SYNTHESIS AND APPLICATION OF ALCOHOL AMINE WITH EXTENDED MAIN CARBON CHAIN

Abstract

Synthesis and application of an alcohol amine with an extended main carbon chain are provided, belonging to the field of chemical building materials. Under the action of a catalyst, tertiary amine is subjected to a two-step substitution reaction, a hydrolytic reaction and a reducing reaction to obtain a novel alcohol amine (NAA). The novel alcohol amine as provided may have a better grinding aid effect than triethanolamine while is added into cement as a cement grinding aid, and thus has a wide application prospect.

Claims

1. A method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain, comprising the following steps: adding a tertiary amine (R—OH) and a catalyst of concentrated sulfuric acid into a reaction vessel to mix uniformly, then adding hydrobromic acid and heating to 80° C.-110° C. for reacting, cooling and distilling to obtain bromoethanolamine after the reacting for 30-60 minutes, wherein a molar ratio of the hydrobromic acid to the tertiary amine is 1:1; adding a cyanating agent and the catalyst into the distilled solution, and reacting for 50-80 minutes at a temperature of 110° C.-240° C. to obtain cyanoethanolamine; after obtaining the cyanoethanolamine, adding an 70%-80% sulfuric acid aqueous solution, heating and hydrolyzing to obtain carboxylolamine; and adding a reducing agent and refluxing, reducing the carboxylolamine to obtain an alcohol amine with an extended main carbon chain.

2. The method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain according to claim 1, wherein a hydroxyl group in the tertiary amine is substituted with a halogen atom and a cyanide ion in two steps, and then hydrolyzed to generate carboxylic acid, and finally an alcohol amine compound with the extended main carbon chain is obtained through a lithium aluminum tetrahydrogen reduction reaction, that is, the —OH in an original structure reacts to be —CH.sub.2—OH.

3. The method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain according to claim 1, wherein the tertiary amine is one or more selected from the group consisting of triethanolamine, diethanol monoisopropanolamine, ethanol diisopropanolamine and triisopropanolamine.

4. The method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain according to claim 1, wherein the cyanating agent is one or two selected from the group consisting of potassium cyanide, sodium cyanide, zinc cyanide and potassium ferrocyanide.

5. The method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain according to claim 1, wherein the catalyst is one of N-methylpyrrolidone and dimethylformamide.

6. The method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain according to claim 1, wherein a temperature of bromine atom substitution reaction ranges from 85° C. to 105° C.

7. The method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain according to claim 1, wherein a temperature of cyanide ion substitution reaction ranges from 150° C. to 200° C., and a time of the cyanide ion substitution reaction lasts for 60-80 minutes.

8. The method for synthesizing a novel alcohol amine (NAA) with an extended main carbon chain according to claim 1, wherein the reducing agent is lithium tetrahydroaluminum.

9. An alcohol amine with an extended main carbon chain prepared by the method according to claim 1.

10. Application of the alcohol amine with the extended main carbon chain prepared by the method according to claim 1, wherein in application in a cement grinding aid, an aqueous solution with 8%-50% by weight of the cement grinding aid of the alcohol amine is added into cement, and a mixing amount of the cement grinding aid of the alcohol amine is 0.02%-0.15% by mass of the cement, and preferably is 0.03%-0.1% by mass.

Description

BRIEF DESCRIPTION OF THE FIGURE

[0018] The FIGURE is a schematic diagram showing adsorption of alcohol amine molecules on surfaces of cement minerals.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0019] The invention is further illustrated in detail in combination with the embodiments hereinafter, but to which the invention is not limited.

Embodiment 1

[0020] 14.9 grams (g) of triethanolamine is added into a flask, 3 milliliters (ml) of concentrated sulfuric acid is slowly added while the flask is shaken to uniformly mix the triethanolamine with the concentrated sulfuric acid, and 22.5 g of 36% (by weight) hydrobromic acid is added into a dropping funnel; then, a reaction bottle is heated to 100° C., and cooled for distillation 50 minutes after the reaction; 5 ml of N-methylpyrrolidone is added and heated to 160° C., a potassium ferrocyanide solution is slowly added, cooled and distilled 60 minutes after the reaction; and finally, 5 ml of a 80% (by weight) sulfuric acid aqueous solution is added, heated and refluxed, and lithium tetrahydroaluminum is added, and distillation is performed after the reaction is ended to obtain a novel alcohol amine with an extended main carbon chain.

Embodiment 2

[0021] 19.1 g of triisopropanolamine is added into a flask, 3 ml of concentrated sulfuric acid is slowly added while the flask is shaken to uniformly mix the triisopropanolamine with the concentrated sulfuric acid, and 22.5 g of 36% (by weight) hydrobromic acid is added into a dropping funnel; then, a reaction bottle is heated to 100° C., and cooled for distillation 50 minutes after the reaction; 5 ml of N-methylpyrrolidone is added and heated to 150° C., a potassium ferrocyanide solution is slowly added, and cooled and distilled 60 minutes after the reaction; and finally, 5 ml of a 80% (by weight) sulfuric acid aqueous solution is added, heated and refluxed, and lithium tetrahydroaluminum is added, and distillation is performed after reaction is ended to obtain a novel alcohol amine with an extended main carbon chain.

Embodiment 3

[0022] 16.3 g of diethanol monoisopropanolamine is added into a flask, 3 ml of concentrated sulfuric acid is slowly added while the flask is shaken to uniformly mix the diethanol monoisopropanolamine with the concentrated sulfuric acid, and 22.5 g of 36% hydrobromic acid is added into a dropping funnel; then, a reaction bottle was heated to 105° C., and cooled for distillation 50 minutes after the reaction; 5 ml of N-methylpyrrolidone is added and heated to 170° C., a potassium ferrocyanide solution is slowly added, and cooled and distilled 60 minutes after the reaction; and finally, 5 ml of a 80% (by weight) sulfuric acid aqueous solution is added, heated and refluxed, and lithium tetrahydroaluminum then is added, and distillation is performed after the reaction is ended to obtain a novel alcohol amine with an extended main carbon chain.

Embodiment 4

[0023] 17.7 g of ethanol diisopropanolamine is added into a flask, 3 ml of concentrated sulfuric acid is slowly added while the flask is shaken to uniformly mix the ethanol diisopropanolamine with the concentrated sulfuric acid, and 22.5 g of 36% hydrobromic acid is added into a dropping funnel; then, a reaction bottle is heated to 105° C., and cooled for distillation 50 minutes after the reaction; 5 ml of N-methylpyrrolidone is added and heated to 170° C., a potassium ferrocyanide solution is slowly added, and cooled and distilled 60 minutes after the reaction; and finally, 5 ml of a 80% sulfuric acid aqueous solution is added, heated and refluxed, and lithium tetrahydroaluminum then is added, and distillation is performed after the reaction is ended to obtain a novel alcohol amine with an extended main carbon chain.

Embodiment 5

[0024] Molecular layer thicknesses of the novel alcohol amine molecules obtained in Embodiments 1-4 on the surfaces of cement minerals are calculated by simulation (in a Material studio calculation software Dmol3 module) (Table 1). Adsorption of the alcohol amine molecules on the surfaces of cement minerals is shown in the FIGURE, and a distance from the most distal ends of the molecules to the surface is selected as a molecular layer thickness. The molecular layer thicknesses of the alcohol amine molecules adsorbed on the surfaces of the cement minerals before and after the reaction are compared, the novel alcohol amines obtained in the four embodiments can increase the thickness of the surface molecular layer compared with the original tertiary amine

TABLE-US-00001 TABLE 1 Simulation results of thickness of the molecular layer formed by alcohol amine on cement surface before and after reaction Molecular layer thickness (angstroms) Serial number Before reaction After reaction Embodiment 1: 7.719 7.918 Embodiment 2: 7.803 8.015 Embodiment 3: 7.786 7.967 Embodiment 4: 7.811 8.022

Embodiment 6: (Application Embodiment)

[0025] The novel alcohol amine with the extended main carbon chain obtained in Embodiments 1-4 is diluted with water to obtain a cement grinding aid sample with a concentration of 40% (by weight). Portland cement clinker is crushed with a jaw crusher, and the crushed materials are screened and processed to control the materials to be about 1-6 mm 3 kg of test materials, of which 2850 g is clinker and 150 g is gypsum are weighed, 1.5 g of the cement grinding aid sample prepared in Embodiments 1-4 is added, ground in a SYMΦ500×500 mm standard cement test mill for 25 min, where discharge time lasted for 5 min. The discharged cement passes through a 0.6 mm standard sieve to remove the large particles that have not been ground, and then is dried and stored in a sealed bag to test fineness and particle size distribution of the sieve residues. A chemical composition and a mineral composition of clinker are shown in Table 2, where gypsum is natural dihydrate gypsum, in which the content of crystal water is 18% and the content of SO.sub.3 is 42%.

[0026] A negative-pressure sieve analyzer is used to test cement sieve residues, and a laser particle size distribution analyzer is used to test the particle distribution of cement by a dry method. Before the test, the cement sample needs to be dried at 105° C. for 2 hours to remove water. During the test, 30 g of the cement sample is weighed, a shading ratio is kept at 10%-20%, and the number of tests is set to 15 times. The test results are shown in Table 3 and Table 4. It could be seen from Table 3 and Table 4 that compared with the original tertiary amine before the reaction, the four novel alcohol amines with extended main carbon chains could reduce the 45 μm sieve residues and increase distribution of 3-32 μm particles. The sieve residues and 3-32 μm particle content are important indicators of the grinding aid effect of cement grinding aid. The smaller the 45 μm sieve residues and the higher 3-32 μm particle content, the better the surface cement grinding aid effect.

TABLE-US-00002 TABLE 2 Chemical composition and mineral composition of clinker (%) Loss SiO.sub.2 Al.sub.2O.sub.3 Fe.sub.2O.sub.3 CaO MgO 0.41 21.39  5.66  5.34 63.22  2.10 f-CaO SO.sub.3 C.sub.3S C.sub.2S C.sub.3A C.sub.4AF 0.60  0.33 47.63 25.42  5.94 16.23

TABLE-US-00003 TABLE 3 45 μm sieve residues of cement particles (%) 45 μm sieve residues (%) Serial number Before reaction After reaction Control group 20.7 Embodiment 1: 17.7 16.9 Embodiment 2: 17.0 16.2 Embodiment 3: 17.6 16.9 Embodiment 4: 17.5 16.7

TABLE-US-00004 TABLE 4 Influence of polyalcohol amines on cement particle size distribution (%) Before Control Diethanol Ethanol reaction group Triethanolamine Triisopropanolamine monoisopropanolamine diisopropanolamine 0-3 μm 7.86 7.34 7.58 7.37 7.41 3-32 μm  54.37 58.92 59.13 58.97 59.05 32-45 μm  5.04 6.02 6.03 5.92 5.97 >45 μm  32.73 27.72 27.26 27.74 27.57 After Control reaction group Embodiment 1: Embodiment 2: Embodiment 3: Embodiment 4: 0-3 μm 7.86 7.41 7.65 7.46 7.52 3-32 μm  54.37 60.34 60.75 60.67 60.62 32-45 μm  5.04 6.12 6.08 5.96 6.14 >45 μm  32.73 26.13 25.52 25.91 25.72