CN111139144A - Low-temperature easy-rinsing super-concentrated liquid detergent and preparation method thereof - Google Patents

Low-temperature easy-rinsing super-concentrated liquid detergent and preparation method thereof Download PDF

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CN111139144A
CN111139144A CN201911366189.5A CN201911366189A CN111139144A CN 111139144 A CN111139144 A CN 111139144A CN 201911366189 A CN201911366189 A CN 201911366189A CN 111139144 A CN111139144 A CN 111139144A
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liquid detergent
concentrated liquid
ultra
reaction
low
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孙永强
周婧洁
孙晋源
张勇
武华萍
梁慧斌
丁莉荣
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China Daily Chemical Industry Research Institute
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China Daily Chemical Industry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Abstract

The invention discloses a low-temperature easy-rinsing hyperconcentration liquid detergent and a preparation method thereof. The detergent comprises the following components: 40-55% of anionic surfactant, 11-15% of nonionic surfactant, 1-5% of auxiliary agent, 0.04-0.10% of preservative, 0.1-1% of essence and the balance of water; the anionic surfactant includes: one of modified grease ethoxylate sulfonate, narrow distribution alcohol ether sulfate or fatty acid methyl ester sulfonate; nonionic surfactants include: one or more of fatty acid methyl ester ethoxylate, fatty alcohol polyoxyethylene or alkyl glycoside. The invention has the advantages of high solid content, low foam, easy rinsing, good low-temperature stability and the like.

Description

Low-temperature easy-rinsing super-concentrated liquid detergent and preparation method thereof
Technical Field
The invention relates to a low-temperature easy-rinsing hyperconcentration liquid detergent and a preparation method thereof, belonging to the technical field of liquid detergents and preparation thereof.
Background
The liquid detergent is more and more popular with consumers because of convenient use, high dissolving (dispersing) speed, good low-temperature washing effect, low system alkalinity, mild property to fabrics and skin, suitability for mechanical washing, flexible formula, simple manufacturing process, less equipment investment, less environmental pollution, low processing cost and the like. In recent years, with the increasing attention of people to environmental problems, development of mild, concentrated, easy-to-rinse and degradable natural environment-friendly green products meeting the environmental protection requirements becomes the mainstream of detergent product development.
Compared with the common liquid detergent, the concentrated liquid detergent has higher active matter content, has more advantages in the aspects of energy conservation and high efficiency, meets the requirements of quick decontamination, easy rinsing, environmental protection and the like, and has comprehensively improved performance on the basis of common liquid detergent products.
With the improvement of energy conservation and environmental protection consciousness of people, cold water washing is more and more popular in the world, so that the problem of the reduction of the detergency of a detergent caused by the reduction of the washing temperature is more and more important to scientific researchers, and the search for a surfactant with a low freezing point and the reduction of the freezing point of the surfactant become a hot problem of the research of the detergent industry at present.
Disclosure of Invention
The invention aims to provide a super-concentrated liquid detergent which has high solid content, low foam, easy rinsing and good low-temperature stability.
The main component of the modified grease ethoxylate sulfonate is a novel surfactant (an independent research and development product), and is characterized by good water solubility, no gel in the whole process of an aqueous solution with the concentration of 70% (the concentration of the product is 70%), low freezing point, good low-temperature stability and low foam, and is easy to rinse, so that the modified grease ethoxylate sulfonate is suitable for developing a super-concentrated liquid detergent with high solid content, low foam, easy rinsing and good low-temperature stability.
The invention provides a low-temperature easy-rinsing hyperconcentration liquid detergent, which comprises the following components:
40-55% of anionic surfactant, 11-15% of nonionic surfactant, 1-5% of auxiliary agent, 0.04-0.1% of preservative, 0.1-1% of essence and the balance of water.
The anionic surfactants as described above include: the modified grease ethoxylate sulfonate may also include one of narrow distribution Alcohol Ether Sulfate (AES) or fatty acid Methyl Ester Sulfonate (MES).
Further, the preparation method of the modified grease ethoxylate sulfonate comprises the following steps: taking modified grease ethoxylate as a raw material, and carrying out gas sulfur trioxide sulfonation or sulfation reaction on a membrane reactor; modified oil ethoxylate and SO3In a molar ratio of 1: 1.10-2.00, SO3SO in mixed gas with air3The volume concentration of (A) is 4% -8%; aging at 25-30 ℃ for 0.5-2 h after reaction; and (3) neutralizing the sulfonated product with NaOH solution, controlling the pH value to be 7-9 and controlling the mass concentration to be 70%, and obtaining the final product. Further, the method for synthesizing the modified grease ethoxylate comprises the following steps:
(1) preparing modified grease by using natural grease and fatty alcohol as raw materials:
the reaction is carried out in a four-mouth bottle, nitrogen protection is carried out in the whole process, the molar ratio of the natural oil to the fatty alcohol is 1: 1-2, solid alkali is used as a catalyst, and the ratio of the catalyst is 2-6 per mill of the mass of the reactant; the temperature is 150 ℃ and 180 ℃, and the reaction time is 1.5-3 h;
(2) carrying out ethoxylation reaction on the modified grease in a high-pressure kettle:
adding the modified oil obtained in the step (1) and a heterogeneous ethoxylation catalyst into a high-pressure reaction kettle, wherein the adding amount of the heterogeneous ethoxylation catalyst is 1% -2% of the mass of the modified oil, introducing nitrogen to replace air in the reaction kettle, heating to 160-180 ℃, introducing ethylene oxide, wherein the mass of the ethylene oxide is 0.05-0.20 times of that of the modified oil, and carrying out an induction reaction at the reaction pressure of 0.3-0.5 MPa; when the pressure is reduced to 0.1 MPa, slowly introducing ethylene oxide into the kettle, wherein the mass ratio of the modified grease to the two times of total ethylene oxide is 1: 1-2, introducing nitrogen when the pressure is constant and the reaction is complete and the temperature in the reaction kettle is reduced to 40-80 ℃, and obtaining the modified oil ethoxylate.
The nonionic surfactant as described above includes: one or more of fatty acid methyl ester ethoxylate (FMEE), fatty alcohol polyoxyethylene ether (AEO) or alkyl glycoside (APG).
The structural formula of the fatty acid methyl ester ethoxylate described above is shown below:
Figure 833416DEST_PATH_IMAGE002
wherein R is C12~C14N is 7 to 12.
Adjuvants as described above include sodium carbonate or sodium citrate.
The preservative for a detergent as described above includes one of cason or paraben.
The invention provides a preparation method of the low-temperature easy-rinsing hyperconcentration liquid detergent, which comprises the following steps: when the nonionic surfactant does not contain alkyl glycoside, the preparation process is as follows: mixing the modified oil ethoxylate sulfonate with a nonionic surfactant at 20-40 ℃, then sequentially adding other anionic surfactants and auxiliaries, stirring at a stirring speed of 300-500 rpm/min for 20-30 min, cooling to room temperature, sequentially adding a preservative and essence, and continuously stirring at a stirring speed of 300-500 rpm/min for 40-60 min until the product is in a uniform and transparent state, thus obtaining the ultra-concentrated liquid detergent which is easy to rinse at low temperature and has good stability.
When the nonionic surfactant contains alkyl glycoside, the preparation process is as follows: mixing modified grease ethoxylate sulfonate with a non-ionic surfactant except APG at 20-40 ℃, heating APG to 60 ℃, adding the APG into the mixed solution, then sequentially adding other anionic surfactants and auxiliaries, stirring at a stirring speed of 300-500 rpm/min for 20-30 min, cooling to room temperature, sequentially adding a preservative and essence, and continuously stirring at a stirring speed of 300-500 rpm/min for 40-60 min until the product is in a uniform and transparent state, thus obtaining the ultra-concentrated liquid detergent with good low-temperature easy rinsing stability.
The invention has the beneficial effects that:
(1) the raw material modified grease ethoxylate sulfonate, fatty acid methyl ester ethoxylate (FMEE), fatty alcohol polyoxyethylene ether (AEO), alkyl glycoside (APG) and the like adopted by the invention are prepared from natural raw materials, and the product is green and environment-friendly and has excellent biodegradability.
(2) The main raw material modified grease ethoxylate sulfonate product adopted by the invention has the characteristics of wide raw material source, low foam, no gel in aqueous solution, excellent low-temperature flow property, good synergistic performance with other products and the like.
(3) The detergent of the present invention has no gel phenomenon in the preparation process, excellent flowing performance and convenient use.
(4) The detergent product of the invention has good low-temperature stability and can be used at a lower temperature;
(5) the detergent product of the invention has low foam, is easy to rinse, and is beneficial to saving water and energy;
(6) the detergent of the invention is a hyperconcentration liquid detergent, has high product activity and is convenient for transportation and use.
Detailed Description
The present invention will be further described with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
40.0% of anionic surfactant modified grease ethoxylate sulfonate and 5% of AES; 5% of non-ionic surfactant APG and 10% of FMEE-24-09. 3 percent of sodium citrate, 0.04 percent of cason, 0.3 percent of essence and the balance of water.
The preparation method of the modified grease ethoxylate comprises the following steps: (1) preparing modified oil by taking palm kernel oil and methanol as raw materials: the reaction is carried out in a four-mouth bottle, the nitrogen protection is carried out in the whole process, the molar ratio of the palm kernel oil to the methanol is 1:2, KOH is adopted as a catalyst, and the ratio of the catalyst is 2 per mill of the mass of the reactants. The temperature is 150 ℃ and the reaction time is 2 h. (2) Carrying out ethoxylation reaction on the modified grease in a high-pressure kettle: modified grease and micron-sized MgO & Al2O3Adding an ethoxylation catalyst into a high-pressure reaction kettle, wherein the adding amount of the catalyst is 1 percent of the mass of the modified grease, introducing nitrogen to replace air in the reaction kettle, heating to 160 ℃, introducing ethylene oxide, the mass of the ethylene oxide is 0.05 times of that of the modified grease, carrying out an induction reaction under the reaction pressure of 0.3 MPa, and slowly introducing the ethylene oxide into the kettle when the pressure is reduced to 0.1 MPa, wherein the mass ratio of the modified grease to the total ethylene oxide in two times is 1: and 1.5, introducing nitrogen when the pressure is constant and the reaction is complete and the temperature in the reaction kettle is reduced to 40-80 ℃, and leading out the modified grease ethoxylate.
Putting the modified grease ethoxylate into a four-mouth bottle according to the ratio of the modified grease ethoxylate to SO3In a molar ratio of 1:1.10, introducing SO3，SO3SO in mixed gas with air3The concentration of (2) is 4V%; after the reaction, aging is carried out for 2h at 30 ℃; and (3) neutralizing the sulfonated product with NaOH solution, wherein the pH value of the neutralization is 7-9, the mass concentration is controlled to be 70%, and thus the modified grease ethoxylate sulfonate is obtained.
Mixing modified grease ethoxylate sulfonate and FMEE at 30 ℃, heating APG to 60 ℃, adding the APG into the mixed solution, then sequentially adding AES and sodium citrate, stirring at a stirring speed of 400rpm/min for 30min, cooling to room temperature, sequentially adding kasong and essence, and continuing stirring at a stirring speed of 400rpm/min for 40min until the product is in a uniform and transparent state, thus obtaining the required ultra-concentrated liquid detergent with low-temperature easy rinsing and good stability.
Example 2
50.0% of anionic surfactant modified grease ethoxylate sulfonate and 5% of AES; 2% of nonionic surfactant APG and AEO9The content was 8%. Sodium carbonate accounts for 1 percent, nipagin ester accounts for 0.06 percent, essence accounts for 0.3 percent, and the balance is water.
At 25 ℃, the modified grease ethoxylate sulfonate is mixed with AEO9And (2) mixing, heating APG to 60 ℃, adding the APG into the mixed solution, then sequentially adding AES and sodium carbonate, stirring for 30min at the stirring speed of 300rpm/min, cooling to room temperature, sequentially adding the nipagin ester and the essence, and continuously stirring for 40min at the stirring speed of 300rpm/min until the product is in a uniform and transparent state, thus obtaining the required ultra-concentrated liquid detergent which is easy to rinse at low temperature and has good stability.
Example 3
55.0% of anionic surfactant modified grease ethoxylate sulfonate, 5% of nonionic surfactant APG and 8% of FMEE. 2 percent of sodium citrate, 0.05 percent of cason, 0.4 percent of essence and the balance of water.
Mixing modified grease ethoxylate sulfonate and FMEE at 30 ℃, heating APG to 60 ℃, adding the APG into the mixed solution, adding sodium citrate, stirring at a stirring speed of 400rpm/min for 30min, cooling to room temperature, sequentially adding the kasong and the essence, and continuously stirring at a stirring speed of 400rpm/min for 40min until the product is in a uniform and transparent state, thus obtaining the required ultra-concentrated liquid detergent with low-temperature easy rinsing and good stability.
Example 4
40.0% of anionic surfactant modified grease ethoxylate sulfonate and 5% of MES; nonionic surfactant AEO9The content was 10%. Citric acid sodium salt2 percent of nipagin ester, 0.08 percent of essence and the balance of water.
At 35 ℃, the modified grease ethoxylate sulfonate is mixed with AEO9And (2) mixing, heating the APG to 60 ℃, adding the APG into the mixed solution, then sequentially adding MES and sodium citrate, stirring for 20min at the stirring speed of 500rpm/min, cooling to room temperature, sequentially adding the nipagin ester and the essence, and continuously stirring for 60min at the stirring speed of 500rpm/min until the product is in a uniform and transparent state, thus obtaining the required ultra-concentrated liquid detergent which is easy to rinse at low temperature and has good stability.
Example 5
45.0% of anionic surfactant modified grease ethoxylate sulfonate and 10% of AES; 5% of nonionic surfactant APG and AEO9The content was 6%. 3 percent of sodium citrate, 0.05 percent of cason, 0.3 percent of essence and the balance of water.
At the temperature of 20-40 ℃, the modified grease ethoxylate sulfonate and AEO9And (2) mixing, heating APG to 60 ℃, adding the APG into the mixed solution, then sequentially adding AES and sodium citrate, stirring for 30min at a stirring speed of 400rpm/min, cooling to room temperature, sequentially adding the kasong and the essence, and continuously stirring for 50min at a stirring speed of 400rpm/min until the product is in a uniform and transparent state, thus obtaining the required ultra-concentrated liquid detergent which is easy to rinse at low temperature and has good stability.
To further demonstrate the easy-rinse performance of the present invention, the foam performance of the examples of the present invention was measured according to the national standard of the people's republic of China GB/T13173-2008 "determination of foaming power of detergent (Ross-Miles)".
The results of the performance tests of the samples prepared in the above embodiments are shown in the following table:
Figure 116630DEST_PATH_IMAGE004
according to the GB/T13173-2008 standard, the foam of the standard laundry detergent is 140 mL at 0S, the foam is 120 mL at 5 min, and the foam basically disappears at 5 min in the embodiment examples listed in the invention, so that the laundry detergent is easier to rinse.
If modified grease ethoxylate sulfonate is not used as a main surfactant, a product compounded by AES generally cannot flow at 5-8 ℃, and the freezing point of the embodiment of the invention can reach-8 ℃, so the invention has good low-temperature stability.

Claims (10)

1. A low-temperature easy-rinsing ultra-concentrated liquid detergent is characterized in that: the detergent comprises the following components in percentage by mass:
40-55% of anionic surfactant, 11-15% of nonionic surfactant, 1-5% of auxiliary agent, 0.04-0.10% of preservative, 0.1-1% of essence and the balance of water.
2. The low temperature easy-rinse ultra-concentrated liquid detergent of claim 1, characterized in that: anionic surfactants include: modified grease ethoxylate sulfonate, narrow distribution alcohol ether sulfate or fatty acid methyl ester sulfonate.
3. The low temperature easy-rinse ultra-concentrated liquid detergent of claim 2, characterized in that: the preparation method of the modified grease ethoxylate sulfonate comprises the following steps: taking modified grease ethoxylate as a raw material, and carrying out gas sulfur trioxide sulfonation or sulfation reaction on a membrane reactor; modified oil ethoxylate and SO3In a molar ratio of 1: 1.10-2.00, SO3SO in mixed gas with air3The volume concentration of (A) is 4% -8%; aging at 25-30 ℃ for 0.5-2 h after reaction; and (3) neutralizing the sulfonated product with NaOH solution, controlling the pH value to be 7-9 and controlling the mass concentration to be 70%, and obtaining the final product.
4. The low temperature easy-rinse ultra-concentrated liquid detergent of claim 3, characterized in that: the synthetic method of the modified grease ethoxylate comprises the following steps:
(1) preparing modified grease by using natural grease and fatty alcohol as raw materials:
the reaction is carried out in a four-mouth bottle, nitrogen protection is carried out in the whole process, the molar ratio of the natural oil to the fatty alcohol is 1: 1-2, solid alkali is used as a catalyst, and the ratio of the catalyst is 2-6 per mill of the mass of the reactant; the temperature is 150 ℃ and 180 ℃, and the reaction time is 1.5-3 h;
(2) carrying out ethoxylation reaction on the modified grease in a high-pressure kettle:
adding the modified oil obtained in the step (1) and a heterogeneous ethoxylation catalyst into a high-pressure reaction kettle, wherein the adding amount of the heterogeneous ethoxylation catalyst is 1% -2% of the mass of the modified oil, introducing nitrogen to replace air in the reaction kettle, heating to 160-180 ℃, introducing ethylene oxide, wherein the mass of the ethylene oxide is 0.05-0.20 times of that of the modified oil, and carrying out an induction reaction at the reaction pressure of 0.3-0.5 MPa; when the pressure is reduced to 0.1 MPa, slowly introducing ethylene oxide into the kettle, wherein the mass ratio of the modified grease to the two times of total ethylene oxide is 1: 1.0-2.0, and introducing nitrogen when the pressure is constant and the reaction is complete and the temperature in the reaction kettle is reduced to 40-80 ℃ to obtain the modified grease ethoxylate.
5. The low temperature easy-rinse ultra-concentrated liquid detergent of claim 1, characterized in that: nonionic surfactants include: one or more of fatty acid methyl ester ethoxylate, fatty alcohol polyoxyethylene or alkyl glycoside.
6. The low temperature easy-rinse ultra-concentrated liquid detergent of claim 5, characterized in that: the structural formula of the fatty acid methyl ester ethoxylate is shown as follows:
Figure 743261DEST_PATH_IMAGE002
wherein R is C12~C14N is 7 to 12.
7. The low temperature easy-rinse ultra-concentrated liquid detergent of claim 1, characterized in that: the auxiliary agent comprises sodium carbonate or sodium citrate.
8. The low temperature easy-rinse ultra-concentrated liquid detergent of claim 1, characterized in that: the preservative for the detergent comprises one of cason or paraben.
9. A method for preparing a low-temperature easy-rinsing ultra-concentrated liquid detergent as claimed in any one of claims 1 to 8, which is characterized in that: when the nonionic surfactant does not contain alkyl glycoside, the preparation process is as follows:
mixing the modified oil ethoxylate sulfonate with a nonionic surfactant at 20-40 ℃, then sequentially adding other anionic surfactants and auxiliaries, stirring at a stirring speed of 300-500 rpm/min for 20-30 min, cooling to room temperature, sequentially adding a preservative and essence, and continuously stirring at a stirring speed of 300-500 rpm/min for 40-60 min until the product is in a uniform and transparent state, thus obtaining the ultra-concentrated liquid detergent which is easy to rinse at low temperature and has good stability.
10. A method for preparing a low-temperature easy-rinsing ultra-concentrated liquid detergent as claimed in any one of claims 1 to 8, which is characterized in that: when the nonionic surfactant contains alkyl glycoside, the preparation process is as follows:
mixing modified grease ethoxylate sulfonate with a nonionic surfactant except alkyl glycoside at 20-40 ℃, heating the alkyl glycoside to 60 ℃, adding the alkyl glycoside into the mixed solution, then sequentially adding other anionic surfactants and auxiliaries, stirring at a stirring speed of 300-500 rpm/min for 20-30 min, cooling to room temperature, sequentially adding a preservative and essence, and continuing stirring at a stirring speed of 300-500 rpm/min for 40-60 min until the product is in a uniform and transparent state, thus obtaining the ultra-concentrated liquid detergent with good low-temperature easy rinsing stability.
CN201911366189.5A 2019-12-26 2019-12-26 Low-temperature easy-rinsing super-concentrated liquid detergent and preparation method thereof Pending CN111139144A (en)

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