CN102516095B - Compound containing multielement alkamines, and preparation method and application thereof - Google Patents

Abstract

The invention relates to a compound containing polyhydric amino alcohols, a preparation method thereof, and an application as a concrete rust inhibitor. The compound containing polyhydric amino alcohols is used as a concrete rust inhibitor, which can improve the adsorption capacity with iron atoms and prevent rust inhibitors Volatilization and loss, improve corrosion resistance. The polyamino alcohol-containing compound has a structural formula (I), wherein R ₁ is H, R ₂ is -(CH ₂ CH ₂ NH) _m H or -(CH ₂ ) _n NH ₂ , m and n are integers from 2 to 6; or R ₁ and R ₂ are each independently -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH One of (CH ₃ ) ₂ , —CH ₂ CH(CH ₃ ) ₂ , —CH(CH ₂ ) ₅ (cyclohexyl) or —C(CH ₃ ) ₂ CH ₂ CH ₃ . The polyamino-containing alcohol compound is obtained by reacting an epoxy derivative and an organic amine under the action of a catalyst.

Description

Polyamino alcohol-containing compound, its preparation method and application

technical field

The invention relates to a compound containing polyhydric amino alcohols, its preparation method and application.

Background technique

Reinforced concrete is currently the most widely used building material. Under normal circumstances, due to the strong alkaline environment inside the concrete, an oxide film will form on the surface of the steel bar, and no corrosion will occur. However, under harsh conditions such as marine environment, deicing salt, and saline-alkali land, steel bars in concrete usually undergo severe corrosion, which leads to concrete cracking and a decrease in structural bearing capacity, resulting in huge economic losses. According to reports, steel corrosion is the most important factor affecting the durability of concrete structures. Preventing and controlling the corrosion of steel bars is an important way to ensure the safety and durability of structures in service.

At present, the treatment methods to prevent the corrosion of steel bars in concrete mainly include: steel bar surface coating (epoxy resin, galvanized layer, etc.), cathodic protection, electrochemical dechlorination, and the use of rust inhibitors. Among them, rust inhibitor is considered to be the most convenient, low-cost and effective concrete protection measure.

The earliest widely used concrete rust inhibitor is nitrite, which can rapidly oxidize the iron on the surface of the steel bar to form a dense oxide film, thereby protecting the steel bar from corrosion. In the early days, US6340438 reported that the mixed use of nitrite and organic amine can significantly inhibit the corrosion of steel bars in concrete, but the nitrite is a sodium salt, which has an adverse effect on the early strength of concrete. US 5527388 uses calcium nitrite mixed with organic acid to improve the impact on concrete performance to a certain extent, and the mixed use of organic acid and calcium nitrite can play a synergistic anti-corrosion effect. Although the nitrite rust inhibitor has very excellent antirust performance, it must be used in a sufficient amount to achieve a good protective effect. Once the amount is insufficient, it will cause serious local corrosion; in addition, nitrite has Carcinogenic, has adverse effects on the environment and human body. At present, it has been restricted in the United States and some European countries. With the continuous deepening of my country's sustainable development, the application of nitrite as a rust inhibitor will be subject to more and more restrictions.

At present, organic corrosion inhibitors have gradually become the main direction of rust inhibitor research. It is mentioned in US5597514 that organic carboxylates, organic sugars (or their salts) and benzotriazole organic compounds are mixed to protect steel bars in concrete. Patents US5916483 and EP34807 mentioned that the reactants of organic amines or alcohol amines and inorganic or organic acids were mixed into cement-based materials, and it was confirmed that they had better antirust effects. In addition, US006174461B1 and US006342101B1 respectively compound rust inhibitors with silane and superplasticizers to prepare multifunctional rust inhibitors. However, the antirust components wherein are mainly amines, ammonium salts, sugars (or their salts), benzotriazoles and their derivatives disclosed in the aforementioned patents. In the above-mentioned patents, the most important anti-rust components are almost all small molecular organic amines or their neutralized products with acids, mainly through the adsorption of nitrogen atoms, hydroxyl groups and other polar groups in the molecule to the surface of the steel bar, so as to prevent rust. effect. However, such molecules usually have a high saturated vapor pressure, are highly volatile, and have a low effective utilization rate during use. Especially in the strong alkaline environment of concrete, even the molecules that have been neutralized into ammonium salts may be re-hydrolyzed into amines, which intensifies the loss of molecules and affects the long-term performance of rust inhibition. At the same time, most of these molecules have only one functional group that can be adsorbed on steel bars, and the adsorption force is weak. To ensure its anti-rust effect, a relatively high dosage is usually required, and the actual application cost is high.

Nmai et al reported another concrete rust inhibitor that has been commercialized, the main component of which is amino esters. After being added to an alkaline system such as concrete, amino esters are hydrolyzed into carboxylic acids and alcohols. Among them, carboxylic acid and calcium ions in concrete form insoluble carboxylate, which is adsorbed on the capillary wall to achieve a certain hydrophobic effect; alcohol adsorbs to iron atoms on the surface of steel bars to isolate harmful ions. The mechanism of action of this type of alcohol is the same as the aforementioned molecules such as amines and alcohol amines, and there are also problems such as too weak adsorption and large losses (reference: Nmai, Charles K, Multi-functional organic corrosion inhibitor, Cement and Concrete Composites. 2004, 26, 199-207).

In addition, JP10324539A reported a concrete rust inhibitor, which is mainly composed of formic acid and its compound with metal salt; US5391349 also reported carbamate and aminocarbonate as concrete rust inhibitor. However, the protective effect of formate and carbonate on steel bars in concrete is still controversial, and this kind of rust inhibitor has not been applied in actual engineering.

The domestic development of anti-corrosion of concrete steel bars started relatively late. ZL 00134393.9 proposes to use the electroosmotic method to move the organic rust inhibitor into the interior of the concrete to prevent the corrosion of steel bars. The rust inhibitor is still the neutralization product of ethanolamine aromatic derivatives and inorganic acids. ZL 20081010234924.2 reported a non-alkali non-nitrite concrete steel reinforcement rust inhibitor, which is a mixture of zinc gluconate, lithium silicate and ammonium benzoate and low molecular weight (alcohol) amines, but the simple mixing of these materials will not It has obvious enhancement effect on their respective adsorption capacity. ZL 200610044239.4 reported a reinforced concrete rust inhibitor, which was mixed with sodium molybdate, diethylenetriamine allylthiourea and butynediol. However, these raw materials are not commonly used chemical raw materials, and the application cost is too high.

On the whole, the current hotspots in the research and application of rust inhibitors for reinforced concrete are mainly amines, alcohol amines, amino carboxylates, and other similar chemical substances. This kind of rust inhibitor has a large volatilization loss during the application process, and the effective utilization rate and long-term rust resistance are greatly affected. At the same time, most of these molecules have only a single adsorption center, and the competitive adsorption with aggressive substances is relatively weak in harsh corrosive environments, resulting in a large amount of actual use and high application costs.

Contents of the invention

The invention provides a polyhydric amino alcohol-containing compound, which is used as a concrete rust inhibitor, which can improve the adsorption capacity with iron atoms, prevent the rust inhibitor from volatilizing and losing, and improve the corrosion resistance.

The present invention also provides a preparation method of the above-mentioned compound containing polyhydric amino alcohols and its application as a concrete rust inhibitor.

Described containing polyhydric amino alcohol compound, its structural formula is the compound shown in (I):

Wherein, R ₁ is H, R ₂ is -(CH ₂ CH ₂ NH) _m H or -(CH ₂ ) _n NH ₂ , m and n are integers from 2 to 6; or R ₁ and R ₂ are each independently -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH(CH ₃ ) ₂ , -CH ₂ CH(CH ₃ ) ₂ , -CH(CH ₂ ) ₅ (cyclohexyl) or one of -C(CH ₃ ) ₂ CH ₂ CH ₃ .

The preparation method of the polyamino alcohol-containing compound is obtained by reacting an epoxy derivative and an organic amine under the action of a catalyst, wherein the epoxy derivative is a compound of the structure shown in the structural formula (II):

R ₃ is Cl, Br or I,

Described organic amine is the compound of structure shown in structural formula (III)

The specific reaction formula is as follows (reference: B.J.Ludwig, W.A.West, and D.W.Farnsworth, Journal of American Chemistry Society.1954, 76, 2891; L.D.Paron, P.Gamez, J.J.M.van Brussel and J.Reedijk, Tetrahedron Letter.2003 , 44, 6025):

R ₁ and R ₂ in formula (I) have the same meaning as R ₁ and R ₂ in formula (III).

Preferably, the catalyst is one of AlCl ₃ , FeCl ₃ , SbCl ₅ , SnCl ₄ , BF ₃ , ZnCl ₂ and TiCl ₃ , and the molar ratio of the catalyst to the epoxy derivative is 0.001:1 to 0.2:1 .

Preferably, the molar ratio of the epoxy derivative to the organic amine is 1:2-1:5, the reaction temperature is 10-120° C., and the reaction time is 1 hour-12 hours.

The present invention proposes an amino alcohol concrete rust inhibitor with hydroxyl group and multiple N heteroatoms as the adsorption center, aiming at increasing the number of N atoms in the adsorption center, improving the charge density on the N atoms, improving the adsorption capacity with iron atoms, Prevent the volatilization and loss of the rust inhibitor; at the same time, by adjusting the size of the non-polar group in the adsorbed molecule, a dense barrier layer is formed to improve the hydrophobic ability of the adsorbed molecule on the surface of the steel bar, and reduce the competitive adsorption of harmful ions in the environment and the surface of the steel bar. Improve corrosion resistance. In addition, this polyamino alcohol-based reinforced concrete rust inhibitor also overcomes the shortcomings of inorganic salt environmental pollution, is green and environmentally friendly, and has no damaging effect on water bodies and soils.

The invention has the advantages that: the designed molecule has two or more N atoms and one O atom, and can form multiple five-membered chelating rings with the steel matrix, making the adsorption more stable and the formed protective film more stable. For compactness, thereby improving the corrosion resistance of steel bars.

When R ₁ is H, R ₂ is -(CH ₂ CH ₂ NH) _m H or -(CH ₂ ) _n NH ₂ , the principle of adsorption between molecules and steel bars can be shown as:

At this time, there are multiple adsorption centers in each molecule designed, which can form multi-point adsorption with Fe on the surface of the steel bar, thereby improving the adsorption stability and the coverage of the steel bar surface, and greatly improving the rust resistance.

When R ₁ is not H, the principle of adsorption between molecules and steel bars can be shown as:

At this time, both R ₁ and R ₂ are alkyl groups, which have obvious electron repelling ability, and significantly increase the charge density of the N atoms connected to them, so the binding ability of the molecule to the Fe atom on the surface of the steel bar and the antirust effect of the molecule are improved.

The synthesis process of the invention is simple and easy to implement, and the prepared polyamino alcohol has the advantages of environmental protection and the like, and the dosage in concrete is 0.5%-2.0%.

Detailed ways

Example 1

Get 18.5g epichlorohydrin and join in the reactor that 10ml water is housed, keep reaction temperature 20 ℃, add 18g dimethylamine and _0.27g AlCl while stirring , continue to stir the reaction for 4h, then stop the stirring, add 10mL of 30% NaOH solution, and obtain the dibasic amino alcohol compound.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 93% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:10), The structure was confirmed by proton nuclear magnetic resonance spectrum and infrared spectrum, and the results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ2.5(s, 12H), 2.3(d, J=6.4Hz, 4H), 3.5(t, 1H), 3.6(d, OH, 1H);

IR(neat): 3440cm ^-1 , 2960cm ^-1 , 2970cm ^-1 , 1465cm ^-1 , 1378cm ^-1 , 1195cm ^-1 , 1081cm ^-1 ;

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 2

Get 18.5g epichlorohydrin and join in the reactor that 10ml water is housed, after being warmed up to 60 ℃, add 44.4g di-n-propylamine and 0.54g zinc dichloride while stirring (three kinds of material molar ratio, 1: 2.2 : 0.002), keep the reaction temperature at 60°C, continue to stir and react for 4h, then stop heating. After cooling, add 10mL of 30% NaOH solution and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 91% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:15), The structure was confirmed by proton nuclear magnetic resonance spectrum and infrared spectrum, and the results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ1.4(t, 6Hz, 12H), 1.6(m, J=6.4Hz, 8H), 2.54(t, J=6.4Hz, 8H), 2.6(d , 5.5Hz, 4H), 3.5(t, 6Hz, 1H), 2.5(d, OH, 1H);

IR(neat): 3449cm ^-1 , 2953cm ^-1 , 2932cm ^-1 , 2863cm ^-1 , 2808cm ^-1 , 1465cm ^-1 , 1378cm ^-1 ; 1178cm ^-1 , 1077cm ^-1 ;

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 3

Get 18.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, after being warmed up to 50 ℃, add 36g ethylenediamine and 1.63g iron trichloride (three kinds of material mol ratios, 1: 3:0.005), keep the reaction temperature at 50°C, continue to stir and react for 8 hours, then stop heating, add 10mL 30% NaOH solution after cooling and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 92% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:10), The structure was confirmed by proton nuclear magnetic resonance spectrum, infrared spectrum and gas chromatography-mass spectrometry. The results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ2.6(t, 6Hz, 4H), 2.8(t, J=6.4Hz, 4H), 2.3(d, 5.5Hz, 4H), 2.3(t, NH ₂ , 4H), 2.5(m, NH, 2H), 3.5(t, 6Hz, 1H), 2.5(d, OH, 1H);

IR(neat): 3338cm ^-1 , 2957cm ^-1 , 2932cm ^-1 , 2863cm ^-1 , 2808cm ^-1 , 1465cm ^-1 , 1378cm ^-1 ; 1180cm ^-1 , 1080cm ^-1 ;

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 4

Get 18.5g epichlorohydrin and join in the reactor that 10mL water is housed, after heating up to 30 ℃, add 58g hexamethylenediamine and 9.12g antimony trichloride (three kinds of material molar ratios, 1: 2.5: 0.2), keep the reaction temperature at 30°C, continue to stir and react for 6h, then stop heating. After cooling, add 10mL of 30% NaOH solution and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 91% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:10), The structure was confirmed by proton nuclear magnetic resonance spectrum and infrared spectrum, and the results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ2.6(t, 6Hz, 4H), 1.2(m, J=6.4Hz, 4H), 1.2(m, 5.5Hz, 4H), 1.3(m, J =5.5Hz, 4H), 2.5(t, J=6Hz, 4H), 2.8(d, J=6Hz, 4H), 2.3(t, NH ₂ , 4H) 2.5(m, NH, 2H), 3.5(t , 6Hz, 1H), 2.5(d, OH, 1H);

IR(neat): 3349cm ^-1 , 2932cm ^-1 , 2863cm ^-1 , 2808cm ^-1 , 1460cm ^-1 , 1378cm ^-1 ; 1172cm ^-1 , 1062cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 5

Get 29.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, after being warmed up to 100 ℃, add 92.7g diethylenetriamine and 2.3g tin dichloride (three kinds of material mol ratios, 1:4.5:0.05), keep the reaction temperature at 100°C, continue to stir the reaction for 1 hour, then stop heating, add 10mL 30% NaOH solution after cooling and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivative having an aminoalcohol structure was determined to be 89% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:10), The structure was confirmed by proton nuclear magnetic resonance spectrum, infrared spectrum and gas chromatography-mass spectrometry. The results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ2.6(t, 6Hz, 8H), 2.8(t, J=6.4Hz, 8H), 2.5(d, J=6Hz, 4H), 2.3(t, NH ₂ , 4H), 2.5(m, NH, 6H), 3.5(t, 6Hz, 1H), 3.0(d, OH, 1H);

IR(neat): 3366cm ^-1 , 3290cm ^-1 , 2957cm -1 , 2932cm ^-1 , 2863cm ^-1 , 2808cm ^-1 , 1640cm ^-1 , 1465cm ^-1 , 1378cm ^{-1 , 1178cm -1 ,} 1065cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 6

Get 29.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, add 132.8g hexaethyleneheptamine and 2.3g tin dichloride (three kinds of material molar ratios, 1: 4: 0.05) while stirring , keep the reaction temperature at 10°C, continue to stir and react for 10h, then add 10mL of 30% NaOH solution and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 85% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:10), The structure was confirmed by proton nuclear magnetic resonance spectrum, infrared spectrum and gas chromatography-mass spectrometry. The results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ2.6(t, 6Hz, 24H), 2.8(t, J=6.4Hz, 24H), 2.3(d, 5.5Hz, 4H), 2.3(t, NH ₂ , 4H), 2.0(m, NH, 14H), 3.5(t, 6Hz, 1H), 3.1(d, OH, 1H);

IR(neat): 3360cm ^-1 , 3295cm ^-1 , 2958cm -1 , 2896cm ^-1 , 2863cm ^-1 , 2810cm ^-1 , 1645cm ^-1 , 1468cm ^-1 , 1380cm ^{-1 , 1170cm -1 ,} 1060cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 7

Get 29.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, after being warmed up to 100 ℃, add 82.6g di-n-butylamine and 2.7g zinc chloride (three kinds of material mol ratios, 1 : 3.2: 0.1), keep the reaction temperature at 100°C, continue to stir the reaction for 10h, stop heating, add 10mL 30% NaOH solution after cooling and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 91% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:15), The structure was confirmed by proton nuclear magnetic resonance spectrum, infrared spectrum and gas chromatography-mass spectrometry. The results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ1.3(t, 6Hz, 12H), 1.5(m, J=6.4Hz, 8H), 1.6(m, J=6.3Hz, 8H), 1.82(t , J=6.4Hz, 8H), 2.4(t, J=5.5Hz, 8H) 2.3(d, J=5.5Hz, 4H), 3.5(t, J=6Hz, 1H), 2.5(d, OH, 1H );

IR(neat): 3452cm ^-1 , 2956cm ^-1 , 2930cm ^-1 , 2863cm ^-1 , 2808cm ^-1 , 1465cm ^-1 , 1378cm ^-1 ; 1180cm ^-1 , 1080cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 8

Get 29.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, after being warmed up to 100 ℃, add 101g diisopropylamine and 1.67 ferric chloride (three kinds of material mol ratios, 1: 5: 0.05), keep the reaction temperature at 120°C, continue to stir and react for 12h, then stop heating, add 10mL 30% NaOH solution after cooling and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 92% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:15), The structure was confirmed by proton nuclear magnetic resonance spectrum and infrared spectrum, and the results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ0.9(d, 6Hz, 24H), 3.02(m, J=6.4Hz, 4H), 2.3(d, J=5.5Hz, 4H), 3.5(t , J=6Hz, 1H), 2.5(d, OH, 1H);

IR(neat): 3443cm ^-1 , 2953cm ^-1 , 2907cm ^-1 , 1465cm ^-1 , 1378cm ^-1 ; 1176cm ^-1 , 1079cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 9

Get 29.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, after being warmed up to 100 ℃, add 129g diisobutylamine and 9.12g antimony trichloride (three kinds of material mol ratios, 1 : 5: 0.2), keep the reaction temperature at 120°C, continue to stir the reaction for 12h and then stop heating, add 10mL 30% NaOH solution after cooling and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 91% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:15), The structure was confirmed by proton nuclear magnetic resonance spectrum and infrared spectrum, and the results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ0.9(d, 6Hz, 24H), 3.02(m, J=6.4Hz, 4H), 2.2(d, 6Hz, 8H), 2.3(d, J= 5.5Hz, 4H), 3.5(tJ=6Hz, 1H), 2.5(d, OH, 1H);

IR ⁽ neat): 3436cm ^-1 , 2957cm ^-1 , 2932cm -1 , 2863cm ^-1 , 2808cm ^-1 , 1473cm ^-1 , 1389cm ^-1 , 1370cm ^-1 ; 1182cm ^-1 , 1078cm ^-1 , 913cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 10

Get 29.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, after being warmed up to 100 ℃, add 60g dicyclohexylamine and 3.06g titanium trichloride (three kinds of material mol ratios, 1 : 5: 0.1), keep the reaction temperature at 120°C, continue to stir the reaction for 12h, then stop heating, add 10mL 30% NaOH solution after cooling and stir evenly to obtain aminoalcohol structural derivatives.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 91% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:15), The structure was confirmed by proton nuclear magnetic resonance spectrum and infrared spectrum, and the results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ1.0-1.5(m, 6Hz, 20H), 3.0(m, J=6.4Hz, 4H), 2.3(d, 5.5Hz, 4H), 3.4(t , 6Hz, 1H), 2.1(d, OH, 1H);

IR(neat): 3443cm ^-1 , 2953cm ^-1 , 2856cm ^-1 , 1450cm ^-1 , 1378cm ^-1 , 1179cm ^-1 , 1070cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Example 11

Get 29.5g epichlorohydrin and join in the reactor that 10ml dehydrated alcohol is housed, after being warmed up to 100 ℃, add 157g di-tert-amylamine and 3.06g titanium trichloride (three kinds of material mol ratios, 1 : 5: 0.1), keep the reaction temperature at 120°C, continue to stir the reaction for 12h and then stop heating, add 10mL 30% NaOH solution after cooling and stir evenly to obtain derivatives with aminoalcohol structure.

The yield of the above-mentioned derivatives having an aminoalcohol structure was determined to be 90% by liquid chromatography. After the above-mentioned derivatives with aminoalcohol structure are purified by column chromatography (using silica gel as filler, the eluent is composed of acetone and ethyl acetate mixed, wherein the volume ratio of acetone and ethyl acetate is 1:15), The structure was confirmed by proton nuclear magnetic resonance spectrum and infrared spectrum, and the results are as follows:

1H-NMR (400MHz, CDCl3, δ, ppm) δ1.0-1.5(m, 6Hz, 20H), 3.0(m, J=6.4Hz, 4H), 2.3(d, 5.5Hz, 4H), 3.4(t , 6Hz, 1H), 2.1(d, OH, 1H);

IR(neat): 3450cm ^-1 , 2953cm ^-1 , 2856cm ^-1 , 1450cm ^-1 , 1378cm ^-1 , 1180cm ^-1 , 1080cm ^-1 .

The above results show that the structural formula of the synthetic rust inhibitor is:

Application Example 1

Concrete was prepared according to the provisions of GB/T 8076-2008 "Concrete Admixtures" to test the influence of rust inhibitors on the performance of concrete. Among them, the standard cement dosage is 330kg/m ³ , the water-binder ratio is 0.55, the rust inhibitor dosage is 2kg/m ³ , and the sand, gravel and sand ratio all meet the standard requirements. The synthesized sample was purified by column chromatography (as described in the examples), and the effect of the purified product on the setting time and strength of the concrete was tested when the purified product was mixed into the concrete. The results are shown in Table 1.

Table 1 Effects on Concrete Properties

It can be seen from the test results that the prepared polyamino alcohol-containing rust inhibitors in the examples of the present invention have no significant impact on the slump and setting time of the concrete mixture, and most of them can slightly improve the concrete Strength after hardening. Generally speaking, the rust inhibitors containing polyamino alcohols prepared in the examples of the present invention will not adversely affect the performance of concrete. Application Example 2

计算浸泡7天后阻锈剂的缓蚀效率，测试结果见表2。A saturated calcium hydroxide solution was prepared, and 0.3mol/L NaCl was added thereto as a contrast solution. Add the purified product (mass fraction is 1% of the solution mass) to the comparison solution respectively to form a solution system for the corrosion resistance of steel bars. A three-electrode system was used for testing. Use cylindrical Q 235 steel bars, encapsulate them with epoxy resin, leave a 1cm ² working area, use 600#, 1000#, 2000# sandpaper to grind and polish, then soak in acetone for 15 minutes and use it as a working electrode after drying . A platinum electrode was used as the counter electrode, and a saturated calomel electrode was used as the reference electrode. Test the linear polarization resistance of the working electrode _in the comparison solution and the solution _containing different rust inhibitors.

Calculate the corrosion inhibition efficiency of the rust inhibitor after soaking for 7 days, and the test results are shown in Table 2.

It can be seen from the test results that the embodiments of the present invention all exhibit obvious rust-inhibiting effects under the condition of high chloride salt concentration. After soaking for 7 days, the rust-inhibiting efficiency is above 90%. It is proved that the multi-polyaminoalcohol rust inhibitor of the present invention can well protect steel bars in a chloride salt environment, and greatly slow down the occurrence of steel bar corrosion.

Claims (5)

1. a kind of compound containing polyhydric amino alcohol, its structural formula is the compound shown in (I):

Wherein, R ₁ is H, R ₂ is -(CH ₂ CH ₂ NH) _m H, m is an integer from 2 to 6; or R ₁ and R ₂ are each independently -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH(CH ₃ ) ₂ , -CH ₂ CH(CH ₃ ) ₂ , -CH(CH ₂ ) ₅ or -C(CH ₃ ) ₂ CH ₂ CH ₃ one of the. 2. the application of polyamino alcohol compound as concrete rust inhibitor described in claim 1. 3. the preparation method that contains polyamino alcohol compound described in claim 1 is characterized in that, obtains by reaction of epoxy derivative and organic amine under catalyst action, and wherein said epoxy derivative is represented by structural formula (II) Compounds showing the structure:

R ₃ is Cl, Br or I, Described organic amine is the compound of structure shown in structural formula (III)

R ₁ and R ₂ in formula (III) have the same meaning as R ₁ and R ₂ in formula (I); The catalyst is one of FeCl ₃ , SbCl ₅ , SnCl ₄ , ZnCl ₂ and TiCl ₃ . 4. The method for preparing polyhydric amino alcohol-containing compounds according to claim 3, wherein the molar ratio of the catalyst to the epoxy derivative is 0.001:1-0.2:1. 5. as claimed in claim 3 or 4, the preparation method of the described polyamino alcohol-containing compound is characterized in that, the mol ratio of epoxy derivative and organic amine is 1:2～1:5, and described The reaction temperature is 10° C. to 120° C., and the reaction time is 1 hour to 15 hours.