Concrete surface treating agent and preparation method thereof

Abstract

The invention relates to the technical field of functional coatings, in particular to a concrete surface treatment agent and a preparation method thereof, and the concrete surface treatment agent comprises the following components in parts by mass: 330-380 parts of a water-retaining agent, 700-800 parts of water, 2-5 parts of cellulose, 1-30 parts of a hydration inhibitor, 0.2-0.5 part of a defoaming agent and 1-2 parts of a preservative. Wherein the hydration inhibitor has a specific structural general formula. The concrete surface treating agent is sprayed on the concrete surface, the hydration effect of the concrete surface can be inhibited for a long time, the labor force of workers is greatly reduced, the construction cost is saved, and the situation that the concrete hydration effect is manually and irregularly checked and judged after a retarder is used in the past is avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of functional coatings, and in particular to a concrete surface treatment agent and a preparation method thereof. Background Art

[0002] As one of the most widely used materials in modern construction, concrete's surface treatment technology is directly related to structural durability, decorative effects, and functional realization. Traditional concrete surface treatment methods often use mechanical chiseling and chemical retarders, but these technologies generally suffer from time-limited effectiveness and complex processes. For example, conventional retarders slow the hydration rate of cement, delaying the setting of the cement paste on the concrete surface by 12-24 hours. High-pressure water jets are then used to flush the exposed aggregate. While this method can achieve surface roughening, it is essentially a temporary intervention that cannot interrupt the long-term progress of the hydration reaction. Furthermore, the retarder dosage, ambient temperature, and flushing timing must be precisely controlled during construction. Otherwise, if the flushing is not carried out in time, the concrete will re-hydrate, rendering all previous treatment work ineffective, significantly increasing manpower, time, and resource costs. Furthermore, while mechanical chiseling can directly create a rough surface, it has the disadvantages of damaging the internal structure of the concrete, generating dust pollution, and consuming high energy, making it difficult to meet the needs of refined construction.

[0003] With the advancement of building industrialization and green construction concepts, the demand for functional treatment of concrete surfaces is becoming increasingly diversified. A large number of researchers have turned their attention to the research and development of concrete additives. For example, CN112299746A discloses "a concrete surface retarder, its production process, and method of use." The retarder is prepared by mixing hydroxypropyl methylcellulose, sodium gluconate, xanthan gum, sorbitol, glycerol, alkylphenol polyoxyethylene ether, silica powder, defoamer, preservative, rust inhibitor, and deionized water as the main raw materials. The retarder can extend the retarding time of concrete to more than 7 days. However, the retarder in this formula mainly relies on the temporary adsorption of organic components such as sodium gluconate and xanthan gum on the surface of cement particles to delay hydration by complexing calcium ions. Its mechanism of action is limited by molecular thermal motion and diffusion effects, and it cannot form a stable physical and chemical barrier, resulting in the retarding effect gradually fading with time and environmental conditions.

[0004] At present, during the use of concrete retarders, it is still necessary to manually check the degree of concrete hydration from time to time and manually judge when to flush. It is extremely difficult for inexperienced workers to make judgments, and once a misjudgment occurs, it will cause irreversible consequences.

[0005] Therefore, it is urgent to develop a concrete surface treatment agent that can permanently dehydrate the concrete surface, reduce labor during use, and save construction costs. Summary of the Invention

[0006] The main purpose of the present invention is to provide a concrete surface treatment agent and a preparation method thereof. The surface treatment agent is sprayed on the concrete surface to permanently inhibit the hydration of the concrete surface, greatly reducing labor, saving construction costs, and avoiding the previous manual irregular inspection and judgment of the concrete hydration effect after the use of the retarder.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] In one aspect, the present invention provides a concrete surface treatment agent comprising the following components by weight: 330-380 parts of a water retaining agent, 700-800 parts of water, 2-5 parts of cellulose, 1-30 parts of a hydration inhibitor, 0.2-0.5 parts of a defoaming agent, and 1-2 parts of a preservative; wherein the hydration inhibitor has any of the following general structural formulas (A) to (C) or a sodium salt formed from the general structural formulas (A) to (C):

[0009] (A) (B)

[0010] (C)

[0011] wherein R1 to R5 are independently any one of: a phosphonic acid group, -CH2COOH, -COCH3, an alkyl group, and hydrogen, wherein the phosphonic acid group must be present, and the functionality of the phosphonic acid group is not less than 2;

[0012] R6~R 15 Independent of each other, any one of: a phosphonic acid group, an amino group, an alkyl group, and hydrogen, wherein the phosphonic acid group must be present, and the functionality of the phosphonic acid group is not less than 2;

[0013] R 16 is: N or H;

[0014] n is an integer from 2 to 5;

[0015] x is an integer from 1 to 3.

[0016] Currently available commercial concrete hydration inhibitors are only effective in inhibiting concrete hydration in the short term. Over time, the hydration inhibition effect significantly weakens the final concrete setting. Therefore, these hydration inhibitors require regular manual monitoring of the concrete surface condition during use. If workers fail to monitor the concrete promptly, irreversible costs and time losses will occur after the concrete sets, requiring extremely high worker experience. For example, CN103449755A discloses a "concrete slow-release agent and preparation method thereof," which is prepared using industrial sucrose, potassium ferrate, sodium dialkylbenzenesulfonate, carboxymethyl hydroxyethyl cellulose, water, and paraffin emulsion as raw materials. This slow-release agent can extend the concrete setting time to 18 hours. However, in actual operation, different natural conditions will affect the setting time of concrete. Therefore, during actual use, this slow-release agent must not only be cleaned strictly within the specified time, but also the concrete setting state must be continuously monitored.

[0017] This application uses a hydration inhibitor with a specific structure, and synergistically combines it with a water-retaining agent, water, cellulose, a defoaming agent, and a preservative to produce a concrete surface treatment agent. After spraying the surface of concrete, this surface treatment agent can permanently dehydrate the concrete surface. The reason for this may be that, firstly, the hydration inhibitor of this application contains a large number of phosphonic acid groups and amine groups, and the sodium salt formed by the hydration inhibitor contains a large number of sodium ions. The three can form a high-density negative charge distribution and a multi-dentate ligand structure, which gives the hydration inhibitor a strong chelating ability, especially for Ca 2+ 、Al 3+ 、Fe 3+ On the other hand, the phosphonic acid group can be adsorbed on the surface of concrete particles through hydrogen bonding and electrostatic interaction, forming a dense physical barrier to prevent the contact between cement and water. On the other hand, the core of cement hydration is the hydrolysis of C3S and C2S to form CSH gel and Ca(OH)2. 2+ The formation of a stable six-membered ring chelate directly blocks the nucleation and growth of the CSH gel, preventing the cement particles from directly forming a strong skeleton. Fourthly, the lattice parameters of the hydration inhibitor of the present application are similar to those of the primary unit cells of the CSH gel, making it easier for the hydration inhibitor to be embedded in the CSH gel lattice, causing lattice structural defects and weakening the mechanical properties of the concrete. Fifthly, the hydration process of concrete will make the surrounding environment alkaline, and the hydration inhibitor of the present application can exist more stably in an alkaline environment and is not easily decomposed or inactivated. The aforementioned action principle synergizes with the hydration reaction to make it irreversible, thereby extending the retarding time of the concrete for a longer period of time.

[0018] In some embodiments, the alkyl group is a C1-C5 branched or straight chain alkyl group.

[0019] By regulating the length of the alkyl chain, this application can prevent excessive steric hindrance from being unfavorable for the phosphonic acid group to form hydrogen bonds to chelate Ca in concrete. 2+ 、Al 3+ 、Fe 3+ The ions are thus unable to achieve the effect of permanently inhibiting concrete hydration.

[0020] In some embodiments, the amine group is a tertiary amine group.

[0021] The present invention uses a tertiary amine structure to enable the hydration inhibitor to maintain its coordination activity in an alkaline environment, thereby allowing the phosphonic acid group and the tertiary amine group to synergistically form a more stable octahedral coordination structure. In addition, the electron-donating effect of the tertiary amine can make the negative charge of the phosphonic acid group more concentrated, thereby enhancing the binding activity with Ca. 2+ 、Al 3+ 、Fe 3+ electrostatic adsorption capacity.

[0022] In some embodiments, the R 16 When it is H, R6~R 15 At least one of them is an amino group.

[0023] In some embodiments, the phosphonic acid group is selected from: -(CH2) a —PO(OH)2 or —(CH2) a —NH—(CH2) b —PO(OH)2; wherein a and b are independently integers of 0 to 6.

[0024] In some embodiments, the general structural formula A is any one of the following structures:

[0025]

[0026]

[0027] In some embodiments, the general structural formula B is any one of the following structures:

[0028]

[0029] In some embodiments, the general structural formula C is any one of the following structures:

[0030]

[0031]

[0032] In some embodiments, after the concrete surface treatment agent is applied to concrete, the final setting time of the concrete is not less than 30 days.

[0033] Another aspect of the present invention provides a method for preparing a concrete surface treatment agent, comprising the following steps: stirring water, cellulose, and a hydration inhibitor at 1600-1800 r / min for 20-30 minutes, then reducing the stirring rate to 300-500 r / min, adding a defoaming agent and a preservative, and continuing to stir until no bubbles are generated. Then, a water retaining agent is added and the stirring is continued at the same speed for 40-60 minutes to obtain the concrete surface treatment agent.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The concrete surface treatment agent of the present invention is prepared by mixing a water retaining agent, water, cellulose, a hydration inhibitor, a defoaming agent and a preservative. The hydration inhibitor has a specific molecular structure. The hydration inhibitor is synergistically compatible with other components. When applied to the concrete surface, it can permanently inhibit the hydration of the concrete surface, greatly reducing labor and saving construction costs. It avoids the previous manual irregular inspection and judgment of the concrete hydration effect after the use of the retarder.

[0036] (2) The hydration inhibitor of the present invention has a specific molecular structure, which must contain no less than 2 phosphonic acid groups and tertiary amine groups, and the sodium salt formed by the hydration inhibitor contains a large amount of sodium ions. The three can form a high-density negative charge distribution and a multi-dentate ligand structure, which gives the hydration inhibitor a strong chelating ability, especially for Ca 2+ 、Al 3+ 、Fe 3+ The phosphonic acid group can be adsorbed on the surface of concrete particles through hydrogen bonding and electrostatic interaction, forming a dense physical barrier to prevent the contact between cement and water; in addition, the phosphonic acid group and Ca 2+ The formation of a stable six-membered ring chelate directly blocks the nucleation and growth of CSH gel. The lattice parameters of the hydration inhibitor are similar to those of the primary unit cell of CSH gel, making it easier for the hydration inhibitor to be embedded in the CSH gel lattice, causing lattice structural defects and weakening the mechanical properties of concrete.

[0037] (3) The hydration inhibitor of the present invention can exist more stably in an alkaline environment, is not easily decomposed or inactivated, and synergistically inhibits the hydration mechanism, making its inhibition of the hydration reaction irreversible, thereby extending the retarding time of concrete for a longer period of time. DETAILED DESCRIPTION

[0038] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0039] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0040] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention. Various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention, as will be apparent to those skilled in the art. Other embodiments obtained from the present invention description will be apparent to those skilled in the art. This application description and examples are exemplary only.

[0041] It should be noted that the operations of "drying", "filtering" and "stirring" described in the present invention are routine operations for those skilled in the art and can be selected according to actual operations.

[0042] It should also be noted that in the following examples and comparative examples, the sodium salts formed by each compound can be prepared by neutralization with sodium hydroxide, which is a routine operation for those skilled in the art and can be selected according to actual operation.

[0043] In the following examples, polyethylene wax emulsion 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.; and HTK-301 preservative was purchased from Shanghai Hongtu Industrial Co., Ltd.

[0044] Preparation Example 1

[0045] The preparation method of the compound represented by formula A-1 comprises the following steps: mixing 100 mmol N,N'-dimethylethylenediamine, 170 mL of 98 wt% concentrated hydrochloric acid, 170 mL of deionized water, and 200 mmol of phosphoric acid, reacting at 120°C for 1 hour, then adding 150 mmol of paraformaldehyde and stirring at constant temperature for 1 hour, concentrating under reduced pressure after the reaction is completed, and performing column chromatography to obtain the compound represented by formula A-1

[0046]

[0047] NMR analysis: 1H NMR (500MHz, Deuterium Oxide) δ3.16 (d, J = 10.0Hz, 4H), 2.93 (s, 4H), 2.53 (s, 6H).

[0048] Preparation Example 2

[0049] The preparation method of the compound shown in formula A-2 is the same as that of Preparation Example 1, except that an equal amount of N N'-diethylethylenediamine is used instead of N,N'-dimethylethylenediamine to obtain the compound shown in formula A-2.

[0050]

[0051] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.12 (d, J = 10.0 Hz, 4H), 2.98 (s, 4H), 2.78 (q, J = 5.0 Hz, 4H), 1.13 (t, J = 5.0 Hz, 6H).

[0052] Preparation Example 3

[0053] The preparation method of the compound represented by formula A-3 is the same as that of Preparation Example 1, except that an equal amount of N,N'-diisopropylethylenediamine is used instead of N,N'-dimethylethylenediamine;

[0054]

[0055] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.18 (d, J = 10.0 Hz, 4H), 2.99 (hept, J = 5.0 Hz, 2H), 2.90 (s, 4H), 1.17 (d, J = 5.0 Hz, 12H).

[0056] Preparation Example 4

[0057] The preparation method of the compound represented by formula A-4 is the same as that of Preparation Example 1, except that an equal amount of N,N-bis(tert-butyl)ethylenediamine is used instead of N,N'-dimethylethylenediamine;

[0058]

[0059] NMR analysis: 1H NMR (500MHz, Deuterium Oxide) δ3.22 (d, J = 10.0Hz, 4H), 2.96 (s, 4H), 1.19 (s, 19H).

[0060] Preparation Example 5

[0061] The preparation method of the compound represented by formula A-5 is the same as that of Preparation Example 1, except that an equal amount of N-methylethylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 300 mmol;

[0062]

[0063] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.27–3.10 (m, 6H), 3.02 (t, J = 5.0Hz, 2H), 2.95 (t, J = 5.0Hz, 2H), 2.53 (s, 3H).

[0064] Preparation Example 6

[0065] The preparation method of the compound represented by formula A-6 is the same as that of Preparation Example 1, except that an equal amount of N-ethylethylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 300 mmol;

[0066]

[0067] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.29–3.07 (m, 6H), 3.07–2.99 (m, 4H), 2.78 (q, J = 5.0Hz, 2H), 1.13 (t, J = 5.0Hz, 3H).

[0068] Preparation Example 7

[0069] The preparation method of the compound represented by formula A-7 is the same as that of Preparation Example 1, except that an equal amount of N-isopropylethylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 300 mmol;

[0070]

[0071] NMR analysis: 1H NMR (500MHz, Deuterium Oxide) δ3.30–3.11(m,6H),3.03(t,J=5.0Hz,2H),2.99(h,J=5.0Hz,1H),2.92(t,J=5.0Hz,2H),1.17(d,J=5.0Hz,6H).

[0072] Preparation Example 8

[0073] The preparation method of the compound represented by formula A-8 is the same as that of Preparation Example 1, except that an equal amount of N-tert-butylethylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 300 mmol;

[0074]

[0075] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.22(dt,J=10.0,5.9Hz,4H),3.14(t,J=10.0Hz,1H),3.05–2.99(m,2H),2.96(dd,J=5.0,3.7Hz,2H),1.19(s,9H).

[0076] Preparation Example 9

[0077] The preparation method of the compound represented by formula A-9 is the same as that of Preparation Example 5, except that the amount of phosphoric acid is 200 mmol;

[0078]

[0079] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.15 (dd, J = 10.0, 2.5Hz, 4H), 2.97–2.87 (m, 4H), 2.54 (s, 3H).

[0080] Preparation Example 10

[0081] The preparation method of the compound represented by formula A-10 is the same as that of Preparation Example 6, except that the amount of phosphoric acid is 200 mmol;

[0082]

[0083] NMR analysis: 1H NMR (500MHz, Deuterium Oxide) δ3.21–3.08(m,4H),2.96(t,J=5.0Hz,2H),2.89(t,J=5.0Hz,2H),2.78(q,J=5.0Hz,2H),1.13(t,J=5.0Hz,3H).

[0084] Preparation Example 11

[0085] The preparation method of the compound represented by formula A-11 is the same as that of Preparation Example 7, except that the amount of phosphoric acid is 200 mmol;

[0086]

[0087] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.16 (dd, J=10.0, 6.2Hz, 4H), 3.04–2.94 (m, 2H), 2.92–2.86 (m, 3H), 1.17 (d, J=5.0Hz, 6H).

[0088] Preparation Example 12

[0089] The preparation method of the compound represented by formula A-12 is the same as that of Preparation Example 8, except that the amount of phosphoric acid is 200 mmol;

[0090]

[0091] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.18 (dd, J=30.0, 11.9Hz, 4H), 3.03–2.86 (m, 2H), 1.19 (s, 9H).

[0092] Preparation Example 13

[0093] The preparation method of the compound represented by formula A-13 is the same as that of Preparation Example 1, except that an equal amount of ethylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 400 mmol;

[0094]

[0095] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.22 (t, J = 10.0 Hz, 4H), 3.14 (t, J = 10.0 Hz, 3H), 3.03 (s, 4H).

[0096] Preparation Example 14

[0097] The preparation method of the compound represented by formula A-14 is the same as that of Preparation Example 1, except that an equal amount of ethylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 300 mmol;

[0098]

[0099] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.22–3.12(m,6H),2.98(t,J=5.0Hz,2H),2.92(t,J=5.0Hz,2H).

[0100] Preparation Example 15

[0101] The preparation method of the compound represented by formula A-15 is the same as that of Preparation Example 1, except that an equal amount of 1,3-propylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 200 mmol;

[0102]

[0103] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.07 (d, J = 10.0 Hz, 4H), 2.88 (t, J = 5.0 Hz, 4H), 1.76 (p, J = 5.0 Hz, 2H).

[0104] Preparation Example 16

[0105] The preparation method of the compound represented by formula A-16 is the same as that of Preparation Example 1, except that an equal amount of N,N'-dimethyl-1,3-propylenediamine is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 200 mmol;

[0106]

[0107] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.22–3.05 (m, 4H), 2.65 (t, J = 5.0Hz, 4H), 2.48 (s, 6H), 1.65 (p, J = 5.0Hz, 2H).

[0108] Preparation Example 17

[0109] The preparation method of the compound represented by formula A-17 is the same as that of Preparation Example 14, except that the amount of phosphoric acid is 300 mmol;

[0110]

[0111] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.25–3.02(m,5H),2.84(t,J=5.0Hz,2H),2.73(t,J=5.0Hz,2H),1.70(p,J=5.0Hz,2H).

[0112] Preparation Example 18

[0113] The preparation method of the compound represented by formula A-18 is the same as that of Preparation Example 14, except that the amount of phosphoric acid is 400 mmol;

[0114]

[0115] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.25–3.07 (m, 7H), 2.76 (t, J = 5.0Hz, 4H), 1.63 (p, J = 5.0Hz, 2H).

[0116] Preparation Example 19

[0117] The preparation method of the compound represented by formula A-19 is the same as that of Preparation Example 1, except that an equal amount of N-(3-aminopropyl)-acetamide is used instead of N,N'-dimethylethylenediamine, and the amount of phosphoric acid is 300 mmol;

[0118]

[0119] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ3.76 (d, J = 10.0 Hz, 2H), 3.48 (t, J = 5.0 Hz, 2H), 3.25–3.18 (m, 2H), 3.18–3.10 (m, 4H), 2.06 (s, 3H).

[0120] Preparation Example 20

[0121] The preparation method of the compound represented by formula B-1 comprises the following steps:

[0122] B11, under N2 atmosphere, add 100mmol of pentamethyldiethylenetriamine to a mixed solution of 136mL of acetonitrile and 34mL of acetic acid, and then add 16mmol of n Bu4NBF4 and 500mmol of triethyl phosphite were electrolyzed at room temperature at a constant current of 5mA for 6 hours. After the reaction was completed, the compound represented by formula B-1(a) was obtained by column chromatography.

[0123]

[0124] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ4.11(dq,J=10.0,7.4Hz,8H),3.50(s,4H),3.27(d,J=10.07Hz,4H),2.43(d,J=15.0Hz,9H),1.33(t,J=5.0Hz,12H);

[0125] B12. Add 100 mmol of the compound represented by B-1(a) in step B11 to 417 mL of 10 wt% hydrochloric acid solution, heat to reflux and stir for 7 h, and obtain the compound represented by formula B-1 by column chromatography.

[0126]

[0127] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ7.92 (s, 4H), 3.15 (d, J = 10.0 Hz, 4H), 2.71 (t, J = 5.0 Hz, 4H), 2.56 (t, J = 5.0 Hz, 4H), 2.44 (s, 6H), 2.34 (s, 3H).

[0128] Preparation Example 21

[0129] The preparation method of the compound represented by formula B-3 comprises the following steps:

[0130] B31. Mix 100 mmol of N-acetylethylenediamine and 100 mmol of N-(2-chloroethyl)acetamide, add 500 mL of toluene and 150 mmol of sodium carbonate, raise the temperature to reflux and stir for 48 hours, and obtain the compound represented by formula B-3(a) by column chromatography.

[0131]

[0132] NMR analysis: 1H NMR (500MHz, DMSO-d6) δ7.69(t,J=5.0Hz,2H),3.22(dt,J=5.0,4.2Hz,4H),2.67(q,J=5.0Hz,4H),2.37(q,J=5.0Hz,1H),1.84(s,6H);

[0133] B32. Mix 100 mmol of the compound represented by formula B-3(a) in step B31 with 500 mmol of phosphorous acid and 200 mL of 37 wt% hydrochloric acid solution, heat to 100°C, and add 300 mmol of 36 wt% formaldehyde aqueous solution and stir at constant temperature for 2 hours. After the reaction is completed, column chromatography is performed to obtain the compound represented by formula B-3.

[0134]

[0135] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ7.82 (s, 2H), 7.74 (s, 4H), 3.73 (d, J = 10.0Hz, 4H), 3. 44(t,J=5.0Hz,4H),3.07(d,J=10.0Hz,2H),2.86–2.67(m,3H),2.02(s,6H).

[0136] Preparation Example 22

[0137] The preparation method of the compound represented by formula B-4 comprises the following steps:

[0138] B41. Add 200 mmol of chloromethanephosphonic acid and 100 mmol of N-methyl-2,2'-diaminodiethylamine to deionized water, mix and heat to reflux, stir at constant temperature for 20 hours, and perform column chromatography to obtain a compound represented by formula B-4(a):

[0139]

[0140] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ4.33 (tt, J=10.0, 5.4Hz, 2H), 4.09 (dq, J=10.0, 7.2Hz, 7H), 3.32 (dd, J= 10.0,6.8Hz,4H),2.69(q,J=5.0Hz,4H),2.56(t,J=5.0Hz,4H),2.28(s,3H),1.40–1.28(m,12H);

[0141] B42. Mix 100 mmol of the compound represented by formula B-3(a) in step B41 with 200 mmol of acetyl chloride and add toluene, add sodium bicarbonate, and stir at room temperature for 5 hours to obtain the compound represented by formula B-4(b):

[0142]

[0143] NMR analysis: 1 H NMR(500MHz,DMSO-d6)δ4.10(dq,J=10.0,7.2Hz,8H),3.83(d,J=10.0Hz,4H),3.45(t, J=5.0Hz,4H),2.58(t,J=5.0Hz,4H),2.24(s,3H),2.02(s,6H),1.33(t,J=5.0Hz,14H);

[0144] B43. Add 100 mmol of the compound shown in B-4(b) in step B42 to 417 mL of 10 wt% hydrochloric acid solution, heat to reflux and stir for 7 h, and obtain the compound shown in formula B-4 by column chromatography.

[0145]

[0146] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ7.74 (s, 4H), 3.73 (d, J = 10.0 Hz, 4H), 3.45 (t, J = 5.0 Hz, 4H), 2.58 (t, J = 5.0 Hz, 4H), 2.24 (s, 3H), 2.02 (s, 6H).

[0147] Preparation Example 23

[0148] The preparation method of the compound represented by formula B-5 comprises the following steps:

[0149] B51. Mix 100 mmol of N-acetylethylenediamine, 200 mmol of phosphorous acid, and 250 mL of a 37 wt% aqueous hydrochloric acid solution, raise the temperature to 100°C, then add 230 mmol of a 36 wt% aqueous formaldehyde solution, stir at this temperature for 2 hours, and perform column chromatography to obtain the compound represented by formula B-5(a).

[0150]

[0151] NMR analysis: 1H NMR (500MHz, DMSO-d6) δ7.85(s,4H),7.72(t,J=5.0Hz,1H),3.28(q,J=5.0Hz,2H),3.15(d,J=10.0Hz,4H),2.79(t,J=5.0Hz,2H),1.84(s,3H);

[0152] B52, 100 mmol of the compound represented by formula B-5(a) in step B51 and 100 mmol of the compound represented by formula B-5(b)

[0153]

[0154] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ7.86 (s, 4H), 3.40 (t, J = 5.0Hz, 2H), 3.16 (d, J = 10.0Hz, 4H), 3.09 (t, J = 5.0Hz, 2H);

[0155] Add 500 mL of acetonitrile and 150 mmol of sodium carbonate to the mixture, heat to reflux, stir at constant temperature for 2 hours, and perform column chromatography to obtain the compound shown in formula B-5.

[0156]

[0157] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ7.85 (s, 8H), 3.42 (t, J = 5.0Hz, 4H), 3.13 (d, J = 10.0Hz, 8H), 2.93–2.71 (m, 2H), 2.01 (s, 3H).;

[0158] The compound represented by formula B-5(b) was synthesized according to patent number EP1932849(A1).

[0159] Preparation Example 24

[0160] The preparation method of the compound represented by formula C-1 comprises the following steps:

[0161] C11. Mix 100 mmol of N,N,3,5-tetramethylaniline and 200 mL of carbon tetrachloride, add 200 mmol of N-bromosuccinimide and 1 g of dibenzoyl peroxide, heat to reflux, stir at constant temperature for 3 hours, and obtain the compound represented by formula C-1(a) by column chromatography.

[0162]

[0163] NMR analysis: 1H NMR (500MHz, DMSO-d6) δ7.03 (tt, J=5.0, 1.0Hz, 1H), 6.66 (d, J=5.0Hz, 2H), 4.66–4.47 (m, 2H), 3.00 (s, 6H);

[0164] C12. Under N2 atmosphere, 100 mmol of the compound represented by formula C-1(a) in step C11 was stirred and mixed with 300 mmol of triethyl phosphite, and 400 mL of dimethyl sulfoxide was added. The mixture was heated to reflux and stirred at constant temperature for 24 h. The mixture was purified by column chromatography to obtain the compound represented by formula C-1(b):

[0165]

[0166] NMR analysis: 1 H NMR(500MHz,DMSO-d6)δ7.44(tt,J=5.0,1.0Hz,1H),6.70(d,J=5.0Hz,2H),4.17(dq ,J=10.0,7.2Hz,8H),3.80(dt,J=10.0,1.0Hz,4H),3.00(s,6H),1.39–1.29(m,12H);

[0167] C13. Add 100 mmol of the compound represented by C-1(b) in step C12 to 400 mL of 10 wt% hydrochloric acid solution, heat to reflux and stir for 7 h, and obtain the compound represented by formula C-1 by column chromatography.

[0168]

[0169] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ8.12(s,4H),7.44(dq,J=5.0,1.1Hz,1H),6.77–6.73(m,2H),3.70(dt,J=10.0,0.9Hz,4H),3.00(s,6H).

[0170] Preparation Example 24

[0171] The preparation method of the compound represented by formula C-2 comprises the following steps: mixing 100 mmol of 3,5-diaminopyridine with 400 mL of tetrahydrofuran, adding 210 mmol of triethylamine and 210 mmol of (3-bromopropyl)phosphoric acid, heating to reflux, stirring at constant temperature for 4 hours, and performing column chromatography to obtain the compound represented by formula C-2

[0172]

[0173] NMR analysis:1 H NMR (500MHz, DMSO-d6) δ8.17(s,4H),7.77(d,J=5.0Hz,2H),7.15(t,J=5.0Hz,2H),6.73(t,J=5.0H z,1H),3.38(td,J=5.0,4.9Hz,4H),2.04(dtdd,J=35.0,12.0,10.3,9.1Hz,2H),1.91–1.81(m,3H).

[0174] Preparation Example 25

[0175] The preparation method of the compound represented by formula C-3 is the same as that of Preparation Example 24, except that an equal molar amount of 3,4,5-triaminopyridine is used instead of 3,5-diaminopyridine, and the amount of (3-bromopropyl)phosphoric acid is 320 mmol and the amount of triethylamine is 350 mmol.

[0176]

[0177] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ8.17(s,6H),7.89(s,2H),6.57(t,J=5.0Hz,2H),6.17(t,J=5.0Hz,1H),3.37(dtd,J=20.0,5.7,4.5Hz,5H),2.19–1.83(m,2H).

[0178] Preparation Example 26

[0179] The preparation method of the compound represented by formula C-4 is the same as that of Preparation Example 25, except that an equal mole of cyanuric chloride is used instead of 3,4,5-triaminopyridine, and an equal mole of 3-aminopropane-1-phosphoric acid is used instead of (3-bromopropyl)phosphoric acid.

[0180]

[0181] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ8.17 (s, 6H), 6.81 (t, J = 5.0Hz, 3H), 3.57–3.46 (m, 5H), 2.16–1.93 (m, 3H).

[0182] Example 1

[0183] A concrete surface treatment agent comprises the following components in parts by mass: 350 parts of polyethylene wax emulsion, 750 parts of water, 3 parts of hydroxypropyl methylcellulose, 14 parts of a compound represented by formula A-7, 0.3 parts of dimethyl silicone oil, and 1.5 parts of HTK-301 preservative.

[0184] A method for preparing a concrete surface treatment agent comprises the following steps: stirring water, hydroxypropyl methylcellulose, and a compound represented by formula A-7 at 1700 r / min for 25 minutes, reducing the stirring rate to 400 r / min, adding dimethyl silicone oil and HTK-301 preservative, and stirring until no bubbles are generated. Thereafter, polyethylene wax emulsion is added and mixing is continued at the same speed for 50 minutes to obtain the concrete surface treatment agent.

[0185] The compound represented by formula A-7 was prepared in Preparation Example 7.

[0186] Example 2

[0187] A concrete surface treatment agent comprises the following components in parts by mass: 330 parts of polyethylene wax emulsion, 700 parts of water, 2 parts of hydroxypropyl methylcellulose, 1 part of a compound represented by formula A-7, 0.2 parts of dimethyl silicone oil, and 1 part of HTK-301 preservative.

[0188] A method for preparing a concrete surface treatment agent comprises the following steps: stirring water, hydroxypropyl methylcellulose, and a compound represented by formula A-7 at 1600 r / min for 30 minutes, reducing the stirring rate to 300 r / min, adding dimethyl silicone oil and HTK-301 preservative, and stirring until no bubbles are generated. Thereafter, polyethylene wax emulsion is added and mixing is continued at the same speed for 60 minutes to obtain the concrete surface treatment agent.

[0189] The compound represented by formula A-7 was prepared in Preparation Example 7.

[0190] Example 3

[0191] A concrete surface treatment agent comprises the following components in parts by mass: 380 parts of polyethylene wax emulsion, 800 parts of water, 5 parts of hydroxypropyl methylcellulose, 30 parts of a compound represented by formula A-7, 0.5 parts of dimethyl silicone oil, and 2 parts of HTK-301 preservative.

[0192] A method for preparing a concrete surface treatment agent comprises the following steps: stirring water, hydroxypropyl methylcellulose, and a compound represented by formula A-7 at 1800 r / min for 20 minutes, reducing the stirring rate to 500 r / min, adding dimethyl silicone oil and HTK-301 preservative, and stirring until no bubbles are generated. Thereafter, polyethylene wax emulsion is added and mixing is continued at the same speed for 40 minutes to obtain the concrete surface treatment agent.

[0193] The compound represented by formula A-7 was prepared in Preparation Example 7.

[0194] Example 4

[0195] A concrete surface treatment agent and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the sodium salt formed by equal parts by mass of the compound represented by formula A-7 is used instead of the compound represented by formula A-7.

[0196] Example 5

[0197] A concrete surface treatment agent and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that equal parts by weight of the compound represented by formula B-3 are used instead of the compound represented by formula A-7.

[0198] The compound represented by formula B-3 was prepared in Preparation Example 21.

[0199] Example 6

[0200] A concrete surface treatment agent and a preparation method thereof. The specific implementation method is the same as that of Example 5, except that the sodium salt formed by equal parts by mass of the compound represented by formula B-3 is used instead of the compound represented by formula B-3.

[0201] Example 7

[0202] A concrete surface treatment agent and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that equal parts by weight of the compound represented by formula C-3 are used instead of the compound represented by formula A-7.

[0203] The compound represented by formula C-3 was prepared by Preparation Example 25.

[0204] Example 8

[0205] A concrete surface treatment agent and a preparation method thereof. The specific implementation method is the same as that of Example 7, except that the sodium salt formed by equal parts by mass of the compound represented by formula C-3 is used instead of the compound represented by formula C-3.

[0206] Example 9

[0207] A concrete surface treatment agent and a preparation method thereof, the specific implementation method is the same as that of Example 1, except that equal parts by weight of the compound shown in formula A-20 are used.

[0208] Substituting the compound represented by formula A-7;

[0209] NMR analysis:1 H NMR(500MHz,DMSO-d6)δ7.85(s,4H),3.91(dq,J=10.0,7.2Hz,4H),3.13(d,J=10.0Hz,4H),2.80(t,J=5.0Hz,2H),2.74(t,J=5.0Hz,2H), 2.58(t,J=5.0Hz,2H),2.46(t,J=5.0Hz,2H),2.12(dt,J=10.0,7.7Hz,2H),1.47(p,J=5.0Hz,2H),1.39–1.23(m,10H),0.96–0.84(m,3H);

[0210] The preparation method of the compound represented by formula A-20 comprises the following steps:

[0211] A201, 100mmol N-(2-bromoethyl)phthalimide, 100mmol 2-aminoethylphosphonic acid and 100mmol bromohexane were mixed, added to 600mL acetonitrile and 300mmol sodium carbonate, heated to reflux and stirred at constant temperature for 24h, and subjected to column chromatography to obtain the compound represented by formula A-20(a):

[0212]

[0213] NMR analysis: 1 H NMR (500MHz, DMSO-d6) δ8.00-7.67(m,4H),3.96-3.86(m,6H),2.79(t,J=10.0Hz,2H),2.72(t,J=5.0Hz,2H),2. 47(t,J=5.0Hz,2H),2.12(dt,J=15.0,7.7Hz,2H),1.47(p,J=5.0Hz,2H),1.36–1.24(m,10H),0.94-0.84(m,3H);

[0214] A202, add 0.8 g of hydrazine hydrate, 100 mL of water and 200 mL of acetonitrile to 100 mmol of the compound represented by formula A-20 (a) in step A201, stir at room temperature for 12 hours, and after the reaction is completed, column chromatography is performed to obtain the compound represented by formula A-20 (b)

[0215]

[0216] NMR analysis: 1H NMR (500MHz, DMSO-d6) δ3.92(dq,J=10.0,7.3Hz,4H),3.02(q,J=5.0Hz,1H),2.78(t,J=10.0Hz,2H),2.71–2.60(m,3H),2.58–2 .52(m,2H),2.44(t,J=5.0Hz,2H),2.12(dt,J=10.0,7.7Hz,2H),1.47(p,J=5.0Hz,2H),1.37–1.22(m,11H),0.97–0.83(m,3H);

[0217] A203. Mix 100 mol of the compound represented by formula A-20(b) in step A202, 200 mmol of phosphorous acid and 250 mL of 37 wt% aqueous hydrochloric acid solution, raise the temperature to 100°C, then add 230 mmol of 36 wt% aqueous formaldehyde solution, stir at constant temperature for 2 hours, concentrate under reduced pressure, then place in 300 mL of 10 wt% hydrochloric acid solution, heat to reflux with stirring for 7 hours, and obtain the compound represented by formula A-20 by column chromatography.

[0218] Example 10

[0219] A concrete surface treatment agent and a preparation method thereof, the specific implementation method is the same as that of Example 1, except that equal weight parts of the compound represented by formula A-21 are used

[0220] Instead of the compound represented by formula A-7.

[0221] The compound represented by formula A-21 was synthesized according to patent number EP1932848 (A1).

[0222] Comparative Example 1

[0223] A concrete surface treatment agent and a preparation method thereof, the specific implementation method is the same as that of Example 1, except that equal weight parts of the compound shown in formula C-5 are used

[0224] Instead of the compound represented by formula A-7.

[0225] NMR analysis: 1 H NMR (500MHz, Deuterium Oxide) δ7.37–7.20 (m, 4H), 3.79 (dd, J = 10.0, 1.0Hz, 4H);

[0226] The preparation method of the compound represented by formula C-5 is the same as that of Preparation Example 24, except that an equal mole of 1,4-di(bromomethyl)benzene is used instead of N,N,3,5-tetramethylaniline.

[0227] Comparative Example 2

[0228] A concrete surface treatment agent and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that an equal mass portion of 2-aminoethylphosphonic acid is used instead of the compound represented by formula A-7.

[0229] Comparative Example 3

[0230] A concrete surface treatment agent and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that an equal mass portion of gluconic acid is used instead of the compound represented by formula A-7.

[0231] Performance testing:

[0232] Concrete sample preparation: After pouring the concrete, wait until there is no obvious water stain on the surface and it is not sticky to the touch, press 2L / m 3 Use the concrete surface treatment agent to spray a 50cm×50cm square. After the concrete surface of other parts is completely cured, use a high-pressure water gun, a brush or a floor scrubber to clean the concrete surface to obtain a concrete sample.

[0233] The concrete formula is shown in Table 1.

[0234] Table 1

[0235] Portland cement / kg Water / kg River sand / kg Gravel / kg 297 112 617 1138

[0236] (1) Concrete failure time: Place each concrete sample sprayed with the surface treatment agent outdoors under normal temperature and pressure to test the final setting time of the concrete. Set up three parallel samples for each group, and take the average of the test results.

[0237] The concrete positive surface treatment agents prepared in each embodiment and comparative example were tested according to the above method. The test results are shown in Table 2.

[0238] Table 2

[0239]

[0240]

[0241] According to the experimental data in Table 2, the concrete surface treatment agents prepared in Examples 1 to 8 have a better hydration inhibition effect than conventional retarders. In particular, the concrete surface treatment agents prepared in Examples 4, 6 and 8 using sodium salts of hydration inhibitors have a final setting time of more than 70 days. Since Examples 1 to 3, Example 5 and Example 7 do not contain sodium ions in their structures, the negative charge distribution density formed is low and the hydration inhibition ability is relatively weak. In Example 9, the steric hindrance of the hydration inhibitor is increased due to the increase in the length of the alkyl linker, resulting in a weakened chelation effect between the surface treatment agent and the metal ions in the concrete, which is not conducive to inhibiting the hydration reaction of the concrete. In Example 10, the electron donating efficiency of the amine group is reduced due to the reduction of the tertiary amine group, which reduces the interaction with Ca 2+ 、Al 3+ 、Fe 3+ The electrostatic adsorption capacity of the compound A-7 is improved, thereby shortening the final setting time. Comparative Example 1 does not contain a tertiary amine group and cannot cooperate with the phosphonic acid group to form a multidentate ligand structure, which reduces the chelating ability of the hydration inhibitor and shortens the final setting time. Comparative Example 2 uses 2-aminoethylphosphonic acid instead of the compound represented by Formula A-7, in which the phosphonic acid group functionality is less than 2 and does not contain a tertiary amine structure, resulting in a shortened final setting time of the concrete surface treatment agent. Comparative Example 3 uses gluconic acid instead of the compound represented by Formula A-7, which is unstable in an alkaline environment, and thus shortens the final setting time.

[0242] Finally, it should be noted that the above specific implementation methods are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to examples, those skilled in the art should understand that the technical solutions of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A concrete surface treatment agent, characterized in that: The invention comprises the following components by weight: 330-380 parts of a water-retaining agent, 700-800 parts of water, 2-5 parts of cellulose, 1-30 parts of a hydration inhibitor, 0.2-0.5 parts of a defoaming agent, and 1-2 parts of a preservative; the hydration inhibitor has any of the following general structural formulas (A) to (C) or a sodium salt formed by the general structural formulas (A) to (C): (A) (B) (C) wherein R1 to R5 are independently any one of: a phosphonic acid group, -CH2COOH, -COCH3, an alkyl group, and hydrogen, wherein the phosphonic acid group must be present, and the functionality of the phosphonic acid group is not less than 2; R6~R 15 Independent of each other, any one of: a phosphonic acid group, an amino group, an alkyl group, and hydrogen, wherein the phosphonic acid group must be present, and the functionality of the phosphonic acid group is not less than 2; R 16 is: N or H; n is an integer from 2 to 5; x is an integer from 1 to 3.

2. The concrete surface treating agent according to claim 1, characterized in that The alkyl group is a C1-C5 branched or straight chain alkyl group.

3. The concrete surface treating agent according to claim 1, characterized in that The amine group is a tertiary amine group.

4. The concrete surface treating agent according to claim 1, characterized in that The R 16 When it is H, R6~R 15 At least one of them is an amino group.

5. The concrete surface treating agent according to claim 1, characterized in that The phosphonic acid group is selected from: -(CH2) a —PO(OH)2 or —(CH2) a —NH—(CH2) b —PO(OH)2; wherein a and b are independently integers of 0 to 6.

6. The concrete surface treating agent according to claim 1, characterized in that The general structural formula A is any one of the following structures:

7. The concrete surface treating agent according to claim 1, characterized in that The general structural formula B is any one of the following structures:

8. The concrete surface treating agent according to claim 1, characterized in that The general structural formula C is any one of the following structures:

9. The concrete surface treating agent according to claim 1, characterized in that After the concrete surface treatment agent is used in concrete, the final setting time of the concrete is not less than 30 days.

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

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