A hydroxyalkyl tertiary amine aminosulfonate, crystal, preparation method and application thereof

Abstract

The present invention discloses a hydroxyalkyl tertiary amine aminosulfonate having the structure of general formula (I), a crystal thereof, and a preparation method thereof. The present invention selects aminosulfonic acid as a raw material to prepare a hydroxyalkyl tertiary amine aminosulfonate and its crystal particles, and for the first time applies both to cement, improving the cement performance, reducing the amount of finished product dust, improving the working environment, and reducing the packaging difficulty and cost.

Description

Technical Field

[0001] The invention belongs to the technical field of compound and material preparation, and in particular relates to a hydroxyalkyl tertiary amine aminosulfonate, a crystal, a preparation method thereof and an application thereof in cement additives. Background Art

[0002] The development of cement additives has shown the characteristics of being based on grinding aid and dispersion, emphasizing the improvement of cement performance. The additives in practical application are centered on amine compounds that have both excellent grinding aid performance and can improve cement hydration performance, supplemented by polyols with good dispersing and grinding aid performance and inorganic materials with a certain strength of stimulation.

[0003] At present, liquid additives widely used on the market are mostly aqueous solutions made of single or compound chemical raw materials such as amines and alcohols, which are added to the cement grinding or crushing system at 0.02% to 0.2% of the total mass of cement materials. The dispersion performance can improve the material transportation of the grinding system, reduce over-grinding of ball mills, improve the powder selection efficiency of the powder selection system, and improve the transportation and storage efficiency of cement products. In addition, adjusting the cement particle grading and promoting cement hydration can improve the quality of cement, directly reduce the cost of cement ingredients, increase the proportion of admixtures, and promote the application of waste slag and waste materials.

[0004] In short, suitable cement additive products can improve factory production efficiency and product quality, which can not only bring direct economic benefits, but also promote more effective utilization of resources. They can also reduce dust and carbon dioxide emissions to protect the environment. Therefore, they are promoted globally as green and energy-saving products.

[0005] Due to the characteristics of cement additives, the products have been rapidly promoted and applied. Its low threshold and strong service nature have led to the emergence of many small and medium-sized cement additive manufacturers or suppliers. These small and medium-sized suppliers have their own unique product performance and comprehensive services, but they also bring production quality risks and the problem of difficulty in fully meeting different individual needs.

[0006] Since the core raw materials of additives are basically triethanolamine, triisopropanolamine, N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine, etc., and these raw materials are all petrochemical products, the price growth trend is obvious, and there are sharp fluctuations and tight supply in some stages.

[0007] Triethanolamine, triisopropanolamine, N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine, etc. are multipolar compounds with low melting points, which are viscous oily or waxy substances at room temperature. As the temperature of the above compounds increases, their vapor pressure also increases, and volatility increases with temperature.

[0008] Compounds such as triethanolamine, triisopropanolamine, N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, and N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine are formed by substituting the three hydrogens on ammonia to form a trigonal pyramid-like structure. The nitrogen atom at the top has a lone pair of electrons.

[0009] Since the above core raw materials are viscous oils or form large wax-like masses at room temperature, it is very inconvenient to produce additives. Therefore, they are mostly pre-prepared into aqueous solutions with a certain fluidity at room temperature and are transported using flow meters, pumps, or manually. This makes it difficult to ensure the accuracy of metering and the production quality.

[0010] The core raw materials of the additives are all highly active alkanolamine compounds with low melting points. The melting point of triethanolamine is 21°C, and the melting point of triisopropanolamine is 48 - 52°C. Amines are easily oxidized, and most oxidants can oxidize amines into tarry substances. Hydrogen peroxide and peracids can oxidize tertiary amines into tertiary amine oxides. (Zhou Hongjun, Jiang Zonglin, Wang Xinliang, Tan Ming, Liang Zhu, He Xiaoying, A New Method for the Synthesis of Tertiary Amine Compounds, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, Sichuan). For the above compounds, as the temperature increases, their vapor pressure also increases, and their volatility increases with temperature. In the cement grinding process, the clinker is usually fired at a maximum temperature of about 1450°C and then transferred to the ball mill. Usually, after cooling, the surface temperature can be reduced to 50 to 90°C, but the internal temperature of the clinker blocks is usually higher. This also means that for the above compounds, as the temperature increases, the degree of volatilization also increases, the loss becomes larger, and the efficacy decreases.

[0011] Currently, cement additives with alkanolamines as the core raw materials generally have excellent performance in most cases, but there are also some deficiencies.

[0012] First of all, due to the structural characteristics of the above raw materials, both the three hydroxyl groups and the tertiary amino group have strong adsorption properties, so they all have very powerful grinding aid and dispersing properties. Since the cement grinding process uses a ball mill process under negative pressure, the overly powerful dispersibility leads to a significant increase in the load of the grinding system, limiting the dosage range and causing phenomena such as dust emission. This is mainly due to the powerful dispersing properties of the alkanolamine raw materials and the limitations of the air flow system capacity of the grinding system. However, modern large-scale cement grinding systems often involve large investments and are reluctant to limit investment for transformation. Instead, they hope to modify the additives to adapt to their grinding systems, which has caused limitations for alkanolamine additives.

[0013] Secondly, the excellent grinding aid and dispersing properties result in a more concentrated and finer particle size distribution of the cement product, leading to a significant increase in the water requirement for standard consistency of the cement, which affects the workability of the cement concrete.

[0014] At present, the application research or development of cement additives focuses on optimization through formula design and screening. The requirements of grinding aid and strength can be partially met. For example, the balance between strength growth and grinding aid can be met through the combination of ethanolamine, sugar, and industrial salt. This combination has become a mainstream formula scheme; by using ethanolamine supplemented with industrial waste materials, such as glycerol, propylene glycol and other low-cost recycled materials or inferior and processed materials in polyols, the cost can be reduced while maintaining grinding aid and strength. There are also some improvements on the core raw material ethanolamine, which mainly focus on the following two aspects:

[0015] One is to esterify and dehydrate hydroxyl-containing alcohol amine with acid to prepare ester-containing amino compounds. This compound may be hydrolyzed and reduced to acid and alcohol amine under the strong alkaline conditions of cement hydration. For example, Huang Jiming et al. controlled the temperature and reaction time in the article "Preparation and Performance Evaluation of Triethanolamine Sulfate Additives", esterified triethanolamine with aminosulfonic acid, separated the product, and dried it at low temperature to obtain triethanolamine sulfate, which was used as an additive. The final product of this scheme is a high-viscosity waxy solid, which is not conducive to storage, transportation and application.

[0016] The second is to neutralize the alcohol amine with an acid to lower the pH value of the alcohol amine to form a less alkaline or acidic mixture.

[0017] Patent 201510069058.6 provides a method for preparing cement additives by mixing industrial waste hydrochloric acid or waste sulfuric acid with diethanol monoisopropanolamine. The product is considered to be diethanol monoisopropanolamine hydrochloride. There is no reaction technical scheme and no characterization of the product. The final product of this scheme is a high-viscosity waxy solid, which is not conducive to storage, transportation and application.

[0018] After diethanol monoisopropanolamine and aminosulfonic acid are mixed and heated to react, the final product is an oily viscous solid or a large block of solid, which can also be used as a cement additive or other.

[0019] From the perspective of acid and base, the neutralization reaction is indeed relatively easy to carry out. However, the salt formation of alcohol amines and acids has the following difficulties: 1. The alkalinity of amines is weaker than that of similar fatty amines, and the reactivity is weakened; the hydroxyalkyl group on the alcohol amine side chain is an electron-withdrawing group, which weakens the electron-donating ability of the nitrogen atom; 2. The alcohol amines used in cement additives are all tertiary amines, but the hydrogen on the atom is replaced by three side chains, forming a steric hindrance effect. The spatial morphology of the acid group also has an important influence on the reaction. The steric hindrance will make it difficult for the acid group to attack the nitrogen atom to form a product; 3. The separation of products in the mixed system of products and reactants requires finding a suitable process for separating crude products. The aforementioned study did not carry out the separation process of products and reactants;

[0020] In addition, the introduction of chloride ions, sulfate ions, and nitrite ions all have an adverse impact on the durability of cement reinforced concrete. Chloride ions can damage the passivation film of steel bars, accelerate the freeze-thaw of concrete and the corrosion of steel bars, affecting the service safety and durability of buildings; sulfate is also an important factor affecting the durability of concrete, which can chemically react with the hydration products of cement in concrete, resulting in poor volume stability and causing the concrete to expand and crack. Therefore, the choice of acid is also very important. Summary of the Invention

[0021] Object of the Invention: The object of the present invention is to provide a hydroxyalkyl tertiary amine aminosulfonate, crystal thereof, preparation method thereof, and application in a cement additive in view of the deficiencies of the prior art. The present invention selects aminosulfonic acid as a raw material, prepares a hydroxyalkyl tertiary amine aminosulfonate and its crystal particles, and for the first time applies both to cement, improving the performance of cement, reducing the amount of finished product dust, improving the working environment, and reducing the packaging difficulty and cost.

[0022] Technical Solution: The object of the present invention is achieved by the following technical solutions:

[0023] The present invention provides a hydroxyalkyl tertiary amine aminosulfonate having a structural formula shown in general formula (I):

[0024]

[0025] Wherein,

[0026] R1 is 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxyisopropyl;

[0027] R2 is 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxyisopropyl;

[0028] R3 is 2-hydroxypropyl, 2-hydroxyisopropyl, N,N-bis(2-hydroxyethyl)aminoethyl, N,N-bis(2-hydroxypropyl)aminoethyl, N-(2-hydroxyethyl)-N-(2-hydroxypropyl)aminoethyl, N,N-bis(2-hydroxyethyl)aminopropyl, N,N-bis(2-hydroxypropyl)aminopropyl or N-(2-hydroxyethyl)-N-(2-hydroxypropyl)aminopropyl.

[0029] The present invention also provides a hydroxyalkyl tertiary amine aminosulfonate crystal prepared from the hydroxyalkyl tertiary amine aminosulfonate of the above general formula (I).

[0030] Preferably, the hydroxyalkyl tertiary amine amidosulfonate crystals include crystals of the following compounds: N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine amidosulfonate, N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine amidosulfonate, N,N,N’,N’-tetrakis(2-hydroxyethyl)ethylenediamine amidosulfonate, N,N,N’-tris(2-hydroxyethyl)-N’-(2-hydroxypropyl)ethylenediamine amidosulfonate, N,N-bis(2-hydroxyethyl)-N’,N’-bis(2-hydroxypropyl)ethylenediamine amidosulfonate, N,N,N’-tris(2-hydroxypropyl)-N’-(2-hydroxyethyl)ethylenediamine amidosulfonate, N,N,N’,N’-tetrakis(2-hydroxypropyl)ethylenediamine amidosulfonate, N,N,N’,N’-tetrakis(2-hydroxyethyl)propylenediamine amidosulfonate, N,N,N’-tris(2-hydroxyethyl)-N’-(2-hydroxypropyl)propylenediamine amidosulfonate, N,N-bis(2-hydroxyethyl)-N’,N’-bis(2-hydroxypropyl)propylenediamine amidosulfonate, N,N,N’-tris(2-hydroxypropyl)-N’-(2-hydroxyethyl)propylenediamine amidosulfonate, N,N,N’,N’-tetrakis(2-hydroxypropyl)propylenediamine amidosulfonate.

[0031] Further, the hydroxyalkyl tertiary amine amidosulfonate crystals include crystals of the following compounds: N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine amidosulfonate, N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine amidosulfonate.

[0032] Furthermore, the N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine amidosulfonate crystals have characteristic absorption peaks at 2θ of 11.0°, 13.1°, 14.2°, 17.0°, 17.9°, 18.7°, 19.1°, 21.0°, 21.3°, 21.8°, 23.6°, 25.0°, 25.4°, 25.9°, 26.7°, 27.5°, 28.0°, 28.3°, 29.4°, 30.6°, 31.1°, 32.0°, 32.5°, 33.0°, 34.1° and 35.4° ± 0.1° in the X-ray diffraction of the crystal powder.

[0033] Furthermore, for the N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate crystal, its crystal powder X-ray diffraction has characteristic absorption peaks at 2θ of 8.2°, 16.4°, 17.8°, 19.3°, 19.5°, 19.8°, 20.4°, 20.8°, 21.4°, 22.5°, 23.0°, 24.6°, 24.9°, 26.0°, 26.7°, 27.2°, 27.6°, 28.8°, 29.1°, 29.8°, 31.1°, 32.9°, 33.2°, 33.9°, 34.2°, 34.8°, 35.2°, 35.4°, 35.8°, 36.0°, 40.1°, 41.4°, 41.6°, 42.6°, 43.0°, 43.2°, 44.2°, 44.6° and 45.7° ± 0.1°.

[0034] The present invention also provides a preparation method for the above-mentioned hydroxyalkyl tertiary amine aminosulfonate crystal, which includes the following steps:

[0035] (1) Add hydroxyalkylamine, aminosulfonic acid and a solvent into a reactor in sequence. Under the condition of N2 replacement, stir and heat to 40 - 90 °C. After constant-temperature reaction for 3 - 6 h, evacuate to -0.098 to -0.06 MPa and maintain for 30 - 60 min to obtain the intermediate product hydroxyalkyl tertiary amine aminosulfonate;

[0036] (2) Dissolve the intermediate product obtained in the above step in an organic solvent, add activated carbon, heat to 40 - 80 °C while stirring, filter while it is hot, stir the filtrate and cool it to below 20 °C to form a crystalline precipitate. Filter and separate the crystalline precipitate, and dry it below 80 °C to obtain the hydroxyalkylamine aminosulfonate crystal;

[0037] (3) Use the filtrate obtained after filtering and separating the crystalline precipitate in step (2) to replace the organic solvent in (2) according to a mass ratio of 1:1 for recycling.

[0038] Preferably, in step (1), the molar ratio of the hydroxyalkylamine to the aminosulfonic acid is 1.0:(0.75 - 1.5);

[0039] The solvent is one or two of deionized water, methanol, ethanol, isopropanol, cyclohexane, petroleum ether;

[0040] The amount of the solvent is 20% - 30% of the total feeding mass of the hydroxyalkylamine and the aminosulfonic acid.

[0041] Preferably, in step (2), the organic solvent is a low-boiling alcohol, ketone, ether, ester or a mixture thereof that is miscible with water, preferably methanol, ethanol, isopropanol, acetone, ether, petroleum ether, ethyl acetate, cyclohexane or a mixture thereof;

[0042] The dosage of the organic solvent is 1 to 2 times the mass of the intermediate product;

[0043] The crystallization process is a process for purifying substances by utilizing the change in the solubility of substances in solvents. A saturated solution is prepared by mixing the substance with the solvent, and then filtered while it is hot to remove insoluble impurities. Subsequently, when the temperature of the solution is lowered, the solution becomes supersaturated and the solute will crystallize out; alternatively, the saturated solution is suction-filtered to remove the solvent, and the solute becomes crystals.

[0044] The selection of the solvent is crucial. It does not participate in chemical reactions, can dissolve a relatively large amount of solute at high temperatures, only a very small amount at low temperatures, and its boiling point should not be too high or too low, and it is easy to be volatilized and removed.

[0045] The principle for selecting the solvent dosage is to make the hot solution close to saturation or reach saturation, and then perform suction filtration or cooling to make the solution become supersaturated, so that crystals will precipitate.

[0046] The stirring speed of the decolorized solution is 50 to 200 r / min, and the cooling rate is 25 °C / h to 55 °C / h.

[0047] The supersaturation of the solution is the driving force for crystal precipitation. The cooling rate is the main process condition for providing the supersaturation of the solution. By controlling the cooling rate, the crystal formation rate can be adjusted. By controlling the stirring speed, the temperature distribution of the solution can be made uniform, the crystallization is complete, and the crystal morphology is prevented from being damaged.

[0048] In the present invention, in the reaction stage, the reaction proceeds sufficiently through the solvent, with a high conversion rate. At the same time, through vacuum filtration, low-boiling impurities are carried out by the solvent, improving the purity of the product; in the crystallization process stage, a suitable organic solvent is selected, and suction filtration, cooling, and stirring processes are adopted, and the best crystallization conditions are selected to obtain a high crystallization yield.

[0049] The present invention also provides the first application of the above-mentioned hydroxyalkyl tertiary amine aminosulfonate and crystals in cement additives.

[0050] Beneficial effects:

[0051] (1) In the present invention, sulfamic acid is selected as the raw material, and a suitable solvent is selected. The reaction temperature is low, the raw material conversion rate is high, the product purity is high, the product has good dispersibility and fluidity, the cost is low, and it is convenient for packaging, transportation, and application.

[0052] (2) Applying the hydroxyalkyl tertiary amine aminosulfonate crystal particles of the present invention to cement can be applied to a higher temperature environment, control the flow rate of cement particles, improve the performance of cement, reduce the amount of finished product dust, improve the working environment, and reduce the packaging difficulty and cost.

[0053] (3) The present invention has successfully prepared hydroxyalkyl tertiary amine sulfonates and their crystals. The prepared hydroxyalkyl tertiary amine sulfonate crystals have a high dissolution rate in water and can be accurately metered, improving the accuracy when used in compound additives. As crystals, their melting points and stabilities have been greatly improved. Compared with liquids, solid quantitative packaging can be used, reducing packaging costs, transportation costs, and storage costs.

[0054] (4) In the present invention, the filtrate after separation and crystallization can be recycled, improving the raw material utilization rate and crystal recovery rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 It is the positive ion diagram of the electrospray mass spectrometry detection of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfonate. The vertical axis represents the relative intensity (%), and the horizontal axis represents the mass-to-charge ratio (m / z) of the ions.

[0056] Figure 2 It is the negative ion diagram of the electrospray mass spectrometry detection of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfonate. The vertical axis represents the relative intensity (%), and the horizontal axis represents the mass-to-charge ratio (m / z) of the ions.

[0057] Figure 3 It is the positive ion diagram of the electrospray mass spectrometry detection of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfonate. The vertical axis represents the relative intensity (%), and the horizontal axis represents the mass-to-charge ratio (m / z) of the ions.

[0058] Figure 4 It is the negative ion diagram of the electrospray mass spectrometry detection of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfonate. The vertical axis represents the relative intensity (%), and the horizontal axis represents the mass-to-charge ratio (m / z) of the ions.

[0059] Figure 5 It is the X-ray diffraction pattern of the N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfonate crystal powder. The vertical axis represents the diffraction intensity (%), and the horizontal axis represents the 2θ diffraction angle (°).

[0060] Figure 6 It is the differential scanning calorimetry diagram of the N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfonate crystal. The vertical axis represents the heat flow rate (w / g), and the horizontal axis represents the temperature (°C).

[0061] Figure 7 It is the X-ray diffraction pattern of the N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfonate crystal powder. The vertical axis represents the diffraction intensity (%), and the horizontal axis represents the 2θ diffraction angle (°).

[0062] Figure 8It is a differential scanning calorimetry graph of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate crystals. The vertical axis represents the heat flow rate (w / g), and the horizontal axis represents the temperature (°C). Detailed implementation manners

[0063] The technical solutions of the present invention will be described in detail below through specific examples, but the protection scope of the present invention is not limited to the described examples.

[0064] Compound and crystal test methods:

[0065] The melting point was measured with a WRS-2 microcomputer melting point instrument; the electrospray mass spectrometry was measured with a Waters Q-TOF Micro TM mass spectrometer; the powder X-ray diffraction pattern was measured with a Bruker AXS D8 Advance X-ray diffractometer; the differential scanning calorimetry graph was measured with a shimadzu DSC-60A Shimadzu analysis detector.

[0066] Additive application test methods:

[0067] The test was carried out according to the standard of GB / T 26748-2011 "Cement grinding aid". The detection methods refer to GB / T 17671-1999 "Test method for cement mortar strength" and GB / T 1346-2011 "Test method for standard consistency water requirement of cement", and the cement strength and standard consistency water requirement were detected.

[0068] The industrial test was carried out according to the actual production.

[0069] The cement raw materials involved in the examples all meet the corresponding standards. Among them, the clinker is the ordinary Portland cement clinker produced by Anhui Conch Cement Company.

[0070] Comparative example 1

[0071] 105.4 g (0.6 mol) of 99% N,N,N-tris(2-hydroxyethyl)amine and 68.3 g (0.7 mol) of 99.5% aminosulfonic acid were added together to a 500 ml reaction flask equipped with a condensing device, and slowly heated to 110 °C while stirring until no more material was recovered by condensation, and then naturally cooled to room temperature to obtain solid triethanolamine sulfate.

[0072] Preparation of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine aminosulfonate crystals in Example 1

[0073] 134.4 g (0.7 mol) of 85% N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, 68.3 g (0.7 mol) of 99.5% sulfamic acid, and 50.6 g of 99.7% ethanol were added together to a 500 ml reaction flask equipped with a heating device. Stirring was carried out under the condition of N2 replacement, and the mixture was slowly heated to 80 - 85 °C. After reacting at a constant temperature for 4.0 h, the vacuum was pumped to -0.098 to -0.06 MPa and maintained for 30 min. Then, it was naturally cooled to room temperature to obtain 217.3 g of crude N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate;

[0074] The above crude product was mixed with 430 g of 99.7% ethanol and heated to 40 °C. 7.2 g of activated carbon was added, and stirring was carried out for 30 min. Then, filtration was performed. The filtrate was stirred at a speed of 50 r / min and cooled to below 20 °C at a speed of 55 °C / h for crystallization. After filtration and drying, 165.0 g of white crystals of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate were obtained, with a yield of 90.5%.

[0075] The positive ion diagram of the electrospray mass spectrometry detection of the prepared N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate crystal is shown in the appendix Figure 1 and the negative ion diagram is shown in the appendix Figure 2 , and the powder X-ray diffraction pattern is shown in the appendix Figure 5 , and the differential scanning calorimetry (DSC) diagram is shown in the appendix Figure 6 , and the measured melting point is 100.5 - 109.3 °C.

[0076] In its electrospray mass spectrometry detection positive ion diagram: the mass-to-charge ratio (m / z) is 164.1 ([M+H] + ),

[0077] In its electrospray mass spectrometry detection negative ion diagram: the mass-to-charge ratio (m / z) is 96.0 ([M-H] - );

[0078] Its differential scanning calorimetry curve has an endothermic peak in the range of approximately 100.5 °C to 109.3 °C.

[0079] Its X-ray powder diffraction data are shown in Table 1:

[0080] Table 1 X-ray powder diffraction data of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate crystal

[0081]

[0082]

[0083] Example 2 Preparation of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate crystals

[0084] 166.6 g (0.8 mol) of 85% N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine, 66.4 g (0.68 mol) of 99.5% aminosulfonic acid, and 60.0 g of 99.7% ethanol were added together to a 500 ml reaction flask equipped with a heating device. Stirring was carried out under the condition of N2 replacement, and the mixture was slowly heated to 80 - 85 °C. After reacting at a constant temperature for 3.5 h, the vacuum was pumped to -0.098 to -0.06 MPa and maintained for 60 min. Then, it was naturally cooled to room temperature to obtain 253.3 g of crude N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate;

[0085] The above crude product was mixed with 260 g of 99.7% ethanol and heated to 80 °C. 7.5 g of activated carbon was added, and stirring was carried out for 30 min for decolorization. After filtration, the filtrate was stirred at a speed of 250 r / min and cooled to below 20 °C at a rate of 25 °C / h for crystallization. After filtration and drying, 156.8 g of white crystals of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate were obtained, with a yield of 84.2%.

[0086] The positive ion graph of the electrospray mass spectrometry detection of the prepared N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate crystals is shown in the appendix Figure 3 and the negative ion graph is shown in the appendix Figure 4 , the powder X-ray diffraction pattern is shown in the appendix Figure 7 , the differential scanning calorimetry (DSC) graph is shown in the appendix Figure 8 , and the measured melting point is 96.1 - 107.1 °C.

[0087] In its electrospray mass spectrometry detection positive ion graph: the mass-to-charge ratio (m / z) is 178.1 ([M+H] + ),

[0088] In its electrospray mass spectrometry detection negative ion graph: the mass-to-charge ratio (m / z) is 96.0 ([M-H] - );

[0089] Its differential scanning calorimetry curve has an endothermic peak in the range of approximately 96.1 °C to 107.1 °C.

[0090] Its X-ray powder diffraction data are shown in Table 2:

[0091] Table 2 X-ray powder diffraction data of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate crystals

[0092]

[0093]

[0094] Example 3 Preparation of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate crystals

[0095] 123.0 g (0.7 mol) of 85% N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, 58.5 g (0.6 mol) of 99.5% sulfamic acid, and 42.5 g of 99.5% methanol were added together to a 500 ml reaction flask equipped with a heating device. Stirring was carried out under the condition of N2 replacement, and the mixture was slowly heated to 70 - 75 °C. After reacting at a constant temperature for 3.5 h, the vacuum was pumped to -0.098 to -0.06 MPa and maintained for 45 min. Then it was naturally cooled to room temperature to obtain 213.6 g of crude N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate;

[0096] The above crude product and 200 g of the filtrate obtained after filtering and separating the crystalline precipitate in Example 2 were heated to 80 °C, 6.0 g of activated carbon was added, and stirring was carried out for 30 min. Then filtration was performed by suction. The filtrate was stirred at a speed of 200 r / min and cooled at a speed of 45 °C / h to below 20 °C for crystallization. After filtration by suction and drying, 136.7 g of white crystals of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate were obtained, with a yield of 92.5%. The melting point measured by a WRS-2 microcomputer melting point apparatus was 101.2 - 109.1 °C.

[0097] As can be seen from Example 3, using the filtrate obtained after filtering and separating the crystalline precipitate in Example 1, with ethanol as the main component, as the solvent in this example, the crystal yield was increased to 92.5%, and the melting range was shortened to 7.9 °C.

[0098] Example 4 Preparation of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate crystals

[0099] 153.6 g (0.8 mol) of 85% N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, 68.3 g (0.7 mol) of 99.5% sulfamic acid, and 55.5 g of 99.7% ethanol were added together to a 500 ml reaction flask equipped with a heating device. Stirring was carried out under the condition of N2 replacement, and the mixture was slowly heated to 80 - 85 °C. After reacting at a constant temperature for 4.0 h, the vacuum was pumped to -0.098 to -0.06 MPa and maintained for 30 min. Then it was naturally cooled to room temperature to obtain 243.3 g of crude N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate;

[0100] The above crude product was mixed with 156 g of 99.7% ethanol and 57 g of 99.5% acetone, heated to 40 °C, 7.2 g of activated carbon was added, stirred for 30 min, filtered by suction, the filtrate was stirred at a speed of 200 r / min, cooled to below 20 °C at a speed of 55 °C / h for crystallization, and after suction filtration and drying, 166.9 g of white crystals of N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine sulfamate were obtained, with a yield of 91.6%; the melting point measured by a WRS-2 microcomputer melting point apparatus was 100.9 - 108.9 °C.

[0101] As can be seen from Example 4, when using a mixed solvent of ethanol and acetone, compared with Example 1, the crystal yield increased to 91.6%, and the melting range was shortened to 8.0 °C.

[0102] Example 5 Preparation of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfamate crystals

[0103] 166.6 g (0.8 mol) of 85% N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine, 66.4 g (0.68 mol) of 99.5% sulfamic acid, and 50.0 g of 99.7% isopropanol were added together to a 500 ml reaction flask equipped with a heating device, stirred under the condition of N2 replacement, and slowly heated to 80 - 85 °C. After reacting at a constant temperature for 3.5 h, the vacuum was pumped to -0.098 to -0.06 MPa and maintained for 60 min, and then naturally cooled to room temperature to obtain 250.7 g of crude N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfamate;

[0104] The above crude product was mixed with 200 g of 99.7% methanol and 100 g of 99.7% isopropanol, heated to 40 °C, 7.5 g of activated carbon was added, stirred for 30 min, filtered by suction, the filtrate was stirred at a speed of 50 r / min, cooled to below 20 °C at a speed of 55 °C / h for crystallization, and after suction filtration and drying, 162.5 g of white crystals of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfamate were obtained, with a yield of 87.2%; the melting point measured by a WRS-2 microcomputer melting point apparatus was 98.0 - 106.9 °C.

[0105] As can be seen from Example 5, when using a mixed solvent of methanol and isopropanol, compared with Example 2, the crystal yield increased to 87.2%, and the melting range was shortened to 8.9 °C.

[0106] Example 6 Preparation of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfamate crystals

[0107] 166.6 g (0.8 mol) of 85% N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine, 117.0 g (1.2 mol) of 99.5% sulfamic acid, and 85.0 g of 99.7% ethanol were added together to a 1000 ml reaction flask equipped with a heating device. Stirring was carried out under the condition of N2 replacement, and the mixture was slowly heated to 40 - 55 °C. After reacting at a constant temperature for 4.5 h, the vacuum was pumped to -0.098 to -0.06 MPa and maintained for 60 min. Then, it was naturally cooled to room temperature to obtain 288.6 g of crude N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfamate;

[0108] The above crude product was heated and dissolved with 280 g of 99.7% ethanol. 9.5 g of activated carbon was added, and the mixture was stirred for 30 min and then filtered by suction. The filtrate was stirred at a speed of 150 r / min and cooled to below 20 °C at a rate of 50 °C / h for crystallization. After filtration by suction and drying, 197.3 g of white crystals of N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfamate were obtained, with a yield of 90.0%. The melting point of the prepared N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine sulfamate crystals was determined by a WRS-2 microcomputer melting point apparatus to be 98.0 - 107.0 °C.

[0109] As can be seen from Example 6, the filtrate obtained after separating and crystallizing the precipitate with ethanol as the main component in Example 2 was used as the solvent in this example, and the crystal yield was increased to 90.0%, and the melting range was shortened to 9.0 °C.

[0110] Referring to GB / T 26748-2001 "Cement grinding aids", the examples with the corresponding serial numbers in the following table were used as cement additives respectively and added for testing according to the corresponding mass dosages.

[0111] Table 3 Cement additives

[0112]

[0113]

[0114] Application comparison of crude hydroxyalkyl tertiary amine sulfamate and comparative sample in cement in Example 7

[0115] In this example, Nos. 1, 2, 4, and 6 were added to the cement composition according to the mass dosages respectively, and the total mass of the cement composition was 5 kg. According to the composition ratio of the cement (by mass percentage), 80% of clinker, 5% of gypsum, 10% of slag powder, and 5% of limestone powder were weighed respectively, totaling 5 kg. According to the dosage, the corresponding masses of 1, 2, 4, and 6 were weighed and put into a standard small mill, and each was ground for 27 minutes. The ground materials were sieved through a 0.2 mm sieve, and the samples passing through the sieve were tested according to the standard.

[0116] The test results are shown in the following table:

[0117] Table 4 Comparison of the compressive strength of the cement prepared from No. 2, 4, 6 and Comparative Example 1

[0118]

[0119] As can be seen from the above table, under the same conditions, the compressive strength and the residue on 45-micron sieve of the examples are better than those of Comparative Example 1. Moreover, the dusting situation of the cement is better than that of Comparative Example 1, indicating that the dusting performance of the crude products in the examples is better than that of the sulfate ester salts in the comparative examples.

[0120] Application comparison of the hydroxyalkyl tertiary amine aminosulfonate crystals in Example 8 and the comparative sample in cement

[0121] In this example, No. 1, 3, 5, and 7 were respectively added to the cement composition according to the mass dosage, and the total mass of the cement composition was 5 kg. According to the composition ratio of the cement (by mass percentage), 85% of clinker, 5% of gypsum, and 10% of slag powder were respectively weighed, totaling 5 kg. According to the dosage, the corresponding masses of 1, 3, 5, and 7 were weighed and put into a standard small mill, and each was ground for 28 minutes. The ground material was sieved through a 0.2-mm sieve, and the sample passing through the sieve was tested according to the standard.

[0122] The test results are shown in the following table:

[0123] Table 5 Comparison of No. 3, 5, 7 and Comparative Example 1

[0124]

[0125] As can be seen from the above table, under the same conditions, the compressive strength and the residue on 45-micron sieve of the examples are better than those of Comparative Example 1. Moreover, the dusting situation of the cement is better than that of Comparative Example 1, indicating that the dusting performance of the crystals in the examples is better than that of the sulfate ester salts in the comparative examples.

[0126] Application comparison of the crude hydroxyalkyl tertiary amine aminosulfonate in Example 9 and the comparative sample in cement at a higher temperature

[0127] In this example, No. 1, 2, 4, and 6 were respectively added to the cement composition according to the mass dosage, and the total mass of the cement composition was 5 kg. According to the composition ratio of the cement (by mass percentage), 80% of clinker, 5% of gypsum, 10% of slag powder, and 5% of limestone powder were respectively weighed, totaling 5 kg. According to the dosage, the corresponding masses of 1, 2, 4, and 6 were weighed and put into a standard small mill, and each was ground for 26 minutes. The ground material was sieved through a 0.2-mm sieve, and the sample passing through the sieve was tested according to the standard. The inlet temperature of the clinker into the mill was 80°C.

[0128] The test results are shown in the following table:

[0129] Table 6 Comparison of the compressive strength of the cement prepared from No. 2, 4, 6 and Comparative Example 1

[0130]

[0131] It can be seen that when the crude product of the embodiment is added to the cement grinding with clinker at a higher temperature, the compressive strength is higher than that of Comparative Example 1. This shows that the crude product of the embodiment has better heat resistance than the sulfate ester salt of the comparative example.

[0132] Comparison of the application of the crystal of hydroxyalkyl tertiary amine aminosulfonate in Example 10 and the comparative sample in cement at a higher temperature

[0133] In this embodiment, Nos. 1, 3, 5, and 7 are respectively added to the cement composition according to the mass dosage, and the total mass of the cement composition is 5 kg. According to the composition ratio of the cement (by mass percentage), 85% of clinker, 5% of gypsum, and 10% of slag powder are respectively weighed, totaling 5 kg. According to the dosage, the corresponding masses of 1, 3, 5, and 7 are weighed and put into a standard small mill, and each is ground for 25 minutes. The ground material is sieved through a 0.2-mm sieve, and the sample under the sieve is tested according to the standard. The inlet temperature of the clinker into the mill is 80°C.

[0134] The test results are shown in the following table:

[0135] Table 7 Comparison of Nos. 3, 5, 7 and Comparative Example 1

[0136]

[0137] It can be seen that when the crystal prepared in the embodiment is added to the cement grinding with clinker at a higher temperature, the compressive strength is better than that of the comparative example. This shows that the crystal of the embodiment has better heat resistance than the sulfate ester salt of the comparative example.

[0138] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as a limitation of the present invention itself. Various changes can be made in its form and details without departing from the spirit and scope of the present invention defined by the appended claims.

Claims

1. Application of a hydroxyalkyl tertiary amine aminosulfonate crystal in improving the dusting performance of cement, characterized in that, The hydroxyalkyl tertiary amine aminosulfonate crystal is N, N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine aminosulfonate crystal, and its powder X-ray diffraction has characteristic absorption peaks at 2θ of 11.0°, 13.1°, 14.2°, 17.0°, 17.9°, 18.7°, 19.1°, 21.0°, 21.3°, 21.8°, 23.6°, 25.0°, 25.4°, 25.9°, 26.7°, 27.5°, 28.0°, 28.3°, 29.4°, 30.6°, 31.1°, 32.0°, 32.5°, 33.0°, 34.1° and 35.4° ± 0.1° respectively; It is prepared by the following method: (1) Add hydroxyalkylamine, aminosulfonic acid and solvent into the reactor in sequence. Under the condition of N2 replacement, stir and heat to 40~90 °C. After constant temperature reaction for 3~6 h, keep the temperature unchanged, evacuate to -0.098~-0.06 MPa and continue for 30~60 min to obtain the intermediate product; (2) Mix the intermediate product obtained in the above step with an organic solvent, heat to 40~80 °C while stirring, add activated carbon, then filter while it is hot. Stir the filtrate and cool it to below 20 °C to form a crystalline precipitate. Filter and separate the crystalline precipitate, and dry it below 80 °C to obtain the hydroxyalkylamine aminosulfonate crystal; (3) Use the filtrate obtained after separating the crystalline precipitate in step (2) to replace the organic solvent in step (2) according to the mass ratio of 1:1 to the intermediate product and recycle it; In step (1), the molar ratio of the hydroxyalkylamine to the aminosulfonic acid is 1.0:(0.75~1.5); The solvent is one or two of deionized water, methanol, ethanol, and isopropanol; The amount of the solvent is 20%~30% of the total feeding mass of the hydroxyalkylamine and the aminosulfonic acid; In step (2), the organic solvent is methanol, ethanol, isopropanol or a mixture thereof; The amount of the organic solvent used is 1~2 times the mass of the intermediate product; The stirring speed of the filtrate is 50~200 r / min, and the cooling speed is 25 °C / h~55 °C / h; The hydroxyalkylamine is N, N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine.

2. Application of a hydroxyalkyl tertiary amine aminosulfonate crystal in improving the dusting performance of cement, characterized in that, The hydroxyalkyl tertiary amine aminosulfonate crystal is N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine aminosulfonate crystal, and its powder X-ray diffraction has characteristic absorption peaks at 2θ of 8.2°, 16.4°, 17.8°, 19.3°, 19.5°, 19.8°, 20.4°, 20.8°, 21.4°, 22.5°, 23.0°, 24.6°, 24.9°, 26.0°, 26.7°, 27.2°, 27.6°, 28.8°, 29.1°, 29.8°, 31.1°, 32.9°, 33.2°, 33.9°, 34.2°, 34.8°, 35.2°, 35.4°, 35.8°, 36.0°, 40.1°, 41.4°, 41.6°, 42.6°, 43.0°, 43.2°, 44.2°, 44.6° and 45.7° ± 0.1°; It is prepared by the following method: (1) Add hydroxyalkylamine, aminosulfonic acid and solvent into the reactor in sequence. Under the condition of N2 replacement, stir and heat to 40~90°C. After constant temperature reaction for 3~6h, keep the temperature unchanged, evacuate to -0.098~-0.06MPa and continue for 30~60min to obtain an intermediate product; (2) Mix the intermediate product obtained in the above step with an organic solvent, heat to 40~80°C while stirring, add activated carbon, then filter while it is hot. Stir the filtrate and cool it to below 20°C to form a crystalline precipitate. Filter and separate the crystalline precipitate, and dry it below 80°C to obtain the hydroxyalkylamine aminosulfonate crystal; (3) Use the filtrate obtained after separating the crystalline precipitate in step (2) to replace the organic solvent in step (2) according to the mass ratio of 1:1 to the intermediate product for recycling; In step (1), the molar ratio of the hydroxyalkylamine to the aminosulfonic acid is 1.0 : (0.75 ~ 1.5); The solvent is one or two of deionized water, methanol, ethanol, and isopropanol; The amount of the solvent is 20% ~ 30% of the total feeding mass of the hydroxyalkylamine and the aminosulfonic acid; In step (2), the organic solvent is methanol, ethanol, isopropanol or a mixture thereof; The amount of the organic solvent used is 1~2 times the mass of the intermediate product; The stirring speed of the filtrate is 50~200r / min, and the cooling speed is 25°C / h~55°C / h; The hydroxyalkylamine is N,N-bis(2-hydroxypropyl)-N-(2-hydroxyethyl)amine.

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