficiency washing composition according to claim 5, characterized in that, The functional active ingredient is selected from at least one of enzymes, enzyme stabilizers, color-protecting agents, bleaching / color bleaching agents, anti-pilling agents, and softening antistatic bactericides; Preferably, the enzyme is selected from at least one of protease, amylase, lipase, and cellulase; Preferably, the enzyme stabilizer is selected from any one of calcium cations, borates, and polyol solvents; Preferably, the color-protecting agent is selected from at least one of polyurethane color-protecting agents, nonionic fluorocarbons, nonionic hydroquinone epoxy ethers, polyvinylpyrrolidone, polyamine polymers, cationic oxidized starch-derived polymers, polydimethyldiallyl ammonium chloride, and fluorescent whitening agents. Preferably, the bleaching / color bleaching agent is selected from at least one of sodium hypochlorite, hydrogen peroxide, sodium peroxide, benzoyl peroxide, calcium hypochlorite, sodium persulfate, and chloroform; Preferably, the anti-pilling agent is selected from at least one of polyvinylpyrrolidone, polyurethane, polyacrylic acid, polyurea and polycarboxylic acid polymers; Preferably, the soft antistatic bactericide is selected from at least one of the following cationic bactericides: dodecyl dimethyl benzyl ammonium chloride (1227), hexadecyl trimethyl ammonium chloride (1631), octadecyl trimethyl ammonium chloride (1831), methyl ditauroyl ethyl-2-hydroxyethyl ammonium sulfate, N-methyl-N-oroxyamidoethyl-2-tauroyl imidazoline methyl sulfate, and cationic guar gum.

8. The high-efficiency washing composition according to claim 5, characterized in that, The aqueous carrier is a composition of water and additives, wherein the additives account for 1-10% of the aqueous carrier by mass. Preferably, the additive is selected from any one or more of thickeners, pH adjusters, preservatives, fragrances, colorants, or chelating agents; More preferably, the thickener is selected from any one or more of associative polyurethane thickeners, xanthan gum, cellulose, polyoxyethylene, polyacrylic acid, gellan gum, guar gum, alginate and its salts, carrageenan and its modified forms, acrylic copolymers, sodium chloride, polyacrylamide, or polyvinylpyrrolidone; and / or The pH adjuster is selected from any one or more of hydrochloric acid, phosphoric acid, citric acid, sodium hydroxide, potassium hydroxide, triethanolamine, aminoethylaminopropyltrimethoxy, or ethylenediamine; and / or The preservative is selected from any one or more of Kathon, parabens, sodium benzoate, salicylic acid, 1,3-dimethylol-5,5-dimethylhydantoin, phenoxyethanol, ethylhexylglycerin, or phenoxyethanol; and / or The fragrance is selected from any one or more of synthetic fragrances and natural fragrances; and / or The pigment is selected from any one or more of water-soluble synthetic pigments and natural pigments; and / or The chelating agent is selected from sodium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid, nitrogen-tritium triacetic acid, nitrogen-tritium triacetic acid, ethylenediaminetetrapropionic acid, sodium ethylenediaminetetrapropionate, preferably one or more of sodium ethylenediaminetetraacetate, sodium citrate, and sodium gluconate, and more preferably sodium ethylenediaminetetraacetate.

9. A method for preparing the high-efficiency detergent composition according to any one of claims 5 to 8, characterized in that, The method includes the step of mixing a liquid composition containing an unsaturated fatty acid hydrophobic modifier dispersant, a surfactant, a functional active ingredient, and an aqueous carrier component in a certain proportion until a homogeneous state is formed.

10. The use of the high-efficiency detergent composition according to any one of claims 5 to 8 or the high-efficiency detergent composition prepared by the preparation method according to claim 9 in detergents.

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