CN109836358B

CN109836358B - Preparation method of guanylurea nitrate copper salt complex

Info

Publication number: CN109836358B
Application number: CN201810463528.0A
Authority: CN
Inventors: 雷晴; 何金选; 卢艳华; 叶丹阳; 任晓婷; 丁宁
Original assignee: Hubei Institute of Aerospace Chemical Technology
Current assignee: Hubei Institute of Aerospace Chemical Technology
Priority date: 2018-05-15
Filing date: 2018-05-15
Publication date: 2021-09-14
Anticipated expiration: 2038-05-15
Also published as: CN109836358A

Abstract

A preparation method of a guanylurea nitrate copper salt complex comprises the following steps of (by mass percent) dicyandiamide, solvent =10% -20%: preparing a solution by 90-80 percent, and heating the solution until the solution is transparent; putting copper nitrate with the dicyandiamide amount of 1.4-1.5 mass ratio into dicyandiamide solution at 50-70 ℃, and adding the copper nitrate within 30 min-1 h; after the feeding is finished, heating to 80-95 ℃, and continuing to react for 2-5 h; stopping the reaction, and cooling until a large amount of products are separated out; filtering, washing and drying at 30-80 ℃ to obtain the CuGUN product. Compared with the prior art, the method provided by the invention adopts excessive copper nitrate with crystal water as a reactant, and can be completely removed in the subsequent washing process.

Description

Preparation method of guanylurea nitrate copper salt complex

Technical Field

The invention relates to a synthetic method of a copper guanylurea nitrate complex (hereinafter referred to as CuGUN) suitable for industrial production and used for a gas generating agent.

Background

Guanidine Nitrate (GN), which is commonly used in the field of automobile safety airbag industry at present, has low price, no toxicity, high gas production and good thermal stability, but GN reduces the burning rate of the formula, forms a eutectic mixture with low melting point with some common components of the gas generating agent, and deteriorates the aging performance of the gas generating agent and the formula performance of the gas generating agent. Thus, there is a need for a new gas generant material that avoids the disadvantages of guanidine nitrate, increases the burn rate of the gas generant formulation, and avoids the formation of low melting eutectic mixtures. The guanylurea nitrate copper salt complex (CuGUN) can overcome the defects, has the characteristics of low sensitivity, good chemical stability, high gas production, low cost and the like, and can further improve the comprehensive performance of the gas generating agent formula. Guanidine Nitrate (GN)/Basic Copper Nitrate (BCN) was selected as a gas generant base component, the amount of CuGUN substituted for GN was increased gradually, and the tablets were pressed into cylindrical tablets having a diameter of 0.5 inch (12.7 mm) under a pressure of 12000 lbs. Burning speed and burning speed pressure index data are obtained through testing, and gas production and gas temperature data are obtained through calculation by adopting PEP (push-to-oil processor) software and are shown in Table 1.

TABLE 1 CuGUN-containing gas generant formulation performance

As can be seen from the above table, the burning rate increases gradually (up to 4 mm/s) with increasing amount of GN partially substituted by CuGUN, while the burning temperature decreases gradually (up to 245 ℃ C.) with increasing amount of GN partially substituted by CuGUN. The addition of CuGUN reduces the combustion temperature of the gas generating agent formula, and directly leads to nitrogen oxide NO in the generated gas product_xThe content is reduced. And the density of the gas generating agent formula is increased after the CuGUN part replaces GN, and although the mass gas production is reduced more, the volume gas production is changed little. In conclusion, CuGUN has the double effects of reducing the combustion temperature and improving the combustion speed, and is greatly superior to GN in the existing formula.

The CuGUN preparation method reported in world patent WO0240430A2 is prepared by reacting dicyandiamide and basic copper carbonate serving as raw materials in a suspension. In the method, excessive reactant basic copper carbonate is not easy to remove, so that the product purity is not high.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the preparation method of the guanylurea nitrate copper salt complex is suitable for industrial production, short in reaction period, free of three-waste discharge, high in product purity and low in cost.

The invention takes dicyandiamide and copper nitrate as reactants to prepare the guanylurea nitrate copper salt complex by one-step reaction, and the technical scheme comprises the following steps:

(1) dicyandiamide by mass percent: solvent =10% to 20%: preparing a solution by 90-80 percent, and heating the solution until the solution is transparent;

(2) putting the copper nitrate with the mass ratio of 1.4-1.5 to the dicyandiamide into a dicyandiamide solution at 50-70 ℃, and adding the copper nitrate in the dicyandiamide solution within 30 min-1 h;

(3) after the feeding is finished, heating to 80-95 ℃, and continuing to react for 2-5 h;

(4) after the reaction is finished, stirring and cooling are carried out at the same time until a large amount of products are separated out;

(5) filtering, washing and drying at 30-80 ℃ to obtain the guanylurea nitrate copper salt complex product.

The dicyandiamide in the step (1) is in an industrial grade, and the purity is 99.5%.

The solvent in the step (1) is one or the combination of water and industrial ethanol.

The heating temperature in the step (1) is 50-80 ℃.

The copper nitrate in the step (2) is industrial grade Cu (NO)₃)₂·2.5H₂O or Cu (NO)₃)₂·3H₂One or a combination of both of O.

The molar ratio of dicyandiamide to copper nitrate in the step (2) is 2: 1-2: 1.2.

and (4) cooling the temperature of the reaction kettle to 0-10 ℃.

And (5) after filtering, washing for 2-3 times by using water or industrial ethanol.

And (5) reserving the filtrate generated after filtering and washing in the step (5) for feeding next time to replace the solvent with the same amount.

The invention obtains the guanylurea nitrate copper salt (CuGUN) product by one-step reaction of the cheap dicyandiamide on the market and the copper nitrate with the crystal water, wherein the calculated yield of the dicyandiamide is higher than 88 percent, and the purity of the product is higher than 99 percent. The method has the advantages of high reaction yield, environmental protection, safety and strong operability, and is particularly suitable for large-scale production, and the actual measurement data of the CuGUN prepared by the method is listed in Table 2.

Detailed Description

Example 1

In a 100L double-layer reaction kettle, 5.5kg of dicyandiamide and 38L of water are prepared into a solution, the solution is heated to 70 ℃, and the solution is transparent. Adding 8.07kgCu (NO)₃)₂·3H₂And O, finishing the addition within 40 min. After the addition, the reaction mixture was heated to 95 ℃ and the reaction was continued for 3 hours. Stopping the reaction, cooling the reaction solution to 0 ℃, filtering, and vacuum drying at 80 ℃ to obtain 11.3kg of blue CuGUN product, wherein the yield (calculated by dicyandiamide) is 88.2%, and the purity is 99.5%.

Example 2

In a 500L double-layer reaction kettle, 30.0kg of dicyandiamide and 200L of ethanol are prepared into a solution, the solution is heated to 55 ℃, and the solution is transparent. Adding 40.00kgCu (NO)₃)₂·2.5H₂And O, finishing the addition within 50 min. After the addition, the reaction mixture was heated to 80 ℃ and the reaction was continued for 4 hours. Stopping the reaction, cooling the reaction solution to 8 ℃, filtering, and vacuum drying at 60 ℃ to obtain 62.9kg of blue CuGUN product, wherein the yield (calculated by dicyandiamide) is 90.0% and the purity is 99.7%.

Example 3

In a 500L double-layer reaction kettle, 29.0kg of dicyandiamide and 190L of water are prepared into a solution, the solution is heated to 50 ℃, and the solution is transparent. 40.20kgCu (NO) was added₃)₂·3H₂And O is added within 60 min. After the addition, the reaction mixture was heated to 85 ℃ and the reaction was continued for 5 hours. Stopping the reaction, cooling the reaction solution to 10 ℃, filtering, and vacuum-drying at 50 ℃ to obtain 60.2kg of blue CuGUN product, wherein the yield (calculated by dicyandiamide) is 89.2%, and the purity is 99.8%.

Example 4

In a 1000L double-layer reaction kettle, 60.0kg of dicyandiamide and 400L of ethanol are prepared into a solution, the solution is heated to 60 ℃, and the solution is transparent. 80.00kg of the additive is addedCu(NO₃)₂·2.5H₂And O, finishing the addition within 50 min. After the addition, the reaction mixture was heated to 70 ℃ and the reaction was continued for 5 hours. Stopping the reaction, cooling the reaction solution to 4 ℃, filtering, and vacuum-drying at 75 ℃ to obtain 127.3kg of blue CuGUN product, wherein the yield (calculated by dicyandiamide) is 90.8% and the purity is 99.4%.

Example 5

55.0kg of dicyandiamide and 390L of recovered filtrate are prepared into a solution in a 1000L double-layer reaction kettle, and the solution is heated to 65 ℃ and is transparent. 80.00kgCu (NO) was added₃)₂·3H₂And O, finishing the addition within 30 min. After the addition, the reaction mixture was heated to 90 ℃ and the reaction was continued for 2 hours. Stopping the reaction, cooling the reaction solution to 4 ℃, filtering, and vacuum-drying at 70 ℃ to obtain 117.5kg of blue CuGUN product, wherein the yield (calculated by dicyandiamide) is 91.7%, and the purity is 99.6%.

The measured performance data of CuGUN prepared according to the present invention is listed in table 2.

TABLE 2

Claims

1. A preparation method of a copper guanylurea nitrate salt complex is characterized by comprising the following steps:

(1) dicyandiamide by mass percent: solvent =10% to 20%: preparing a solution by 90-80 percent, and heating the solution until the solution is transparent; the solvent is one or the combination of water and industrial ethanol;

(2) putting copper nitrate with the mass ratio of 1.4-1.5 to the dicyandiamide into a dicyandiamide solution at 50-70 ℃, and finishing adding within 30 min-1 h; the copper nitrate in the step (2) is industrial grade Cu (NO)₃)₂·2.5H₂O or Cu (NO)₃)₂·3H₂One or a combination of both of O;

(5) filtering, washing and drying at 30-80 ℃ to obtain a blue guanylurea nitrate copper salt complex product.

2. The method for preparing a copper guanylurea nitrate salt complex according to claim 1, characterized in that: the dicyandiamide in the step (1) is in an industrial grade, and the purity is 99.5%.

3. The method for preparing a copper guanylurea nitrate salt complex according to claim 1, characterized in that: the heating temperature in the step (1) is 50-80 ℃.

4. The method for preparing a copper guanylurea nitrate salt complex according to claim 1, characterized in that: the molar ratio of dicyandiamide to copper nitrate in the step (2) is 2: 1-2: 1.2.

5. the method for preparing a copper guanylurea nitrate salt complex according to claim 1, characterized in that: and (4) cooling the temperature of the reaction kettle to 0-10 ℃.

6. The method for preparing a copper guanylurea nitrate salt complex according to claim 1, characterized in that: and (5) washing the product for 2-3 times by using water or industrial ethanol after filtering.

7. The method for preparing a copper guanylurea nitrate salt complex according to claim 1, characterized in that: and (5) reserving the filtrate generated after filtering and washing in the step (5) for feeding next time to replace the solvent with the same amount.