Preparation method of surfactant and cleaning agent

Abstract

The invention relates to a preparation method of a surfactant and a cleaning agent, in particular to a cleaning agent mainly applied to a food industrial equipment CIP cleaning technology, the surfactant provided by the invention comprises sodium gluconate, branched chain polyoxyethylene ether and a modified cellulose-based branched copolymer surfactant, compared with the prior art, the modified cellulose-based branched copolymer surfactant provided by the invention has the advantages that the cleaning effect is better and the efficiency is higher due to excellent performance brought by a copolymerization product.

Description

Technical Field

[0001] The invention belongs to the technical field of surfactants, and in particular relates to a preparation method of a surfactant and a cleaning agent. Technical Background

[0002] Since surfactant molecules have both hydrophilic and hydrophobic groups, they have the functions of reducing interfacial tension, solubilizing, emulsifying, cleaning, foaming, and dispersing, and they play an irreplaceable role in daily chemical, food, textile, oil extraction and other industries.

[0003] Chinese patent CN202110514459.3 discloses a low-temperature foam cleaning agent for meat processing sites and a preparation method thereof, which can be used for in-situ cleaning (cleaning inplace, i.e. CIP) of production equipment, which is often required in the food processing industry. It helps prevent the proliferation of bacteria and other contaminants, thereby avoiding product loss, degradation, substandard products, etc. The surfactant used in this patent is a C fatty alcohol ether surfactant, a glycoside surfactant, or a compound thereof. Although the product effect is relatively significant, in this patent, its surfactant is still a relatively simple straight-chain surfactant compound product, and although its surfactant enables the product to achieve the cleaning effect of a detergent without using phosphoric acid, its simple compound has not yet brought about a functional breakthrough in the molecular structure, and the cleaning of the stainless steel surface is still limited to the principle of conventional surfactants, and the performance is relatively limited.

[0004] Therefore, it is necessary to develop a surfactant with a molecular structure that can bring stronger decontamination ability, and to go a step further on the interfacial activity mechanism of existing conventional surfactants, so as to serve as a surfactant in CIP and bring better cleaning effects to food production equipment. Summary of the invention

[0005] In view of the limitations of the existing methods described above, the purpose of the present invention is to provide a method for preparing a surfactant and a cleaning agent to solve one or more technical problems existing in the prior art and at least provide a beneficial choice or create conditions.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] A preparation method of a surfactant and a cleaning agent, wherein the surfactant comprises sodium gluconate, branched polyoxyethylene ether, and a modified cellulose-based branched copolymer surfactant.

[0008] Furthermore, the modified cellulose-based branched copolymer surfactant comprises a cellulose structure polymer backbone, a first monomer, a second monomer, and a third monomer.

[0009] Furthermore, the main substance of the cellulose structural polymer includes cellulose and modified cellulose; the modified cellulose includes cellulose acetate.

[0010] The cellulose involved in the present application is microcrystalline cellulose.

[0011] Further, the first monomer of the modified cellulose-based branched polymer surfactant includes N-triethyl-(4-vinylbenzyl) chloride.

[0012] Furthermore, the second monomer of the modified cellulose-based branched copolymer surfactant includes methylene succinic acid and methylene succinic acid derivative compounds.

[0013] Furthermore, the third monomer of the modified cellulose-based branched copolymer surfactant includes methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium bromide, and methacryloyloxyethyltrimethylammonium.

[0014] The second monomer, methylene succinic acid and its derivatives, not only contain carboxyl groups that can increase the water solubility of the polymer, but also increase the polarity of the molecular chain, which can make the flocculation effect brought by the third monomer more significant.

[0015] Furthermore, the preparation method of the modified cellulose-based branched copolymer surfactant comprises:

[0016] A101, polymerizing a cellulose structure polymer backbone substance with a first monomer to obtain a cellulose structure preliminary polymer S1;

[0017] A102, copolymerizing the preliminary polymer S1 with the second monomer and the third monomer to obtain a modified cellulose-based branched copolymer surfactant.

[0018] Furthermore, the preparation method of the cellulose structure preliminary polymer S1 comprises:

[0019] B101, taking 1 part of the main substance of the cellulose structure polymer by mass, dissolving it in a solvent, the solvent comprising a low-carbon organic solvent with a carbon content of less than or equal to 4, water, and an imidazole ionic liquid, to obtain a liquid L1 in which the main substance of the cellulose structure polymer is dissolved;

[0020] The low-carbon organic solvent with a carbon content of less than or equal to 4 includes methanol, ethanol, propanol, dichloromethane, and ethyl acetate; the water includes double distilled water; and the imidazole ionic liquid includes 1-allyl-3-methylimidazole chloride (AmimCl).

[0021] In this step, you only need to add an appropriate amount of solvent so that the main substance of the cellulose structure polymer can be dissolved.

[0022] B102, polymerizing the liquid L1 with the first monomer to obtain a preliminary polymer S1.

[0023] Furthermore, in step A102, the method for copolymerizing the preliminary polymer S1 with the second monomer and the third monomer is:

[0024] The preliminary polymer S1 is dissolved in deionized water under inert gas protection throughout the process, and the second monomer and the third monomer are added. After the monomers are dissolved, an initiator is added, and the reaction is carried out for 10-15 hours. Subsequently, a low-carbon organic solvent is used for precipitation separation to obtain a modified cellulose-based branched copolymer surfactant; wherein the initiator includes ammonium persulfate and sodium sulfite; and the low-carbon organic solvent includes alcohol and ester organic solvents with a carbon content of less than 5.

[0025] 2-Bromoisobutyryl bromide and pyridine are used as catalysts in the reaction process.

[0026] A cleaning agent, wherein any product obtained in the above technical solution is used in its formula.

[0027] Since the first monomer, the second monomer and the third monomer are laterally grafted onto the cellulose structural polymer backbone, the polymer has hydrophilicity and lipophilicity. The long-chain macromolecular polymerization brought by the first monomer allows subsequent monomers to be wrapped after grafting due to the charge effect of the main chain of the cellulose structural polymer backbone, so that the substances formed by the surfactant groups of the final copolymer are entangled with each other, presenting a three-dimensional structure with elliptical flocculation characteristics, thereby more comprehensively contacting the liquid, thereby further improving its surface activity effect. Moreover, on the basis of amphiphilicity, the copolymer has an improved structural strength brought by the macromolecules, so that it can more effectively activate the substances on the surface of the pipeline and scrape off with high resistance at the same time, thereby further improving its effect.

[0028] The beneficial effects of the present invention are as follows: by modifying and polymerizing cellulose compounds, a macromolecular surfactant with amphiphilicity is formed, and the copolymer produced by graft copolymerization has a three-dimensional structure with elliptical flocculation characteristics. While having stronger amphiphilicity in performance, its spatial structure enables the third monomer linked by the polar second monomer to cause the surfactant to lead the detergent to flocculate microscopically, thereby stretching and entanglement of its microscopic side chains, and increasing the rigidity of the microscopic particles. Therefore, compared with the prior art, the surfactant disclosed in the present application has microscopic characteristics brought by the three-dimensional structure with elliptical flocculation characteristics at the microscopic level, so that it can more effectively impact and penetrate the dirt on the surface of the production pipeline, and thus can more effectively disintegrate the stains from a microscopic perspective, so it has more excellent performance compared with the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1This is an electron microscope photograph of the modified cellulose-based branched copolymer surfactant obtained in Example 1. DETAILED DESCRIPTION

[0030] The following will be combined with the embodiments to clearly and completely describe the concept, specific structure and technical effects of the present invention, so as to fully understand the purpose, scheme and effect of the present invention. It should be noted that the embodiments and features in the embodiments of this application can be combined with each other without conflict.

[0031] 1. Example 1

[0032] 3.24g of microcrystalline cellulose was weighed as the main material of cellulose structural polymer, placed in a 50mL round-bottom flask, protected by nitrogen, and emptied and replaced three times to complete the preparation of anaerobic conditions, then 20ml of AmimCl was added, and the temperature was 80℃ and magnetic stirring was stirred until it was completely dissolved to obtain a homogeneous yellow transparent solution of cellulose. Subsequently, 2-bromoisobutyryl bromide and pyridine were slowly added dropwise with a syringe in an ice water bath, and the temperature was 40℃ and the reaction was continued for 12 hours to finally obtain a milky white solution. After the solution was allowed to stand, the supernatant was taken; distilled water was dripped in to obtain a white flocculent substance, and the precipitated product was washed with distilled water two to three times to finally obtain white solid particles.

[0033] Take 2g of the white solid particles obtained in the previous step, place them in a 100ml flask, protect with nitrogen, empty and replace three times to complete the preparation of anaerobic conditions, then add 50ml of 1,4-dioxane while stirring until it is completely dissolved to obtain a transparent solution; add 2g of N-triethyl-(4-vinylbenzyl) chloride as the first monomer, then add 2ml of pentamethyldiethylenetriamine, stir and mix well, add 1g of cuprous bromide, react in an oil bath at 70℃ for 30 minutes, add 3g of methylene succinic acid as the second monomer and 2g of methacryloyloxyethyl trimethylammonium chloride as the third monomer, raise the oil bath temperature to 85℃, and react for 2h. After the reaction, dissolve the product in tetrahydrofuran and drip it dropwise into excess anhydrous ethanol and filter it to obtain white solid particles, which are the target product, the modified cellulose-based branched copolymer surfactant.

[0034] 2. Example 2-6

[0035] The steps are the same as above. The composition of the target product, the modified cellulose-based branched copolymer surfactant, is shown in Table 1.

[0036] Table 1. Configuration table of Examples 1-6.

[0037]

[0038]

[0039] 3. Examples 7-15

[0040] Examples 1-6 were formulated into cleaning agents according to the following method to obtain Examples 7-15, as shown in Table 2 for details.

[0041] Stir and dissolve 30g of citric acid in 150ml of water; add 5g of nitric acid, 10g of acetic acid, 3g of surfactant, 0.01g of isopropylbenzene sulfonate, and 0.02g of amine compound in sequence, and stir and dissolve evenly, wherein the amine compound is a mixture of polyethyleneimine, polyethyleneamine, and aminomethyl-substituted polystyrene.

[0042] 4. Comparative Examples 1-3

[0043] 30g of citric acid was stirred and dissolved in 150ml of water; 5g of nitric acid, 10g of acetic acid, 3g of surfactant, 0.01g of cumene sulfonate, and 0.02g of amine compound were added in sequence and stirred to dissolve evenly. The amine compound was a mixture of polyethyleneimine, polyethyleneamine, and aminomethyl-substituted polystyrene, as shown in Table 2.

[0044] Table 2. Components and contents of Examples 7-15 and Comparative Examples 1-3

[0045]

[0046]

[0047]

[0048] 5. The performance tests of Examples 7-15 and Comparative Examples 1-3 were performed, and the items and methods were as follows:

[0049] (1) Test of cleaning agent impact decontamination ability:

[0050] Clean the stainless steel sheet (100mm×50m) with anhydrous ethanol, weigh m1, wrap tin foil around it, heat the container in an oven to 90℃, then add a certain amount of milk to each container, then put it back into the oven to air dry, add a certain amount of milk after the surface is air dried, and then dry again. Repeat this process to complete a total of 4 cycles. Each drying cycle takes 45 minutes. Remove the tin foil, then rinse the dried milk container with deionized water to eliminate unattached residues, and then dry it. Weigh it again and measure m2. Take the prepared cleaning agent, prepare 500mL of a dilute solution diluted fifty times, put it in an 800mL beaker, heat it in a water bath to 40-60°C, place the stainless steel sheet with the milk scale face down in the beaker, stir it on a magnetic stirrer at 50r / min for 10min, then put the stainless steel sheet in an oven at 60℃ to dry for 6h, take it out and cool it naturally to room temperature, and weigh it again and measure m3. The decontamination rate (D) is D = m2-m3 / m2-m1×100%.

[0051] The cleaning agents prepared in Examples 7-15 and Comparative Examples 1-3 were subjected to a cleaning agent impact decontamination ability test according to this method. The results are shown in Table 3.

[0052] (2) Foaming power test:

[0053] The method was carried out in accordance with the "Test Methods for Surfactant Detergents" (GB / T13173-2008). The product was diluted 50 times for testing. The test results are shown in Table 3.

[0054] Table 3. Test results of cleaning agent impact decontamination ability and foaming power

[0055]

[0056]

[0057] It can be seen from the experimental results in Table 3 that the cleaning agent prepared from the modified cellulose-based branched copolymer surfactant disclosed in the technical solution provided in this application has a good cleaning effect.

[0058] By comparison with Examples 7-12, it can be judged that when microcrystalline cellulose is used as the main surfactant, its foam height and cleaning effect are slightly better than those of the surfactant with cellulose acetate as the main body, and it is judged that the agglomeration effect of the microcrystalline cellulose body is better than that of cellulose acetate; compared with Comparative Examples 1-3, the effects are better than the surfactants in the prior art, proving that the effects are significant; the data of Examples 13-15 show that although the effect of using the modified cellulose-based branched copolymer surfactant disclosed in the present application alone can still be maintained, compared with Examples 7-12, compounding with the prior art can have a certain improvement effect.

[0059] according to Figure 1 From the electron microscope microstructure photograph of Example 1 of the present application, it can be seen that its elliptical flocculation characteristics are obvious. In the subsequent cleaning agent examples, the cleaning agent product obtained by the technical solution provided by the present application has a better cleaning effect than the prior art in the test of the cleaning agent's impact cleaning ability when diluted fifty times. Figure 1 The reasons for the provided microstructure and the technical solution provided in the present application can be analyzed as follows: during the process of liquid impacting stains, the elliptical flocculation structure not only penetrates the stains, but also wraps the stains, allowing them to be more fully peeled off and dispersed. Moreover, as the cleaning process progresses, the density of the elliptical flocculation structure that wraps the stains is increased, and its impact penetration ability on the stains is further enhanced, providing a basis for the subsequent decontamination of the elliptical flocculation structure, thereby further improving the decontamination rate.

[0060] Although the description of the present invention has been quite detailed and has been described in particular with respect to several described embodiments, it is not intended to be limited to any of these details or embodiments or any particular embodiment, so as to effectively cover the intended scope of the present invention. In addition, the present invention is described above with the embodiments foreseeable by the inventors, and its purpose is to provide a useful description, and those non-substantial changes to the present invention that are not currently foreseen may still represent equivalent changes of the present invention.

Claims

1. A method for preparing a surfactant, characterized in that: The surfactants include sodium gluconate, branched polyoxyethylene ether, and modified cellulose-based branched copolymer surfactants.

2. The method for preparing a surfactant according to claim 1, characterized in that: The modified cellulose-based branched copolymer surfactant comprises a cellulose structural polymer main substance, a first monomer, a second monomer and a third monomer.

3. The method for preparing a surfactant according to claim 2, characterized in that: The main substance of the cellulose structural polymer includes cellulose and modified cellulose; the modified cellulose includes cellulose acetate.

4. The method for preparing a surfactant according to claim 2, characterized in that: The first monomer of the modified cellulose-based branched polymer surfactant includes N-triethyl-(4-vinylbenzyl) chloride; The second monomer of the modified cellulose-based branched copolymer surfactant includes methylene succinic acid and methylene succinic acid derivative compounds; The third monomer of the modified cellulose-based branched copolymer surfactant includes methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium bromide, and methacryloyloxyethyl trimethyl ammonium.

5. The method for preparing a surfactant according to claim 2, characterized in that: The preparation method of the modified cellulose-based branched copolymer surfactant comprises: A101, polymerizing a cellulose structure polymer backbone substance with a first monomer to obtain a cellulose structure preliminary polymer S1; A102, copolymerizing the preliminary polymer S1 with the second monomer and the third monomer to obtain a modified cellulose-based branched copolymer surfactant.

6. The method for preparing a surfactant according to claim 5, characterized in that: The preparation method of the cellulose structure preliminary polymer S1 comprises: B101, taking 1 part of the main substance of the cellulose structure polymer by mass, dissolving it in a solvent, the solvent comprising a low-carbon organic solvent with a carbon content of less than or equal to 4, water, and an imidazole ionic liquid, to obtain a liquid L1 in which the main substance of the cellulose structure polymer is dissolved; B102, polymerizing the liquid L1 with the first monomer to obtain a preliminary polymer S1.

7. The method for preparing a surfactant according to claim 5, characterized in that: The method for copolymerizing the preliminary polymer S1 with the second monomer and the third monomer in step A102 is: The preliminary polymer S1 is dissolved in deionized water under inert gas protection throughout the process, and the second monomer and the third monomer are added. After the monomers are dissolved, an initiator is added, and the reaction is carried out for 10-15 hours. Subsequently, a low-carbon organic solvent is used for precipitation separation to obtain a modified cellulose-based branched copolymer surfactant; wherein the initiator includes ammonium persulfate and sodium sulfite; and the low-carbon organic solvent includes alcohol and ester organic solvents with a carbon content of less than 5.

8. A cleaning agent, characterized in that: The formula of the invention uses a product obtained by the preparation method of any one of claims 1 to 7.

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