CN116023281A - Hydroxyalkyl tertiary amine sulfamate, crystal, preparation method and application thereof - Google Patents

Abstract

The invention discloses a hydroxyalkyl tertiary amine sulfamate with a general formula (I), a crystal and a preparation method thereof.

Description

Hydroxyalkyl tertiary amine sulfamate, crystal, preparation method and application thereof

Technical Field

The invention belongs to the technical field of compound and material preparation, and particularly relates to hydroxyalkyl tertiary amine sulfamate, a crystal, a preparation method thereof and application thereof in cement additives.

Background

Cement additive development has been shown to be based on grinding aid dispersion, emphasizing the feature of improving cement properties. The additive for practical application takes an alcohol amine compound which has excellent grinding assisting performance and can improve the hydration performance of cement as a core, and takes polyalcohol with better dispersion grinding assisting performance and inorganic material with certain strength excitation effect as an auxiliary.

At present, a large amount of liquid additives used in the market are aqueous solutions formed by single or compound chemical raw materials such as alcohol amines, alcohols and the like, and the aqueous solutions are added into a cement grinding or crushing system according to 0.02-0.2% of the total mass of cement materials, so that the material conveying of the grinding system is improved, the ball milling and grinding is reduced, the powder selecting efficiency of a powder selecting system is improved, and the transportation and storage efficiency of cement products is improved through dispersion performance; in addition, the cement grain composition is adjusted, the cement hydration is promoted, the quality of cement can be improved, the cost of cement ingredients is directly reduced, the proportion of the admixture is improved, and the application of waste residues and waste materials is promoted.

In a word, the suitable cement additive product can improve factory production efficiency and product quality, can try direct economic benefit, can promote more full utilization of resources, and can reduce dust and carbon dioxide emission to achieve the effect of protecting environment, so the cement additive product is popularized as a green energy-saving product worldwide.

Due to the characteristics of cement additive products, the products are rapidly popularized and applied. Its lower threshold and stronger service properties have led to the advent of numerous small and medium-sized cement additive manufacturers or suppliers. These small and medium-sized suppliers have various distinctive product performances and comprehensive services, but also bring hidden production quality hazards, and are difficult to completely meet the different demands of individuality.

The core raw materials of the additive are basically triethanolamine, triisopropanolamine, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine and the like, and the raw materials are petrochemical products, so that the price increase trend is obvious, and part of the raw materials fluctuate severely and are supplied with tension.

Triethanolamine, triisopropanolamine, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine and the like are multipolar compounds with lower melting points, and are viscous oil or wax substances at normal temperature. The vapor pressure of the above compound increases with temperature, and the volatility increases with temperature.

The compounds such as triethanolamine, triisopropanolamine, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine and the like are all three hydrogen on ammonia to replace to form a triangular pyramid-like structure. The top nitrogen atom has a pair of lone pair electrons.

Since the core raw materials are viscous oil or are in a waxy mass form at normal temperature, and the production of additives is very inconvenient, the core raw materials are often prepared into an aqueous solution with certain fluidity at normal temperature in advance, and a flowmeter, a pump or manual conveying is used, so that the accuracy of measurement and the production quality are difficult to ensure.

The core raw materials of the additive are alcohol amine compounds with high activity, the melting point is low, the melting point of triethanolamine is 21 ℃, and the melting point of triisopropanolamine is 48-52 ℃. The amine is easily oxidized and most oxidizing agents oxidize the amine to a tar, hydrogen peroxide and peracids oxidize the tertiary amine to tertiary amine oxides. (Zhou Gongjun, jiang Zonglin, wang Xinliang, tan Ming, beam columns, he Xiaoying, novel method for synthesizing tertiary amine compounds, university of West China chemical society, south Sichuan Share, 637002). The vapor pressure of the above compound increases with temperature, and the volatility increases with temperature. In cement grinding processes, clinker is usually burned at a maximum temperature of about 1450 ℃ and then transferred to a ball mill, and after cooling, the surface temperature can be reduced to 50 to 90 ℃, but the internal temperature of the clinker is usually higher. This also means that the above compounds increase in volatility with increasing temperature, and the losses become large and the efficacy decreases.

At present, the cement additive taking alcohol amine as a core raw material has excellent performance in most cases, but has some defects.

Firstly, because of the structural characteristics of the raw materials, the trihydroxy and tertiary amino have strong adsorptivity, so the grinding aid dispersion performance is very strong. Because the cement grinding adopts a ball milling process under the negative pressure condition, the load of a grinding system is greatly increased due to the excessively strong dispersibility, the mixing range is limited, and the phenomena of ash discharge and the like occur. This is mainly due to the strong dispersion of the alcohol amine raw material and the limitation of the air flow system capacity of the grinding system. However, modern large cement grinding systems tend to be relatively invested, are not willing to limit investment modification, and the desire to modify additives to accommodate their grinding systems creates limitations in alcohol amine additives.

Secondly, the excellent grinding assisting dispersion performance leads to more concentrated grain composition of cement products and finer grain composition, leads to the great increase of water demand of standard consistence of cement, and influences the working performance of cement concrete.

At present, application research or development of cement additives is focused on optimization through formulation design and screening. The requirements of grinding aid and strength can be partially met, for example, the balance of strength increase and grinding aid is met by a combination of alcohol amine, sugar and industrial salt, which has become a mainstream formulation; the alcohol amine is used as an auxiliary material for industrial leftovers, such as glycerin, propylene glycol and other low-cost reclaimed materials or secondary and processed materials in the polyol, so that the cost is reduced under the condition of maintaining the grinding assisting property and strength. There are also some improvements to the core alcohol amine, mainly focused on the following two aspects:

firstly, alcohol amine containing hydroxyl and acid are subjected to esterification dehydration to prepare amino compound containing ester groups. The compound may be reduced to acids and alcohol amines by hydrolysis under the strongly alkaline conditions of cement hydration. For example Huang Jiming, in the text of "preparation of triethanolamine sulfate additive and evaluation of its properties", the preparation of triethanolamine sulfate is carried out by esterifying triethanolamine with sulfamic acid, separating the product, and oven drying at low temperature, and the triethanolamine sulfate is obtained and applied to additives. The final product of this scheme is a high viscosity waxy solid which is detrimental to storage, transportation and application.

Secondly, neutralizing alcohol amine with acid to lower the PH value of the alcohol amine, so as to form a mixture with low alkalinity or acidity.

The patent 201510069058.6 provides a cement additive prepared by mixing and reacting industrial waste hydrochloric acid or waste sulfuric acid with diethanol monoisopropanolamine, wherein the product is regarded as diethanol monoisopropanolamine hydrochloride, and the technical scheme of the reaction is not provided, and the product is not characterized at all. The final product of this scheme is a high viscosity waxy solid which is detrimental to storage, transportation and application.

The diethanol monoisopropanolamine and sulfamic acid are mixed and then heated for reaction, and the final product is oily sticky solid or massive solid, and can also be used for cement additives or other products.

The neutralization reaction is certainly easy to carry out from the acid-base perspective. However, salification of alcohol amine with acid presents the following difficulties: 1. the alkalinity of the amine is weaker than that of the similar fatty amine, and the reactivity is weakened; the hydroxyalkyl on the alcohol amine branched chain is an electron withdrawing group, so that the electron donating capacity of nitrogen atoms is weakened; 2. the alcohol amine used in the cement additive is tertiary amine, but hydrogen on atoms is replaced by three branched chains to form a steric hindrance effect, the steric morphology of acid radical also has an important influence on the reaction, and the steric hindrance can lead the acid radical to be difficult to attack nitrogen atoms to form a product; 3. the separation of the product from the reactant mixture requires finding a suitable crude product separation process, and the separation process of the product and the reactant is not performed in the previous study;

in addition, the introduction of chloride ions, sulfate ions and nitrite ions all adversely affect the durability of cement reinforced concrete. The chloride ions can damage the reinforced bar passivation film, quicken the freezing and thawing of the concrete and rust the reinforced bar, and influence the use safety and durability of the building; sulfate is also an important factor affecting the durability of concrete, and can react chemically with the muddy water product in concrete, resulting in poor volume stability and cracking of the concrete due to expansion, so that the selection of acid is also important.

Disclosure of Invention

The invention aims to: the invention aims at overcoming the defects of the prior art and provides a hydroxyalkyl tertiary amine sulfamate, a crystal, a preparation method thereof and application thereof in cement additives. The invention selects sulfamic acid as raw material to prepare the hydroxyalkyl tertiary amine sulfamate and crystal particles thereof, and applies the hydroxyalkyl tertiary amine sulfamate and crystal particles thereof to cement for the first time, thereby improving the cement performance, reducing the dust content of finished products, improving the working environment and reducing the packaging difficulty and cost.

The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:

the invention provides a hydroxyalkyl tertiary amine sulfamate, which has a structural formula shown in a general formula (I):

wherein,,

R ₁ 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxyisopropyl;

R ₂ 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxyisopropyl;

R ₃ is 2-hydroxypropyl, 2-hydroxyisopropyl, N-bis (2-hydroxyethyl) aminoethyl, N-bis (2-hydroxypropyl) aminoethyl, N- (2-hydroxyethyl) -N- (2-hydroxypropyl) aminoethyl, N-bis (2-hydroxyethyl) aminopropyl, N-bis (2-hydroxypropyl) aminopropyl or N- (2-hydroxyethyl) -N- (2-hydroxypropyl) aminopropyl.

The invention also provides a hydroxyalkyl tertiary amine sulfamate crystal prepared from the hydroxyalkyl tertiary amine sulfamate of the general formula (I).

Preferably, the crystals of the hydroxyalkyl tertiary amine sulfamate include crystals of: n, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate, N, N, N ', N ' -tetrakis (2-hydroxyethyl) ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxyethyl) -N ' - (2-hydroxypropyl) ethylenediamine sulfamate, N, N-bis (2-hydroxyethyl) -N ', N ' -bis (2-hydroxypropyl) ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxypropyl) -N ' - (2-hydroxyethyl) ethylenediamine sulfamate, N, N, N ', N ' -tetrakis (2-hydroxypropyl) ethylenediamine sulfamate, N, N, N ', N ' -tetrakis (2-hydroxyethyl) propylenediamine sulfamate, N, N ' -tris (2-hydroxyethyl) -N ' - (2-hydroxypropyl) propylenediamine sulfamate, N, N-bis (2-hydroxyethyl) -N ', N ' -bis (2-hydroxypropyl) ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxyethyl) -ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxypropyl) ethylenediamine sulfamate, N, N ' -tris (2-hydroxyethyl) ethylenediamine sulfamate, n' -tetrakis (2-hydroxypropyl) propanediamine sulfamate.

Further, the crystals of the hydroxyalkyl tertiary amine sulfamate include crystals of: n, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate.

Still further, the crystalline N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate 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 °, respectively.

Still further, the crystalline powder X-ray diffraction of the N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate crystal 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 °, respectively.

The invention also provides a preparation method of the hydroxyalkyl tertiary amine sulfamate crystal, which comprises the following steps:

(1) Sequentially adding hydroxyalkylamine, sulfamic acid and solvent into a reactor, wherein N is as follows ₂ Stirring under the replacement condition, heating to 40-90 ℃, reacting for 3-6 hours at constant temperature, vacuumizing to-0.098-0.06 MPa, and continuing for 30-60 min to obtain the final productThe intermediate hydroxyalkyl tertiary amine sulfamate;

(2) Dissolving the intermediate product obtained in the steps in an organic solvent, adding active carbon, heating to 40-80 ℃ while stirring, filtering while the mixture is hot, stirring the filtrate, cooling to below 20 ℃ to form a crystal precipitate, filtering and separating the crystal precipitate, and drying at below 80 ℃ to obtain a hydroxyalkyl amine sulfamate crystal;

(3) And (3) filtering and separating the crystal precipitate in the step (2), and replacing the organic solvent in the step (2) according to the mass ratio of 1:1 for recycling.

Preferably, in the step (1), the molar ratio of the hydroxyalkyl amine to the sulfamic acid is 1.0 (0.75-1.5);

the solvent is one or two of deionized water, methanol, ethanol, isopropanol, cyclohexane and petroleum ether;

the amount of the solvent is 20-30% of the total feeding mass of the hydroxyalkyl amine and the sulfamic acid.

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

the dosage of the organic solvent is 1-2 times of the mass of the intermediate product;

the crystallization process is a substance purification process that uses a change in the solubility of a substance in a solvent. Preparing a saturated solution from the substance and a solvent, filtering while the solution is hot, removing insoluble impurities, and then reducing the temperature of the solution to change the solution into a supersaturated solution, wherein the solute is crystallized and separated out; or filtering the saturated solution, removing the solvent, and changing the solvent into crystals.

The choice of solvent is critical, does not participate in chemical reaction, can dissolve a large amount of solute at high temperature, can only dissolve a small amount at low temperature, and has a boiling point which is not too high, is not too low, and is easy to volatilize and remove.

The solvent is used in a quantity selected to make the hot solution close to saturation or reach saturation, and suction-filtering or cooling to make the solution become supersaturated solution, so that crystals are separated out.

The stirring speed of the decolorized solution is 50-200 r/min, and the cooling speed is 25-55 ℃/h.

The supersaturation of the solution is the driving force for the precipitation of crystals. The cooling speed is a main process condition for providing supersaturation degree of the solution, and the crystal generation speed can be adjusted by controlling the cooling speed. The stirring speed is controlled, so that the temperature distribution of the solution is uniform, the crystallization is complete, and the crystal form is prevented from being damaged.

In the invention, in the reaction stage, the reaction is fully carried out by the solvent, the conversion rate is high, and meanwhile, the low-boiling-point impurities are carried out by the solvent through vacuum filtration, so that the purity of the product is improved; in the crystallization process stage, a proper organic solvent is selected, suction filtration, cooling and stirring processes are adopted, and the optimal crystallization conditions are selected, so that the high crystallization yield is obtained.

The invention also provides the first application of the hydroxyalkyl tertiary amine sulfamate and the crystal in cement additives.

The beneficial effects are that:

(1) The invention selects sulfamic acid as raw material, selects proper solvent, has low reaction temperature, high raw material conversion rate, high product purity, good product dispersibility and fluidity, low cost, and convenient package and transportation and application.

(2) The hydroxyalkyl tertiary amine sulfamate crystal particles can be applied to cement, can be applied to higher temperature environments, can control the flowing speed of cement particles, improve the cement performance, reduce the dust content of finished products, improve the working environment and reduce the packaging difficulty and cost.

(3) The invention successfully prepares the hydroxyalkyl tertiary amine sulfamate and the crystal thereof, and the prepared hydroxyalkyl tertiary amine sulfamate crystal has higher dissolution rate in water, can be accurately metered, and improves the accuracy when the hydroxyalkyl tertiary amine sulfamate crystal is used for compounding additives. As a crystal, the melting point and stability of the crystal are greatly improved, and compared with liquid, the crystal can be quantitatively packaged by adopting solid, and the packaging cost, the transportation cost and the storage cost are reduced.

(4) The filtrate after separation and crystallization can be recycled, so that the utilization rate of raw materials and the recovery rate of crystals are improved.

Drawings

FIG. 1 is a chart of electrospray mass spectrometry detection positive ions of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, with the vertical axis representing relative intensity (%), and the horizontal axis representing mass-to-charge ratio (m/z) of ions.

FIG. 2 shows negative ion patterns detected by electrospray mass spectrometry of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, the vertical axis shows relative intensity (%), and the horizontal axis shows mass-to-charge ratio (m/z) of ions.

FIG. 3 is a chart of electrospray mass spectrometry detection positive ions of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate, with the vertical axis representing relative intensity (%), and the horizontal axis representing mass-to-charge ratio (m/z) of ions.

FIG. 4 shows negative ion patterns detected by electrospray mass spectrometry of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate, the vertical axis shows relative intensity (%), and the horizontal axis shows mass-to-charge ratio (m/z) of ions.

FIG. 5 is an X-ray diffraction pattern of crystalline N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, with the vertical axis representing diffraction intensity (%), and the horizontal axis representing the 2-theta diffraction angle (°).

FIG. 6 is a differential scanning calorimetry chart of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate crystals, with the vertical axis representing heat flow rate (w/g) and the horizontal axis representing temperature (. Degree. C.).

FIG. 7 is an X-ray diffraction pattern of crystalline N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate, the vertical axis representing diffraction intensity (%), and the horizontal axis representing the 2-theta diffraction angle (°).

FIG. 8 is a differential scanning calorimetry chart of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate crystals, with the vertical axis representing heat flow rate (w/g) and the horizontal axis representing temperature (. Degree. C.).

Detailed Description

The technical scheme of the present invention is described in detail below through specific examples, but the scope of the present invention is not limited to the examples.

Compound and crystal test method:

the melting point is measured by a WRS-2 microcomputer melting point instrument; electrospray mass spectrometry (Waters Q-TOF Micro) ^TM Measuring by a mass spectrometer; powder X-ray diffraction pattern was measured using a Bruker AXS D8 Advance X-ray diffractometer; differential scanning calorimetry patterns were measured using a shimadzu DSC-60A shimadzu assay detector.

Additive application test method:

the test is carried out according to the GB/T26748-2011 standard of cement grinding aid. The detection method refers to GB/T17671-1999 'cement mortar strength test method', GB/T1346-2011 'cement standard consistency water consumption test method', and detects cement strength and standard consistency water consumption.

Industrial tests are carried out according to production practice.

The cement raw materials referred to in the examples all meet the corresponding standards. Wherein the clinker is common silicate cement clinker produced by Anhui conch cement company.

Comparative example 1

99% of N, N, N-tris (2-hydroxyethyl) amine (105.4 g, 0.6 mol) and 99.5% of sulfamic acid (68.3 g, 0.7 mol) are added into a 500ml reaction bottle equipped with a condensing device, and the mixture is slowly heated to 110 ℃ while stirring until the condensation recovery is stopped, and naturally cooled to room temperature, thus obtaining solid triethanolamine sulfate salt.

EXAMPLE 1 preparation of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate crystals

Into a 500ml reaction flask equipped with a heating device were charged, together with 134.4g (0.7 mol) of 85% N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, 68.3g (0.7 mol) of 99.5% sulfamic acid and 50.6g of 99.7% ethanol, and the mixture was fed into a flask equipped with a heating device, at N ₂ Stirring under the replacement condition, slowly heating to 80-85 ℃, reacting at constant temperature for 4.0h, vacuumizing to-0.098-0.06 MPa, continuously cooling to room temperature for 30min, and obtaining 217.3g of crude N, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate;

mixing the crude product with 430g of 99.7% ethanol, heating to 40 ℃, adding 7.2g of active carbon, stirring for 30min, carrying out suction filtration, stirring filtrate at a speed of 50r/min, cooling to below 20 ℃ at a speed of 55 ℃/h, crystallizing, filtering, and drying to obtain 165.0g of white crystal of the product N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, wherein the yield is 90.5%.

The electrospray mass spectrum detection positive ion diagram of the prepared N, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate crystal is shown in figure 1, the negative ion diagram is shown in figure 2, the powder X-ray diffraction diagram is shown in figure 5, the Differential Scanning Calorimetry (DSC) diagram is shown in figure 6, and the measured melting point is 100.5-109.3 ℃.

In the electrospray mass spectrometry detection positive ion chart: the mass-to-charge ratio (M/z) was 164.1 ([ M+H)] ⁺ )，

In the electrospray mass spectrum detection negative ion chart: the mass-to-charge ratio (M/z) was 96.0 ([ M-H)] ^- )；

The differential scanning calorimetry trace has an endotherm in the range of about 100.5 ℃ to 109.3 ℃.

The X-ray powder diffraction data are shown in table 1:

TABLE 1X-ray powder diffraction data for crystalline N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate

EXAMPLE 2 preparation of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate crystals

Into a 500ml reaction flask equipped with a heating device were charged 166.6g (0.8 mol) of 85% N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine, 66.4g (0.68 mol) of 99.5% sulfamic acid and 60.0g of 99.7% ethanol together, and the mixture was introduced into a flask containing a heating device under N ₂ Stirring under the replacement condition, slowly heating to 80-85 ℃, reacting at constant temperature for 3.5h, vacuumizing to-0.098 to-0.06 MPa, continuously cooling to room temperature for 60min, and obtaining 253.3g of crude N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate;

mixing the crude product with 260g of 99.7% ethanol, heating to 80 ℃, adding 7.5g of active carbon, stirring for 30min for decoloration, carrying out suction filtration, stirring filtrate at the speed of 250r/min, cooling to below 20 ℃ at the speed of 25 ℃/h for crystallization, carrying out suction filtration, and drying to obtain 156.8g of product N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate white crystal, wherein the yield is 84.2%.

The electrospray mass spectrum detection positive ion graph of the prepared N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate crystal is shown in figure 3, the negative ion graph is shown in figure 4, the powder X-ray diffraction graph is shown in figure 7, the Differential Scanning Calorimetry (DSC) graph is shown in figure 8, and the measured melting point is 96.1-107.1 ℃.

In the electrospray mass spectrometry detection positive ion chart: mass to charge ratio (M/z) of 178.1 ([ M+H)] ⁺ )，

In the electrospray mass spectrum detection negative ion chart: the mass-to-charge ratio (M/z) was 96.0 ([ M-H)] ^- )；

The differential scanning calorimetry trace has an endotherm in the range of about 96.1 ℃ to 107.1 ℃.

The X-ray powder diffraction data are shown in table 2:

TABLE 2X-ray powder diffraction data for crystalline N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate

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Example 3 preparation of crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate

Into a 500ml reaction flask equipped with a heating device were charged 85% N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine 123.0g (0.7 mol), 99.5% sulfamic acid 58.5g (0.6 mol) and 99.5% methanol 42.5g together, at N ₂ Stirring under the replacement condition, slowly heating to 70-75 ℃, reacting at constant temperature for 3.5h, vacuumizing to-0.098 to-0.06 MPa, continuously cooling to room temperature for 45min, and obtaining 213.6g of crude N, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate;

filtering the crude product and 200g of the example 2, separating the crystal precipitate, heating the filtrate to 80 ℃, adding 6.0g of active carbon, stirring for 30min, carrying out suction filtration, stirring the filtrate at the speed of 200r/min, cooling to below 20 ℃ at the speed of 45 ℃/h, crystallizing, carrying out suction filtration, and drying to obtain 136.7g of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) sulfamate white crystal with the yield of 92.5%; the melting point measured by a WRS-2 microcomputer melting point meter is 101.2-109.1 ℃.

As is clear from example 3, the filtrate obtained by separating the crystalline precipitate whose main component is ethanol in example 1 was used as the solvent in this example, the crystal yield was increased to 92.5%, and the melting range was shortened to 7.9 ℃.

EXAMPLE 4 preparation of crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate

To a 500ml reaction flask equipped with a heating device were charged 153.6g (0.8 mol) of 85% N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, 68.3g (0.7 mol) of 99.5% sulfamic acid, and 55.5g of 99.7% ethanol, followed by adding the mixture to the flask in N ₂ Stirring under the replacement condition, slowly heating to 80-85 ℃, reacting at constant temperature for 4.0h, vacuumizing to-0.098-0.06 MPa, continuously cooling to room temperature for 30min, and obtaining 243.3g of crude N, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate;

mixing the crude product with 156 g of 99.7% ethanol and 57g of 99.5% acetone, heating to 40 ℃, adding 7.2g of active carbon, stirring for 30min, suction filtering, stirring filtrate at a speed of 200r/min, cooling to below 20 ℃ at a speed of 55 ℃/h for crystallization, and performing suction filtering and drying to obtain 166.9g of white crystal of the product N, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) sulfamate, wherein the yield is 91.6%; the melting point measured by a WRS-2 microcomputer melting point meter is 100.9-108.9 ℃.

As is clear from example 4, the use of a mixed solvent of ethanol and acetone improves the crystal yield to 91.6% and shortens the melting range to 8.0℃as compared with example 1.

EXAMPLE 5 preparation of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate crystals

To a 500ml reaction equipped with a heating device were added together 166.6g (0.8 mol) of 85% N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine, 66.4g (0.68 mol) of 99.5% sulfamic acid and 50.0g of 99.7% isopropyl alcoholIn the bottle, in N ₂ Stirring under the replacement condition, slowly heating to 80-85 ℃, reacting at constant temperature for 3.5h, vacuumizing to-0.098 to-0.06 MPa, continuously cooling to room temperature for 60min, and obtaining 250.7g of crude N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate;

mixing the crude product with 200g of 99.7% methanol and 100g of 99.7% isopropanol, heating to 40 ℃, adding 7.5g of active carbon, stirring for 30min, suction filtering, stirring the filtrate at a speed of 50r/min, cooling to below 20 ℃ at a speed of 55 ℃/h for crystallization, and performing suction filtering and drying to obtain 162.5g of white crystal of the product N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate, wherein the yield is 87.2%; the melting point measured by a WRS-2 microcomputer melting point meter is 98.0-106.9 ℃.

As is clear from example 5, the use of a mixed solvent of methanol and isopropanol improves the crystal yield to 87.2% and shortens the melting range to 8.9℃as compared with example 2.

EXAMPLE 6 preparation of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate crystals

Adding 166.6g (0.8 mol) of 85% N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine, 117.0g (1.2 mol) of 99.5% sulfamic acid and 85.0g of 99.7% ethanol into a 1000ml reaction bottle provided with a heating device, stirring under the condition of N2 replacement, slowly heating to 40-55 ℃, reacting at constant temperature for 4.5h, vacuumizing to-0.098 to-0.06 MPa, continuing for 60min, and naturally cooling to room temperature to obtain 288.6g of crude N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate;

the crude product is heated and dissolved by 280g of 99.7 percent ethanol, 9.5g of active carbon is added, stirring is carried out for 30min, the filtrate is stirred at the speed of 150r/min, the temperature is reduced to below 20 ℃ at the speed of 50 ℃/h for crystallization, 197.3g of product N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate white crystal is prepared through suction filtration and drying, and the yield is 90.0 percent. The melting point of the prepared N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate crystal measured by a WRS-2 microcomputer melting point instrument is 98.0-107.0 ℃.

As is clear from example 6, the filtrate obtained by separating the crystalline precipitate whose main component was ethanol in example 2 was used as the solvent in this example, the crystal yield was increased to 90.0%, and the melting range was shortened to 9.0 ℃.

With reference to GB/T26748-2001 cement grinding aid, examples of corresponding serial numbers in the following tables are each used as cement additives and are added in corresponding mass mixing amounts for testing.

TABLE 3 Cement additives

EXAMPLE 7 comparison of crude hydroxyalkyltertiary amine sulfamate with control in Cement

In this example, serial numbers 1, 2, 4, and 6 were added to the cement composition in the mass blending amounts, respectively, and the total mass of the cement composition was 5 kg. According to the composition proportion (in mass percent) of cement, 80 percent of clinker, 5 percent of gypsum, 10 percent of slag powder and 5 percent of limestone powder are respectively weighed, and the total weight is 5 kilograms. According to the mixing amount, 1, 2, 4 and 6 of corresponding mass are weighed and put into a standard small mill, each mill is ground for 27 minutes, the ground materials are sieved by a 0.2 millimeter sieve, and the undersize samples are tested according to the standard.

The detection results are shown in the following table:

table 4 compressive strength of cements produced in accordance with Ser. No. 2, 4 and 6 and comparative example 1

As can be seen from the above table, under the same conditions, the compressive strength and 45 μm screen residue of the examples are better than those of comparative example 1, and the dusting condition of cement is better than that of comparative example 1, indicating that the dusting performance of the crude product of the examples is better than that of the sulfate salt of comparative example.

EXAMPLE 8 comparison of the use of crystals of hydroxyalkyltertiary amine sulfamate with a control in Cement

In this example, serial numbers 1, 3, 5, and 7 were added to the cement composition in the mass blending amounts, respectively, and the total mass of the cement composition was 5 kg. According to the composition proportion (in mass percent) of cement, 85% of clinker, 5% of gypsum and 10% of slag powder are respectively weighed, and the total weight is 5 kg. According to the mixing amount, 1, 3, 5 and 7 of the corresponding mass are weighed and put into a standard small mill, each mill is carried out for 28 minutes, the milled materials are sieved by a 0.2 millimeter sieve, and the undersize sample is detected according to the standard.

The detection results are shown in the following table:

table 5 comparison of sequence numbers 3, 5, 7 with comparative example 1

As can be seen from the above table, under the same conditions, the compressive strength and 45 μm screen residue of the example are both superior to those of comparative example 1, and the dusting condition of cement is superior to that of comparative example 1, indicating that the dusting performance of the crystals of the example is superior to that of the sulfate salt of comparative example.

EXAMPLE 9 comparison of crude hydroxyalkyltertiary amine sulfamate with control in higher temperature Cement

In this example, serial numbers 1, 2, 4, and 6 were added to the cement composition in the mass blending amounts, respectively, and the total mass of the cement composition was 5 kg. According to the composition proportion (in mass percent) of cement, 80 percent of clinker, 5 percent of gypsum, 10 percent of slag powder and 5 percent of limestone powder are respectively weighed, and the total weight is 5 kilograms. According to the mixing amount, 1, 2, 4 and 6 of corresponding mass are weighed and put into a standard small mill, each mill is milled for 26 minutes, the milled materials are sieved by a 0.2 millimeter sieve, and the undersize samples are tested according to the standard. The clinker grinding temperature is 80 ℃.

The detection results are shown in the following table:

table 6 compressive strength of cements produced in accordance with Nos. 2, 4 and 6 and comparative example 1

From this, it can be seen that the compressive strength of the crude product of the example was obtained by adding the crude product of the example to cement grinding with clinker at a higher temperature. Illustrating that the crude product of the examples has better temperature resistance than the sulfate salt of the comparative example.

EXAMPLE 10 comparison of hydroxyalkyl tertiary amine sulfamate crystals with comparative sample in higher temperature Cement

In this example, serial numbers 1, 3, 5, and 7 were added to the cement composition in the mass blending amounts, respectively, and the total mass of the cement composition was 5 kg. According to the composition proportion (in mass percent) of cement, 85% of clinker, 5% of gypsum and 10% of slag powder are respectively weighed, and the total weight is 5 kg. According to the mixing amount, 1, 3, 5 and 7 of the corresponding mass are weighed and put into a standard small mill, each mill is carried out for 25 minutes, the milled materials are sieved by a 0.2 millimeter sieve, and the undersize sample is detected according to the standard. The clinker grinding temperature is 80 ℃.

The detection results are shown in the following table:

table 7 comparison of sequence numbers 3, 5, 7 with comparative example 1

From this, it can be seen that the compressive strength of the crystals prepared in the examples was superior to that of the comparative examples in the cement grinding with the clinker at higher temperature. The example shows that the temperature resistance of the crystals is better than that of the sulfate salt of the comparative example.

As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. A hydroxyalkyltertiary amine sulfamate, which is characterized by having a structural formula shown in a general formula (I):

wherein,,

R ₁ 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxyisopropyl;

R ₂ 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxyisopropyl;

R ₃ is 2-hydroxypropyl, 2-hydroxyisopropyl, N-bis (2-hydroxyethyl) aminoethyl, N-bis (2-hydroxypropyl) aminoethyl, N- (2-hydroxyethyl) -N- (2-hydroxypropyl) aminoethyl, N-bis (2-hydroxyethyl) aminopropyl, N-bis (2-hydroxypropyl) aminopropyl or N- (2-hydroxyethyl) -N- (2-hydroxypropyl) aminopropyl.

2. A crystal of hydroxyalkyltertiary amine sulfamate produced from the hydroxyalkyltertiary amine sulfamate of claim 1.

3. The crystals of hydroxyalkyltertiary amine sulfamate of claim 2, comprising crystals of: n, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate, N, N, N ', N ' -tetrakis (2-hydroxyethyl) ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxyethyl) -N ' - (2-hydroxypropyl) ethylenediamine sulfamate, N, N-bis (2-hydroxyethyl) -N ', N ' -bis (2-hydroxypropyl) ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxypropyl) -N ' - (2-hydroxyethyl) ethylenediamine sulfamate, N, N, N ', N ' -tetrakis (2-hydroxypropyl) ethylenediamine sulfamate, N, N, N ', N ' -tetrakis (2-hydroxyethyl) propylenediamine sulfamate, N, N ' -tris (2-hydroxyethyl) -N ' - (2-hydroxypropyl) propylenediamine sulfamate, N, N-bis (2-hydroxyethyl) -N ', N ' -bis (2-hydroxypropyl) ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxyethyl) -ethylenediamine sulfamate, N, N, N ' -tris (2-hydroxypropyl) ethylenediamine sulfamate, N, N ' -tris (2-hydroxyethyl) ethylenediamine sulfamate, n' -tetrakis (2-hydroxypropyl) propanediamine sulfamate; crystals of the following compounds are preferred: n, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate.

4. The crystals of hydroxyalkyltertiary amine sulfamate of claim 3, wherein the crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine sulfamate 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 °, respectively.

5. The crystals of hydroxyalkyltertiary amine sulfamate of claim 3, wherein the crystals of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine sulfamate have 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 °, respectively.

6. The method for producing a crystal of hydroxyalkyltertiary amine sulfamate according to any one of claims 2 to 5, comprising the steps of:

(1) Sequentially adding hydroxyalkylamine, sulfamic acid and solvent into a reactor, wherein N is as follows ₂ Stirring under the replacement condition, heating to 40-90 ℃, reacting at constant temperature for 3-6 hours, keeping the temperature unchanged, vacuumizing to-0.098 to-0.06 MPa, and continuing for 30-60 min to obtain an intermediate product;

(2) Mixing the intermediate product obtained in the steps with an organic solvent, heating to 40-80 ℃ while stirring, adding active carbon, filtering while the mixture is hot, stirring the filtrate, cooling to below 20 ℃ to form a crystal precipitate, filtering and separating the crystal precipitate, and drying at below 80 ℃ to obtain hydroxyalkylamine sulfamate crystals;

(3) And (3) replacing the organic solvent in the step (2) with the filtrate obtained after separating the crystal precipitate in the step (2) according to the mass ratio of 1:1, and recycling.

7. The method according to claim 6, wherein in the step (1), the molar ratio of the hydroxyalkyl amine to the sulfamic acid is 1.0 (0.75 to 1.5);

the solvent is one or two of deionized water, methanol, ethanol, isopropanol, cyclohexane and petroleum ether;

the amount of the solvent is 20-30% of the total feeding mass of the hydroxyalkyl amine and the sulfamic acid.

8. The process according to claim 6, wherein in step (2), the organic solvent is a water-miscible low boiling alcohol, ketone, ether, ester or mixture thereof, preferably methanol, ethanol, isopropanol, acetone, diethyl ether, petroleum ether, ethyl acetate, cyclohexane or mixture thereof;

the dosage of the organic solvent is 1-2 times of the mass of the intermediate product;

the stirring speed of the filtrate is 50-200 r/min, and the cooling speed is 25-55 ℃/h.

9. Use of the crystals of hydroxyalkyltertiary amine sulfamate according to any one of claims 2-5 in cement additives.

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