Environmentally friendly and efficient cleaning agent and preparation method thereof

Abstract

The present invention discloses an environmentally friendly and efficient cleaning agent and a preparation method thereof, which comprises an efficient surfactant, citric acid, sodium metasilicate and water. The efficient surfactant has a structure as shown below. The efficient surfactant is a Gemini-type fluorocarbon surfactant, which has excellent surface activity and good thermal stability and chemical stability, so that the cleaning agent can be applied to a variety of fields, and can reduce the addition of surfactants and phosphorus-containing additives, greatly reducing pollution to the environment. The environmentally friendly and efficient cleaning agent provided by the present invention has a wide range of applications, high efficiency, high performance and environmentally friendly effects.

Description

Technical Field

[0001] The invention relates to the field of detergents, and in particular to an environmentally friendly and efficient detergent and a preparation method thereof. Background Art

[0002] Detergent is a liquid cleaning product used to wash clothes, utensils, furniture, etc. Its main component is surfactant, which has strong detergency, is easy to rinse, and is non-irritating to the skin. It is most suitable for washing kitchen utensils, furniture, and fruits and vegetables. Detergents can be divided into three categories according to the nature of their ingredients: water-based detergents, semi-aqueous detergents, and non-aqueous detergents.

[0003] Water-based detergents are usually water-soluble detergents made from surfactants (such as sodium alkylbenzene sulfonate) and various additives (such as sodium tripolyphosphate) and auxiliary agents. When washing dirt on the surface of an object, water-based detergents can change the surface activity of water and improve the decontamination effect. For example, washing powder is the most typical water-based detergent. Therefore, water-based detergents are still the most convenient, widely used, and largest-volume detergents.

[0004] The most widely used surfactant in detergents (cleaners) produced around the world today is sodium alkylbenzene sulfonate, which is also the main ingredient in more than 90% of various brands of laundry detergents on the market. Additives generally refer to carbonates, sulfates, silicates, and phosphates. About 60% of detergents in the world contain phosphates, and sodium tripolyphosphate is the most widely used inorganic additive in laundry detergents. At the same time, ordinary laundry detergents also add fluorescent whitening agents to improve the whitening effect.

[0005] However, detergents made of sodium alkylbenzene sulfonate, phosphate, fluorescent agent and other components in the prior art have poor biodegradability, are not easy to dissolve and remove, and will pollute the environment; and sodium alkylbenzene sulfonate has insufficient surface activity, and needs to be compounded with a large number of other surfactants, and a large number of additives need to be added to have sufficient cleaning ability. The sodium alkylbenzene sulfonate surfactant can be replaced with a fluorocarbon surfactant to improve the cleaning ability of the detergent.

[0006] Fluorocarbon surfactants are a type of surfactant in which all or part of the hydrogen atoms in the hydrocarbon chain of hydrocarbon surfactants are replaced by fluorine atoms. Due to the smaller atomic radius, larger electronegativity, and larger single bond energy of fluorine atoms, fluorocarbon surfactants have excellent surface activity, thermal stability, and chemical stability, and can be used in situations where hydrocarbon surfactants are insufficient or simply cannot perform.

[0007] However, the macromolecular fluorocarbon surfactants in the prior art are difficult to be used in cleaning agents, while the small molecule fluorocarbon surfactants have insufficient cleaning ability. Therefore, there is an urgent need for a cleaning agent using a small molecule fluorocarbon surfactant. Summary of the invention

[0008] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide an environmentally friendly and efficient cleaning agent with a wide range of applications, high efficiency, high performance and environmental friendliness, and a preparation method thereof.

[0009] Technical solution:

[0010] An environmentally friendly and efficient cleaning agent comprising a high-efficiency surfactant, citric acid, sodium metasilicate and water;

[0011] Taking the total mass fraction as 100%, the mass percentage of each component is:

[0012] High-efficiency surfactant 2-3%

[0013] Citric acid 10-15%

[0014] Sodium metasilicate 10-15%

[0015] The balance is water.

[0016] Furthermore, the high-efficiency surfactant has the structure shown below:

[0017] .

[0018] The high-efficiency surfactant is a fluorocarbon surfactant, which has excellent surface activity, thermal stability and chemical stability due to the smaller atomic radius, larger electronegativity and larger single bond energy of the fluorine atom, so that the detergent has strong cleaning ability and can be applied to most fields.

[0019] Furthermore, the preparation of the high-efficiency surfactant comprises the following steps:

[0020] (1) Perfluorohexyl iodide is reacted with sodium dithionite to generate perfluorohexyl sulfinate, which is dissolved in concentrated sulfuric acid to generate perfluorohexyl sulfinic acid, and then perfluorohexyl sulfinic acid is reacted with thionyl chloride to obtain perfluorohexyl sulfenyl chloride;

[0021] (2) Perfluorohexylsulfenyl chloride is reacted with N,N'-dimethylethylenediamine to prepare perfluorohexylsulfenamide;

[0022] (3) After perfluorohexylsulfenamide reacts with 1,3-propane sultone, an ethanol solution of sodium hydroxide is added and heated to obtain the high-efficiency surfactant.

[0023] Furthermore, the specific method of step (1) comprises the following steps:

[0024] (a) In a reactor, perfluorohexyl iodide, acetonitrile and distilled water are added in sequence, and sodium dithionite and sodium bicarbonate are added while stirring, and the mixture is reacted for 6-8 hours. After the acetonitrile is removed, the perfluorohexyl sulfinate is obtained after extraction, washing and drying;

[0025] (b) dissolving perfluorohexyl sulfinate in concentrated sulfuric acid under an ice-water bath, and distilling under reduced pressure to obtain perfluorohexyl sulfinic acid;

[0026] (c) Add thionyl chloride into the reactor, add perfluorohexylsulfinic acid dropwise under ice-salt bath conditions, keep the reaction warm for 4-6 hours, and then distill under reduced pressure to obtain the perfluorohexylsulfinyl chloride.

[0027] Furthermore, in the step (a), the molar ratio of perfluorohexyl iodide, sodium dithionite and sodium bicarbonate is 1:(1.2-1.5):(1.2-1.5); the mass fraction of concentrated sulfuric acid in the step (b) is 70-98%; and the molar ratio of perfluorohexyl sulfinic acid and thionyl chloride in the step (c) is 1:1.1-1.3.

[0028] Furthermore, the specific method of step (2) is: adding perfluorohexylsulfenyl chloride, N,N'-dimethylethylenediamine and triethylamine into a reactor, heating to 80-95°C, refluxing for 6-8 hours, cooling for crystallization, filtering, drying, and purifying to obtain the perfluorohexylsulfenamide.

[0029] The high-efficiency surfactant used in the present invention contains not only fluorocarbon chains and sodium alkyl sulfonate structures but also sulfenamide and quaternary ammonium structures, so that the cleaning agent has certain disinfection and sterilization capabilities.

[0030] Furthermore, the molar ratio of the perfluorohexylsulfenyl chloride to N,N'-dimethylethylenediamine is 1:2-2.5.

[0031] Furthermore, the specific method of step (3) is as follows: adding anhydrous tetrahydrofuran, perfluorohexylsulfenamide and 1,3-propane sultone into a reactor, heating to 60-70°C, reflux reaction for 36-48 hours, standing to remove the supernatant, adding an ethanol solution of sodium hydroxide, heating to 50-60°C, reacting for 30-50 minutes, filtering while hot, cooling and crystallizing, filtering by suction, and drying to obtain the high-efficiency surfactant.

[0032] The high-efficiency surfactant used in the present invention is a Gemini-type surfactant, which contains two hydrophilic groups and two lipophilic groups in the molecule, has high surface activity and low critical concentration, and can have strong surface activity when added in small amounts, thereby making the detergent have high-efficiency and high-performance cleaning ability, and can reduce the use of surfactants and phosphorus-containing additives, greatly enhancing the environmental friendliness of the detergent.

[0033] Furthermore, the molar ratio of the perfluorohexylsulfenamide to 1,3-propane sultone is 1:6-8.

[0034] The method for preparing any of the above-mentioned environmentally friendly and efficient cleaning agents comprises the following steps:

[0035] (1) First add citric acid, sodium metasilicate and water and stir until uniform;

[0036] (2) Then, a high-efficiency surfactant is added and stirred until uniform to obtain the environmentally friendly and high-efficiency cleaning agent.

[0037] Beneficial effects:

[0038] (1) The high-efficiency surfactant used in the environmentally friendly and high-efficiency cleaning agent provided by the present invention is a fluorocarbon surfactant. Due to the small atomic radius, large electronegativity, and large single bond energy of the fluorine atom, it has excellent surface activity, thermal stability, and chemical stability, so that the cleaning agent has a strong cleaning ability and can be applied to most fields.

[0039] (2) The high-efficiency surfactant used in the environmentally friendly and high-efficiency cleaning agent provided by the present invention is a Gemini-type surfactant, which contains two hydrophilic groups and two lipophilic groups in the molecule, has high surface activity and low critical concentration, and can have strong surface activity when added in small amounts, thereby making the cleaning agent have high efficiency and high performance cleaning ability, and can reduce the use of surfactants and phosphorus-containing additives, greatly enhancing the environmental friendliness of the cleaning agent.

[0040] (3) The high-efficiency surfactant used in the environmentally friendly and high-efficiency cleaning agent provided by the present invention contains not only a fluorocarbon chain and a sodium alkyl sulfonate structure but also a sulfenamide and a quaternary ammonium structure, so that the cleaning agent has a certain disinfection and sterilization ability. DETAILED DESCRIPTION

[0041] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0042] The commercially available cleaning agent is 821 type high-efficiency cleaning agent purchased from Bengbu Nanhai Chemical Reagent Factory; the commercially available fluorocarbon surfactant is TF281 purchased from Shanghai Laiguo Chemical Co., Ltd.; and the remaining reagents and equipment are conventional reagents and equipment in the technical field.

[0043] Prepare perfluorohexylsulfenyl chloride as follows:

[0044] (a) In a reactor, 0.1 mol of perfluorohexyl iodide, 100 ml of acetonitrile and 200 ml of distilled water are added in sequence, 0.15 mol of sodium dithionite and 0.15 mol of sodium bicarbonate are mixed evenly, and the evenly mixed sodium dithionite and sodium bicarbonate are added under stirring, reacting for 8 hours, removing acetonitrile by rotary evaporator, extracting, washing and drying to obtain perfluorohexyl sulfinate;

[0045] (b) dissolving perfluorohexyl sulfinate in 100 ml of 75% by mass concentrated sulfuric acid in an ice water bath, performing reduced pressure distillation, and collecting the fractions to obtain perfluorohexyl sulfinic acid;

[0046] (c) 0.12 mol of thionyl chloride was added to a round-bottom flask, and 0.1 mol of perfluorohexylsulfinic acid was added dropwise in an ice-salt bath. After the reaction was carried out for 6 hours, the perfluorohexylsulfinyl chloride was obtained by vacuum distillation.

[0047] Preparation of High Efficiency Surfactant-1

[0048] Prepare high-efficiency surfactant-1 by the following steps:

[0049] (1) In a four-necked flask equipped with a spherical condenser, a mechanical stirrer, a thermometer, and a hollow stopper, 0.1 mol of perfluorohexylsulfenyl chloride, 0.2 mol of N,N'-dimethylethylenediamine, and 100 ml of triethylamine were added, heated to 85°C, refluxed for 6 hours, cooled for crystallization, filtered, dried, and purified to obtain the perfluorohexylsulfenamide;

[0050] (2) In a four-necked flask equipped with a reflux condenser, a mechanical stirrer, a drying tube, a thermometer, and a hollow flask, 100 ml of anhydrous tetrahydrofuran, 0.05 mol of perfluorohexylsulfenamide, and 0.3 mol of 1,3-propane sultone were added, heated to 70° C., refluxed for 48 hours, allowed to stand to remove the supernatant, and then 40 ml of an ethanol solution containing 0.8 g of sodium hydroxide was added, heated to 60° C., reacted for 40 minutes, filtered while hot, cooled for crystallization, filtered by suction, and dried to obtain the highly efficient surfactant-1.

[0051] Mass spectrometry data of high-efficiency surfactant-1: The product was analyzed by LC-MS, and the m / z of the product was 554.98 (100%), 555.70 (44.5%), 556.15 (12.9%), and 556.62 (2.7%).

[0052] Preparation of High Efficiency Surfactant-2

[0053] The preparation method is basically the same as that of high-efficiency surfactant-1, except that perfluorohexylsulfenyl chloride in step (1) is replaced by an equal amount of 2-hexylsulfonyl chloride.

[0054] Preparation of High Efficiency Surfactant-3

[0055] The preparation method is basically the same as that of high-efficiency surfactant-1, except that in step (1), N,N'-dimethylethylenediamine is replaced by an equal amount of propylenediamine.

[0056] Example 1

[0057] Follow these steps to prepare an environmentally friendly and efficient cleaning agent:

[0058] (1) First add citric acid, sodium metasilicate and water and stir until uniform;

[0059] (2) Then add the high-efficiency surfactant-1 and stir until uniform to obtain the environmentally friendly and high-efficiency cleaning agent.

[0060] Wherein, taking the total mass fraction as 100%, the mass percentage of each component is:

[0061] High efficiency surfactant -1 2%

[0062] Citric acid 15%

[0063] Sodium metasilicate 15%

[0064] The balance is water. Example 2

[0065] The same as Example 1, except that the total mass fraction is 100%, and the components and their mass percentages are:

[0066] High efficiency surfactant-1 3%

[0067] Citric acid 10%

[0068] Sodium metasilicate 10%

[0069] The balance is water. Example 3

[0070] The same as Example 1, except that the total mass fraction is 100%, and the components and their mass percentages are:

[0071] High efficiency surfactant-1 2.5%

[0072] Citric acid 12.5%

[0073] Sodium metasilicate 12.5%

[0074] The balance is water. Comparative Example 1

[0075] Commercially available cleaning agents. Comparative Example 2

[0076] The process is basically the same as Example 1, except that the high-efficiency surfactant-1 is replaced by an equal amount of sodium dodecylbenzene sulfonate. Comparative Example 3

[0077] The method is basically the same as Example 1, except that the high-efficiency surfactant-1 is replaced by an equal amount of a commercially available fluorocarbon surfactant. Comparative Example 4

[0078] The method is basically the same as Example 1, except that the high-efficiency surfactant-1 is replaced by an equal amount of high-efficiency surfactant-2. Comparative Example 5

[0079] The method is basically the same as Example 1, except that the high-efficiency surfactant-1 is replaced by an equal amount of high-efficiency surfactant-3.

[0080] Performance Testing

[0081] Surface tension test: measured according to the ring method in JIS K3362-1998 test methods for synthetic detergents, corresponding to ISO304.

[0082] Decontamination rate test: A marble tile with a length and width of 20 cm, measure its weight W1, apply a layer of 50 grams of dirt on the marble tile, bake it at 230℃ for one hour, measure its weight W2, spray 20 grams of multi-purpose cleaner evenly on the marble tile, leave it at room temperature for 2 hours, then rinse it with a sponge under 60℃ hot water flow, dry it in an oven at 60℃, and measure its weight W3. Decontamination rate is obtained by weight method. The above dirt is composed of 50wt% chicken fat, 30wt% vegetable oil, 10wt% flour, 5wt% tomato sauce and 5wt% granulated sugar. Decontamination rate (%) = [(W2-W3) / (W2-W1)]×100. Each sample is tested three times and the average value is taken.

[0083] Antibacterial ability test: refer to GB15981-1995, Q / 02GZS001 test method and standard to test the antibacterial performance of the cleaning agent (calculated by colony count).

[0084] The test results are shown in the following table:

[0085]

[0086] According to the comparison of the test results of Examples 1-3 with those of Comparative Example 1, it can be seen that the environmentally friendly and efficient cleaning agent provided by the present invention has superior surface activity, excellent decontamination ability and antibacterial ability compared with commercially available cleaning agents.

[0087] According to the comparison of the test results of Examples 1-3 with Comparative Examples 2 and 3, it can be seen that the high-efficiency surfactant added in the environmentally friendly and high-efficiency cleaning agent provided by the present invention has better surface activity than the commonly used sodium alkylbenzene sulfonate and fluorocarbon surfactants, can improve the cleaning ability of the cleaning agent, reduce the addition of additives and surfactants, and reduce pollution to the environment.

[0088] According to the comparison of the test results of Examples 1-3 with Comparative Examples 4 and 5, it can be seen that the fluorocarbon structure contained in the high-efficiency surfactant added to the environmentally friendly and high-efficiency cleaning agent provided by the present invention can improve the surface activity ability, and the quaternary ammonium structure can improve the antibacterial ability, thereby making the cleaning agent have high efficiency and multifunctional effects.

[0089] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. An environmentally friendly and efficient cleaning agent, characterized in that: Contains highly effective surfactant, citric acid, sodium metasilicate and water; Taking the total mass fraction as 100%, the mass percentage of each component is: High-efficiency surfactant 2-3% Citric acid 10-15% Sodium metasilicate 10-15% The balance is water; The preparation method of the high-efficiency surfactant comprises the following steps: S1: Preparation of perfluorohexylsulfenyl chloride: (a) In a reactor, 0.1 mol of perfluorohexyl iodide, 100 ml of acetonitrile and 200 ml of distilled water are added in sequence, 0.15 mol of sodium dithionite and 0.15 mol of sodium bicarbonate are mixed evenly, and the evenly mixed sodium dithionite and sodium bicarbonate are added under stirring, reacting for 8 hours, removing acetonitrile by rotary evaporator, extracting, washing and drying to obtain perfluorohexyl sulfinate; (b) dissolving perfluorohexyl sulfinate in 100 ml of 75% by mass concentrated sulfuric acid in an ice water bath, performing reduced pressure distillation, and collecting the fractions to obtain perfluorohexyl sulfinic acid; (c) Add 0.12 mol of thionyl chloride to a round-bottom flask, add 0.1 mol of perfluorohexylsulfinic acid dropwise in an ice-salt bath, keep the reaction warm for 6 hours, and then distill under reduced pressure to obtain perfluorohexylsulfinyl chloride; S2: Preparation of highly efficient surfactants: (1) In a four-necked flask equipped with a spherical condenser, a mechanical stirrer, a thermometer, and a hollow stopper, 0.1 mol of perfluorohexylsulfenyl chloride, 0.2 mol of N,N'-dimethylethylenediamine, and 100 ml of triethylamine were added, heated to 85°C, refluxed for 6 hours, cooled and crystallized, filtered, dried, and purified to obtain perfluorohexylsulfenamide; (2) In a four-necked flask equipped with a reflux condenser, a mechanical stirrer, a drying tube, a thermometer, and a hollow stopper, 100 ml of anhydrous tetrahydrofuran, 0.05 mol of perfluorohexylsulfenamide, and 0.3 mol of 1,3-propane sultone were added, heated to 70° C., refluxed for 48 hours, allowed to stand and the supernatant removed, 40 ml of an ethanol solution containing 0.8 g of sodium hydroxide was added, heated to 60° C., reacted for 40 minutes, filtered while hot, cooled for crystallization, filtered by suction, and dried to obtain the high-efficiency surfactant; The prepared high-efficiency surfactant has the following structure: 。 2. The method for preparing the environmentally friendly and efficient cleaning agent according to claim 1, characterized in that: The following steps are involved: (1) First add citric acid, sodium metasilicate and water and stir until uniform; (2) Then, a high-efficiency surfactant is added and stirred until uniform to obtain the environmentally friendly and high-efficiency cleaning agent.

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