WO2023087570A1 - Gas generating agent composition, gas generating agent, preparation method, and use - Google Patents

Abstract

Embodiments of the present disclosure provide a gas generating agent composition, a gas generating agent, a preparation method, and a use, and relate to the technical field of automobile airbags. The gas generating agent composition comprises guanidine nitrate that acts as fuel, basic copper nitrate that acts as a main oxidant, and an auxiliary oxidant and slagging agent; the auxiliary oxidant is ammonium perchlorate, and the slagging agent is at least one zirconate; in mass percentage, the content of each component is: 40%-60% of guanidine nitrate; 25%-50% of basic copper nitrate; 0.5%-7% of ammonium perchlorate; and 1%-10% of the slagging agent; the oxygen balance of the gas generating agent composition is 0 to -3%. In the gas generating agent composition, the gas generating agent, the preparation method and the use, by adjusting the formula components and proportion of the gas generating agent, the content of toxic and harmful gases and suspended solids in the air that are generated during combustion meet the limit requirements of USCAR for the content of toxic and harmful gases and suspended solids in the air.

Description

A kind of gas generant composition, gas generant and its preparation method and application

Cross References to Related Applications

This disclosure claims the priority of the Chinese patent application with the application number "CN202111358289.0" and the title "a gas generating agent composition, gas generating agent, preparation method and application" submitted to the Chinese Patent Office on November 16, 2021 , the entire contents of which are incorporated by reference in this disclosure.

technical field

The present disclosure relates to the technical field of automobile airbags, in particular, to a gas generating agent composition, a gas generating agent, a preparation method and an application.

Background technique

With the rapid development of the automobile industry, the number of motor vehicles is increasing day by day, and the frequency of traffic accidents is becoming more and more frequent. As a protective device on automobiles, people pay more and more attention to airbags. The core component of the automobile airbag is the gas generator, and the core component of the gas generator is the gas generating agent, that is, the gas-producing medicine. The working principle of the airbag is that when the gas generator receives a pulsed electrical signal, the electric ignition tube inside the ignition system is excited to detonate, and the heat generated by the combustion of the primer inside the electric ignition tube will ignite the ignition powder. After the ignition powder burns, it will produce The gas medicine is ignited, and a large amount of gas generated by the combustion of the gas producing medicine will fill the air bag, so as to achieve the purpose of protecting passengers.

After the gas generating agent is burned, a large amount of gas will be produced, its main components are N ₂ , CO ₂ , H ₂ O, and it also contains toxic and harmful gases such as NO _x , Cl ₂ , HCl, CO, NH ₃ , and these toxic and harmful gases escape After all, there will be certain harm to the occupants in the car, and these toxic and harmful gases will also pollute the environment. Moreover, when the gas generating agent is burned, a large amount of suspended matter will be produced, and these suspended matters will also cause harm to the human body and pollute the environment after entering the air.

Among the internationally recognized standards, USCAR (United States Consortium for Automotive Research, United States Consortium for Automotive Research) has clear restrictions on the content of toxic and harmful gases and suspended solids: the CO content in the effluent must not exceed 461ppm, and the Cl ₂ content The content of HCl shall not exceed 5ppm, the content of NO shall not exceed 75ppm, the content of _NO2 shall not exceed 5ppm, the content of _NH3 shall not exceed 50ppm, and the content of suspended matter in the air shall not exceed 125mg/ ^m3 . AK-LV also has clear restrictions on the content of toxic and harmful gases: the CO content in the effluent shall not exceed 500ppm, the _Cl2 content shall not exceed 5ppm, the HCl content shall not exceed 25ppm, the NO content shall not exceed 50ppm, and the _NO2 content shall not exceed 10ppm. ₃ The content shall not exceed 150ppm.

At present, many gas generating agents adopt the GN/BCN formula system, that is, guanidine nitrate GN and basic copper nitrate BCN are used as the main components. Although many gas generants of GN/BCN formula systems can meet the gas production requirements, they cannot meet the limit requirements of USCAR and AK-LV for the content of toxic and harmful gases and the content of suspended solids in the air.

Contents of the invention

The present disclosure provides a gas generant composition, which includes guanidine nitrate as fuel, basic copper nitrate as main oxidant, and auxiliary oxidant and slagging agent, the auxiliary oxidizing agent is ammonium perchlorate, and the slagging agent is at least A kind of zirconate, by mass percentage, the content of each component is:

The oxygen balance of the gas generant composition is 0 to -3%.

In the above technical solution, the applicant found that strontium nitrate is often used as an auxiliary oxidant in the gas generating agent at present. After burning, it will not only produce nitrogen oxides, increase the release of toxic and harmful gases, but also produce strontium oxide, and oxidize Strontium is an extremely fine particle that adds weight to suspended matter in the air and does not meet USCAR standards.

The gas generating agent composition according to the embodiment of the present disclosure removes the auxiliary oxidizing agent commonly used in the prior art formula, such as strontium nitrate, by adjusting the selection of the auxiliary oxidizing agent, and only retains ammonium perchlorate as ammonium perchlorate, and adjusts the remaining components of the formula To adjust the overall oxygen balance to 0～-3%, so that the toxic and harmful gases (including NO _x , Cl ₂ , HCl, CO, NH ₃ etc.) content all meet the limit requirements of USCAR and AK-LV for toxic and harmful gas content.

In addition, on the basis of a certain oxygen balance, zirconate is used as the slagging agent in the formula, and zirconate is used as a shape retaining agent to effectively maintain the shape of the residue after it is applied to the detonation of the gas generator, ensuring that the shape of the residue remains relatively Complete; and by using ammonium perchlorate as an auxiliary oxidant, combined with basic copper nitrate as the main oxidant, the molten copper residue is reduced, thereby reducing the concentration of suspended solids in the air after the gas generating agent is burned, and meeting USCAR's requirements for suspended solids in the air limit requirements.

In a possible implementation, by mass percentage, the content of each component is:

In a possible implementation manner, the oxygen balance of the gas generant composition is 0-1.5%, optionally -0.03%--1%.

In the above-mentioned technical scheme, the applicant found that when the gas generating agent formed by different formulations of the gas generating agent composition burns, as the oxygen balance of the gas generating agent composition formulation decreases, the CO, NO, NH _and The content of HCl showed an increasing trend, while the content of _NO2 and _Cl2 showed a downward trend; while when the oxygen balance of the gas generant composition formulation was increased, the opposite trend was shown, that is, the content of CO, NO, _NH3 and HCl showed a downward trend, while the contents of NO ₂ and Cl ₂ showed an upward trend. Therefore, if the oxygen balance of the gas generating agent composition formulation is too high or too low, the content of at least a part of the toxic and harmful gases generated when the gas generating agent is burned exceeds the limit content specified in USCAR, and thus does not meet the requirements of the standard USCAR. Thereby harming the user's body and polluting the environment.

After a lot of research, the applicant found that when the oxygen balance of the gas generating agent composition formulation is 0-3%, the toxic and harmful gases (including NO _x , Cl ₂ , HCl, CO , NH ₃ , etc.) all meet the standard USCAR and AK-LV limit requirements for toxic and harmful gas content. In order to achieve the above-mentioned oxygen balance, the formulation of the gas generating agent composition needs to be adjusted.

In a possible implementation manner, the slagging agent is barium zirconate, and the content ratio of barium zirconate to ammonium perchlorate is (1-3):1, optionally (1.5-2.5):1.

In the above technical solution, a certain content of barium pickate can not only be used as a slagging agent, but also can be used as a pressure sensitivity regulator to ensure that the pressure index of the linear combustion rate of the gas generating agent during combustion is lower than 0.3, making the combustion more stable.

In a possible implementation manner, the particle size D90 of the basic copper nitrate is not greater than 5 μm, and the specific surface area is 1.0-8.0 m ² /g, optionally 2.0-6.0 m ² /g.

The present disclosure provides a gas generating agent, which includes the gas generating agent composition provided in the first aspect, and a lubricant, and the content of the lubricant is 0.05%-5% of the total amount of the gas generating agent composition.

In the above technical solution, the lubricant in the gas generating agent facilitates uniform mixing and demoulding of the gas generating agent composition, thereby forming gas generating agents with different shapes. The gas generating agent has a specific oxygen balance, so that the toxic and harmful gas components such as _NOx , Cl ₂ , HCl, CO, NH ₃ produced by combustion meet the requirements of USCAR and AK-LV; it can also effectively maintain the morphology of the residue after detonation, Thereby reducing the concentration of suspended matter in the air after the gas generating agent is burned.

In a possible implementation manner, the gas generating agent composition is composed of guanidine nitrate, basic copper nitrate, ammonium perchlorate, and barium zirconate, and the gas generating agent is composed of the gas generating agent composition and a lubricant.

In the above technical solution, the composition of the gas generating agent is simple, which can meet the requirements of use, and can also ensure that the content of toxic and harmful gases generated during combustion and the content of suspended solids in the air meet the requirements of USCAR on the content of toxic and harmful gases and suspended solids in the air. Content limit requirements.

In a possible implementation, the lubricant is at least one of talcum powder, graphite, calcium stearate, magnesium stearate, molybdenum disulfide and boron nitride; optionally, the lubricant is stearic acid calcium.

In the above technical solution, calcium stearate can improve the moisture absorption resistance of the gas generating agent.

The present disclosure provides a method for preparing the gas generating agent provided by the second aspect, which mainly comprises uniformly mixing all raw materials and molding them.

The present disclosure provides an application of the gas generating agent provided in the second aspect, and the gas generating agent is used as a gas generating agent for an automobile airbag.

Description of drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the accompanying drawings that are used in the embodiments of the present disclosure will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present disclosure, so It should not be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings according to these drawings without creative work.

Fig. 1 is the residue form diagram after the combustion of the gas generating agent in Comparative Example 5;

FIG. 2 is a diagram showing the morphology of the residue after the combustion of the gas generating agent in Example 1. FIG.

Detailed ways

In order to make the objectives, technical solutions and advantages of the embodiments and examples of the present disclosure clearer, the technical solutions in the embodiments and examples of the present disclosure will be clearly and completely described below. Where specific conditions are not indicated in the implementation modes and examples, proceed according to conventional conditions or conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

The gas generant compositions, gas generants, preparation methods and applications of the embodiments and examples of the present disclosure will be described in detail below.

The purpose of the embodiments and examples of the present disclosure is to provide a gas generating agent composition, a gas generating agent and its preparation method and application. By adjusting the formula components and proportions of the gas generating agent, the toxic and harmful gases generated during combustion The content of toxic and harmful gases and the content of suspended solids in the air meet the limit requirements of USCAR and AK-LV for the content of toxic and harmful gases and the content of suspended solids in the air.

The embodiment of the present disclosure provides a gas generant composition, which adopts the GN/BCN formula system, including fuel, oxidant and slagging agent, the oxidant is divided into main oxidant and auxiliary oxidant, the fuel is guanidine nitrate GN, the main oxidant It is basic copper nitrate BCN, the auxiliary oxidant is ammonium perchlorate AP, and the slagging agent is at least one zirconate.

The content of the above-mentioned components in terms of mass percentage is: 40%-60% of guanidine nitrate; 25%-50% of basic copper nitrate; 0.5%-7% of ammonium perchlorate; 1%-10% of zirconate. Optionally, the contents of the above components are: 50%-55% of guanidine nitrate; 38%-45% of basic copper nitrate; 1%-5% of ammonium perchlorate; 2%-6% of zirconate.

In the above gas generant composition, the mass percentage of guanidine nitrate can be but not limited to 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50% %, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60%.

In the above gas generant composition, the mass percentage of basic copper nitrate can be but not limited to 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% , 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%.

In the above gas generant composition, the mass percentage of ammonium perchlorate can be, but not limited to, 1%, 2%, 3%, 4%, 5%, 6% or 7%.

In the above gas generant composition, the mass percentage of zirconate may be, but not limited to, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10%.

Each component of the gas generant composition according to the embodiment of the present disclosure needs to be within the above content range, and the oxygen balance OB is 0-3%, optionally, the oxygen balance is 0-1.5%. In some typical embodiments, the oxygen balance is optionally between -0.03% and -1%. In the above gas generant composition, the oxygen balance of the gas generant composition can be, but not limited to, 0, -0.03%, -0.1%, -0.2%, -0.5%, -0.7%, -0.9%, -1 %, -1.5% or -3%.

It should be noted that in explosives, oxygen balance refers to the amount of excess or insufficient oxygen per gram of explosives after the oxygen in explosives is used to completely oxidize combustible elements, expressed by OB. Oxygen balance is the difference between the actual oxygen content of 1g gas generating agent composition and the quality of oxygen produced by complete combustion. The sum of the products expressed in percent %) is calculated.

In the embodiment of the present disclosure, the zirconate may be one or a combination of strontium zirconate, barium zirconate or calcium zirconate; as an embodiment, the slagging agent is barium zirconate, and barium zirconate and perchlorate The content ratio of ammonium acid is (1-3):1, and may be (1.5-2.5):1.

In the embodiment of the present disclosure, the particle size D90 of the basic copper nitrate raw material is not greater than 5 μm, and the specific surface area is 1.0 to 8.0 m ² /g, optionally 2.0 to 6.0 m ² /g; the particle size D90 of ammonium perchlorate is not Greater than 20 μm; the particle size D90 of zirconate is not greater than 5 μm.

In addition, an embodiment of the present disclosure provides a gas generating agent, which includes the above-mentioned gas generating agent composition and a lubricant, and the content of the lubricant is 0.05% to 5% of the total amount of the gas generating agent composition. The sum of water content of each component of the gas generating agent is not more than 1% of the total mass of each component. In the above-mentioned gas generating agent, the mass percentage of the lubricant may be, but not limited to, 0.05%, 0.5%, 1%, 2%, 3%, 4% and 5%. As an embodiment, the content of the above-mentioned gas generating agent in terms of mass percentage is: 40% to 60% of guanidine nitrate; 25% to 50% of basic copper nitrate; 0.5% to 7% of ammonium perchlorate; 1% of zirconate %~10%; lubricant 0.05%~5%.

In the above gas generating agent, the lubricant is at least one of talcum powder, graphite, calcium stearate, magnesium stearate, molybdenum disulfide and boron nitride. As an embodiment, the lubricant is calcium stearate.

It should be noted that the oxygen balance of the gas generating agent composition can be regarded as the oxygen balance of the gas generating agent because the content of the lubricant is small and has almost no influence on the oxygen balance.

As an embodiment, the gas generating agent is composed of a gas generating agent composition and a lubricant, the gas generating agent composition is composed of guanidine nitrate, basic copper nitrate, ammonium perchlorate, and zirconate, and the gas generating agent is composed of guanidine nitrate , basic copper nitrate, ammonium perchlorate, barium zirconate and calcium stearate. It should be noted that the composition of the gas generating agent refers to the composition of the active ingredient, and does not limit the impurities and moisture that are inevitably introduced.

It should be noted that the gas generating agent refers to a product that can be directly applied in the gas generator of the automobile airbag, and usually has a certain shape. For example, the gas generating agent is a round or oval sheet structure, a round or oval columnar structure, a special-shaped sheet or columnar structure, a round or oval single-hole structure, a round or oval porous structure, a special-shaped single or porous structure.

In actual use, the diameter of the circular flake-shaped gas generating agent is generally 3-15 mm, and the height is generally 2-5 mm; the diameter of the circular columnar structure gas generating agent is generally 3-15 mm, and the height is generally 5-5 mm. 15mm; the inner diameter of the gas generating agent with circular single-hole structure is generally 0.5-2.5mm, the outer diameter is generally 3-15mm, and the height is generally 3-15mm; the inner diameter of the gas generating agent with oval single-hole structure is generally 0.5-2.5mm 2.5mm, the long diameter is generally 3-20mm, the short diameter is generally 2-12mm, and the height is generally 3-15mm.

In addition, the embodiments of the present disclosure provide a method for preparing the above-mentioned gas generating agent, which mainly comprises uniformly mixing various raw materials and molding them.

In the embodiment of the present disclosure, the gas generant can be prepared by wet granulation, spray granulation or dry granulation. For the preparation of wet granulation with simple process and easy implementation, the lubricant (release agent) can be mixed together with the components of the gas generating agent composition before wet granulation, or the gas generating agent can be mixed first The components of the composition are mixed and subjected to wet granulation, and the lubricant is finally added, and the preparation method is flexible.

As an embodiment, the specific preparation method of the gas generating agent includes the following steps:

(1) Mix guanidine nitrate, basic copper nitrate, ammonium perchlorate and zirconate in a mixing equipment. The mixing equipment can be a pneumatic mixer, a V-type mixer, a three-dimensional multi-directional motion mixer, an automatic lifting Hopper mixer, vibrating mill, ribbon mixer or acoustic resonance mixer, mixing time ≥ 5min to obtain the first material.

(2), add distilled water to the first material and carry out wet mixing, the equipment for wet mixing is a kneader or a mixer, for example, a horizontal kneader, a vertical kneader, a ribbon mixer or an acoustic resonance mixer can be selected, The amount of water added is 5% to 15% of the total mass of the first material, and the wet mixing time is 20 minutes to 60 minutes to obtain the second material.

(3) passing the second material through a 10-40 mesh screen to obtain a third material.

(4), the third material is dried, and the drying equipment can be an electric heating oven, an oil bath oven, a steam oven, a double cone oven, a vibrating fluidized bed or a belt vacuum dryer, and it is dried until the water content is less than the first 0.5% of the total mass of the third material is passed through a 10-40 mesh screen again to obtain the fourth material.

(5) Add a lubricant to the fourth material to form the material. The forming equipment can be an oil press, a rotary tablet press or a powder forming machine to obtain a gas generating agent.

As another embodiment, the specific preparation method of the gas generating agent includes the following steps:

(1) Mix guanidine nitrate, basic copper nitrate, ammonium perchlorate, zirconate and lubricant in a mixing equipment. The mixing equipment can be a V-type mixer, a three-dimensional multi-directional motion mixer, or an automatic lifting hopper Mixer, vibration mill, ribbon mixer or acoustic resonance mixer, mixing time ≥ 5min, to obtain the first material.

(2), add distilled water to the first material and carry out wet mixing, the equipment for wet mixing is a kneader or a mixer, for example, a horizontal kneader, a vertical kneader, a ribbon mixer or an acoustic resonance mixer can be selected, The amount of water added is 5% to 15% of the total mass of the first material, and the wet mixing time is 20 minutes to 60 minutes to obtain the second material.

(3) passing the second material through a 10-40 mesh screen to obtain a third material.

(4), the third material is dried, and the drying equipment can be an electric heating oven, an oil bath oven, a steam oven, a double cone oven, a vibrating fluidized bed or a belt vacuum dryer, and it is dried until the water content is less than the first 0.5% of the total mass of the third material is passed through a 10-40 mesh screen again to obtain the fourth material.

(5) The fourth material is subjected to material molding, and the molding equipment can be a hydraulic press, a rotary tablet press or a powder molding machine to obtain a gas generating agent.

The embodiment of the present disclosure provides an application of the above-mentioned gas generating agent. The gas generating agent is used as a gas generating drug for an automobile airbag, usually as a part of a gas generator, such as a DAB generator (CN111071200B), PAB generator gas generator (CN111071201A), CAB generator or SAB generator.

Correspondingly, the embodiment of the present disclosure also provides a gas generator, which has the above-mentioned gas generating agent.

As an embodiment, the embodiment of the present disclosure provides a gas generator (CN111071200B), which includes a shell formed by combining an upper shell and a lower shell, the upper shell is provided with an exhaust hole, and the inner cavity of the shell is an accommodating cavity; An ignition device chamber and a combustion chamber that surrounds the ignition device chamber and is filled with a gas generating agent are arranged in the accommodating chamber; the combustion chamber includes a combustion chamber cover and an annular filter arranged to face the lower housing; the annular filter is directly or indirectly supported Combustion chamber cover; when working, the combustion chamber cover is pushed by the impact generated by the gas generant in the combustion chamber and is directly or indirectly limited by the annular filter to stop the movement, thereby closing the opening between the combustion chamber cover and the annular filter.

The features and properties of the present disclosure will be described in detail below in conjunction with the examples.

Test group one

Example 1

This embodiment provides a gas generating agent, which is a disc with a diameter of 5 mm and a thickness of 1.9 mm, and is composed of a gas generating agent composition and a lubricant. The gas generating agent composition is composed of 54% guanidine nitrate, basic nitric acid Composed of 38% copper, 2% ammonium perchlorate and 6% barium zirconate, the oxygen balance of the gas generating agent composition is -0.96%; the lubricant is calcium stearate, and the consumption is 1% of the total amount of the gas generating agent composition %.

The preparation process of the gas generating agent is:

Mix guanidine nitrate, basic copper nitrate, ammonium perchlorate and barium zirconate through mixing equipment to obtain the first material; add 15% distilled water to the first material and carry out wet kneading for 60 minutes to obtain the second material; The material passes through a 40-mesh screen to obtain a third material; the third material is dried until the water content is less than 0.5% of the total mass of the third material, and the fourth material is obtained through a 40-mesh screen; the fourth material is Calcium stearate is added, and the material is shaped by a rotary tablet press to obtain a gas generating agent.

Comparative example 1-4

Each comparative example provides a gas generating agent whose preparation method is basically the same as in Example 1, except that the formulation of the gas generating agent composition is different, and the gas generating agent combinations of Example 1 and Comparative Examples 1-4 The formulations of the ingredients are shown in Table 1.

The formula of the gas generant composition of table 1 embodiment 1 and comparative examples 1-4

Combustion experiment: put the gas generant into the PAB generator used for the test, conduct the ignition combustion test, and use the Fourier transform infrared gas analyzer to measure the composition and content of the gas generated after combustion, and compare it with the relevant data in USCAR .

It should be noted that due to the difference in combustion, the USCAR limit corresponding to the combustion experiment of the gas generating agent loaded into the PAB generator is 2/3 of the general USCAR limit (recorded in the background technology). That is to say, if the gas generating agent meets the corresponding USCAR limit requirements in the combustion test, it means that it meets the general USCAR limit requirements.

The gas component content (unit: ppm) result of the combustion experiment of the gas generant of embodiment 1 and comparative example 1-4 is as shown in table 2:

The gas component content after the combustion of the gas generant of table 2 embodiment 1 and comparative examples 1-4

It can be seen from the data in Table 1 and Table 2 that the content of each component of the gas generant composition is within the range defined in the examples of the present disclosure, which does not mean that the oxygen balance of the gas generant composition can be maintained in the implementation of the present disclosure. Therefore, it is necessary to adjust the oxygen balance according to the content of each component of the gas generating agent composition, and at the same time adjust the content of each component of the gas generating agent composition according to the oxygen balance, in order to meet the content requirements of each component and the composition Oxygen balance requirements.

Moreover, as the oxygen balance of the gas generant composition decreases, the contents of CO, NO, NH ₃ and HCl show an upward trend; the contents of NO ₂ and Cl ₂ show a downward trend. Among them, reducing the content of chlorine-containing material components in the formula can effectively reduce the content of Cl ₂ in the exhaust gas. Compared with the formula of the existing embodiment 1, the content of Cl ₂ is reduced by up to about 84%. Comprehensively reducing the formula oxygen balance and the content of chlorine-containing material components can effectively reduce the content of NO _x and Cl ₂ .

The results show that only Example 1 can meet the USCAR's "Standards for Toxic and Harmful Gases in Exhaust after Detonation of Safety Airbags".

Test group two

Comparative example 5

This comparative example provides a gas generating agent whose preparation method is basically the same as that of Example 1, except that strontium titanate is used instead of barium zirconate as the slagging agent in this comparative example.

After the combustion experiment, the morphology of the residue after detonation in Comparative Example 5 is shown in FIG. 1 , and the morphology of the residue after detonation in Example 1 is shown in FIG. 2 . As shown in Figure 1 and Figure 2, compared with Comparative Example 5, the gas generating agent of Example 1 is in the form of a sheet of the original drug after high-temperature combustion, which has a significant coagulation effect, and the residue is close to the inner wall of the filter screen. Larger, the tablet retains its original shape very well, and has a harder strength and higher density to support it to maintain its original shape.

The concentration of suspended solids in the air after the combustion of the gas generating agent of Example 1 and Comparative Example 5, the results are shown in Table 3:

Total suspended particles in the air after the combustion of the gas generating agent of Table 3 Example 1 and Comparative Example 5

It can be seen that Embodiment 1 can meet the requirements of USCAR for suspended solids in the air.

Test group three

Example 2

This embodiment provides a gas generating agent, which is basically the same as the preparation method in Example 1, except that the mass percentage of the gas generating agent composition in this embodiment consists of: guanidine nitrate 52%; basic copper nitrate 42%; ammonium perchlorate 2%; barium zirconate 4%, the oxygen balance of the gas generant composition formulation is -0.353%.

Example 3

This embodiment provides a gas generating agent, which is basically the same as the preparation method in Example 1, except that the mass percentage of the gas generating agent composition in this embodiment consists of: guanidine nitrate 52%; basic copper nitrate 41%; ammonium perchlorate 2%; barium zirconate 5%, the oxygen balance of the gas generant composition formulation is -0.653%.

Example 4

This embodiment provides a gas generating agent, which is basically the same as the preparation method in Example 1, except that the mass percentage of the gas generating agent composition in this embodiment consists of: guanidine nitrate 52.0%; basic copper nitrate 42.2%; ammonium perchlorate 2.8%; barium zirconate 3%, the oxygen balance of the gas generant composition formulation is -0.02%.

Example 5

This embodiment provides a gas generating agent, which is basically the same as the preparation method in Example 1, except that the mass percentage of the gas generating agent composition in this embodiment consists of: guanidine nitrate 53.8%; basic copper nitrate 39.8%; ammonium perchlorate 2.4%; barium zirconate 4%, the oxygen balance of the gas generant composition formulation is -1.35%.

Comparative example 6

This comparative example provides a gas generating agent whose preparation method is basically the same as that of Example 1, except that: the gas generating agent composition in this comparative example consists of 51.0% by mass of guanidine nitrate; basic nitric acid 41.5% of copper; 2.5% of strontium nitrate; 2% of ammonium perchlorate; 3% of strontium titanate, the oxygen balance of the gas generating agent composition formula is 0.704%; the lubricant is talcum powder.

Comparative example 7

This comparative example provides a gas generating agent, which is basically the same as the preparation method of Example 1, except that the gas generating agent composition in this comparative example consists of 52.1% by mass of guanidine nitrate; basic nitric acid Copper 39.9%; strontium nitrate 2%; ammonium perchlorate 2%; barium zirconate 4%, the oxygen balance of the gas generant composition formulation is -0.253%.

Combustion experiment: put the gas generating agent into the DAB generator used for the test, conduct the ignition combustion test, and use the Fourier transform infrared gas analyzer to measure the composition and content of the gas generated after combustion, and compare it with the relevant data in USCAR .

It should be noted that due to the difference in combustion, the USCAR limit corresponding to the combustion experiment of the gas generating agent loaded into the DAB generator is 1/4 of the general USCAR limit (recorded in the background technology). That is to say, if the gas generating agent meets the corresponding USCAR limit requirements in the combustion test, it means that it meets the general USCAR limit requirements.

The gas component content result of the combustion experiment of embodiment 2-3 and comparative example 6-7 is as shown in table 4:

The gas component content (unit: ppm) of table 4 embodiment 2-3 and comparative example 6-7

Total suspended particles in the air after the combustion of the gas generating agent of Table 5 embodiment 2-3 and comparative example 6-7

From the above experimental results, it can be seen that although the content of some gases after combustion in Comparative Example 6 containing strontium nitrate is low (such as CO and NH ₃ ), the content of nitrides rises sharply, much higher than that of USCAR However, the content of each toxic and harmful gas generated by the gas generating agent composition of Example 2-3 after combustion is far lower than the limit content given in USCAR, which meets the USCAR standard.

In addition, although the content of harmful gas components in Example 4 and Example 5 can meet the USCAR standard, their content of harmful gas components is still higher than that of Examples 2-3. It can be inferred that the gas generant The oxygen balance of the composition is not as high as possible, nor as low as possible. It needs to be controlled within a certain range. For example, the oxygen balance is -0.03% to -1%, and the corresponding combustion produces relatively less harmful gases.

In addition, the applicant also found that by conducting experiments on different slagging agents, when the other components and contents of the formula remain unchanged, the appearance of the residue after the detonation of the generator is different, and the amount of suspended matter in the air after the gas generating agent is burned Concentrations are also different. In comparison, using barium zirconate as the slagging agent to form the gas generant residue morphology is better maintained, and the concentration of suspended matter in the air is lower.

Therefore, screening the slagging agent to determine the most suitable slagging agent can keep the residue morphology of the prepared gas generant composition relatively complete after combustion; and the concentration of suspended solids in the air generated is lower than that given in USCAR. The limit concentration meets the USCAR standard.

To sum up, the gas generating agent composition, gas generating agent, preparation method and application of the embodiments of the present disclosure, by adjusting the formula components and proportions of the gas generating agent, the content of toxic and harmful gases generated during combustion and the air The content of suspended solids in the air meets the limit requirements of USCAR for the content of toxic and harmful gases and the content of suspended solids in the air.

The above descriptions are only examples of the present disclosure, and are not intended to limit the protection scope of the present disclosure. For those skilled in the art, the present disclosure may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present disclosure shall be included within the protection scope of the present disclosure.

Claims (10)

1. A gas generant composition is characterized in that it includes guanidine nitrate as fuel, basic copper nitrate as main oxidant, and auxiliary oxidant and slagging agent, the auxiliary oxidant is ammonium perchlorate, and the composition The slag agent is at least one zirconate, and the content of each component is:

   

   The oxygen balance of the gas generant composition is 0-3%.
2. The gas generant composition according to claim 1, wherein, by mass percentage, the content of each component is:

   
3. The gas generant composition according to claim 1, wherein the oxygen balance of the gas generant composition is 0-1.5%, optionally -0.03%--1%.
4. The gas generant composition according to claim 1, wherein the slagging agent is barium zirconate, and the content ratio of the barium zirconate to the ammonium perchlorate is (1-3): 1, optional (1.5～2.5):1.
5. The gas generant composition according to claim 1, characterized in that the particle size D90 of the basic copper nitrate is not greater than 5 μm, and the specific surface area is 1.0-8.0 m ² /g, optionally 2.0-6.0 m ² /g.
6. A gas generating agent, characterized in that it comprises the gas generating agent composition as claimed in any one of claims 1 to 4, and a lubricant, the content of the lubricant being the total amount of the gas generating agent composition 0.05% to 5% of the amount.
7. The gas generating agent according to claim 6, wherein the gas generating agent composition is composed of guanidine nitrate, basic copper nitrate, ammonium perchlorate, and barium zirconate, and the gas generating agent is composed of the gas A generator composition and the lubricant composition.
8. The gas generating agent according to claim 6, wherein the lubricant is at least one of talcum powder, graphite, calcium stearate, magnesium stearate, molybdenum disulfide and boron nitride; optional Preferably, the lubricant is calcium stearate.
9. A preparation method of a gas generating agent as claimed in claim 6, characterized in that it mainly comprises uniformly mixing the raw materials and molding them.
10. An application of the gas generating agent as claimed in claim 6, characterized in that, the gas generating agent is used as a gas generating drug for an automobile safety air bag.

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