Forward coating-free surface treating agent for concrete as well as preparation method and application of forward coating-free surface treating agent

Abstract

The invention belongs to the technical field of functional coatings, and particularly relates to a concrete forward film-coating-free surface treating agent and a preparation method and application thereof.The concrete forward film-coating-free surface treating agent is prepared from, by mass, 300-400 parts of a water-retaining agent, 550-850 parts of water, 2-5 parts of cellulose, 0.2-35 parts of a hydration inhibitor, 0-8 parts of inorganic pigment, 0.1-0.7 part of a defoaming agent and 0.5-2.5 parts of a preservative; the structure of the hydration inhibitor contains an amino group and a phosphate group. The prepared surface treating agent can make the concrete surface strength lose efficacy for a long time, the construction period is prolonged, meanwhile, the construction process steps can be reduced, the effect of long-term failure of the concrete surface strength can be achieved without covering and curing the concrete after spraying, the implementation mode is simple and easy to implement, and the cost is low. The surface of the prepared image concrete is smoother and more attractive, and the effect of controllable texture depth can be achieved by adjusting the ratio of the raw materials.

Description

Technical Field

[0001] The invention belongs to the technical field of functional coatings, and particularly relates to a concrete positive non-filming surface treatment agent and a preparation method and application thereof. Background Art

[0002] With the continuous development of society, people's aesthetic tastes are constantly changing, especially in today's world where buildings are everywhere and concrete surfaces can be seen everywhere. People are paying more attention to beauty. Some good-looking buildings and artistic floors can attract more people to take pictures, especially in some scenic spots and parks. The flow of these people has undoubtedly increased the economic development of the place, and the preparation of these beautiful buildings or artistic floors has also attracted a large number of engineers to devote themselves to this.

[0003] At present, the preparation process of concrete with pattern art on the market is mostly to add a retarder, glucose or sodium citrate to the ink of the photo machine, and spray the printing ink on the photo paper through the electrospray nozzle without changing the ink performance. Since there is a layer of water-based film on the photo paper, when the water-based film absorbs the printing ink, the photo paper is covered on the concrete surface in the initial setting stage, and the concrete is washed after solidification to form a pattern or texture. However, this method is not easy to control the cleaning depth, and excessive addition of the retarder will lead to the problem of failure to print. In addition, the concrete retarders currently available on the market need to be coated and cured to achieve the effect of slow setting. In response to this problem, CN103449755A discloses "a concrete slow-release agent and its preparation method" prepared by a composite solution and a paraffin emulsion. The concrete slow-release agent does not need to be cured when used, which reduces the construction process steps, but the concrete slow-release agent takes a short time to completely solidify the concrete. When used in some large concrete buildings, the slow-setting time is far from enough, and it has high requirements on the construction ability of the workers.

[0004] Therefore, it is urgent to develop a positive surface treatment agent for the preparation method of image concrete that can achieve the effect of long-term failure of concrete surface strength, extend the construction period, and do not require concrete coating and maintenance after spraying. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a concrete positive non-filming surface treatment agent and a preparation method and application thereof. The surface treatment agent can make the concrete surface strength fail for a long time, extend the construction period, and reduce the construction process steps. After spraying, there is no need to cover the concrete with a film for maintenance to achieve the effect of long-term failure of the concrete surface strength. The implementation method is simple and easy. The obtained image concrete surface is smoother and more beautiful. At the same time, the texture depth can be controlled by adjusting the raw material ratio.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] On the one hand, the present invention provides a concrete positive non-filming surface treatment agent, comprising the following components by weight: 300-400 parts of water retaining agent, 600-860 parts of water, 2-5 parts of cellulose, 0.3-30 parts of hydration inhibitor, 0-8 parts of inorganic pigment, 0.1-0.7 parts of defoaming agent and 0.5-2.5 parts of preservative; the hydration inhibitor structure contains amino group and phosphate group.

[0008] In some embodiments, the water retaining agent is one or more of polyethylene wax emulsion, polyamide wax emulsion, water glass, polypropylene super absorbent resin and acrylic acid-acrylamide copolymer super absorbent resin.

[0009] In some embodiments, the cellulose is one or more of methyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose.

[0010] The present application selects cellulose as a component of the concrete positive non-film-covering surface treatment agent, which can increase the viscosity of the concrete positive non-film-covering surface treatment agent to play a role in thickening and retaining water, thereby preventing water from volatilizing.

[0011] In some embodiments, the mass ratio of the water retaining agent, water and hydration inhibitor is 1:(1.9-2.1):(0.001-0.08).

[0012] Preferably, the mass ratio of the water retaining agent, water and hydration inhibitor is 1:2:0.04.

[0013] The applicant disclosed a method for preparing an artistic cement floor in patent number CN116446233A, which comprises mixing ink and retarder in a certain proportion, spraying a pattern onto water-based photo paper through an electrospray nozzle, and then pasting the water-based photo paper on the concrete surface in the initial setting stage. The part without the retarding water-based ink solidifies normally, and then washing with a high-pressure water gun to obtain the artistic cement floor. However, with the continuous development and innovation of the company, the applicant found that there were some problems with the preparation process of the method after repeated use of the aforementioned method, such as difficulty in controlling the cleaning depth, and excessive addition of retarder will lead to the problem of being unable to print, and the process is complicated and has certain difficulties in construction on the surface of large concrete walls, especially since the surface of the photo paper has a water-based coating, once friction or vibration occurs, the image on the concrete will have defects, so the construction requirements are extremely stringent.

[0014] The present application adopts a specific ratio of water retaining agent, water and hydration inhibitor, which can play a synergistic role, so that the concrete surface loses strength and stops the hydration reaction, and the effect lasts for a long time. At the same time, by adjusting the mass ratio of the three, it can prevent the phenomenon of insufficient moisture content and solidification of the concrete surface due to the continuous absorption of water during the cement hydration process. In addition, it can also prevent the ion concentration in the hydration inhibitor from being too low in the initial stage of spraying, resulting in a weakened adsorption effect of cement particles, so that the agglomeration effect of concrete is enhanced to form agglomerates of different sizes, resulting in uneven texture at the interface between the surface treatment agent and the concrete, and reducing the aesthetics.

[0015] In some embodiments, the structure of the hydration inhibitor is as shown in Formula I:

[0016]

[0017] In some embodiments, the method for preparing the hydration inhibitor comprises the following steps:

[0018] (1) Add formaldehyde solution dropwise to 8-hydroxyquinoline, then add concentrated hydrochloric acid and stir to dissolve, continue to introduce hydrogen chloride gas into the system until no more precipitation is produced to stop the reaction, filter, rinse with ether, and dry to obtain compound A;

[0019] (2) Under an inert protective gas atmosphere, compound A in step (1), 1,2-di(2-chloroethoxy)ethane, potassium iodide and an acid binding agent are added to a solvent, the temperature is raised to 110-120° C. and stirred at a constant temperature for 46-50 hours. After the reaction is completed, the mixture is concentrated under reduced pressure, extracted, and the organic phases are combined and dried under reduced pressure and subjected to column chromatography to obtain a compound represented by formula II

[0020]

[0021] (3) Mix the compound represented by formula II in step (2) with N,N-dimethylaminomethanediphosphonic acid, add a solvent, heat to 100-120° C. and stir for 2-4 hours. After the reaction is completed, cool to room temperature, filter, wash with ethyl acetate, and concentrate and dry under reduced pressure to obtain a hydration inhibitor.

[0022] In the past, hydration inhibitors usually used citric acid and its salts, but their effect in this system is poor and they cannot permanently make the concrete surface lose strength. The reason may be that in the process of hindering the hydration of concrete, the citric acid and its salts produce unstable complexes that decompose, causing the hydration reaction of the concrete to continue. Therefore, the citric acid and its salts have a short-term effect on retarding the setting of concrete and cannot permanently make the concrete surface lose strength. The self-made hydration inhibitor of the present application contains polyphosphate groups and amine groups, which cooperate to chelate calcium ions through different chelation mechanisms, so that the product produced by the chelation of calcium ions by the hydration inhibitor is more stable and not easy to decompose. At the same time, the hydration inhibitor of the present application also contains a quaternary ammonium salt structure, which can generate charge attraction with concrete particles in water, coat the concrete surface, and make the concrete particles have a certain lubrication and dispersion effect under the action of ether bonds. At the same time, the hydration inhibitor can form a relatively stable hydrogen bond with water, and cooperate with the water retaining agent to form a hydration film on the concrete surface to hinder the hydration of the concrete. The water retaining agent forms a waterproof film on the surface of the hydration film to further prevent the evaporation of concrete water, thereby making the concrete surface strength fail for a long time and can also play a role in curing the concrete. The construction time of the image concrete can be adjusted at will to avoid the failure of the concrete surface retarder to recover the strength after long-term placement, so that the image concrete cannot be produced.

[0023] In some embodiments, in step (1), the mass concentration of the formaldehyde solution is 30-40%.

[0024] In some embodiments, in step (1), the volume ratio of the mass of 8-hydroxyquinoline to the formaldehyde solution is 1:(3-4).

[0025] In some embodiments, in step (2), the molar ratio of compound A, 1,2-bis(2-chloroethoxy)ethane, potassium iodide and acid binding agent is 1:(0.5-0.6):(0.1-0.2):(1.2-1.4).

[0026] Preferably, in step (2), the molar ratio of compound A, 1,2-bis(2-chloroethoxy)ethane, potassium iodide and acid binding agent is 1:0.55:0.15:1.3.

[0027] The present application can make the phenolic hydroxyl group in compound A react with the halogen at both ends of 1,2-bis(2-chloroethoxy)ethane by regulating the molar ratio of compound A, 1,2-bis(2-chloroethoxy)ethane, potassium iodide and acid binding agent, thereby improving the product yield and reducing the by-products formed by the reaction of compound A itself.

[0028] In some embodiments, in step (3), the molar ratio of the compound represented by formula II to N,N-dimethylaminomethanediphosphonic acid is 1:(2 to 2.2).

[0029] Preferably, in step (3), the molar ratio of the compound represented by formula II to N,N-dimethylaminomethanediphosphonic acid is 1:2.1.

[0030] The present application can make the halogens at both ends of the compound shown in formula II react more completely with N,N-dimethylaminomethanediphosphonic acid by regulating the molar ratio of the compound shown in formula II and N,N-dimethylaminomethanediphosphonic acid, thereby increasing the content of phosphate groups and quaternary ammonium salts, thereby improving the ability to inhibit concrete hydration, the water retention capacity of concrete and the dispersion capacity.

[0031] The present application does not specifically limit the type of the defoaming agent, which can be purchased commercially, including but not limited to dimethyl silicone oil.

[0032] On the other hand, the present invention provides a method for preparing a concrete positive non-filming surface treatment agent, comprising the following steps: stirring water, cellulose, a hydration inhibitor and an inorganic pigment at 1600-1800 r / min for 20-30 min, reducing the stirring rate to 300-500 r / min, adding a defoamer and a preservative thereto, and adding a water retaining agent thereto until no bubbles are generated, and continuing to maintain the speed and mixing for 40-60 min to obtain the concrete positive non-filming surface treatment agent.

[0033] On the other hand, the present invention provides an application of a concrete positive non-filming surface treatment agent in the preparation of image concrete, comprising the following steps: after the concrete is poured, wait until there is no obvious water stain on its surface and it is not sticky to the touch, spray the concrete positive non-filming surface treatment agent according to a pre-obtained pattern, wait until the concrete surface of other parts is completely cured, and then wash the concrete surface to obtain image concrete with patterns and textures.

[0034] In addition, the present application adopts a specific process to prepare the surface treatment agent. After mixing water, cellulose, hydration inhibitor and inorganic pigment, the specific stirring rate is adjusted to improve the dispersibility of cellulose. At the same time, since a large number of bubbles will be generated in the system under high-speed stirring, the applicant then adds a defoaming agent to eliminate the bubbles by adjusting the specific stirring rate, which can prevent the water retaining agent from separating and precipitating. At the same time, the specific addition order can also prevent the problem that the bubbles in the system cannot be effectively removed.

[0035] The present application adopts a spraying method to evenly spray the surface treatment agent on the concrete surface. During the hydration process of the concrete, water will be absorbed to bring the water retaining agent, cellulose, hydration inhibitor, inorganic pigment and defoaming agent into the interior of the concrete. The hydration inhibitor preferentially forms a hydration film with the concrete particles to complex the calcium ions in the concrete to prevent the hydration. Subsequently, the water retaining agent further forms a waterproof film on the hydration film layer, which can not only play a role in curing the concrete but also prevent the concrete from cracking. The cellulose can continuously maintain sufficient free water around the concrete to keep the concrete moist. The complex product formed by the hydration inhibitor has a stable structure. Several components work together to weaken the strength of the concrete surface for a long time. When the concrete in other parts is completely cured, the uncured concrete on the surface is cleaned to form an image concrete.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The present invention adopts a mixture of a water retaining agent, water, cellulose, a hydration inhibitor containing amino groups and phosphate groups in its structure, an inorganic pigment, a defoaming agent and a preservative to prepare a concrete positive non-filming surface treatment agent. The surface treatment agent is used in the preparation of image concrete. Its construction process is simple and has good practicality and operability. After spraying, it is not necessary to coat and maintain the concrete to achieve the effect of long-term failure of concrete surface strength, which can make the concrete surface lose strength for a long time. The image surface of the image concrete obtained is smoother and more beautiful, avoiding the effect of conventional retarders on the concrete surface, which leads to the quality decline of the product due to the influence of factors such as ambient temperature and construction cycle.

[0038] (2) The hydration inhibitor of the present invention chelates calcium ions by means of polyphosphate groups and amine groups, making the product produced by the chelation of calcium ions by the hydration inhibitor more stable and not easy to decompose. In addition, the quaternary ammonium salt structure of the hydration inhibitor can generate charge attraction with concrete particles in water, coating the concrete surface, and giving the concrete particles a certain lubricating and dispersing effect under the action of ether bonds. At the same time, the hydration inhibitor can form a relatively stable hydrogen bond with water, and cooperate with the water retaining agent to form a hydration film on the concrete surface, thereby hindering the hydration of the concrete.

[0039] (3) The present invention can achieve a synergistic effect through the specific ratio of water retaining agent, water and hydration inhibitor. On the one hand, the concrete surface loses strength and stops the hydration reaction, and the effect lasts for a long time; on the other hand, it can prevent the cement hydration process from continuously absorbing water, so that the hydration inhibitor can better participate in the hydration process of the concrete, thereby preventing the concrete surface from solidifying; thirdly, it can prevent the ion concentration in the hydration inhibitor from being too low at the initial stage of spraying, resulting in a weakened adsorption effect of cement particles, so that the agglomeration effect of the concrete is enhanced to form agglomerates of different sizes, resulting in uneven texture at the interface between the surface treatment agent and the concrete, thereby reducing the aesthetics. DETAILED DESCRIPTION

[0040] 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.

[0041] In the following preparation examples, embodiments and comparative examples, the polyethylene wax emulsion used was purchased from Hai'an Petrochemical Plant in Jiangsu Province; hydroxypropyl methylcellulose was purchased from Hebei Tuohai Biotechnology Co., Ltd.; dimethyl silicone oil was purchased from Jinan Guigang Chemical Co., Ltd.; HTK-301 preservative was purchased from Shanghai Hongtu Industrial Co., Ltd.

[0042] Preparation Example 1

[0043] The preparation method of the hydration inhibitor comprises the following steps:

[0044] (1) 25 mL of a 35% formaldehyde solution was added dropwise to 50 mmol of 8-hydroxyquinoline at a rate of 10 mL / min, followed by the addition of 80 mL of 37 wt% concentrated hydrochloric acid, followed by stirring and dissolution, and hydrogen chloride gas was continuously introduced into the system until no precipitation was produced to stop the reaction, and the mixture was filtered, rinsed with ether, and dried to obtain compound A;

[0045] (2) Under N2 atmosphere, 50 mmol of compound A in step (1), 27 mmol of 1,2-di(2-chloroethoxy)ethane, 7.5 mmol of potassium iodide and 65 mmol of potassium carbonate were added to 90 mL of N,N-dimethylformamide, the temperature was raised to 115°C and stirred at constant temperature for 48 hours. After the reaction was completed, the mixture was concentrated under reduced pressure, extracted, and the organic phases were combined and dried under reduced pressure and subjected to column chromatography to obtain a compound of formula II.

[0046]

[0047] The NMR data of the compound represented by Formula II are analyzed as follows: 1H NMR (500 MHz, DMSO-d6) δ8.78 (dd, J=5, 2.2 Hz, 1H, H at the adjacent position of nitrogen), 8.44–8.38 (m, 1H, H at the para position of nitrogen), 7.50 (dd, J=10, 4.3 Hz, 1H, H at the meta position of nitrogen), 7.40–7.34 (m, 1H, H at the halogen side of the benzene ring), 7.00 (d, J=10 Hz, 1H, H at the ether bond side of the benzene ring), 4.76 (s, 2H, H of the methylene group at the adjacent position of the halogen), 4.23 (t, J=5.0 Hz, 2H, H of the methylene group at the middle ether bond), 3.73 (t, J=5.0 Hz, 2H, H of the methylene group at the middle ether bond), 3.63 (s, 2H, H of the methylene group at the middle ether bond);

[0048] (3) Mix 50 mmol of the compound represented by formula II in step (2) with 105 mmol of N,N-dimethylaminomethanediphosphonic acid, add 130 mL of N,N-dimethylformamide, heat to 110° C. and stir for 3 h. After the reaction is completed, cool to 27° C., filter, wash with ethyl acetate, and concentrate and dry under reduced pressure to obtain a hydration inhibitor;

[0049] NMR data analysis of hydration inhibitor: 1H NMR (500MHz, Deuterium Oxide) δ8.74 (dd, J=5, 2.4Hz, 1H, H of the nitrogen element in the nitrogen heterocycle), 8.47 (dd, J=10, 2.1Hz, 1H, H of the nitrogen element in the nitrogen heterocycle), 7.51 (dd, J=10, 4.1Hz, 1H, H of the nitrogen element in the nitrogen heterocycle), 7.28-7.24 (m, 1H, H of the outer side of the benzene ring), 7.06 (d, J=105Hz, 1H, H of the inner side of the benzene ring) ,4.69 (ddp, J=15,9.8,1.5Hz,1H, H on the carbon connecting the two phosphate groups),4.37 (s,2H, H of the methylene group on the quaternary ammonium salt),4.28 (t,J=5.0Hz,2H, H of the methylene group on the ether bond),3.78 (t,J=5.0Hz,2H, H of the methylene group on the ether bond),3.70 (s,2H, H of the methylene group on the ether bond),3.45 (d,J=5Hz,6H, H of the methyl group).

[0050] Preparation Example 2

[0051] The preparation method of the hydration inhibitor is the same as that of Preparation Example 1, except that in step (2), the amount of 1,2-bis(2-chloroethoxy)ethane is 58 mmol.

[0052] Preparation Example 3

[0053] The preparation method of the hydration inhibitor is the same as that of Preparation Example 1, except that in step (3), the amount of N,N-dimethylaminomethanediphosphonic acid is 50 mmol.

[0054] Preparation Example 4

[0055] The preparation method of the hydration inhibitor is the same as that of Preparation Example 1, except that an equal amount of 2-aminoethylphosphonic acid is used instead of N,N-dimethylaminomethanediphosphonic acid.

[0056] Example 1

[0057] A concrete positive non-filming surface treatment agent comprises the following components by weight: 350 parts of polyethylene wax emulsion, 700 parts of water, 3 parts of hydroxypropyl methylcellulose, 14 parts of hydration inhibitor, 4 parts of titanium dioxide, 0.4 parts of dimethyl silicone oil and 1.5 parts of HTK-301 preservative.

[0058] The hydration inhibitor is prepared in Preparation Example 1.

[0059] The preparation method of the concrete positive non-filming surface treatment agent of this embodiment includes the following steps: stirring water, hydroxypropyl methylcellulose, a hydration inhibitor, and titanium dioxide at 1700 r / min for 25 minutes, then reducing the stirring rate to 400 r / min, adding dimethyl silicone oil and HTK-301 preservative thereto, and adding polyethylene wax emulsion thereto until no bubbles are generated, and continuing to maintain the speed and mixing for 50 minutes to obtain the concrete positive non-filming surface treatment agent.

[0060] Example 2

[0061] A concrete positive non-filming surface treatment agent comprises the following components by weight: 300 parts of polyethylene wax emulsion, 570 parts of water, 3 parts of hydroxypropyl methylcellulose, 0.3 parts of hydration inhibitor, 1 part of titanium dioxide, 0.1 parts of dimethyl silicone oil and 0.5 parts of HTK-301 preservative.

[0062] The hydration inhibitor is prepared in Preparation Example 1.

[0063] The preparation method of the concrete positive non-filming surface treatment agent of this embodiment includes the following steps: stirring water, hydroxypropyl methylcellulose, hydration inhibitor, and titanium dioxide at 1800 r / min for 20 minutes, then reducing the stirring rate to 300 r / min, adding dimethyl silicone oil and HTK-301 preservative thereto, and adding polyethylene wax emulsion thereto until no bubbles are generated, and then continuing to maintain the speed and mix for 60 minutes to obtain the concrete positive non-filming surface treatment agent.

[0064] Example 3

[0065] A concrete positive non-filming surface treatment agent comprises the following components by weight: 300 parts of polyethylene wax emulsion, 840 parts of water, 5 parts of hydroxypropyl methylcellulose, 32 parts of hydration inhibitor, 8 parts of titanium dioxide, 0.7 parts of dimethyl silicone oil and 2.5 parts of HTK-301 preservative.

[0066] The hydration inhibitor is prepared in Preparation Example 1.

[0067] The preparation method of the concrete positive non-filming surface treatment agent of this embodiment includes the following steps: stirring water, hydroxypropyl methylcellulose, a hydration inhibitor, and titanium dioxide at 1600 r / min for 30 minutes, then reducing the stirring rate to 500 r / min, adding dimethyl silicone oil and HTK-301 preservative thereto, and adding polyethylene wax emulsion thereto until no bubbles are generated, and then continuing to maintain the speed and mixing for 40 minutes to obtain the concrete positive non-filming surface treatment agent.

[0068] Example 4

[0069] A concrete positive non-filming surface treatment agent and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the hydration inhibitor is prepared by Preparation Example 2.

[0070] Example 5

[0071] A concrete positive non-filming surface treatment agent and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the hydration inhibitor is prepared by Preparation Example 3.

[0072] Example 6

[0073] A concrete positive non-filming surface treatment agent and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the hydration inhibitor is prepared by Preparation Example 4.

[0074] Example 7

[0075] A concrete positive non-filming surface treatment agent and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the amount of polyethylene wax emulsion is 300 parts.

[0076] Example 8

[0077] A concrete positive non-filming surface treatment agent comprises the following components by weight: 350 parts of polyethylene wax emulsion, 700 parts of water, 3 parts of hydroxypropyl methylcellulose, 14 parts of hydration inhibitor, 4 parts of titanium dioxide, 0.4 parts of dimethyl silicone oil and 1.5 parts of HTK-301 preservative.

[0078] The hydration inhibitor is prepared in Preparation Example 1.

[0079] The preparation method of the concrete positive non-filming surface treatment agent of this embodiment comprises the following steps: stirring water, hydroxypropyl methylcellulose, hydration inhibitor and titanium dioxide at 1700 r / min for 25 minutes, adding dimethyl silicone oil, HTK-301 preservative and polyethylene wax emulsion thereto while maintaining the stirring rate and continuing to mix for 50 minutes to obtain the concrete positive non-filming surface treatment agent.

[0080] Example 9

[0081] A concrete positive non-filming surface treatment agent comprises the following components by mass: 350 parts of polyethylene wax emulsion, 700 parts of water, 3 parts of cellulose, 14 parts of hydration inhibitor, 4 parts of titanium dioxide, 0.4 parts of dimethyl silicone oil and 1.5 parts of HTK-301 preservative; the hydration inhibitor contains an amino group and a phosphate group in its structure.

[0082] The hydration inhibitor is prepared in Preparation Example 1.

[0083] The preparation method of the concrete positive non-filming surface treatment agent of this embodiment comprises the following steps: stirring water, hydroxypropyl methylcellulose, hydration inhibitor and titanium dioxide at 1700 r / min for 25 min, then reducing the stirring rate to 400 r / min, adding polyethylene wax emulsion, dimethyl silicone oil and HTK-301 preservative thereto, and continuing to maintain the speed and mixing for 50 min to obtain the concrete positive non-filming surface treatment agent.

[0084] Comparative Example 1

[0085] A concrete positive non-filming surface treatment agent and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that sodium citrate is used instead of a hydration inhibitor.

[0086] Performance Test:

[0087] Preparation of concrete samples: After pouring the concrete, wait until there is no obvious water stain on the surface and it is not sticky to the touch, spray a 50cm×50cm square with a concrete positive non-filming surface treatment agent. After the concrete surface of other parts is completely cured, use a high-pressure water gun, brush or floor scrubber to clean the concrete surface to obtain a concrete sample.

[0088] The concrete formula is shown in Table 1.

[0089] Table 1

[0090] Portland cement / kg Water / kg River sand / kg Crushed stone / kg 302 116 616 1134

[0091] (1) Surface roughness test: Use a surface roughness tester to test, take a 40 cm long concrete sample, and measure the surface roughness parameter Ra; use a plane-type special friction coefficient tester to measure the friction coefficient μ of the concrete surface.

[0092] (2) Concrete failure time: Place each concrete sample sprayed with the surface treatment agent outdoors under normal temperature and pressure conditions to test the final setting time of the concrete.

[0093] The concrete positive surface treatment agents prepared in the embodiments and comparative examples were tested according to the above method. The test results are shown in Table 2.

[0094] Table 2

[0095] Surface roughness Ra Surface friction coefficient μ Final setting time / Day Example 1 0.015 0.62 ＞30 Example 2 0.017 0.69 ＞30 Example 3 0.012 0.57 ＞30 Example 4 0.013 0.59 26 Example 5 0.018 0.70 27 Example 6 0.021 0.73 ＞30 Example 7 0.010 0.58 26 Example 8 0.019 0.69 ＞30 Example 9 0.23 0.76 ＞30 Comparative Example 1 0.039 0.86 3

[0096] According to the data in Table 1, it can be seen that the image concrete prepared by using the concrete positive non-filming surface treatment agent prepared in Examples 1 to 3 has a smoother pattern surface and a simple construction process. After spraying the concrete positive non-filming surface treatment agent, it can have a long-term effect of making the concrete ineffective, thereby obtaining a longer construction period. In Example 4, due to the change in the molar ratio of compound A, 1,2-bis(2-chloroethoxy)ethane, potassium iodide and acid binding agent, the final setting time of the concrete treated with the surface treatment agent is shortened. The reason may be that on the one hand, the content of phosphate and amine groups in the surface treatment agent is reduced, and on the other hand, it may be due to the lack of a benzene ring structure in the first part of the surface treatment agent, and the stable complex product structure formed by the original π-π stacking is reduced, so that during the hydration of the concrete, the complex product decomposes the concrete and rehydrates, resulting in a shortened final setting time of the concrete; In Example 5, due to the change in the molar ratio of the compound shown in Formula II to N,N-dimethylaminomethanediphosphonic acid, the phosphate group on one side of the surface treatment agent structure is missing, and its ability and stability to complex calcium ions in the concrete are weakened, thereby shortening the final setting time of the concrete; In Example 6, due to the use of equimolar 2-aminoethylphosphonic acid instead of N,N-dimethylaminomethanediphosphonic acid, the obtained surface treatment agent does not contain quaternary ammonium salt, resulting in a rough surface of the image concrete In Example 7, the water retention performance of the surface treatment agent decreased due to the change in the mass ratio of the water retaining agent, water and the hydration inhibitor. As the water loss caused the concrete to continue the hydration reaction, the final setting time was shortened. In Example 8, the rotation speed after the addition was changed, which caused the polyethylene wax emulsion in the system to separate and precipitate, affecting the performance of the surface treatment agent, thereby reducing the surface smoothness of the image concrete. In Example 9, the addition order was changed. After the polyethylene wax emulsion and the defoamer were added at the same time, the bubbles generated in the system could not be effectively removed, resulting in a large number of bubbles in the surface treatment agent, making the surface of the image concrete uneven. In Comparative Example 1, sodium citrate was used instead of the hydration inhibitor, resulting in a weakened complexing ability of the surface treatment agent for calcium ions in the concrete, and the formed complex product had poor stability and decomposed, thereby greatly shortening the final setting time of the concrete. At the same time, since it did not contain a quaternary ammonium salt structure and an ether bond, it was impossible to evenly disperse the concrete particles, resulting in a high surface roughness of the image concrete.

[0097] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A concrete positive non-filming surface treatment agent, characterized in that: The invention comprises the following components by weight: 300-400 parts of water retaining agent, 600-860 parts of water, 2-5 parts of cellulose, 0.2-34 parts of hydration inhibitor, 0-8 parts of inorganic pigment, 0.1-0.7 parts of defoaming agent and 0.5-2.5 parts of preservative; the hydration inhibitor contains amino group and phosphate group in its structure.

2. A concrete positive non-filming surface treatment agent according to claim 1, characterized in that: The water retaining agent is one or more of polyethylene wax emulsion, polyamide wax emulsion, water glass, polypropylene super absorbent resin and acrylic acid-acrylamide copolymer super absorbent resin.

3. A concrete positive non-filming surface treatment agent according to claim 1, characterized in that: The cellulose is one or more of methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose.

4. A concrete positive non-filming surface treatment agent according to claim 1, characterized in that: The mass ratio of the water retaining agent, water and hydration inhibitor is 1:(1.9-2.1):(0.001-0.08).

5. The concrete positive non-filming surface treatment agent according to claim 1, characterized in that: The structure of the hydration inhibitor is shown in Formula I:

6. A concrete positive non-filming surface treatment agent according to claim 5, characterized in that: The preparation method of the hydration inhibitor comprises the following steps: (1) Add formaldehyde solution dropwise to 8-hydroxyquinoline, then add concentrated hydrochloric acid and stir to dissolve, continue to introduce hydrogen chloride gas into the system until no more precipitation is produced to stop the reaction, filter, rinse with ether, and dry to obtain compound A; (2) Under an inert protective gas atmosphere, compound A in step (1), 1,2-di(2-chloroethoxy)ethane, potassium iodide and an acid binding agent are added to a solvent, the temperature is raised to 110-120° C. and stirred at a constant temperature for 46-50 hours. After the reaction is completed, the mixture is concentrated under reduced pressure, extracted, and the organic phases are combined and dried under reduced pressure and subjected to column chromatography to obtain a compound represented by formula II (3) Mix the compound represented by formula II in step (2) with N,N-dimethylaminomethanediphosphonic acid, add a solvent, heat to 100-120° C. and stir for 2-4 hours. After the reaction is completed, cool to room temperature, filter, wash with ethyl acetate, and concentrate and dry under reduced pressure to obtain a hydration inhibitor.

7. A concrete positive non-filming surface treatment agent according to claim 6, characterized in that: In step (2), the molar ratio of compound A, 1,2-bis(2-chloroethoxy)ethane, potassium iodide and acid binding agent is 1:(0.5-0.6):(0.1-0.2):(1.2-1.4).

8. The concrete positive non-filming surface treatment agent according to claim 6, characterized in that: In step (3), the molar ratio of the compound represented by formula II to N,N-dimethylaminomethanediphosphonic acid is 1:(2-2.2).

9. A method for preparing the concrete positive non-filming surface treatment agent according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: stirring water, cellulose, hydration inhibitor and inorganic pigment at 1600-1800 r / min for 20-30 min, reducing the stirring speed to 300-500 r / min, adding defoamer and preservative thereto, adding water retaining agent thereto until no bubbles are generated, and continuing to mix at the same speed for 40-60 min to obtain a concrete positive non-filming surface treatment agent.

10. Use of the concrete positive non-filming surface treatment agent according to any one of claims 1 to 8 in the preparation of image concrete, characterized in that: The method comprises the following steps: after pouring the concrete, wait until there is no obvious water stain on its surface and it is not sticky to the touch, spray the concrete positive non-filming surface treatment agent according to the pre-obtained pattern, wait until the concrete surface of other parts is completely cured, clean it with a high-pressure water gun, a brush or a floor scrubber to obtain image concrete with patterns and textures on the concrete surface.

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