Large-scale continuous production method of diimide derivative

Abstract

The invention discloses a large-scale continuous production method of a diimide derivative, and belongs to the technical field of chemical synthesis, and the method comprises the following steps: stirring and heating a precursor A composed of acid and anhydride and a raw material B in a reaction base solution to prepare a reaction solution; cooling the reaction liquid to room temperature, filtering, and collecting a filter cake and filtrate; and washing and drying the filter cake to obtain the target diimide derivative. And circularly feeding the filtrate as a secondary reaction base solution to continue the reaction. According to the process disclosed by the invention, the raw materials are completely utilized, the reaction process is simpler and more efficient, the production cycle is shortened, the operation steps are simplified, the whole production process is more convenient and safer, and the kilogram-level large-scale continuous production can be safely and efficiently realized.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a large-scale continuous production method of imide derivatives. Background Art

[0002] Energy is the basis of human survival and material development. With the continuous growth of global energy demand, primary energy reserves are rapidly decreasing and environmental pollution problems are becoming increasingly serious. Therefore, the development of renewable secondary energy is the best way for human development. However, some new energy sources are greatly affected by the environment, such as solar energy and wind energy. How to effectively store these energies is particularly important. Liquid flow batteries, as a large-capacity electrochemical energy storage device, are the preferred technology for large-scale application of renewable energy. Among liquid flow batteries, neutral aqueous organic redox batteries have attracted widespread attention due to their large capacity, high safety, low cost, environmental friendliness, flexible design, and the ability to adjust organic molecules to achieve high (cathode) or low (anode) redox potentials.

[0003] As an indispensable core component of flow batteries, the performance and cost of electrolyte materials directly affect the development prospects of aqueous organic flow batteries. Given the current high prices of organic raw materials, the cost of organic electrolytes accounts for more than half of the cost of the entire energy storage system, far exceeding the cost burden of inorganic electrolytes. Therefore, a synthesis process with simple process, convenient operation, short production cycle, high yield, low cost and safety is proposed to promote the rapid development of aqueous organic flow batteries.

[0004] Imide derivatives are an important class of organic compounds, which refer to compounds formed by introducing other groups or atoms into the imide molecules (such as naphthalene diimide, florenzimide, etc.). Most of the existing synthesis strategies rely on high-pressure solvent thermal and hydrothermal synthesis technology to carry out imidization reaction: by the reaction of acyl chloride and amine, imide and its derivatives are synthesized. This method is simple to operate and is an important way to synthesize imide derivatives. However, on the one hand, this process not only requires the use of a large amount of organic solvents, but also requires a high-pressure reaction device, resulting in high production costs. On the other hand, the high-pressure operating environment poses significant safety risks in the large-scale production process. These two drawbacks seriously restrict the kilogram-scale preparation process of imide derivatives. Summary of the invention

[0005] In order to overcome the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a large-scale continuous production method of diimide derivatives, which can effectively solve the technical problems of the prior art such as harsh synthesis conditions, inability to recycle raw materials and low yield.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention discloses a large-scale continuous production method of imide derivatives, comprising the following steps:

[0008] 1) Under normal pressure, the precursor A and the raw material B are stirred and heated in a reaction base liquid to obtain a reaction liquid;

[0009] Wherein, the precursor A is composed of an acid and an anhydride in any proportion; is composed of one or more acids and anhydrides in any proportion;

[0010] The structural formula of raw material B is as follows:

[0011] Among them, R1 is Any of the groups, n is 1 or 2;

[0012] 2) Cooling the reaction solution to room temperature, filtering, and collecting the filter cake and filtrate;

[0013] 3) washing and drying the filter cake to obtain the target imide derivative; and recycling the filtrate as the secondary reaction bottom liquid to step 1) to continue the reaction.

[0014] Preferably, the structural formulas of the anhydride and acid constituting the precursor A are as follows:

[0015]

[0016]

[0017] Among them, it is composed of one or more acids and anhydrides in any proportion, which can be one acid and one anhydride, one acid and multiple anhydrides, multiple acids and one anhydride, or multiple acids and multiple anhydrides.

[0018] Preferably, in step 1), the reaction molar ratio of precursor A to raw material B is 1:2-10.

[0019] Preferably, in step 1), the heating temperature is 110-130°C.

[0020] Preferably, in step 1), the stirring and heating treatment time is 40-50 hours.

[0021] Preferably, in step 1), the reaction base liquid is acetonitrile, N,N-dimethylformamide or toluene.

[0022] Preferably, in step 1), the volume ratio of the reaction base liquid to the raw material B is 10-6:1.

[0023] Preferably, in step 3), the filter cake is washed with water and ethanol in sequence.

[0024] Further preferably, in step 3), the volume ratio of water to filter cake is 2-6:1, and the volume ratio of anhydrous ethanol to filter cake is 2-5:1.

[0025] Preferably, in step 3), when the secondary reaction bottom liquid returns to step 1) to continue the reaction, the volume of the reaction solvent added additionally V = the volume of the initial reaction bottom liquid V1 - the volume of the secondary reaction bottom liquid V2.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The large-scale continuous production method of diimide derivatives disclosed in the present invention adopts a normal pressure environment for reaction operation, reduces the use of high-pressure equipment, thereby reducing production costs, and avoids the safety hazards caused by high-pressure reactions. Through the verification of large-scale production practice, the process is highly efficient and its yield is stably maintained at more than 90%. Significant results have also been achieved in cost control. On the one hand, the cost of raw materials and equipment has been effectively compressed, and the cost is only one thousandth of the original cost; on the other hand, the filtrate produced by the process is used as the bottom liquid for the secondary reaction. This recycling strategy not only greatly reduces the consumption of organic solvents, but also realizes the secondary value mining of incompletely reacted raw materials, further improving the overall reaction yield. While the process of the present invention realizes 100% utilization of raw materials, the reaction process is more streamlined and efficient, shortens the production cycle, simplifies the operating steps, makes the entire production process more convenient and safe, and can safely and efficiently realize large-scale continuous production at the kilogram level. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a process flow chart of the large-scale continuous production method of the present invention;

[0029] Figure 2 This is a photo of the imide derivative prepared in Example 1 of the present invention;

[0030] Figure 3 This is a photo of the imide derivative produced by the 100 kg scale production of the present invention being dried;

[0031] Figure 4 This is a real photo of the imide derivative obtained by the 100-kilogram-level scale-up production of the present invention. DETAILED DESCRIPTION

[0032] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0033] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged where appropriate, so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0034] The present invention is further described in detail below in conjunction with the accompanying drawings:

[0035] The present invention discloses a kilogram-scale large-scale synthesis method for preparing imide derivatives. Figure 1 ,as follows:

[0036] Step 1: Add precursor A into a pressure-resistant bottle or a normal pressure reactor (condensation reflux), then add an organic solvent, add raw material B, and stir and heat.

[0037] Step 2: After the reaction is completed, the solution is cooled to room temperature and filtered, and the mother liquor is collected separately as the secondary reaction bottom liquid;

[0038] Step 3: Wash the filter cake with deionized water, then add ethanol for a second wash, and then dry it; the filtrate is recycled as the secondary reaction bottom liquid to step 1 for further reaction.

[0039] Preferably, the synthesis method adopted in step 1 is a normal pressure method, and the reaction kettle used is a pressure-resistant bottle or flask (condensation reflux) to prevent the reaction solution from volatilizing.

[0040] Preferably, the heating device used in step 1 includes but is not limited to a jacket heating device, an electric heating device (such as microwave heating);

[0041] Preferably, the main component of the filtrate is an organic solvent, which can be recycled, and the amount of organic solvent used in the secondary reaction = aV 初始-V 母液 .

[0042] Example 1

[0043] The structural formula of the precursor A used in this embodiment is as follows, wherein the anhydride accounts for 60% and the acid accounts for 40%.

[0044]

[0045] The chemical reaction formula for synthesizing NDI-N in this embodiment is:

[0046]

[0047] Precursor A is added to a normal pressure reactor (condensation reflux), followed by toluene, and then 3-dimethylaminopropylamine is slowly added. The reactor is placed in an oil bath, the reaction temperature is controlled to 120°C, and kept warm for 24 hours. After the reaction is completed, stirring is turned off, the solution is naturally cooled to room temperature, and a golden solid is obtained by filtration. The mother liquor is then collected separately as a secondary reaction bottom liquid. The filter cake is washed with deionized water, and then ethanol is added for secondary washing. After completion, it is dried to obtain a product named NDI-N with a yield of 95%.

[0048] The equivalent ratio of precursor A to 3-dimethylaminopropylamine is 1:5, the volume ratio of toluene to 3-dimethylaminopropylamine is 6:1, and the volume ratio of filter cake to deionized water and anhydrous ethanol is 1:3:2.

[0049] Recycling of mother liquor: First, add precursor A into the atmospheric pressure reactor (condensation reflux), then add the mother liquor into the reactor, and add toluene (V = 1.05V 初始 -V 母液 ), then slowly add 3-dimethylaminopropylamine. Place the reactor in an oil bath, control the reaction temperature to 120°C, and keep warm for 24 hours. After the reaction is completed, turn off the stirring, cool the solution naturally to room temperature, filter to obtain a golden solid, and then collect the mother liquor separately as the secondary reaction bottom liquid. Wash the filter cake with deionized water, then add ethanol for secondary washing, and dry it after completion to obtain a product named NDI-N with a yield of 95%. The structural formula of NDI-N is as follows:

[0050]

[0051] The specific hydrogen spectrum data of the obtained imide derivative NDI-N are as follows:

[0052] 1H NMR (400MHz, CDCl3) δ8.75 (s, 4H), 4.35–4.17 (m, 4H), 2.43 (t, J = 7.1Hz, 4H), 2.23 (s, 12H), 1.99–1.85 (m, 4H).

[0053] Example 2

[0054] In this embodiment, raw material B is selected:

[0055] Take n-2, R1 is

[0056] 1,4,5,8-naphthalenetetracarboxylic anhydride is added to a normal pressure reactor (condensation reflux), followed by toluene, and then 1-(3-aminopropyl)imidazole is slowly added. The reactor is placed in an oil bath, the reaction temperature is controlled to 120°C, and the mixture is kept warm for 24 hours. After the reaction is completed, stirring is turned off, the solution is naturally cooled to room temperature, and a gray-yellow solid is obtained by filtration. The mother liquor is then collected separately as a secondary reaction bottom liquid. The filter cake is washed with deionized water, and then ethanol is added for secondary washing. After completion, it is dried to obtain a product named NDI-mz with a yield of 85%.

[0057] The equivalent ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride and 1-(3-aminopropyl)imidazole is 1:3, the volume ratio of toluene and 1-(3-aminopropyl)imidazole is 8:1, and the volume ratio of the filter cake to deionized water and anhydrous ethanol is 1:3:2.

[0058] Mother liquor recycling: first add 1,4,5,8-naphthalenetetracarboxylic anhydride into a normal pressure reactor (condensation reflux), then add the mother liquor into the reactor, add toluene (V = 1.05V 初始 -V 母液 ), then slowly add 1-(3-aminopropyl)imidazole. Place the reactor in an oil bath, control the reaction temperature to 120°C, and keep warm for 24 hours. After the reaction is completed, turn off the stirring, cool the solution naturally to room temperature, filter to obtain a golden solid, and then collect the mother liquor separately as the secondary reaction bottom liquid. Wash the filter cake with deionized water, then add ethanol for secondary washing, and dry it after completion to obtain a product named NDI-mz with a yield of 87%. The structural formula of NDI-mz is as follows:

[0059]

[0060] The specific hydrogen spectrum data of the obtained imide derivative NDI-mz are as follows:

[0061] 1H NMR (400MHz, DMSO) δ8.68 (s, 4H), 7.79 (s, 2H), 7.27 (s, 2H), 6.94 (s, 2H), 4.10 (dt, J = 14.0, 6.8Hz, 8H), 2.20-2.08 (m, 4H).

[0062] Example 3

[0063] In this embodiment, raw material B is selected:

[0064] Take n = 2, R1 is

[0065] 1,4,5,8-naphthalenetetracarboxylic anhydride is added to a normal pressure reactor (condensation reflux), followed by toluene, and then 1-(3-aminopropyl)pyrrole is slowly added. The reactor is placed in an oil bath, the reaction temperature is controlled to be 120°C, and the mixture is kept warm for 24 hours. After the reaction is completed, stirring is turned off, the solution is naturally cooled to room temperature, and a brown-yellow solid is obtained by filtration. The mother liquor is then collected separately as a secondary reaction bottom liquid. The filter cake is washed with deionized water, and ethanol is added for secondary washing. After completion, it is dried to obtain a product named NDI-pry with a yield of 89%.

[0066] The equivalent ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride and 1-(3-aminopropyl)pyrrole is 1:3, the volume ratio of toluene and 11-(3-aminopropyl)pyrrole is 8:1, and the volume ratio of the filter cake to deionized water and anhydrous ethanol is 1:3:2.

[0067] Mother liquor recycling: first add 1,4,5,8-naphthalenetetracarboxylic anhydride into a normal pressure reactor (condensation reflux), then add the mother liquor into the reactor, add toluene (V = 1.05V 初始 -V 母液 ), then slowly add 1-(3-aminopropyl)pyrrole. Place the reactor in an oil bath, control the reaction temperature to 120°C, and keep warm for 24 hours. After the reaction is completed, turn off the stirring, cool the solution naturally to room temperature, filter to obtain a brown-yellow solid, and then collect the mother liquor separately as the secondary reaction bottom liquid. Wash the filter cake with deionized water, then add ethanol for secondary washing, and dry it after completion to obtain a product named NDI-pry with a yield of 90%. The structural formula of NDI-pry is as follows:

[0068]

[0069] The specific hydrogen spectrum data of the obtained imide derivative NDI-pry are as follows:

[0070] 1H NMR (400MHz, CDCl3) δ8.77(s,4H),4.35–4.29(m,4H),2.63(t,J=7.2Hz,4H),2.51(s,8H),2.03–1.96(m,4H),1.67(s,8H).

[0071] Example 4

[0072] This example is an industrial scale-up production example of 100 kg level carried out according to the synthesis method of Example 1, and the raw materials and reaction conditions used are the same as those of Example 1.

[0073] Specifically, it includes: adding 600kg of toluene to a 2000L enameled reactor, turning on the stirring, adding 100kg of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), and then adding 116kg of N,N-dimethyl-1,3-diaminopropane. After the feeding is completed, turn on the steam heating, heat for 45 minutes, and the temperature rises to 100-105°C until the raw materials are completely dissolved. Adjust the steam valve to control the temperature of the reaction liquid at 110-112°C. After the temperature stabilizes, react for 24-36 hours. After the reaction is completed, reduce the stirring speed, and the solution is naturally cooled to 80°C. Then, use circulating water to quickly cool to room temperature, centrifuge to obtain a golden solid, and collect the mother liquor separately as the secondary reaction bottom liquid. Then, put the filter cake back into the reactor, and use 400L of pure water for pulping and washing. After filtering, use 280L of anhydrous ethanol for online washing. After drying, 144kg (dry basis) of product is obtained, and the yield is 88.34%. Actual photos are as follows Figure 3 and Figure 4 shown.

[0074] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A large-scale continuous production method of imide derivatives, characterized in that: The following steps are involved: 1) Under normal pressure, the precursor A and the raw material B are stirred and heated in a reaction base liquid to obtain a reaction liquid; Wherein, the precursor A is composed of an acid and an anhydride in any proportion; is composed of one or more acids and anhydrides in any proportion; The structural formula of raw material B is as follows: Among them, R1 is Any of the groups, n is 1 or 2; 2) Cooling the reaction solution to room temperature, filtering, and collecting the filter cake and filtrate; 3) washing and drying the filter cake to obtain the target imide derivative; and recycling the filtrate as the secondary reaction bottom liquid to step 1) to continue the reaction.

2. The large-scale continuous production method of imide derivatives according to claim 1, characterized in that: The structural formulas of the anhydride and acid constituting the precursor A are shown below:

3. The large-scale continuous production method of imide derivatives according to claim 1, characterized in that: In step 1), the reaction molar ratio of precursor A to raw material B is 1:2-10.

4. The large-scale continuous production method of imide derivatives according to claim 1, characterized in that: In step 1), the heating temperature is 110-130°C.

5. The large-scale continuous production method of imide derivatives according to claim 1, characterized in that: In step 1), the stirring and heating treatment time is 40-50 hours.

6. The large-scale continuous production method of imide derivatives according to claim 1, characterized in that: In step 1), the reaction base liquid is acetonitrile, N,N-dimethylformamide or toluene.

7. The large-scale continuous production method of imide derivatives according to claim 1, characterized in that: In step 1), the volume ratio of the reaction base liquid to the raw material B is 10-6:

1.

8. The large-scale continuous production method of imide derivatives according to claim 1, characterized in that: In step 3), the filter cake is washed with water and ethanol in sequence.

9. The large-scale continuous production method of imide derivatives according to claim 8, characterized in that: In step 3), the volume ratio of water to filter cake is 2-6:1, and the volume ratio of anhydrous ethanol to filter cake is 2-5:

1.

10. The large-scale continuous production method of imide derivatives according to any one of claims 1 to 9, characterized in that: In step 3), when the secondary reaction bottom liquid returns to step 1) to continue the reaction, the volume of the additionally added reaction solvent V = the volume of the initial reaction bottom liquid V1 - the volume of the secondary reaction bottom liquid V2.

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