阅读说明：本技术 一种羟基叔胺盐酸盐晶体的制备方法 (Preparation method of hydroxyl tertiary amine hydrochloride crystal ) 是由 李国华 陈云龙 张书 于 2019-09-23 设计创作，主要内容包括：本发明公开了一种羟基叔胺盐酸盐晶体的制备方法,包括如下步骤：(1)将盐酸溶于低级醇中形成盐酸醇溶液；(2)将步骤(1)中的盐酸醇溶液与羟基叔胺加入到反应器中,在N-2保护条件进行反应,得羟基叔胺盐酸盐初品；(3)将步骤(2)中得到的羟基叔胺盐酸盐初品用有机溶剂加热溶解后,脱色、降温、结晶,分离结晶沉淀物,干燥后制得羟基叔胺盐酸盐晶体。本发明所制备的羟基叔胺盐酸盐晶体在水中具有较高的溶解速度,并可精确计量,提高了将其用于复配添加剂时的精准度。作为晶体,相较于液体,可采用固体定量包装,包装成本、运输成本、存储成本均降低。本发明的步骤少,中间产物的分离简单,结晶提纯方法易于操作,生产成本低。(The invention discloses a preparation method of hydroxyl tertiary amine hydrochloride crystals, which comprises the following steps: (1) dissolving hydrochloric acid in lower alcohol to form hydrochloric acid alcohol solution; (2) adding the hydrochloric acid alcohol solution and the hydroxyl tertiary amine in the step (1) into a reactor, and reacting in N 2 Reacting under a protective condition to obtain a primary hydroxyl tertiary amine hydrochloride product; (3) and (3) heating and dissolving the primary hydroxyl tertiary amine hydrochloride obtained in the step (2) by using an organic solvent, decoloring, cooling, crystallizing, separating a crystallized precipitate, and drying to obtain a hydroxyl tertiary amine hydrochloride crystal. The hydroxyl tertiary amine hydrochloride crystal prepared by the invention has higher dissolution speed in water, can be accurately metered, and improves the precision when the crystal is used for compounding additives. Compared with liquid, the crystal can be quantitatively packaged by solid, and the packaging cost, the transportation cost and the storage cost are all reduced. The invention has the advantages of few steps, simple separation of intermediate products, easy operation of the crystallization and purification method and low production cost.)

1. A preparation method of hydroxyl tertiary amine hydrochloride crystals is characterized by comprising the following steps:

(1) dissolving hydrochloric acid in lower alcohol to form hydrochloric acid alcohol solution, wherein the mass percent of hydrogen chloride in the hydrochloric acid alcohol solution is 20-30%;

(2) adding the hydrochloric acid alcohol solution and the hydroxyl tertiary amine in the step (1) into a reactor, and reacting in N₂Stirring under a protective condition, heating to 30-90 ℃, reacting at a constant temperature for 2-4 h, and vacuumizing to remove volatile substances to obtain a primary hydroxyl tertiary amine hydrochloride;

the molar ratio of the hydroxyl tertiary amine to the hydrogen chloride in the hydrochloric acid alcohol solution in the step (1) is 1.0: 1.0-1.6;

(3) heating and dissolving the primary hydroxyl tertiary amine hydrochloride obtained in the step (2) by using an organic solvent, decoloring by using activated carbon, stirring the decolored solution, cooling to 0-25 ℃ to form a crystalline precipitate, separating the crystalline precipitate, and drying to obtain a hydroxyl tertiary amine hydrochloride crystal;

the organic solvent is one or a mixture of more than two of alcohol, ketone, ether and ester with low boiling point and can be mixed with water;

the hydroxyl tertiary amine has a general structural formula shown in formula (I):

in the formula (I), the compound is shown in the specification,

R₁is 2-hydroxypropyl;

R₂is 2-hydroxyethyl or 2-hydroxypropyl;

R₃is 2-hydroxyethyl or 2-hydroxypropyl.

2. The method according to claim 1, wherein the lower alcohol in step (1) is one of methanol, ethanol and isopropanol.

3. The preparation method according to claim 1, wherein the amount of the organic solvent is 1-3 times of the mass of the primary hydroxy tertiary amine hydrochloride in the step (2).

4. The method according to claim 1, wherein the organic solvent is one or a mixture of two or more of methanol, ethanol, isopropanol, acetone, diethyl ether, petroleum ether, and ethyl acetate.

5. The preparation method according to claim 1, wherein in the step (3), the stirring speed of the decolorized solution is 50 to 250r/min, and the cooling speed is 5 to 55 ℃/h.

6. The method according to claim 1, wherein electrospray mass spectrometry of the N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystals in the produced hydroxy tertiary amine hydrochloride crystals detects: the mass-to-charge ratio (M/z) was 164.1([ M-HCl + H)]⁺Of the formula C₇H₁₇NO₃The relative molecular mass of HCl is 199.67); the positive ion diagram of electrospray mass spectrometry detection is shown in FIG. 1;

electrospray mass spectrometry detection of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystals in the positive ion diagram: the mass-to-charge ratio (M/z) was 178.1([ M-HCl + H)]⁺Of the formula C₈H₁₉NO₃Relative molecular mass of HCl 213.70), its electrospray mass spectrometry detection positive ion profile is shown in fig. 2;

electrospray mass spectrometry detection of N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystals in the positive ion diagram: the mass-to-charge ratio (M/z) was 192.1([ M-Hcl + H)]⁺Of the formula C₉H₂₂NO₃HCl relative molecular mass 227.73), whose electrospray mass spectrometry detection positive ion pattern is shown in fig. 2.

7. The process according to claim 1, wherein the crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride in the produced crystals of the hydroxy tertiary amine hydrochloride have characteristic peaks at 13.1 °, 14.2 °, 15.6 °, 16.6 °, 17.2 °, 19.4 °, 21.5 °, 22.2 °, 23.2 °, 24.4 °, 26.0 °, 27.4 °, 28.1 °, 28.3 °, 28.8 °, 29.4 °, 30.5 °, 31.2 °, 31.9 °, 33.3 °, 34.3 °, 36.7, 37.2 ° and 39.0 ° ± 0.1 ° in terms of degrees 2 θ of the powder X-ray diffraction pattern;

the crystal of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride has characteristic peaks at the 2 theta degrees of the powder X-ray diffraction pattern of 13.3 degrees, 14.3 degrees, 16.9 degrees, 17.8 degrees, 18.9 degrees, 20.0 degrees, 21.8 degrees, 22.8 degrees, 23.6 degrees, 24.0 degrees, 24.3 degrees, 24.8 degrees, 25.8 degrees, 26.8 degrees, 28.6 degrees, 29.0 degrees, 29.8 degrees, 30.0 degrees, 31.5 degrees, 33.7 degrees, 34.3 degrees, 34.8 degrees, 37.4 degrees, 37.6 degrees, 38.6 degrees, 40.7 degrees and 41.0 degrees +/-0.1 degrees;

the crystal of N, N, N-tris (2-hydroxypropyl) amine hydrochloride has characteristic peaks at 2 theta degrees of 8.3 DEG, 10.0 DEG, 10.6 DEG, 12.4 DEG, 13.9 DEG, 16.9 DEG, 17.2 DEG, 18.7 DEG, 19.4 DEG, 20.5 DEG, 21.4 DEG, 22.2 DEG, 22.7 DEG, 23.0 DEG, 24.4 DEG, 24.9 DEG, 26.6 DEG, 28.0 DEG, 29.9 DEG, 31.5 DEG and 33.0 DEG + -0.1 DEG in its powder X-ray diffraction pattern.

8. The process according to claim 1, wherein the crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride in the produced crystals of the hydroxy tertiary amine hydrochloride have a powder X-ray diffraction pattern as shown in FIG. 4;

the powder X-ray diffraction pattern of the N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystal is shown in FIG. 6;

a powder X-ray diffraction pattern of the N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystals is shown in FIG. 8.

9. The method according to claim 1, wherein the obtained crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride have an endothermic peak at 146.1 to 155.9 ℃ in a Differential Scanning Calorimetry (DSC) curve;

the differential scanning calorimetry curve of the N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystal has an endothermic peak at 134.0-144.5 ℃;

the differential scanning calorimetry curve of the N, N, N-tri (2-hydroxypropyl) amine hydrochloride crystal respectively has an endothermic peak at 109.8-120.0 ℃ and 185.0-199.0 ℃.

10. The method of claim 1, wherein the obtained crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride are represented by the differential scanning calorimetry chart of FIG. 5;

differential scanning calorimetry plot 7 of crystalline N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride;

the differential scanning calorimetry curve of the N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystals is shown in FIG. 9.

Technical Field

The present invention relates to a method for producing a crystal of a hydroxy tertiary amine hydrochloride such as a crystal of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride, a crystal of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride, a crystal of N, N, N-tris (2-hydroxypropyl) amine hydrochloride, and the like.

Background

Tertiary amines are widely used in textile, mining, metal processing, coatings, petroleum, plastics, cosmetics, daily chemicals and other industries. Tertiary amines are important intermediates for the preparation of quaternary ammonium salt cationic surfactants (also including the preparation of alkyl betaines and amine oxides) and are useful as disinfectants, preservatives, algicides, antistatic agents, fabric softeners, fabric leveling agents, emulsifiers, demulsifiers, mineral flotation agents, ion exchangers, foaming agents, foam stabilizers, wetting agents, detergents, and the like. The tertiary amines in cement can also be used as additives in cement clinker and in post-treatment sections to prolong the shelf life of the final product.

N, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine and N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine are tertiary amine low-toxicity and environment-friendly alcamines fine chemical products, are mainly used for surfactants, are more applied to cement additives, skin care products and textile fabric softeners, do not generate three wastes in the production process, and are green and environment-friendly. At present, the grinding aid is mainly applied to cement grinding aids, is used for replacing triethanolamine and triisopropanolamine in raw materials of the grinding aids, has excellent grinding aid effect and has the characteristic of obviously improving the early and later strength of cement. However, when stored under normal conditions, a slow chemical reaction occurs, resulting in a structural change of the components, such as a gradual darkening of color. Particularly, under the condition of being prepared into an aqueous solution, a substance for accelerating a chemical reaction is more easily introduced into water, and the structural change and the color deepening are accelerated. Although there is no clear evidence that these changes affect the performance of the product, the shelf life of these materials is artificially shortened to ensure the performance of the product, which may cause some loss.

In order to improve the availability of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, salts thereof have been developed, but research on N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine salts, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine salts, and N, N-tris (2-hydroxypropyl) amine salts has been relatively rare so far, particularly in China. Patent application 201510069058.6 provides a cement grinding aid prepared by mixing industrial waste hydrochloric acid or waste sulfuric acid with diethanolisopropanolamine, wherein the reaction product is diethanolisopropanolamine hydrochloride, but in the application, the purity of the prepared product is low, and all functions of the amine salt cannot be fully embodied in the using process.

At present, the salt substances of the alcohol amine have fewer varieties, and the salt formation of the alcohol amine and acid mainly has the following difficulties:

(1) the amine is weaker in alkalinity than similar aliphatic amine and weaker in reactivity; hydroxyalkyl on the branched chain of the alcohol amine is an electron-withdrawing group, so that the electron-donating capability of a nitrogen atom is weakened;

(2) in tertiary amine, hydrogen on a nitrogen atom is replaced by three branched chains to form a steric hindrance effect, the steric shape of an acid radical group also has an important influence on the reaction, and the steric hindrance can cause that the acid radical group is difficult to attack the nitrogen atom to form a product;

(3) after the alcohol amine reacts with the acid, the separation of the product does not have an effective separation process.

Disclosure of Invention

The invention aims to further enrich the variety of the alcamines, especially the variety of the hydramine hydrochloride crystal, and is convenient for carrying out deep research on the alcamines while being convenient for metering, transporting and storing. The preparation method of the hydroxyl tertiary amine hydrochloride crystal comprises the following steps:

(1) dissolving hydrochloric acid in lower alcohol to form hydrochloric acid alcohol solution, wherein the mass percent of hydrogen chloride in the hydrochloric acid alcohol solution is 20-30%;

(2) adding the hydrochloric acid alcohol solution and the hydroxyl tertiary amine in the step (1) into a reactor, and reacting in N₂Stirring under a protective condition, heating to 30-90 ℃, reacting at a constant temperature for 2-4 h, and vacuumizing to remove volatile substances to obtain a primary hydroxyl tertiary amine hydrochloride;

the molar ratio of the hydroxyl tertiary amine to the hydrogen chloride in the hydrochloric acid alcohol solution in the step (1) is 1.0: 1.0-1.6;

(3) heating and dissolving the primary hydroxyl tertiary amine hydrochloride obtained in the step (2) by using an organic solvent, decoloring by using activated carbon, stirring the decolored solution, cooling to 0-25 ℃ to form a crystalline precipitate, separating the crystalline precipitate, and drying to obtain a hydroxyl tertiary amine hydrochloride crystal;

the organic solvent is one or a mixture of more than two of alcohol, ketone, ether and ester with low boiling point and can be mixed with water;

the hydroxyl tertiary amine has a general structural formula shown in formula (I):

in the formula (I), R₁Is 2-hydroxypropyl; r₂Is 2-hydroxyethyl or 2-hydroxypropyl; r₃Is 2-hydroxyethyl or 2-hydroxypropyl. Namely, the formula (I) may be specifically N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine and N, N, N-tris (2-hydroxypropyl) amine, and the corresponding hydrochloride salts are N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride, N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride and N, N, N-tris (2-hydroxypropyl) amine hydrochloride, respectively.

Further, in the step (1), the lower alcohol is preferably one of methanol, ethanol and isopropanol. These lower alcohols are not only miscible with water in any ratio, but also provide good solubility of the hydroxy tertiary amines.

Further, the amount of the organic solvent is 1-3 times of the mass of the primary hydroxyl tertiary amine hydrochloride in the step (2). Within the proportion range, the primary hydroxyl tertiary amine hydrochloride can be completely dissolved, and the excessive degree of the solvent is less, so that the subsequent process can be economically carried out, and the production cost can be reduced.

Further, the organic solvent is preferably one or a mixture of two or more of methanol, ethanol, isopropanol, acetone, diethyl ether, petroleum ether and ethyl acetate. The organic solvent is miscible with water due to the presence of a certain amount of water in the intermediate product, and can dissolve the intermediate product well at higher temperatures, while the effective components of the intermediate product can crystallize at lower temperatures.

Further, in the step (3), the stirring speed of the decolorized solution is 50-250 r/min, and the cooling speed is 5-55 ℃/h. The proper stirring speed and cooling speed can ensure that the effective components in the intermediate product are smoothly and fully precipitated, the particles of the precipitated crystals are fine, and the optimal range of the stirring speed and the cooling speed can ensure that the effective components in the solution are precipitated to the maximum extent.

Further, in the electrospray mass spectrometry detection positive ion diagram of the N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystal in the prepared hydroxyl tertiary amine hydrochloride crystal: the mass-to-charge ratio (M/z) was 164.1([ M-HCl + H)]⁺Of the formula C₇H₁₇NO₃The relative molecular mass of HCl is 199.67); the positive ion diagram of electrospray mass spectrometry detection is shown in FIG. 1;

electrospray mass spectrometry detection of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystals in the positive ion diagram: the mass-to-charge ratio (M/z) was 178.1([ M-HCl + H)]⁺Of the formula C₈H₁₉NO₃Relative molecular mass of HCl 213.70), its electrospray mass spectrometry detection positive ion profile is shown in fig. 2;

electrospray mass spectrometry detection of N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystals in the positive ion diagram: the mass-to-charge ratio (M/z) was 192.1([ M-Hcl + H)]⁺Of the formula C₉H₂₂NO₃HCl relative molecular mass 227.73), its electrospray mass spectrometry detection positive ion profile is shown in fig. 3.

Further, the N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystals in the produced crystals of the hydroxy tertiary amine hydrochloride have characteristic diffraction peaks at the points of the powder X-ray diffraction pattern of 13.1 °, 14.2 °, 15.6 °, 16.6 °, 17.2 °, 19.4 °, 21.5 °, 22.2 °, 23.2 °, 24.4 °, 26.0 °, 27.4 °, 28.1 °, 28.3 °, 28.8 °, 29.4 °, 30.5 °, 31.2 °, 31.9 °, 33.3 °, 34.3 °, 36.7, 37.2 ° and 39.0 ° ± 0.1 °, and the powder X-ray diffraction pattern is as shown in fig. 4;

the crystal of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride has characteristic diffraction peaks at the 2 theta degrees of the powder X-ray diffraction pattern of 13.3 degrees, 14.3 degrees, 16.9 degrees, 17.8 degrees, 18.9 degrees, 20.0 degrees, 21.8 degrees, 22.8 degrees, 23.6 degrees, 24.0 degrees, 24.3 degrees, 24.8 degrees, 25.8 degrees, 26.8 degrees, 28.6 degrees, 29.0 degrees, 29.8 degrees, 30.0 degrees, 31.5 degrees, 33.7 degrees, 34.3 degrees, 34.8 degrees, 37.4 degrees, 37.6 degrees, 38.6 degrees, 40.7 degrees and 41.0 degrees +/-0.1 degrees, and the powder X-ray diffraction pattern is shown in FIG. 6;

the crystal of N, N, N-tris (2-hydroxypropyl) amine hydrochloride has characteristic peaks at 2 theta degrees of its powder X-ray diffraction pattern of 8.3 DEG, 10.0 DEG, 10.6 DEG, 12.4 DEG, 13.9 DEG, 16.9 DEG, 17.2 DEG, 18.7 DEG, 19.4 DEG, 20.5 DEG, 21.4 DEG, 22.2 DEG, 22.7 DEG, 23.0 DEG, 24.4 DEG, 24.9 DEG, 26.6 DEG, 28.0 DEG, 29.9 DEG, 31.5 DEG and 33.0 DEG + -0.1 DEG, and the powder X-ray diffraction pattern is shown in FIG. 8.

Further, a differential scanning calorimetry curve of the N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystals in the prepared hydroxyl tertiary amine hydrochloride crystals has an endothermic peak at 146.1-155.9 ℃, and a specific differential scanning calorimetry curve is shown in FIG. 5;

the differential scanning calorimetry curve of the N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystal has an endothermic peak at 134.0-144.5 ℃, and the specific differential scanning calorimetry curve is shown in FIG. 7;

the differential scanning calorimetry curve of the N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystal respectively has an endothermic peak at 109.8-120.0 ℃ and 185.0-199.0 ℃, and the specific differential scanning calorimetry curve is shown in figure 9.

The invention successfully prepares the hydroxyl tertiary amine hydrochloride crystal, and the prepared hydroxyl tertiary amine hydrochloride crystal has higher dissolution speed in water and can be accurately measured, thereby improving the precision when the hydroxyl tertiary amine hydrochloride crystal is used for compounding additives. Compared with liquid, the crystal can be quantitatively packaged by solid, and the packaging cost, the transportation cost and the storage cost are all reduced.

The invention has the advantages of few steps, simple separation of intermediate products, easy operation of the crystallization and purification method and low production cost.

The hydroxyl tertiary amine hydrochloride crystal produced by the preparation method can be used for additives of cement concrete and potential fields such as cosmetics, medicines and the like.

Drawings

FIG. 1 is a graph showing positive ions detected by electrospray mass spectrometry of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystals, in which the vertical axis represents relative intensity (%), and the horizontal axis represents the mass-to-charge ratio (m/z) of the ions.

FIG. 2 is a graph showing positive ions detected by electrospray mass spectrometry of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystals, in which the vertical axis represents relative intensity (%), and the horizontal axis represents the mass-to-charge ratio (m/z) of the ions.

FIG. 3 is a graph showing positive ions detected by electrospray mass spectrometry of N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystals, in which the vertical axis represents relative intensity (%), and the horizontal axis represents the mass-to-charge ratio (m/z) of the ions.

FIG. 4 is a powder X-ray diffraction chart of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystals, in which the vertical axis represents diffraction intensity (%), and the horizontal axis represents 2. theta. diffraction angle (. degree.).

FIG. 5 is a Differential Scanning Calorimetry (DSC) chart of the crystals of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride, in which the vertical axis represents the heat flow rate (w/g) and the horizontal axis represents the temperature (. degree. C.).

FIG. 6 is a powder X-ray diffraction chart of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystals, in which the vertical axis represents diffraction intensity (%), and the horizontal axis represents 2. theta. diffraction angle (. degree.).

FIG. 7 is a Differential Scanning Calorimetry (DSC) chart of the crystals of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride, in which the vertical axis represents the heat flow rate (w/g) and the horizontal axis represents the temperature (. degree. C.).

FIG. 8 is a powder X-ray diffraction chart of N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystals, in which the vertical axis represents diffraction intensity (%), and the horizontal axis represents 2. theta. diffraction angle (. degree.).

FIG. 9 is a Differential Scanning Calorimetry (DSC) chart of the crystals of N, N, N-tris (2-hydroxypropyl) amine hydrochloride, in which the vertical axis represents the heat flow rate (w/g) and the horizontal axis represents the temperature (. degree. C.).

Detailed Description

Herein, the melting point was measured with a WRS-2 micro-computer melting point apparatus; waters Q-TOF Micro for electrospray mass spectrometry^TMMeasuring by a mass spectrometer; powder X-ray diffractometry was determined using a Bruker-AXS D8 Advance X-ray diffractometer; differential scanning calorimetry traces were measured using a shimadzu DSC-60A Shimadzu Analyzer.

Example 1

Dissolving 81.1g (0.8mol) of 36 wt% hydrochloric acid in 64.9g of 99.7 wt% ethanol to form an alcoholic hydrochloric acid solution;

85 wt% of% of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine 115.2g (0.6mol) and hydrochloric acid alcoholic solution were added successively to a 500ml reaction flask equipped with a heating device₂Stirring under the protection condition, heating to 85 ℃, reacting at constant temperature for 3h, and removing ethanol and unreacted hydrogen chloride under reduced pressure at the vacuum degree of-0.06-0.09 MPa and the temperature of 75-85 ℃ to obtain 124g of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride primary product;

dissolving the primary product by heating with 120g of 99.7 wt% ethanol, adding 5.5g of activated carbon, stirring for 30min for decolorization, performing suction filtration, stirring the filtrate, cooling to 0-25 ℃ for crystallization, and finally performing suction filtration and drying to obtain 106.8g of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystal with the yield of 89.1%;

stirring the filtrate after decolorization at 50r/min, and cooling at 5 ℃/h;

the prepared N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystal has an electrospray mass spectrometry positive ion diagram shown in figure 1, a powder X-ray diffraction diagram shown in figure 4, a Differential Scanning Calorimetry (DSC) curve shown in figure 5, and a melting point measured by a WRS-2 microcomputer melting point instrument of 143.4-147.6 ℃.

The powder X-ray diffraction data of the compound is shown in a peak list 1:

peak Listing 1

Angle 2 theta/degree	Peak height/cts	Half width/° 2Th	d/spacing	Intensity/%)
					6.361	21	0.660	13.8844	38.7
13.137	131	0.144	6.7335	52.6
					14.277	73	0.146	6.1986	29.7
15.642	21	0.183	5.6606	10.7
					16.623	68	0.128	5.3285	24.3
17.206	18	0.098	5.1495	4.9
					19.458	133	0.107	4.5581	39.7
21.527	45	0.152	4.1245	19.1
					22.223	73	0.208	3.9969	42.3
23.241	38	0.197	3.8241	20.9
					24.518	221	0.162	3.6278	100.0
26.060	34	0.170	3.4165	16.1
					27.419	49	0.127	3.2501	17.4
28.156	58	0.304	3.1667	49.3
					28.363	45	0.363	3.1441	45.7
28.922	77	0.208	3.0845	44.6
					29.459	28	0.168	3.0295	13.1
31.256	27	0.205	2.8593	15.5
					31.958	33	0.297	2.7981	27.4
33.365	25	0.200	2.6832	14.0
					34.397	17	0.393	2.6051	18.7
36.761	45	0.224	2.4428	28.1
					37.276	16	0.133	2.4102	5.9
39.083	23	0.221	2.3029	14.2

Example 2

Dissolving 81.1g (0.8mol) of 36 wt% hydrochloric acid in 35.7g of 99.7 wt% ethanol to form an alcoholic hydrochloric acid solution;

85 wt% of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine 124.9g (0.6mol) and hydrochloric acid alcohol solution are added successivelyTo 500ml of a reaction flask equipped with a heating device, in N₂Stirring under the protection condition, slowly heating to 90 ℃, reacting at constant temperature for 4 hours, and removing ethanol and unreacted hydrogen chloride under reduced pressure at the vacuum degree of-0.06-0.09 MPa and the temperature of 75-90 ℃ to obtain 206g of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride primary product;

dissolving the primary product by 100g of 99.7 wt% ethanol and 150g of 99.8 wt% diethyl ether under heating, adding 5.9g of activated carbon, stirring for 30min for decolorization, performing suction filtration, slowly stirring the filtrate, cooling to 0-25 ℃ for crystallization, and finally performing suction filtration and drying to obtain 187g of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystal with the yield of 87.6%;

stirring the filtrate after decolorization at 250r/min, and cooling at 55 ℃/h;

the prepared N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystal has an electrospray mass spectrometry positive ion pattern shown in figure 2, a powder X-ray diffraction pattern shown in figure 6, a Differential Scanning Calorimetry (DSC) curve shown in figure 7, and a melting point of 134.5-136.3 ℃ measured by a WRS-2 microcomputer melting point instrument.

The powder X-ray diffraction data of the compound is shown in a peak list 2:

peak Listing 2

Example 3

97.3g (0.96mol) of 36 wt% hydrochloric acid is dissolved in 77.8g of 99.7 wt% ethanol to form an alcoholic hydrochloric acid solution;

85 wt% of N, N, N-tris (2-hydroxypropyl) amine 180.0g (0.8mol) and hydrochloric acid alcohol solution are added in succession to a 500ml reaction flask equipped with a heating device in the presence of N₂Stirring under protection condition, slowly heating to 85 deg.C, reacting at constant temperature for 4 hr, removing ethanol and unreacted chloride under reduced pressure at vacuum degree of-0.06-0.09 MPa and temperature of 80-85 deg.CHydrogen is added to obtain 203.2g of N, N, N-tri (2-hydroxypropyl) amine hydrochloride primary product;

dissolving the above primary product with 260g of 99.7 wt% ethanol under heating, adding 8.5g of activated carbon, stirring for 30min for decolorization, performing suction filtration, slowly stirring the filtrate, cooling to 0-25 ℃ for crystallization, performing suction filtration, and drying to obtain 161.1g of N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystal with the yield of 88.4%.

The stirring speed of the filtrate after decolorization is 100r/min, and the cooling speed is 40 ℃/h.

The positive ion pattern of the prepared N, N, N-tris (2-hydroxypropyl) amine hydrochloride by electrospray mass spectrometry is shown in figure 3, the powder X-ray diffraction pattern is shown in figure 8, the Differential Scanning Calorimetry (DSC) curve is shown in figure 9, and the melting point measured by a WRS-2 microcomputer melting point instrument is 188.1-194.4 ℃.

The powder X-ray diffraction data of the compound is shown in a peak list 3:

peak Listing 3

Example 4

Dissolving 81.1g (0.8mol) of 36 wt% hydrochloric acid in 35.7g of 99.7 wt% isopropanol to form an alcoholic hydrochloric acid solution;

85 wt% of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine 153.6g (0.8mol) and hydrochloric acid alcohol solution are added in succession to a 500ml reaction flask equipped with a heating device in which N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine is placed₂Stirring under the protection condition, slowly heating to 80 ℃, reacting at constant temperature for 3h, and removing isopropanol and unreacted hydrogen chloride under reduced pressure at the vacuum degree of-0.06-0.09 MPa and the temperature of 75-85 ℃ to obtain 157g of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride primary product;

heating and dissolving the primary product by 35g of 99.5 wt% acetone and 240g of 98 wt% petroleum ether (30-60 ℃) to obtain a solution, adding 6.7g of activated carbon, stirring for 30min to decolorize, performing suction filtration, slowly stirring the filtrate, cooling to 0-25 ℃ to crystallize, performing suction filtration and drying to obtain 182.1g of N, N-bis (2-hydroxyethyl) -N- (2-hydroxypropyl) amine hydrochloride crystal, wherein the yield is 91.2%.

Stirring the decolored filtrate at 200r/min, and cooling at 20 ℃/h.

Example 5

Dissolving 81.1g (0.8mol) of 36 wt% hydrochloric acid in 45.8g of 99.7 wt% methanol to form a hydrochloric acid alcohol solution;

85 wt% of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine 104.1g (0.5mol) and hydrochloric acid alcohol solution are added in succession to a 500ml reaction flask equipped with a heating device, and a small amount of N is introduced₂Stirring under the protection condition, slowly heating to 90 ℃, reacting at constant temperature for 4 hours, and removing methanol and unreacted hydrogen chloride under reduced pressure at the vacuum degree of-0.06-0.09 MPa and the temperature of 75-90 ℃ to obtain 119g of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride primary product;

heating and dissolving the primary product by using 190g of 99.7 wt% methanol and 65g of 99.8 wt% petroleum ether, adding 4.8g of activated carbon, stirring for 30min for decolorization, performing suction filtration, slowly stirring the filtrate, cooling to 0-25 ℃ for crystallization, performing suction filtration and drying to obtain 97.1g of N, N-bis (2-hydroxypropyl) -N- (2-hydroxyethyl) amine hydrochloride crystal with the yield of 90.8%.

The stirring speed of the filtrate after decolorization is 150r/min, and the cooling speed is 30 ℃/h.

Example 6

Dissolving 81.1g (0.8mol) of 36 wt% hydrochloric acid in 64.9g of 99.7 wt% ethanol to form an alcoholic hydrochloric acid solution;

85 wt% of N, N, N-tris (2-hydroxypropyl) amine 180.0g (0.8mol) and hydrochloric acid alcohol solution are added in succession to a 500ml reaction flask equipped with a heating device in the presence of N₂Stirring under the protection condition, slowly heating to 90 ℃, reacting at constant temperature for 4 hours, and removing ethanol and unreacted hydrogen chloride under reduced pressure at the vacuum degree of-0.06-0.09 MPa and the temperature of 85-90 ℃ to obtain 217.7g of an N, N, N-tris (2-hydroxypropyl) amine hydrochloride primary product;

heating and dissolving the primary product by 270g of 99.7 wt% ethanol, adding 8.3g of activated carbon, stirring for 30min for decolorization, performing suction filtration, slowly stirring the filtrate, cooling to 0-25 ℃ for crystallization, performing suction filtration, and drying to obtain 165.0g of the product N, N, N-tris (2-hydroxypropyl) amine hydrochloride crystal, wherein the yield is 90.6%.

The stirring speed of the filtrate after decolorization is 150r/min, and the cooling speed is 50 ℃/h.

The hydroxyl tertiary amine hydrochloride prepared by the invention can be used as a cement additive, and the crystals prepared in the above embodiments are used as a cement grinding aid for experiments and detection.

With reference to GB/T26748-. The test cement material mixture ratio is as follows: 88 wt% of clinker, 5 wt% of gypsum, 5 wt% of limestone and 2 wt% of slag.

The cement prepared by grinding is detected according to GB/T17671-1999 cement mortar strength detection method and GB/T1346-2011 cement standard consistency water consumption detection method, and the detection results are shown in the following table 1:

TABLE 1 Experimental test results of hydroxy tertiary amine hydrochloride crystals as cement grinding aid

Table 1 shows that when the hydroxyl tertiary amine hydrochloride crystal is used as a cement grinding aid, the compressive strength is averagely increased by 10.9 percent in 3 days, and the increase amplitude is between 5.6 and 19.9 percent; the compressive strength is increased by 18.4 percent on average in 28 days, and the increase amplitude is between 16.0 and 20.6 percent.

The hydroxy tertiary amine hydrochloride crystals produced by the preparation method in the application can also be used for replacing triethanolamine salts in cosmetics. Ethanolamine has low volatility and is hardly poisoned by inhalation, but the direct contact with the skin of the hand may cause dermatitis and eczema. The highest limit of trialkanolamines in 2009 of China is 2.5%, and triethanolamine is widely used in the substances. The specification for monoalkanolamine is that dialkanolamine cannot exceed 0.5% and both monoethanolamine and diethanolamine are in this range. The maximum limit of trialkanolamine species in 2007 edition "cosmetic hygiene Specifications" non-leaching products and other products is 2.5%, and triethanolamine is used more widely among such species.

Along with the gradual enhancement of environmental awareness, the defect of high toxicity of ethanolamine substances is obvious, and experiments show that: triethanolamine may cause vitamin B deficiency in human body and increase incidence of liver tumor, and low-toxicity ethanolamine products represented by N, N, N-tri (2-hydroxypropyl) amine, N, N-di (2-hydroxyethyl) -N- (2-hydroxypropyl) amine, N, N-di (2-hydroxypropyl) -N- (2-hydroxyethyl) amine and other salts are gradually substituted by ethanolamine.