A high-efficiency anti-sticking agent for concrete machinery and equipment, its preparation method and application

Abstract

This invention relates to the field of concrete processing and machinery, and particularly to a high-efficiency anti-sticking agent for concrete machinery, its preparation method, and its application. The invention uses a polyacrylate coating as a matrix, and imparts certain hydrophobic properties to the coating by introducing fluorinated functional monomers and silane coupling agents. Furthermore, the hardness and alkali resistance of the coating are further improved by introducing rigid styrene monomers, resulting in a high-efficiency anti-sticking agent with excellent hydrophobic properties and superior alkali and wear resistance. When sprayed onto the inner wall of the tank of concrete machinery, it forms a uniform coating, effectively improving the hydrophobicity of the metal inner wall, reducing concrete residue after unloading, and avoiding problems such as uneven concrete mixing, reduced output, and decreased performance caused by excessive material residue. Simultaneously, the presence of this coating reduces corrosion and wear on the tank interior during concrete mixing and transportation.

Description

Technical Field

[0001] This invention relates to the field of concrete processing and machinery equipment, and in particular to a high-efficiency anti-sticking agent for concrete machinery equipment, its preparation method and application. Background Technology

[0002] Modern ready-mixed concrete is primarily produced centrally by large-scale concrete batching plants and transported to various construction sites by concrete mixer trucks. This production method effectively improves the production efficiency and performance of concrete while saving costs and reducing environmental pollution.

[0003] In practical applications, after the material is unloaded from the mixing system, pumps, and mixer trucks of a concrete mixing plant, some concrete residue remains inside the equipment, especially near the spiral blades. If not cleaned promptly, this residual concrete will gradually solidify inside the tank, occupying space, reducing tank volume, and decreasing material output and transport capacity. It will also lead to uneven mixing of the concrete, affecting its performance. Furthermore, for concrete mixer trucks, the gradually accumulating solidified material increases the weight of the mixing tank, increases vehicle energy consumption, and accelerates wear on tires, reducers, and other components, leading to vehicle malfunctions. Currently, after using concrete machinery, construction workers use large amounts of water to flush the inside of the equipment and regularly clean the tank manually. However, this cleaning and maintenance process generates a large amount of wastewater and waste, and the forceful knocking and peeling during regular maintenance can easily cause irreversible damage to the tank. Therefore, if the stain resistance of the inner walls of concrete equipment can be improved from the source, and the residue of concrete materials during the unloading stage can be reduced, the output and quality of concrete materials can be effectively guaranteed, the wear and maintenance of mechanical equipment and the generation of wastewater and waste materials can be reduced, which is of great significance in saving construction costs and improving economic efficiency. At present, there are no reports on anti-sticking agents and corresponding technologies for concrete machinery and equipment. Summary of the Invention

[0004] The purpose of this invention is to address the technological gaps in the existing technology by providing a highly efficient anti-sticking agent for concrete machinery, its preparation method, and its application. The highly efficient anti-sticking agent prepared by this invention, when sprayed onto the inner wall of the tank of concrete machinery, forms a hydrophobic and wear-resistant coating on the metal inner wall surface, thereby effectively improving the hydrophobicity of the metal inner wall and reducing concrete material residue inside the tank.

[0005] To achieve the above objectives, the present invention provides the following solution:

[0006] One of the technical solutions of this invention is a method for preparing a high-efficiency anti-sticking agent, comprising the following steps:

[0007] Dissolve the pH stabilizer and emulsifier in water and mix well to obtain the base solution;

[0008] Emulsifier, hard segment monomer, and soft segment monomer are added to water and ultrasonically emulsified to obtain a pre-emulsified core monomer emulsion.

[0009] Emulsifier, hard segment monomer, soft segment monomer, fluorinated monomer and silane coupling agent are added to water and ultrasonically emulsified to obtain a pre-emulsified shell monomer emulsion.

[0010] The initiator is added to water and mixed well to obtain an initiator solution;

[0011] Heat the base solution to 70-85℃, add some pre-emulsified nucleomonomer emulsion to it, stir evenly, and then add 1 / 3 volume of initiator solution to the reaction system.

[0012] After the free radical polymerization reaction of the core monomer in the system is triggered to form a seed emulsion and exhibits a blue light effect, the remaining pre-emulsified core monomer emulsion and 1 / 3 volume of initiator solution are added to the reaction system, and then the temperature is maintained (70-85℃ for 30-50 min) to prepare a stable core emulsion with uniformity and narrow particle size distribution.

[0013] The pre-emulsified shell monomer emulsion and 1 / 3 volume of initiator solution were added to the reaction system, and then the temperature was maintained (70-85℃ for 60-120 min) to allow the pre-emulsified shell monomer to continue to grow on the surface of the core latex particles, thus obtaining a stable latex containing latex particles with a uniform core-shell structure.

[0014] The stable latex containing uniform core-shell structured latex particles is diluted, and then a film-forming aid and silicone oil are added. After stirring evenly, a high-efficiency anti-sticking agent is obtained.

[0015] The reason for setting the reaction temperature and reaction steps as described above in the preparation of a stable core emulsion with uniform particle size distribution and a stable latex containing latex particles with uniform core-shell structure is as follows:

[0016] The reaction temperature of 70–85℃ is used to effectively trigger the free radical polymerization of the monomers. This reaction procedure is designed to form a core-shell latex with uniform and stable particle size. Adjusting the reaction procedure, such as directly mixing the raw materials used to prepare the pre-emulsified core monomer emulsion and the pre-emulsified shell monomer emulsion together, will not yield latex particles with a core-shell structure. Alternatively, if the emulsified core monomer emulsion and 2 / 3 of the initiator solution are added to the base solution together, the particle size and distribution of the latex particles will not be as uniform and stable as with this method, and may even affect the stability of subsequent synthesis.

[0017] In a preferred embodiment of the present invention, the mass ratio of pH stabilizer to emulsifier in the primer is 0.42:(0.56-0.90); the pH stabilizer is sodium bicarbonate; and the emulsifier in the primer is one or two of fatty alcohol polyoxyethylene ether, OP-10, and sodium dodecyl sulfate. In a more preferred embodiment of the present invention, the emulsifier in the primer is a mixture of fatty alcohol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 1.25:1 to 1:2, or a mixture of OP-10 and sodium dodecyl sulfate in a mass ratio of 1.25:1 to 1:2.

[0018] In a preferred embodiment of the present invention, the mass ratio of emulsifier, hard segment monomer, and soft segment monomer in the pre-emulsified core monomer emulsion is (1.11-1.80):(10.02-18.00):(9.00-15.06); the emulsifier in the pre-emulsified core monomer emulsion is one or two of fatty alcohol polyoxyethylene ether, OP-10, and sodium dodecyl sulfate; in a more preferred embodiment of the present invention, the emulsifier in the pre-emulsified core monomer emulsion is a mixture of fatty alcohol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 1.25:1 to 1:2, or a mixture of OP-10 and sodium dodecyl sulfate in a mass ratio of 1.25:1 to 1:2. The hard segment monomer in the pre-emulsified core monomer emulsion is one or two of methyl methacrylate, ethyl methacrylate, and styrene (more preferably, when styrene and one of the acrylate monomers are used together, their mass ratio is 1:1.5 to 2:1); the soft segment monomer in the pre-emulsified core monomer emulsion is one or two of n-butyl acrylate, isooctyl acrylate, and ethyl acrylate (more preferably, when two soft monomers are used together, the mass ratio of one of n-butyl acrylate / ethyl acrylate to isooctyl acrylate is 1:1 to 1.5:1).

[0019] In a preferred embodiment of the present invention, the mass ratio of emulsifier, hard segment monomer, soft segment monomer, fluorinated monomer, and silane coupling agent in the pre-emulsified shell monomer emulsion is (1.11-1.80):(10.02-18.00):(9.00-15.06):(3.40-5.40):(1.62-2.16g); the emulsifier in the pre-emulsified shell monomer emulsion is one or two of fatty alcohol polyoxyethylene ether, OP-10, and sodium dodecyl sulfate (when one of fatty alcohol polyoxyethylene ether and OP-10 is used simultaneously with sodium dodecyl sulfate, the mass ratio is 1.25:1 to 1:2); the hard segment monomer in the pre-emulsified shell monomer emulsion is methyl methacrylate, ethyl methacrylate, and styrene. The preemulsified shell monomer emulsion contains one or two of the following monomers (when styrene and one of the acrylate monomers are used together, the mass ratio is 1:1.5 to 2:1); the soft segment monomer in the preemulsified shell monomer emulsion is one or two of the following: n-butyl acrylate, isooctyl acrylate, and ethyl acrylate (when two soft monomers are used together, the mass ratio is 1:1 to 1.5:1); the fluorinated monomer in the preemulsified shell monomer emulsion is at least one of the following: perfluorohexylethylene, dodecafluoroheptyl methacrylate, 2,2,2-trifluoroethyl methacrylate, or tridecafluorooctyl acrylate; the silane coupling agent in the preemulsified shell monomer emulsion is γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, or vinyltrimethoxysilane.

[0020] The initiator is ammonium persulfate, potassium persulfate, or azobisisobutyramidine hydrochloride;

[0021] The film-forming aid is dipropylene glycol, propylene glycol butyl ether, or dodecyl alcohol ester;

[0022] The silicone oil is dimethyl silicone oil or benzyl silicone oil.

[0023] In a preferred embodiment of the present invention, the mass ratio of the pH stabilizer in the base coat to the emulsifier in the pre-emulsified core monomer emulsion, the emulsifier in the pre-emulsified shell monomer emulsion, the initiator, the film-forming aid, and the silicone oil is 0.42:(1.11-1.80):(1.11-1.80):(0.30-0.36):(0.5-1.0):(0.5-1.0).

[0024] In a preferred embodiment of the present invention, after a portion of the pre-emulsified nucleomonomer emulsion is added to the base solution and stirred evenly, 1 / 3 of the volume of the initiator solution is added dropwise to the reaction system at a rate of 0.253 mL / min to 0.404 mL / min.

[0025] After the emulsion emits blue light, the remaining pre-emulsified nucleomonomer emulsion and 1 / 3 volume of initiator solution are added to the reaction system. The drop rate of the remaining pre-emulsified nucleomonomer emulsion is 0.513 mL / min to 0.869 mL / min, and the drop rate of the initiator is 0.112 mL / min to 0.169 mL / min.

[0026] The pre-emulsified shell monomer emulsion and 1 / 3 volume of initiator solution were added to the reaction system, wherein the droplet acceleration rate of the pre-emulsified shell monomer emulsion was 0.367 mL / min to 0.515 mL / min, and the droplet acceleration rate of the initiator was 0.056 mL / min to 0.084 mL / min.

[0027] In each step, the dropping rate of the pre-emulsified core / shell monomer emulsion affects the stability of the final latex. If the dropping rate of the pre-emulsified core / shell monomer emulsion is too slow, the pre-emulsion may break down; if the dropping rate is too fast, the pre-emulsification reaction will be incomplete, and even the shell monomer latex particles may self-aggregate, affecting the formation of core-shell latex particles.

[0028] Similarly, the dropping rate of the initiator also affects the stability of the final latex system and the uniformity of the latex particles. If the dropping rate of the initiator is too slow, the resulting latex particles will be too large; if the dropping rate is too fast, the reaction may proceed rapidly, leading to explosive polymerization.

[0029] In a preferred embodiment of the present invention, the homogeneous latex is diluted with water to a solid content of 8%-30%.

[0030] The second technical solution of the present invention is a high-efficiency anti-sticking agent prepared by the above-mentioned preparation method.

[0031] The third technical solution of the present invention is the application of the above-mentioned high-efficiency anti-sticking agent in the mechanical equipment used in the preparation or transportation of commercial concrete.

[0032] The high-efficiency anti-sticking agent prepared by this invention can effectively improve the hydrophobicity and stain resistance of the inner wall of the tank when sprayed into the tank of concrete machinery and equipment, reduce material residue when concrete is discharged, simplify equipment cleaning and maintenance procedures, alleviate equipment wear and failure problems, and improve the output, performance and economic benefits of commercial concrete.

[0033] The present invention discloses the following technical effects:

[0034] 1. The raw materials used in the preparation method of this invention are widely available, and there are already relatively mature industrial emulsion polymerization production processes and equipment, which are easy to use for large-scale production and engineering applications.

[0035] 2. This invention uses a polyacrylate coating with strong adhesion, good weather resistance, and is not easy to peel off as a base. The hardness and adhesion of the coating are adjusted by adjusting the ratio of soft and hard segments in the polymer. Styrene monomer is introduced to further improve the hardness and alkali resistance of the coating. At the same time, fluorinated monomer and silane coupling agent are introduced into the polyacrylate coating to improve the hydrophobicity and wear resistance of the coating. Thus, the prepared high-efficiency anti-sticking agent for concrete machinery and equipment has good adhesion, alkali resistance, wear resistance and hydrophobicity.

[0036] 3. The high-efficiency anti-sticking agent prepared in this invention can form a hydrophobic and wear-resistant coating on the inner wall of the tank of concrete machinery. It can effectively improve the hydrophobicity of the metal inner wall, thereby reducing the residue of concrete materials after unloading. It can be cleaned with a small amount of water, simplifying the subsequent cleaning and maintenance procedures. This reduces problems such as uneven concrete mixing, reduced output and performance caused by excessive concrete residue. At the same time, it reduces the wear and maintenance of machinery and the generation of wastewater and waste materials, saving a lot of economic costs.

[0037] 4. The high-efficiency anti-sticking agent prepared by this invention, when sprayed onto the inner wall of the tank of concrete machinery, forms a coating that can reduce the corrosion and wear of the tank interior by materials during concrete mixing and transportation, thereby improving the service life of the machinery. Attached Figure Description

[0038] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0039] Figure 1 The wear of tungsten carbide plates coated with high-efficiency anti-sticking agents from different embodiments and comparative examples is shown; where (a) is Comparative Example 1, (b) is Example 1, (c) is Example 2, (d) is Example 3, (e) is Example 4, and (f) is Example 5. Detailed Implementation

[0040] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0041] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0042] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0043] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0044] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0045] Unless otherwise specified, the "%" mentioned in this invention refers to a percentage by mass.

[0046] This invention provides a method for preparing a high-efficiency anti-sticking agent for use in concrete machinery, comprising the following steps:

[0047] Step 1: Dissolve 0.42g of pH stabilizer and 0.56-0.90g of emulsifier in 50g of deionized water according to their weight, and stir well to obtain the base solution;

[0048] Step 2: Add 1.11-1.80g of emulsifier, 10.02-18.00g of hard segment monomer, and 9.00-15.06g of soft segment monomer to 30g of deionized water in sequence according to mass. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 30-50 minutes to obtain a pre-emulsified nucleomonomer emulsion.

[0049] Step 3: Add 1.11-1.80g of emulsifier, 10.02-18.00g of hard segment monomer, 9.00-15.06g of soft segment monomer, 3.40-5.40g of fluorinated monomer and 1.62-2.16g of silane coupling agent to 30g of deionized water in that order by weight. After stirring evenly, transfer the mixture to an ultrasonic cell disruptor and ultrasonically emulsify for 30-50 minutes to obtain a pre-emulsified shell monomer emulsion.

[0050] Step 4: Add 0.30-0.36g of initiator to 30g of deionized water and stir until homogeneous to obtain an initiator solution;

[0051] Step 5: Heat the base solution obtained in Step 1 to 70-85℃, add 10-15g of the pre-emulsified nucleomonomer emulsion obtained in Step 2, stir for 10-20min, and then add 1 / 3 of the initiator solution obtained in Step 4 dropwise into the reaction system over a period of 25-40min.

[0052] Step 6: After the reaction emulsion in step 5 shows blue light, add the remaining pre-emulsified nucleus monomer emulsion obtained in step 2 and 1 / 3 of the initiator solution obtained in step 4 to the reaction system dropwise over a period of 50-90 minutes, and then continue to keep warm for 30-50 minutes.

[0053] Step 7: Add the pre-emulsified shell monomer emulsion obtained in step 3 and 1 / 3 of the initiator solution obtained in step 4 dropwise into the reaction system. The dropwise addition time is 120-180 min, and then continue to keep warm for 60-120 min to obtain a homogeneous emulsion.

[0054] Step 8: Dilute the homogeneous latex obtained in Step 7 with distilled water to a solid content of 8%-30%, then add 0.5-1.0g of film-forming agent and 0.5-1.0g of silicone oil, stir evenly to obtain a high-efficiency anti-sticking agent for concrete machinery and equipment.

[0055] The high-efficiency anti-sticking agent prepared by this invention can be applied to concrete machinery and equipment to reduce concrete residue in the machinery and equipment, reduce internal wear, cleaning water consumption and maintenance costs, and effectively save the cost of commercial concrete and transportation costs. It has great application value and economic benefits.

[0056] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.

[0057] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0058] Example 1

[0059] A method for preparing a high-efficiency anti-sticking agent for use in concrete machinery and equipment, comprising the following steps:

[0060] Step 1: Dissolve 0.42g sodium bicarbonate and 0.90g emulsifier in 50g deionized water according to their mass ratio, and stir evenly to obtain the base liquid. The emulsifier is fatty alcohol polyoxyethylene ether and sodium dodecyl sulfate, with a mass ratio of 1.25:1.

[0061] Step 2: Add 1.80g of emulsifier (1.0g of fatty alcohol polyoxyethylene ether + 0.80g of sodium dodecyl sulfate), 17.04g of hard segment monomer (8.52g of methyl methacrylate + 8.52g of styrene), and 11.30g of soft segment monomer (5.80g of n-butyl acrylate + 5.5g of isooctyl acrylate) to 30g of deionized water in sequence by weight. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 40 minutes to obtain a pre-emulsified nucleomonomer emulsion.

[0062] Step 3: Add 1.80g emulsifier (1.0g fatty alcohol polyoxyethylene ether + 0.80g sodium dodecyl sulfate), 17.04g hard segment monomer (8.52g methyl methacrylate + 8.52g styrene), 11.30g soft segment monomer (5.80g n-butyl acrylate + 5.5g isooctyl acrylate), 4.54g perfluorohexylethylene and 1.82g vinyltriethoxysilane to 30g deionized water in sequence according to mass. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 40min to obtain a pre-emulsified shell monomer emulsion.

[0063] Step 4: Add 0.36g of ammonium persulfate to 30g of deionized water and stir until homogeneous to obtain the initiator solution;

[0064] Step 5: Heat the base solution obtained in Step 1 to 85°C, add 12g of the pre-emulsified nucleomonomer emulsion obtained in Step 2, stir for 15min, and then add 1 / 3 (volume) of the initiator solution obtained in Step 4 dropwise into the reaction system at a dropping rate of 0.337mL / min.

[0065] Step 6: After the reaction system in Step 5 shows blue light, add the remaining pre-emulsified nucleomonomer emulsion obtained in Step 2 and 1 / 3 of the initiator solution obtained in Step 4 to the reaction system. The dropping rate of the remaining pre-emulsified nucleomonomer emulsion is 0.802 mL / min, and the dropping rate of the initiator is 0.168 mL / min. Then continue to keep warm for 40 min.

[0066] Step 7: The pre-emulsified shell monomer emulsion obtained in step 3 and 1 / 3 of the initiator solution obtained in step 4 are added dropwise to the reaction system. The drop rate of the pre-emulsified shell monomer emulsion is 0.443 mL / min and the drop rate of the initiator is 0.067 mL / min. Then, the mixture is kept warm for 90 min to obtain a homogeneous latex.

[0067] Step 8: Dilute the homogeneous latex obtained in Step 7 with distilled water to a solid content of 10%, then add 0.6g of dipropylene glycol and 0.6g of dimethyl silicone oil, stir evenly to obtain a high-efficiency anti-sticking agent for concrete machinery and equipment.

[0068] Example 2

[0069] A method for preparing a high-efficiency anti-sticking agent for use in concrete machinery and equipment, comprising the following steps:

[0070] Step 1: Dissolve 0.42g sodium bicarbonate and 0.56g emulsifier in 50g deionized water according to their mass ratio, and stir evenly to obtain the base liquid. The emulsifier is fatty alcohol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 1:2.

[0071] Step 2: Add 1.11g of emulsifier (0.37g of fatty alcohol polyoxyethylene ether + 0.74g of sodium dodecyl sulfate), 10.02g of hard segment monomer (methyl methacrylate), and 15.06g of soft segment monomer (7.53g of ethyl acrylate + 7.53g of isooctyl acrylate) to 30g of deionized water in sequence by weight. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 30 minutes to obtain a pre-emulsified nucleomonomer emulsion.

[0072] Step 3: In order of mass, add 1.11g of emulsifier (0.37g fatty alcohol polyoxyethylene ether + 0.74g sodium dodecyl sulfate), 10.02g of hard segment monomer (methyl methacrylate), 15.06g of soft segment monomer (7.53g ethyl acrylate + 7.53g isooctyl acrylate), 4.00g of dodecyl fluoroheptyl methacrylate and 1.62g of γ-methacryloyloxypropyltrimethoxysilane to 30g of deionized water, stir evenly, and then transfer to an ultrasonic cell disruptor for ultrasonic emulsification for 30min to obtain a pre-emulsified shell monomer emulsion.

[0073] Step 4: Add 0.30g of potassium persulfate to 30g of deionized water and stir until homogeneous to obtain an initiator solution;

[0074] Step 5: Heat the base solution obtained in Step 1 to 80°C, add 10g of the pre-emulsified nucleomonomer emulsion obtained in Step 2, stir for 10min, and then add 1 / 3 of the initiator solution obtained in Step 4 dropwise into the reaction system at a dropping rate of 0.404mL / min.

[0075] Step 6: After the reaction system in Step 5 shows blue light, add the remaining pre-emulsified nucleomonomer emulsion obtained in Step 2 and 1 / 3 of the initiator solution obtained in Step 4 to the reaction system. The dropping rate of the remaining pre-emulsified nucleomonomer emulsion is 0.513 mL / min, and the dropping rate of the initiator is 0.112 mL / min. Then continue to keep warm for 30 min.

[0076] Step 7: The pre-emulsified shell monomer emulsion obtained in step 3 and 1 / 3 of the initiator solution obtained in step 4 are respectively added dropwise to the reaction system. The drop rate of the pre-emulsified shell monomer emulsion is 0.513 mL / min and the drop rate of the initiator is 0.084 mL / min. Then, the mixture is kept warm for 120 min to obtain a homogeneous latex.

[0077] Step 8: Dilute the homogeneous latex obtained in Step 7 with distilled water to a solid content of 8%, then add 0.5g of dipropylene glycol and 0.5g of benzyl silicone oil, stir evenly to obtain a high-efficiency anti-sticking agent for concrete machinery and equipment.

[0078] Example 3

[0079] A method for preparing a high-efficiency anti-sticking agent for use in concrete machinery and equipment, comprising the following steps:

[0080] Step 1: Dissolve 0.42g sodium bicarbonate and 0.72g emulsifier in 50g deionized water according to their mass ratio, and stir evenly to obtain the base liquid. The emulsifier is OP-10 and sodium dodecyl sulfate in a mass ratio of 1:1.

[0081] Step 2: Add 1.44g of emulsifier (0.72g OP-10 + 0.72g sodium dodecyl sulfate), 18g of hard segment monomer (styrene), and 9g of soft segment monomer (5.4g n-butyl acrylate + 3.60g isooctyl acrylate) to 30g of deionized water in sequence by weight. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 50min to obtain a pre-emulsified nucleomonomer emulsion.

[0082] Step 3: In step 2, add 1.44g of emulsifier (0.72g OP-10 + 0.72g sodium dodecyl sulfate), 18g of hard segment monomer (styrene), 9g of soft segment monomer (5.4g n-butyl acrylate + 3.60g isooctyl acrylate), 5.40g of 2,2,2-trifluoroethyl methacrylate and 2.16g of vinyltrimethoxysilane to 30g of deionized water in that order by weight. After stirring evenly, transfer the mixture to an ultrasonic cell disruptor and ultrasonically emulsify for 50 minutes to obtain a pre-emulsified shell monomer emulsion.

[0083] Step 4: Add 0.32g of azobisisobutyramidine hydrochloride to 30g of deionized water and stir until homogeneous to obtain an initiator solution;

[0084] Step 5: Heat the base solution obtained in Step 1 to 70°C, add 15g of the pre-emulsified nucleomonomer emulsion obtained in Step 2, stir for 20min, and then add 1 / 3 of the initiator solution obtained in Step 4 dropwise into the reaction system at a dropping rate of 0.253mL / min.

[0085] Step 6: After the reaction system in Step 5 shows blue light, add the remaining pre-emulsified nucleomonomer emulsion obtained in Step 2 and 1 / 3 of the initiator solution obtained in Step 4 to the reaction system. The dropping rate of the remaining pre-emulsified nucleomonomer emulsion is 0.869 mL / min, and the dropping rate of the initiator is 0.202 mL / min. Then continue to keep warm for 50 min.

[0086] Step 7: The pre-emulsified shell monomer emulsion obtained in step 3 and 1 / 3 of the initiator solution obtained in step 4 are respectively added dropwise to the reaction system. The drop rate of the pre-emulsified shell monomer emulsion is 0.367 mL / min and the drop rate of the initiator is 0.056 mL / min. Then, the mixture is kept warm for 60 min to obtain a homogeneous latex.

[0087] Step 8: Dilute the homogeneous latex obtained in Step 7 with distilled water to a solid content of 30%, then add 1.0g dodecyl alcohol ester and 1.0g benzyl silicone oil, stir evenly to obtain a high-efficiency anti-sticking agent for concrete machinery and equipment.

[0088] Example 4

[0089] A method for preparing a high-efficiency anti-sticking agent for use in concrete machinery and equipment, comprising the following steps:

[0090] Step 1: Dissolve 0.42g sodium bicarbonate and 0.60g sodium dodecyl sulfate in 50g deionized water according to their weight, and stir well to obtain the base liquid;

[0091] Step 2: Add 1.20g sodium dodecyl sulfate, 14.20g hard segment monomer (8.52g ethyl methacrylate + 5.68g styrene), and 14.50g soft segment monomer (isooctyl acrylate) to 30g deionized water in sequence by weight. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 30 minutes to obtain a pre-emulsified nucleoside emulsion.

[0092] Step 3: In step 2, add 1.20g sodium dodecyl sulfate, 14.20g hard segment monomer (8.52g ethyl methacrylate + 5.68g styrene), 14.50g soft segment monomer (isooctyl acrylate), 4.54g tridecyl fluorooctyl acrylate and 1.82g vinyltriisopropylsilane to 30g deionized water in that order by weight. After stirring evenly, transfer the mixture to an ultrasonic cell disruptor and ultrasonically emulsify for 30 minutes to obtain a pre-emulsified shell monomer emulsion.

[0093] Step 4: Add 0.32g of ammonium persulfate to 30g of deionized water and stir until homogeneous to obtain the initiator solution;

[0094] Step 5: Heat the base solution obtained in Step 1 to 82°C, add 12g of the pre-emulsified nucleoside emulsion obtained in Step 2, stir for 20min, and then add 1 / 3 of the initiator solution obtained in Step 4 dropwise into the reaction system at a dropping rate of 0.253mL / min.

[0095] Step 6: After the reaction system in Step 5 shows blue light, add the remaining pre-emulsified nucleomonomer emulsion obtained in Step 2 and 1 / 3 of the initiator solution obtained in Step 4 to the reaction system. The dropping rate of the remaining pre-emulsified nucleomonomer emulsion is 0.684 mL / min, and the dropping rate of the initiator is 0.144 mL / min. Then continue to keep warm for 40 min.

[0096] Step 7: The pre-emulsified shell monomer emulsion obtained in step 3 and 1 / 3 of the initiator solution obtained in step 4 are respectively added dropwise to the reaction system. The drop rate of the pre-emulsified shell monomer emulsion is 0.442 mL / min and the drop rate of the initiator is 0.067 mL / min. Then, the mixture is kept warm for 90 min to obtain a homogeneous latex.

[0097] Step 8: Dilute the homogeneous latex obtained in Step 7 with distilled water to a solid content of 20%, then add 0.8g of propylene glycol butyl ether and 0.8g of benzyl silicone oil, stir evenly to obtain a high-efficiency anti-sticking agent for concrete machinery and equipment.

[0098] Example 5

[0099] A method for preparing a high-efficiency anti-sticking agent for use in concrete machinery and equipment, comprising the following steps:

[0100] Step 1: Dissolve 0.42g sodium bicarbonate and 0.72g fatty alcohol polyoxyethylene ether in 50g deionized water according to their weight, and stir well to obtain the base liquid;

[0101] Step 2: Add 1.44g fatty alcohol polyoxyethylene ether, 20.00g hard segment monomer (6.66g methyl methacrylate + 13.34g styrene), and 10g soft segment monomer (n-butyl acrylate) to 30g deionized water in sequence by weight. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 40 minutes to obtain a pre-emulsified nucleomonomer emulsion.

[0102] Step 3: In order of mass, add 1.44g fatty alcohol polyoxyethylene ether, 20.00g hard segment monomer (6.66g methyl methacrylate + 13.34g styrene), 10g soft segment monomer (n-butyl acrylate), 3.40g perfluorohexylethylene and 1.70g vinyltriethoxysilane to 30g deionized water in order of mass in step 2. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 40 minutes to obtain a pre-emulsified shell monomer emulsion.

[0103] Step 4: Add 0.36g of ammonium persulfate to 30g of deionized water and stir until homogeneous to obtain the initiator solution;

[0104] Step 5: Heat the base solution obtained in Step 1 to 85°C, add 15g of the pre-emulsified nucleomonomer emulsion obtained in Step 2, stir for 20min, and then add 1 / 3 of the initiator solution obtained in Step 4 dropwise into the reaction system at a dropping rate of 0.253mL / min.

[0105] Step 6: After the reaction system in Step 5 shows blue light, add the remaining pre-emulsified nucleomonomer emulsion obtained in Step 2 and 1 / 3 of the initiator solution obtained in Step 4 to the reaction system. The dropping rate of the remaining pre-emulsified nucleomonomer emulsion is 0.744 mL / min, and the dropping rate of the initiator is 0.169 mL / min. Then continue to keep warm for 30 min.

[0106] Step 7: The pre-emulsified shell monomer emulsion obtained in step 3 and 1 / 3 of the initiator solution obtained in step 4 are added dropwise to the reaction system. The drop rate of the pre-emulsified shell monomer emulsion is 0.444 mL / min and the drop rate of the initiator is 0.067 mL / min. Then, the mixture is kept warm for 90 min to obtain a homogeneous latex.

[0107] Step 8: Dilute the homogeneous latex obtained in Step 7 with distilled water to a solid content of 10%, then add 0.6g of dipropylene glycol and 0.6g of dimethyl silicone oil, stir evenly to obtain a high-efficiency anti-sticking agent for concrete machinery and equipment.

[0108] Comparative Example 1

[0109] Sample A of commercially available anti-sticking agent was purchased from Shandong Anrui, model: Fuxun Concrete Anti-sticking Agent.

[0110] To verify the hydrophobic modification effect of the high-efficiency anti-sticking agent (hereinafter referred to as high-efficiency anti-sticking agent) applied to concrete machinery equipment of the present invention on the inner wall of the tank of concrete machinery equipment, tungsten steel plate, a common material for tanks, was selected as the substrate. The anti-sticking agent sample A in Comparative Example 1 and the high-efficiency anti-sticking agents prepared in Examples 1, 2, 3, 4 and 5 were uniformly sprayed on the clean surface of the tungsten steel plate using a spraying device and placed at room temperature for drying for 24 hours. After film formation, the samples were tested and compared.

[0111] First, contact angle tests were performed on the cleaned tungsten carbide substrate, the tungsten carbide plate of Comparative Example 1, the tungsten carbide plate of Example 1, the tungsten carbide plate of Example 2, the tungsten carbide plate of Example 3, the tungsten carbide plate of Example 4, and the tungsten carbide plate of Example 5. The test results are shown in Table 1.

[0112] Table 1. Contact angles of tungsten carbide plates before and after treatment with high-efficiency anti-sticking agent.

[0113]

[0114] The test results show that the contact angle of the tungsten carbide plate substrate surface is 88° and it is not hydrophobic. However, after spraying the anti-sticking agent sample A of Comparative Example 1 and the high-efficiency anti-sticking agents prepared in Examples 1, 2, 3, 4, and 5 onto the substrate surface, the contact angle of the tungsten carbide plate surface is greater than 90°. This confirms that the anti-sticking agent sample A and the high-efficiency anti-sticking agents prepared in Examples 1, 2, 3, 4, and 5 can impart a certain degree of hydrophobicity to the surface of cement machinery equipment, thereby reducing material residue during unloading.

[0115] Then, several coated tungsten carbide plates were immersed in a 15% sodium hydroxide solution for a specified time. Afterward, the plates were removed, cleaned, dried, and their surface contact angles were tested. The alkali resistance of the anti-sticking agent sample A in Comparative Example 1 and the high-efficiency anti-sticking agents prepared in Examples 1, 2, 3, 4, and 5 was evaluated by monitoring the changes in the surface contact angles of the tungsten carbide plates after immersion for different times. The test results are shown in Table 2.

[0116] Table 2. Changes in contact angle of tungsten carbide plates after immersion in 15% sodium hydroxide.

[0117]

[0118] As shown in Table 2, the contact angle of the tungsten carbide plate sprayed with the anti-sticking agent sample A from Comparative Example 1 decreased continuously with the increase of immersion time in alkaline solution. After immersion for 195 minutes, the contact angle of the tungsten carbide plate surface was 89°, a decrease of 25.8% compared to the initial value. However, the tungsten carbide plates sprayed with the high-efficiency anti-sticking agents prepared in Examples 1, 2, 3, 4, and 5 of this invention all maintained excellent hydrophobicity after immersion in alkaline solution for 195 minutes, with the contact angle decreasing by no more than 6%. This confirms that the high-efficiency anti-sticking agent in this invention has good alkali resistance, can resist long-term alkaline corrosion of cement materials, and extends the service life of the coating.

[0119] Subsequently, the abrasion resistance of several tungsten carbide plate surface coatings was tested using an abrasion testing machine. The test method is as follows: the coated tungsten carbide plate was fixed in the fixture of the abrasion testing machine, and then glass wool (0000 specification, produced by BON STAR Corporation of Japan) was wrapped around the grinding head of the testing machine and a 1kg weight was placed on it. Then the grinding head was lowered and the testing machine was started, allowing the grinding head to linearly reciprocate rub the coating surface 50 times. After that, the plate was removed and the wear condition of the tungsten carbide plate surface coating was observed. Figure 1 The wear conditions of the tungsten carbide plates sprayed with Comparative Example 1, Example 1, Example 2, Example 3, Example 4, and Example 5 are listed respectively. Figure 1 As can be seen in (a), after 50 cycles of linear reciprocating friction, a large area of ​​bright silver appeared on the test area of ​​the tungsten steel plate sprayed with anti-sticking agent sample A of Comparative Example 1, and the coating was worn down in large quantities, indicating that the coating formed by anti-sticking agent sample A of Comparative Example 1 has poor wear resistance. Figure 1 (b) shows that the tungsten carbide plate sprayed with the high-efficiency anti-stick agent prepared in Example 1 exhibited only a very small bright silver area after 50 cycles of linear reciprocating rubbing, and the coating remained intact, confirming that the high-efficiency anti-stick agent prepared in Example 1 has good alkali resistance. The tungsten carbide plate sprayed with the high-efficiency anti-stick agent prepared in Example 2 showed a slight increase in the bright silver area after 50 cycles of linear reciprocating rubbing. This is because the high-efficiency anti-stick agent does not contain styrene, resulting in a slight decrease in coating hardness and wear resistance, but still higher than Comparative Example 1. The high-efficiency anti-stick agent prepared in Example 3 contains a large amount of styrene, which, while increasing coating hardness, negatively impacts coating adhesion. Therefore, the tungsten carbide plate sprayed with Example 3 also showed a certain bright silver area after the wear resistance test. Figure 1 (d) However, the coating coverage area is also higher than that of Comparative Example 1. The wear resistance of the tungsten carbide plate sprayed with the high-efficiency anti-sticking agent prepared in Examples 4 and 5 after 50 cycles of linear reciprocating friction is similar to that of Example 1. However, the wear resistance of the high-efficiency anti-sticking agent prepared in Example 4 is slightly inferior to that of Examples 1 and 5.

[0120] Based on the above experimental results, compared with the anti-sticking agent sample A in Comparative Example 1, the high-efficiency anti-sticking agent prepared in this invention not only imparts hydrophobicity to the metal substrate but also has good alkali resistance and wear resistance. It can effectively resist the alkaline corrosion of cement materials during service, reduce the wear of solid particles on the inner wall of the tank, and thus ensure the service life of the coating and mechanical equipment while reducing cement material residue.

[0121] This invention relates to a highly efficient anti-sticking agent for concrete machinery, characterized by its wide availability of raw materials, mature production processes and equipment, and ease of large-scale industrial production. Using a polyacrylate coating as the base, the invention imparts hydrophobic properties to the coating by introducing fluorinated functional monomers and silane coupling agents. Furthermore, the introduction of rigid styrene monomers further improves the coating's hardness and alkali resistance, resulting in a highly efficient anti-sticking agent with excellent hydrophobic properties and superior alkali and wear resistance. When sprayed onto the inner wall of the tank of concrete machinery, it forms a uniform coating, effectively improving the hydrophobicity of the metal inner wall, reducing concrete residue after unloading, and preventing problems such as uneven concrete mixing, reduced output, and decreased performance caused by excessive material residue. Simultaneously, the coating reduces corrosion and wear on the tank interior during concrete mixing and transportation, allowing the machinery to be cleaned with a small amount of water after use, simplifying subsequent cleaning and maintenance procedures, reducing wastewater and waste generation, and minimizing equipment wear and tear, thus saving significant economic costs.

[0122] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. The application of a high-efficiency anti-sticking agent in mechanical equipment used in the preparation or transportation of ready-mixed concrete, characterized in that, The preparation method of the high-efficiency anti-sticking agent includes the following steps: Step 1: Dissolve 0.42g sodium bicarbonate and 0.90g emulsifier in 50g deionized water according to their mass ratio, and stir evenly to obtain the base liquid. The emulsifier is fatty alcohol polyoxyethylene ether and sodium dodecyl sulfate, with a mass ratio of 1.25:

1. Step 2: Add 1.0g fatty alcohol polyoxyethylene ether, 0.80g sodium dodecyl sulfate, 8.52g methyl methacrylate, 8.52g styrene, 5.80g n-butyl acrylate, and 5.5g isooctyl acrylate to 30g deionized water in sequence by weight. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 40 minutes to obtain a pre-emulsified nuclear monomer emulsion. Step 3: Add 1.0g fatty alcohol polyoxyethylene ether, 0.80g sodium dodecyl sulfate, 17.04g hard segment monomer, 8.52g methyl methacrylate, 8.52g styrene, 5.80g n-butyl acrylate, 5.5g isooctyl acrylate, 4.54g perfluorohexylethylene and 1.82g vinyltriethoxysilane to 30g deionized water in sequence according to mass. After stirring evenly, transfer to an ultrasonic cell disruptor and ultrasonically emulsify for 40 min to obtain a pre-emulsified shell monomer emulsion. Step 4: Add 0.36g of ammonium persulfate to 30g of deionized water and stir until homogeneous to obtain the initiator solution; Step 5: Heat the base solution obtained in Step 1 to 85°C, add 12g of the pre-emulsified nucleomonomer emulsion obtained in Step 2, stir for 15min, and then add 1 / 3 volume of the initiator solution obtained in Step 4 dropwise into the reaction system at a dropping rate of 0.337mL / min. Step 6: After the reaction system in Step 5 shows blue light, add the remaining pre-emulsified nucleomonomer emulsion obtained in Step 2 and 1 / 3 of the initiator solution obtained in Step 4 to the reaction system. The dropping rate of the remaining pre-emulsified nucleomonomer emulsion is 0.802 mL / min, and the dropping rate of the initiator is 0.168 mL / min. Then continue to keep warm for 40 min. Step 7: The pre-emulsified shell monomer emulsion obtained in step 3 and 1 / 3 of the initiator solution obtained in step 4 are added dropwise to the reaction system. The drop rate of the pre-emulsified shell monomer emulsion is 0.443 mL / min and the drop rate of the initiator is 0.067 mL / min. Then, the mixture is kept warm for 90 min to obtain a homogeneous latex. Step 8: Dilute the homogeneous latex obtained in Step 7 with distilled water to a solid content of 10%, then add 0.6g of dipropylene glycol and 0.6g of dimethyl silicone oil, stir evenly to obtain a high-efficiency anti-sticking agent.

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