A method for preparing sterically hindered amine

Abstract

The present invention relates to the technical field of organic synthesis, and discloses a preparation method of a sterically hindered amine, the preparation method comprising: reacting a substrate 1 and a substrate 2 in the presence of a solvent and a catalyst, and performing a reaction of formula 1; after the reaction liquid is cooled to room temperature, a base is added to perform a reaction of formula 2, and after the reaction is completed, a sterically hindered amine product is separated. Wherein, R1 is selected from H, a straight or branched alkyl of C1-C6, R2 and R3 are independently selected from a straight or branched alkyl of C1-C6, and R4 is selected from H, a straight or branched alkyl of C1-C6 substituted with a hydroxyl group; in formula 1, the catalyst is a mixture of TiCl4 and tartrate. The present invention adopts a bimetallic catalytic active center to catalyze the reaction, which can reduce the activation energy of the main reaction and the temperature required for the reaction, make the reaction conditions milder, reduce the occurrence of side reactions, and reduce production costs; the preparation method has a wide range of applications and is suitable for the preparation of a variety of sterically hindered amines.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing a sterically hindered amine. Background Art

[0002] Steric hindered amines are a new type of organic alcohol amine desulfurizer. 2 It has a good absorption effect on S and other organic sulfur substances, and has great application potential in various desulfurization scenarios such as natural gas, oil refinery gas, oil field associated gas, synthesis gas, coal gas and liquid hydrocarbons. In addition, sterically hindered amines also have the advantages of easy solubility, low volatility and non-corrosiveness. As my country implements the sustainable development strategy, builds a resource-saving and environmentally friendly society, and develops clean energy, etc., it is increasingly valued. The application scenarios of desulfurizers will be rapidly expanded, and the corresponding consumer market of sterically hindered amines will also expand rapidly.

[0003] Compared with the widely used N-methyldiethanolamine (MDEA), tert-butylaminoethoxyethanol (TBEE) has a unique molecular structure (large steric hindrance, strong alkalinity, etc.), and steric hindered amines are more sensitive to H 2 S has better absorption selectivity and absorption capacity, especially in CO 2 In scenarios with high content and large acid gas load, the amount of desulfurizer used, desorption cycle energy consumption, and desulfurization equipment investment can be reduced. The traditional synthesis process of sterically hindered amine TBEE uses tert-butylamine and dichlorodiglycol as raw materials, and is carried out without a catalyst and at high temperature (150°C). The target product is obtained through two steps of nucleophilic substitution and acid-base neutralization (such as patents with publication numbers US4471138A and CN1623978A), and the product separation yield is about 80%. However, affected by the price of raw materials and the efficiency of the synthesis reaction, the price of TBEE prepared by this process is much higher than that of MDEA, about 8-9 times that of the latter, which seriously hinders the market replacement of MDEA.

[0004] The use of diethylene glycol as an alternative raw material to diethylene glycol chloride to synthesize TBEE is currently a research hotspot in the laboratory (such as the patent with publication number US4487967A). This process uses a nickel-based catalyst to catalyze the reaction. Under hydrogen conditions, tert-butylamine and diethylene glycol undergo a two-step dehydrogenation and hydrogenation reaction to obtain TBEE. This process is low-cost and has mild reaction conditions. It is a very promising synthesis process. Relevant research groups have also made good progress. However, the current results still have problems such as the inability to maintain both conversion rate and selectivity and high separation costs. It is still a long way from industrialization. Summary of the invention

[0005] In order to solve the problems of low synthesis efficiency and high material consumption cost of sterically hindered amines, the present invention provides a method for preparing sterically hindered amines, which uses primary amine compounds and chlorohydrin compounds as substrates and a Lewis acid complex as a catalyst, can efficiently prepare sterically hindered amines, has the advantages of high reaction yield, low material consumption, mild reaction conditions, simple separation, etc., and is suitable for industrial production.

[0006] The purpose of the present invention is achieved by the following technical scheme: A method for preparing a sterically hindered amine, the reaction equation of which is as follows:

[0007]

[0008] Wherein, R1 is selected from H, C1-C6 straight chain or branched alkyl, R2 and R3 are independently selected from C1-C6 straight chain or branched alkyl, and R4 is selected from H, hydroxyl-substituted C1-C6 straight chain or branched alkyl; in Formula 1, the catalyst is TiCl 4 and a mixture of tartrates.

[0009] Sterically hindered amines for H 2 The high selectivity of S absorption is mainly attributed to the steric hindrance effect of the substituent directly connected to the nitrogen atom, so the carbon atom directly connected to the nitrogen atom of the selected primary amine substrate is required to be at least a secondary carbon, and the tertiary carbon is better. For chlorohydrin substrates, the hydroxyl functional group can increase the boiling point and solubility of the prepared sterically hindered amine, avoid its volatilization problem during application, and reduce losses.

[0010] Traditional S N 2 The nucleophilic substitution reaction to synthesize sterically hindered amines needs to be carried out at high temperature (150°C) in order to overcome the high activation energy during the reaction. However, high temperature conditions will also lead to the intensification of side reactions, making it difficult to ensure an ideal yield. As shown in Formula 3, the catalyst used in the present invention can form a bimetallic catalytic center during the reaction. Its coordination effect can not only activate the substrate and reduce the activation energy of the main reaction, but also promote the contact of the two reaction substrates, thereby reducing the occurrence of side reactions and improving the reaction yield. 4 In comparison, other Lewis acid catalysts such as AlCl 3 ,FeCl 3 ,SbCl 3 ,ZnCl 2 etc. have stronger catalytic activity, especially for the chlorodiglycol substrate, which has a strong activation effect, which will lead to polymerization between the chlorodiglycol substrates, significantly reducing the reaction yield. In addition, due to the difference in d orbital configuration and the number of electrons, FeCl 3 ,SbCl 3 ,ZnCl2 The present invention also cannot effectively form a bimetallic catalytic center with the tartaric acid ligand. In addition, the present invention has found through research that the tartrate titanium complex can efficiently catalyze the oxidation of allyl alcohol compounds by peroxides, and both substrates will be coordinated and activated during the catalytic process, so it is a suitable catalyst for the synthesis of sterically hindered amines.

[0011] Preferably, in Formula 1, the molar ratio of substrate 1 to substrate 2 is 2 to 3:1.

[0012] Preferably, the TiCl 4 The molar ratio of tartaric acid to sodium tartrate is 1:1 to 1.5. The tartrate is one or more of sodium tartrate, potassium tartrate, potassium sodium tartrate or lithium tartrate.

[0013] The proportion of tartrate as a ligand is slightly higher than that of the central metal atom Ti to ensure that all Ti exists in a coordinated form. Too much ligand will increase the cost.

[0014] Preferably, the TiCl 4 The molar ratio of the first and second substrates is 0.005 to 0.05:1.

[0015] Taking into account the catalyst cost and reaction effect, the amount of catalyst needs to be controlled within an appropriate range. Too little catalyst will lead to prolonged reaction time, decreased reaction efficiency and increased side reactions, while too much catalyst will lead to increased costs and may also lead to deep reactions of the products, such as the formation of tert-butylmorpholine TBM.

[0016] Preferably, in Formula 1, the solvent is a three-component mixed solvent, wherein component one is water, component two is methanol or ethanol, and component three is a C4-C12 monohydric alcohol or polyhydric alcohol; the mass ratio of component one, component two and component three is 1-5:1:1-5.

[0017] The properties of the solvent have a significant effect on nucleophilic substitution reactions, mainly in terms of its ability to stabilize the transition state / intermediate and its ability to dissolve the substrate. N2 reaction, the stabilizing effect of proton solvents on transition states / intermediates presents a comprehensive result. On the one hand, proton solvents have a solvating effect on leaving groups, which is beneficial to the reaction. On the other hand, when the nucleophile has a negative charge, solvation will also occur, which is not conducive to its contact with the substrate. The synthesis of sterically hindered amines is a process of amino nucleophilic substitution of chloride ions. The solvating effect of proton solvents on leaving groups occupies a major position. Therefore, proton solvents are superior to dipolar solvents and non-polar solvents and are the preferred solvent type for this reaction. In terms of the solubility of substrate molecules, when the solvent has insufficient solubility for the substrate, the substrate molecules will exist in an associated state and cannot be evenly dispersed. If the reaction is to proceed, the intermolecular association must be overcome first, which will greatly reduce the reactivity.

[0018] In summary, the reaction solvent needs to be formulated with suitable solvation capacity and dissolving capacity. The present invention selects three components as a mixed solvent. Water can fully solvate the chloride ions, the long-chain alcohol can ensure that the chlorohydrin substrate exists in a non-associated form, and methanol or ethanol makes water and the long-chain alcohol miscible to form a uniform reaction system.

[0019] Preferably, the component three is n-butanol, tert-butanol, n-pentanol, tert-pentanol, isoamyl alcohol, n-hexanol, 2-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 3,3-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, n-heptanol, 2-heptanol, n-octanol, 2-octanol, 1-nonanol, 1-decanol, lauryl alcohol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 1,6-hexanediol or dipropylene glycol. Further preferably, n-butanol, n-pentanol, n-hexanol, 2-hexanol, n-heptanol, 2-heptanol, n-octanol, 2-octanol, 1,4-butanediol, diethylene glycol or 1,6-hexanediol.

[0020] Preferably, in Formula 1, the ratio of the mass of the solvent to the total mass of the substrate 1 and the substrate 2 is 0.3-0.6:1.

[0021] Preferably, the reaction temperature of formula 1 is 25-60°C, and the reaction time is 2-6 hours. More preferably, the reaction temperature is 40-50°C, and the reaction time is 3-5 hours.

[0022] Preferably, the second formula is: after the reaction of the first formula is completed, the mixture is cooled to room temperature, and then a base is added and heated for reaction, the reaction temperature is 80 to 120°C, and the reaction time is 0.5 to 2 hours. More preferably, the reaction temperature is 90 to 100°C, and the reaction time is 1 to 1.5 hours.

[0023] Since the reaction requires a certain amount of activation energy, when the temperature is too low, the reaction will remain at the intermediate stage or the substrate cannot be completely converted into the product, while when the temperature is too high, the side reactions will intensify and the yield will decrease. In addition, when the reaction time is too short, the substrate cannot fully react, and when the time is extended, the reaction efficiency will decrease, which is also not conducive to industrial production.

[0024] Preferably, the molar ratio of substrate 2 to base is 1:1 to 1.2.

[0025] Preferably, the base is NaOH or KOH.

[0026] Preferably, after the reaction of formula 2 is completed, the sterically hindered amine product is separated; the separation method is filtration and vacuum distillation.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The present invention prepares the sterically hindered amine in a three-component mixed solvent, which significantly improves the product yield and makes the reaction conditions milder, thereby significantly reducing material consumption and energy consumption, which is conducive to reducing product costs;

[0029] (2) The present invention uses a bimetallic catalytic active center to catalyze the reaction, which can greatly reduce the activation energy of the main reaction and the temperature required for the reaction, thereby reducing the occurrence of side reactions;

[0030] (3) The preparation method provided by the present invention has a wide range of applications and is suitable for the preparation of a variety of sterically hindered amines. DETAILED DESCRIPTION

[0031] The technical solution of the present invention is described below with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0032] Example 1

[0033] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2, 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reaction kettle was sealed and heated to 45 °C, and the reaction was carried out for 4 h under vigorous stirring;

[0034] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0035] Example 2

[0036] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-pentanol (C 5 H 11 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45 ° C, and the reaction was carried out under vigorous stirring for 4 h.

[0037] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0038] Example 3

[0039] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-hexanol (C 6 H 13 OH, 26.7 g), TiCl 4(2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45 ° C, and the reaction was carried out under vigorous stirring for 4 h.

[0040] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0041] Example 4

[0042] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), 2-hexanol (C 6 H 13 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0043] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0044] Example 5

[0045] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-heptanol (C 7 H 15 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0046] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0047] Example 6

[0048] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), diethylene glycol (C 4 H 10 O 3 , 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0049] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0050] Example 7

[0051] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), 1,6-hexanediol (C 4 H 10 O 3 , 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0052] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0053] Example 8

[0054] (1) Add water (H) to a 500 mL reactor. 2 O, 30g), ethanol (C 2 H 5 OH, 20 g), n-butanol (C 4 H 9 OH, 30 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0055] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0056] Example 9

[0057] (1) Add water (H) to a 500 mL reactor. 2 O, 35g), ethanol (C 2 H 5 OH, 20 g), n-butanol (C 4 H 9 OH, 25 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0058] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0059] Example 10

[0060] (1) Add water (H) to a 500 mL reactor. 2 O, 25g), ethanol (C 2 H 5 OH, 20 g), n-butanol (C 4 H 9 OH, 35 g), TiCl 4(2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0061] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0062] Embodiment 11

[0063] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 97.5 g) and diethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0064] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0065] Example 12

[0066] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 146.2 g) and diethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0067] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0068] Example 13

[0069] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 2.58 g, accounting for 2 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0070] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0071] Embodiment 14

[0072] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (1.26 g, accounting for 1 mol% of the molar fraction of dichloroethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 1.55 g, accounting for 1.2 mol% of the molar fraction of diethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0073] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0074] Embodiment 15

[0075] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (3.78 g, accounting for 3 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 4.65 g, accounting for 3.6 mol% of the molar fraction of diethylene glycol), tert-butylamine (C 4 H9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0076] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0077] Example 16

[0078] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 35°C, and the reaction was carried out for 6 h under vigorous stirring.

[0079] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0080] Embodiment 17

[0081] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0082] (2) The reaction solution was then cooled to room temperature, and the reactor was opened and 29.3 g of NaOH was added, and the reaction was continued at 90° C. for 1.5 h. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0083] Embodiment 18

[0084] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), isopropylamine (C 3 H 7 NH 2 , 98.3 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0085] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product isopropylaminoethoxyethanol IPEE.

[0086] Embodiment 19

[0087] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of diethylene glycol), tert-amylamine (C 5 H 11 NH 2 , 144.9 g) and diethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0088] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-amylaminoethoxyethanol TPEE.

[0089] Embodiment 20

[0090] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), 2-methylhexane-2-amine (C 6 H 13 NH 2 , 168.2 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0091] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product 2-methylhexane-2-aminoethoxyethanol MPEE.

[0092] Embodiment 21

[0093] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of diethylene glycol dichloride), 3-methylheptane-3-amine (C 8 H 17 NH 2 , 214.9 g) and diethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0094] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product 3-methylheptane-3-aminoethoxyethanol MHEE.

[0095] Embodiment 22

[0096] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of 2-chloroethoxymethanol), sodium tartrate (C 4 H 4 Na 2 O 6, 3.1 g, accounting for 2.4 mol% of the molar fraction of 2-chloroethoxymethanol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and 2-chloroethoxymethanol (C 3 H 7 O 2 Cl, 73.5 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0097] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxymethanol TBEM.

[0098] Embodiment 23

[0099] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of 1-(2-chloroethoxy)propan-2-ol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of 1-(2-chloroethoxy)propan-2-ol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and 1-(2-chloroethoxy)propan-2-ol (C 5 H 11 O 2 Cl, 92.5 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0100] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxypropan-2-ol TBEP.

[0101] Embodiment 24

[0102] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of 2-[2-(2-chloroethoxy)ethoxy]ethanol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of 2-[2-(2-chloroethoxy)ethoxy]ethanol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and 2-[2-(2-chloroethoxy)ethoxy]ethanol (C 6 H 13 O 3 Cl, 112.6 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0103] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was removed by filtration, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethoxyethanol TBEEE.

[0104] Comparative Example 1

[0105] The difference from Example 1 is that water is used as the single solvent.

[0106] (1) Add water (H) to a 500 mL reactor. 2 O, 80g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0107] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0108] Comparative Example 2

[0109] The difference from Example 1 is that n-butanol is used as the single solvent.

[0110] (1) Add n-butanol (C 4 H 9 OH, 80 g), TiCl 4 (2.52 g, accounting for 2 mol% of the molar fraction of diethylene glycol), sodium tartrate (C 4 H 4 Na 2 O 6 , 3.1 g, accounting for 2.4 mol% of the molar fraction of dichloroethylene glycol), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2 Cl, 82.8 g), the reactor was sealed and heated to 45 ° C, and the reaction was carried out under vigorous stirring for 4 h.

[0111] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0112] Comparative Example 3

[0113] The difference from Example 1 is that no catalyst is used.

[0114] (1) Add water (H) to a 500 mL reactor. 2 O, 26.7 g), ethanol (C 2 H 5 OH, 26.7 g), n-butanol (C 4 H 9 OH, 26.7 g), tert-butylamine (C 4 H 9 NH 2 , 121.6 g) and dichloroethylene glycol (C 4 H 9 O 2Cl, 82.8 g), the reactor was sealed and heated to 45°C, and the reaction was carried out for 4 h under vigorous stirring.

[0115] (2) The reaction solution was then cooled to room temperature, the reactor was opened, 29.3 g of NaOH was added, and the reaction was continued at 100° C. for 1 hour. After the reaction was completed, the NaCl generated during the reaction was filtered out, and the filtrate was subjected to vacuum distillation to obtain the product tert-butylaminoethoxyethanol TBEE.

[0116] The sterically hindered amine products obtained in the examples and comparative examples were subjected to gas chromatography analysis, and biphenyl was used as an internal standard substance to calculate the product yield.

[0117] Table 1 Reaction conditions and product yields of Example 1

[0118]

[0119] Table 2 Preparation of sterically hindered amines in different solvent systems

[0120]

[0121]

[0122] Table 3 Preparation of sterically hindered amines under different reaction conditions

[0123] Group Differences in reaction conditions from Example 1 Product yield / % Example 1 -- 98 Embodiment 11 The molar ratio of substrate 1 to substrate 2 is 2:1 93 Example 12 The molar ratio of substrate 1 to substrate 2 is 3:1 87 Example 13 <![CDATA[TiCl 4 The molar ratio with tartrate is 1:1]]> 96 Embodiment 14 <![CDATA[TiCl 4 The molar fraction of substrate 2 is 1 mol%]]> 91 Embodiment 15 <![CDATA[TiCl 4 The molar fraction of substrate 2 is 3 mol%]]> 98 Example 16 The first step reaction was carried out at 35°C for 6 h 83 Embodiment 17 The second step reaction was carried out at 90 °C for 1.5 h 97 Comparative Example 3 No catalyst used 3

[0124] Table 4 Synthesis of different sterically hindered amines

[0125]

[0126] Table 1 shows the reaction conditions and product yields of Example 1. Examples 2-24 and Comparative Examples 1-3 are single reaction conditions or substrate transformations according to Example 1, and the obtained product yields are shown in Table 2-4.

[0127] Table 2 shows that the selection and ratio of solvents will affect the product yield, but the use of a single solvent in Comparative Example 1-2 will significantly reduce the product yield. This is because the present invention uses three components as a mixed solvent, which can obtain a balanced solvation capacity and dissolution capacity to form a uniform reaction system. Table 3 shows the molar ratio of substrate 1 to substrate 2, TiCl 4 The molar ratio of tartrate, TiCl 4 The molar fraction of substrate 2, reaction temperature, time and other reaction conditions will affect the product yield, but the reaction conditions within the scope of the present invention cooperate with each other and synergize to obtain a higher product yield, which has a better technical effect. Table 3 shows that the preparation method of the present invention can be applied to the preparation of various sterically hindered amines and obtain a higher product yield.

[0128] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the specification of the present invention, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a sterically hindered amine, characterized in that: The reaction equation is as follows: ； Wherein, in formula 1, the solvent is a three-component mixed solvent, wherein component one is water, component two is methanol or ethanol, and component three is a C4-C12 monohydric alcohol or polyhydric alcohol; R1 is selected from H, a C1-C6 straight chain or branched alkyl, R2 and R3 are independently selected from C1-C6 straight chain or branched alkyl, and R4 is selected from H, a hydroxyl-substituted C1-C6 straight chain or branched alkyl; in formula 1, the catalyst is a mixture of TiCl4 and tartrate.

2. The method for preparing a sterically hindered amine according to claim 1, characterized in that: In formula 1, the molar ratio of substrate 1 to substrate 2 is 2-3:

1.

3. The method for preparing a sterically hindered amine according to claim 1, characterized in that: The molar ratio of TiCl4 to tartrate is 1:1-1.

5.

4. The method for preparing a sterically hindered amine according to any one of claims 1 to 3, characterized in that: The molar ratio of TiCl4 to substrate 2 is 0.005-0.05:

1.

5. The method for preparing the sterically hindered amine according to any one of claims 1 to 3, characterized in that: In Formula 1, the solvent is a three-component mixed solvent, and the mass ratio of component one, component two and component three is 1-5:1:1-5.

6. The method for preparing a sterically hindered amine according to claim 5, characterized in that: In formula 1, the ratio of the mass of the solvent to the total mass of the substrate 1 and the substrate 2 is 0.3-0.6:

1.

7. The method for preparing the sterically hindered amine according to any one of claims 1 to 3, characterized in that: The reaction temperature of formula 1 is 25~60ºC, and the reaction time is 2~6h.

8. The method for preparing a sterically hindered amine according to claim 1, characterized in that: Formula 2 is: After the reaction of Formula 1 is completed, it is cooled to room temperature, and then heated to react after adding alkali. The reaction temperature is 80~120ºC and the reaction time is 0.5~2h.

9. The method for preparing a sterically hindered amine according to claim 1 or 8, characterized in that: The molar ratio of substrate 2 to base is 1:1~1.

2.

10. The method for preparing a sterically hindered amine according to claim 9, characterized in that: The base is NaOH or KOH.

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