WO2020133956A1 - Porous gas-generating agent molded product and preparation process therefor - Google Patents

Abstract

The present invention relates to a porous gas-generating agent molded product and a preparation process therefor. The porous gas-generating agent molded product is a columnar body having a plurality of holes arranged in the height direction therein. The ratio of the height to the largest dimension of the cross-section of the columnar body is in a range of 0.3 to 1.8, and the ratio of the total area of the cross-section of a plurality of holes of the columnar body to the total area of the cross-section of the columnar body is in a range of 0.03 to 0.15. The combustion process of the compressed porous gas-generating agent can realize equal-area combustion or progressive combustion, or multiple stages of combustion in different conditions, and can adjust the P-t performance of a gas generator according to requirements, thereby reducing material costs of the gas generator and the quality of the generator. The compressed porous gas-generating agent is mainly used for gas generators for automobile airbag. The present invention uses a compression molding process, and for the first time realizes the use of compression molding to prepare a small porous gas-generating agent, making the preparation process simple, efficient, and easy to operate and control.

Description

Moulded product of porous gas generating agent and preparation process thereof

This application requires the priority of the Chinese patent application filed on December 29, 2018 in the Chinese Patent Office, with the application number 201811633581.7 and the invention titled "a porous gas-generating agent molded product and its preparation process", the entire content of which is cited by reference Incorporated in this application.

Technical field

The invention relates to a porous gas generating agent molded product and a preparation process thereof, in particular to a small porous gas generating agent molded product prepared by a compression molding process, and belongs to the technical field of airbag gas generators.

Background technique

The automobile airbag system is composed of a gas generator that generates gas, an airbag for protection, and an exterior trim supporting the above two parts. The gas generator contains a gas generating agent, which is excited when needed, and the gas generating agent burns to generate a large amount of gas, and the airbag is filled to protect personal safety.

At present, the mainstream gas generating agents worldwide are guanidine nitrate and basic copper nitrate gas generating agents, guanidine nitrate is the main fuel, and basic copper nitrate is the main oxidant. The shape of the tablets of this type of gas-generating agent is usually in the form of ordinary discs. The general combustion process is surface-reduction combustion. The gas production in the first half of the combustion is large, which causes great damage to the airbag, easily damages the airbag, and cannot form effective protection. Fast, too fierce, coupled with the damage to the exterior, these are easy to cause harm to the human body, and the high pressure strength of the filter and the shell of the generator requires higher generator cost; in addition, the second half of the combustion, The burning area is reduced sharply, the gas production efficiency is reduced, the airbag maintains the function for a short time, it can not protect the personnel when the side impact or the personnel is in the non-positive position, and may not be completely burned, which promotes the increase of the amount of residue and increases the generator Filter cost.

Therefore, it is necessary to improve the drug form of the guanidine nitrate and basic copper nitrate formula gas-generating agents, and adding porous is one of the ways. The principle lies in that, due to the existence of porosity, the tablet burning process will be improved to surface-enhancing or iso-surface burning, or to achieve multiple stages of combustion under different conditions, improve the burning time period, and overcome the above defects.

At present, solid tablets are generally used as gas generating agents in the airbag gas generating agent industry. For the molding method of small porous medicament, there is currently only extrusion molding, and there is currently no compression molding. The extrusion molding method requires the use of a special binder, which has certain restrictions on the formulation, and the extrusion process is complicated and costly; the compression molding method can only compress large tablets, and the small porous tablets cannot be compressed at present, large porous or porous The inner diameter and outer diameter of the tablets are large, and there are special requirements for the structure of the generator. They are generally used for tubular generators. For the cake generator, only small porous or porous tablets can be used.

For example, the patent CN2786115Y discloses a molded product of a gas-generating composition, including its preparation process. The pellet has a hole in it, and the tablet has a groove to increase the initial ignition surface and improve the ignition efficiency and reliability, but the patent The use of hydraulic presses to press pharmaceutical tablets has low output efficiency, high requirements for molds, increased mold manufacturing costs, and large grain size, which makes it difficult to adjust the amount of drugs in the generator.

For another example, the patent CN1173901C discloses a gas generating agent for an airbag, which uses porous control of tablet burning time and adopts a formula with low burning rate, which can also meet the performance requirements of the generator. The burning linear velocity is lower than that of conventional medicines, which improves the burning performance of tablets by changing the medicine type. However, its pharmaceutical process adopts the method of extruding and cutting, which has higher requirements on the fluidity of pharmaceuticals and the cost of the extruding process increases.

For another example, the patent CN1220650A discloses a gas generating agent for an airbag. The gas generating composition has low toxicity or low risk, is easy to use, has excellent combustion efficiency and gas generating efficiency, and reduces the amount of residues and energy generated during combustion. It is produced safely and has good molding strength under molding conditions. However, the agent contains an ammonium nitrate formula and uses an extrusion molding process. Due to the extremely high hygroscopicity of the ammonium nitrate formula, it leaves a hidden danger to the safety of the generator.

Summary of the invention

The purpose of the present invention is to overcome the shortcomings of the prior art, and to provide a porous gas generating agent with a small size, the combustion process can realize surface-increasing or iso-surface combustion, or realize multiple stages of combustion in different conditions to improve The Pt performance of the generator reduces the material cost of the gas generator.

Another object of the present invention is to provide a process for preparing a porous gas generating agent. The process uses a guanidine nitrate and basic copper nitrate formulation to obtain particles by wet granulation, and obtains a small porous gas generating agent by compression molding. The process is simple and flexible, and the production cost is low.

Still another object of the present invention is to provide a pressing mold for use in the manufacturing process of porous gas generating agent molded products. The mold has a simple structure and flexible application, and is suitable for the preparation of molded products of porous gas generating agents of various shapes.

Yet another object of the present invention is to provide applications of porous gas generating agents.

The above objects of the present invention are mainly achieved by the following technical solutions:

A porous gas-generating agent molded product, which is a columnar body with a plurality of holes inside in the height direction, wherein the ratio of the height of the columnar body to the maximum size of the cross-section is 0.3 to 1.8; the columnar body is porous The ratio of the total cross-sectional area to the total cross-sectional area of the columnar body ranges from 0.03 to 0.15.

According to the molded article of the porous gas generating agent of the present invention, the pores are randomly distributed inside the columnar body, preferably uniformly or symmetrically.

According to the porous gas-generating agent molded product of the present invention, the maximum cross-sectional size of the columnar body is in the range of 2.0 to 20 mm, the height of the columnar body is in the range of 2.0 to 20 mm, and the maximum cross-sectional size of the hole is 0.5 to 5 mm Within range.

According to the porous gas generating agent molded product of the present invention, the maximum cross-sectional size of the columnar body is in the range of 3-15 mm, the height is in the range of 2.0-10 mm, and the maximum cross-sectional size of the hole is in the range of 0.8-4 mm.

In some preferred embodiments of the present invention, the maximum size of the cross section of the columnar body is in the range of 5-15 mm, the height is in the range of 2.0-10 mm, and the maximum size of the hole cross-section is in the range of 0.8-4 mm.

In some further preferred embodiments of the present invention, the largest dimension of the cross section of the columnar body is in the range of 5-12 mm, the height is in the range of 2.0-8 mm, and the largest dimension of the cross section of the hole is in the range of 0.8-3 mm.

In some further preferred embodiments of the present invention, the maximum dimension of the cross-section of the columnar body is in the range of 8-10 mm, the height is in the range of 3.0-7.5 mm, and the maximum dimension of the cross-section of the hole is in the range of 0.8-2 mm Inside.

According to the porous gas generating agent molded product of the present invention, the cross-section of the columnar body is selected from a circle, an equilateral triangle with rounded corners, a rounded quadrilateral, a clover shape, a four-leaf clover shape, or is composed of a straight line, a curve or an arc Any one of the closed shapes, as shown in Figure 1.

The above porous gas generating agent molded product, the cross-sectional shape of the columnar body is shown in FIG. 2a, which includes a first arc, a second arc, a third arc, a fourth arc, a fifth arc and The sixth arc is a closed shape formed by connecting end to end in a clockwise direction, wherein the second arc is tangent to the first arc and the third arc respectively, and the fourth arc is connected to the third arc The fifth arc is tangent respectively, the sixth arc is tangent to the first arc and the fifth arc respectively; the first arc, the third arc and the fifth arc of the cross section of the cylindrical body The arcs are concentric with the corresponding holes; the opening directions of the first arc, the third arc, and the fifth arc are toward the inside of the closed shape, the center line of the arc is an equilateral triangle, and the radius is R1, the range of R1 1～10mm; the opening direction of the second arc, the fourth arc and the sixth arc is outward of the closed shape, the center line of the circle is an equilateral triangle, and the radius is R2, of which the second arc, the fourth The arc and the sixth arc may be straight lines.

The above porous gas generating agent molded product, the cross-sectional shape of the columnar body is shown in FIG. 2b, which includes a first arc, a second arc, a third arc, a fourth arc, a fifth arc, A sixth circular arc, a seventh circular arc, and an eighth circular arc in a clockwise direction, a closed shape formed by connecting end to end, wherein the second circular arc is tangent to the first circular arc and the third circular arc, respectively, The fourth arc is tangent to the third arc and the fifth arc, the sixth arc is tangent to the fifth arc and the seventh arc, the eighth arc is equal to the first arc The seventh circular arcs are tangent; the first circular arc, the third circular arc, the fifth circular arc, and the seventh circular arc of the cross section of the columnar body are concentric with the corresponding holes respectively; the first circular arc , The opening directions of the third arc, the fifth arc, and the seventh arc are toward the inside of the closed shape, the center line of the circle is a square, the radius is R1, and the range of R1 is 1-10mm; the second arc, The opening directions of the fourth arc, the sixth arc and the eighth arc are toward the outside of the closed shape, the center line of the circle is a square, and the radius is R2, of which the second arc, the fourth arc, the sixth arc and The eighth arc can be a straight line.

In the above porous gas generating agent molded product, the number of the holes can be arbitrarily selected, preferably the number of holes is the same as the number of odd-numbered arcs of the corresponding columnar body.

According to the porous gas-generating agent molded product of the present invention, the porous is a cylindrical, square, rectangular or any shape that can penetrate the gas-generating agent compressed product as shown in FIG. 3a.

According to the molded article of porous gas generating agent of the present invention, the porous is cylindrical, square, rectangular, or any other shape that does not penetrate as shown in FIG. 3b or has partial pores as shown in FIG. 3c.

In the above porous gas generant molded product, the pores may be distributed arbitrarily within the columnar body, preferably the pores are uniformly or symmetrically distributed in the gas generant compressed product.

The invention also provides a preparation process of the above-mentioned porous gas-generating agent molded product. The preparation process is: mixing raw material components containing at least fuel and an oxidant to obtain a direct mixture, or granulating to obtain a granulated material , The directly mixed material or the granulated material is loaded into a compression mold, and the compressed gas-forming agent molded product with holes is obtained by compression molding.

According to the preparation process of the present invention, in the first material, the content of the fuel is 35% to 60%; the content of the oxidant is 25% to 58%; the fuel is selected from guanidine nitrate and aminoguanidine Nitrate, melamine cyanurate, melamine, nitroguanidine, 5-aminotetrazole, 3-nitro-1,2,4-triazol-5-one, amidinourea copper nitrate, ammonium nitrate, bistetrazolium One or more of salt, bistetrazolium potassium salt, NTO, new energy-containing materials FOX7, FOX12, TKX-50, LLM-105; the oxidant is selected from metal basic nitrate, metal basic carbonate , One or more of metal nitrate, ammonium perchlorate, metal perchlorate, chlorate; functional additives are metal titanate, titanium dioxide, strontium titanate, aluminum hydroxide, aluminum oxide, kaolin , One or more of copper phthalocyanine, boron nitride, silica, fumed silica, graphite, talc; catalysts are metal oxides, ferrocene and its derivatives, cobalt oxide organic lead compounds, One or more organic complexes of copper.

According to the preparation process of the present invention, the particle size of the granulated material is 10 to 200 mesh, and the particle bulk density is 0.5 g/cm ³ to 2.0 g/cm ³ .

According to the preparation process of the present invention, the compression molding equipment is a rotary tablet press, the number of punching groups of the rotary tablet press is in the range of 6-100 punches, and the compression capacity of the rotary tablet press is in the range of 1-30t , The rotation speed is 1 ~ 25 rpm.

The present invention also provides a pressing die used in the preparation process of the present invention, as shown in FIG. 4, the pressing die includes an upper punch 4-1, a middle die 4-5, a lower punch 4-8 and a core The rod 4-13; the middle mold 4-5 is provided with a through hole 4-6; through the upper punch, the lower punch and the movement of the core rod, the hole-type gas generating agent molded product is formed in the middle mold by pressing.

According to the pressing mold of the present invention, the number, shape, and size of the core rods 4-13 correspond to the number, shape, and size of the porous inside the columnar body; the internal through holes 4- of the middle mold 4-5 The shape and size of 6 correspond to the external shape and size of the molded product of the porous gas generant; the end faces of the upper punch 4-1 and the lower punch 4-8 respectively correspond to the outer shape of the upper and lower end faces of the columnar body correspond.

According to the pressing die of the present invention, the upper punch 4-1 and the lower punch 4-8 can be provided with the corresponding number, shape and size of through holes 4-2 and 4 according to the number, shape and size of the core rod 4-13 -11, you can also choose not to set holes or set a part of the number of holes according to the needs of the medicine type.

In some specific embodiments of the present invention, the upper punch 4-1 and the lower punch 4-8 have through holes 4-2 and 4-11 corresponding to the number, shape, and size of the core rods 4-13, The plurality of core rods extend from the through holes 4-11 corresponding to the lower punch, as shown in FIG. 4a, the upper punch and the lower punch move simultaneously, and the core rods extend into the upper punch through holes 4-2, Finally, the inner mold 4-5 through holes 4-6 are pressed to form a gas-generating agent molded product with multiple through holes.

In some specific embodiments of the present invention, the undercuts 4-8 have through holes 4-11 corresponding to the number, shape, and size of the core rods 4-13. The through hole extends, the upper punch 4-1 does not have a hole or a part of the hole corresponding to the core rod, the upper punch and the lower punch move at the same time, by adjusting the length of the core rod and the gas generating agent in At the location of the in-mold press molding, the gas-generating agent molded product with multiple non-through holes or the gas-generating agent molded product with multiple through and non-through holes at the same time is finally pressed into the middle mold through holes 4-6.

In some embodiments of the present invention, the upper punch 4-1 and the lower punch 4-8 have through holes 4-2 and 4-11 corresponding to the number, shape and size of the core rod, A core rod 4-13 extends from the through hole corresponding to the upper punch, the upper punch and the lower punch move at the same time, the core rod extends into the lower punch through hole, and finally is made by pressing in the middle die through hole 4-6 Gas-generating agent molded product with multiple through holes.

In some specific embodiments of the present invention, the upper punch has a through hole 4-2 corresponding to the number, shape, and size of the core rods 4-13, and the core rod extends from the through punch through hole Out, the lower punch 4-8 does not have holes inside or has some holes corresponding to the core rod, the upper punch and the lower punch move at the same time, and are pressed in the middle mold by adjusting the length of the core rod and the gas generating agent At the molding position, finally, a plurality of gas-generating agent molded products with non-through holes or a gas-generating agent molded product with multiple through and non-through holes are simultaneously pressed in the middle mold through holes 4-6.

In some specific embodiments of the present invention, the upper punch 4-1 and the lower punch 4-8 have through holes 4-2 and 4-11 corresponding to the number, shape, and size of the core rods 4-13, The plurality of core rods protrude from the through holes corresponding to the upper punch and the lower punch, the upper punch and the lower punch move simultaneously, by adjusting the length of the core rod and the gas generating agent in the middle mold 4-5 At the position of the press molding, the gas-generating agent molded product having a plurality of through holes or a plurality of non-through holes or a plurality of through and non-through holes at the same time is finally pressed into the middle mold through holes 4-6.

According to the pressing die of the present invention, the working parts of the upper punch 4-1, the lower punch 4-8, the middle die 4-5, and the core rod 4-13 are provided with a plating layer, and the middle die is composed of two types of inner and outer Material composition, external material hardness is lower than internal material hardness. The internal and external materials are connected by welding. The low hardness of the external material facilitates processing, and the high hardness of the internal material is beneficial to the shape of the molding agent.

According to the pressing mold of the present invention, a chamfer is provided at the connection between the outer side surface of the middle mold and the upper and lower end surfaces, so that the middle mold enters the rotary tableting device; the opening edge of the inner through hole 4-6 of the middle mold is provided with an inverted The angle is used to guide the entrance of the die up and down.

According to the pressing mold of the present invention, the plurality of core rods can be fixedly arranged on the core rod base body and integrated with the core rod base body, and the core rod mold is generally easy to disassemble, as shown in FIG. 4c. The multiple core rods can also be separated from the core rod base. These core rods are replaceable, and need to be installed and fixed in the corresponding holes in the core rod base during use, as shown in FIG. 5.

According to the pressing die of the present invention, the upper punching side is provided with a discharge hole 4-3 corresponding to each through-hole. When pressing the through-hole gas generating agent molded product, the core rod can be removed when passing through the upper punching through-hole The excess material attached to the core rod can be extended to extend the durability of the mold.

According to the pressing mold of the present invention, the upper punch, the lower punch, the middle die and the core rod are all provided with positioning units, and the positioning unit includes a positioning groove, a positioning hole or a positioning key to realize the upper punch, the lower punch, The middle mold corresponds to multiple core rods.

The invention also provides the application of the porous gas generating agent molded product, which is applied to systems such as automobile airbag gas generators, fire extinguishers, solid oxygen generators or lifeboat inflators.

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

(1) The molded product of the porous gas-generating agent of the present invention adjusts the combustion surface of the gas-generating agent, reduces the initial combustion surface, and burns the gas-generating agent into an equal surface or an increased surface, or multiple stages of combustion under different conditions. The combustion surface of the first half of the agent is smaller than the flake gas generating agent, which protects the airbag under the pressure of high-temperature gas injection, and the gas production rate in the second half is accelerated. The continuous inflation of the airbag ensures the timely deployment of the airbag and adopts a porous Gas generating agent, which can adjust the burning duration of the agent, can continuously supply gas to the air bag, improve the protection efficiency and protection time for people, and improve the suitability of the use of the air bag; and the molded product of the porous gas generating agent of the present invention has a small size , Suitable for all types of generators.

(2) The molded product of the porous gas-generating agent of the present invention burns more smoothly, the internal pressure of the generator is smaller, which is beneficial to reduce the number of filter layers, reduce the thickness of the steel plate of the generator shell, and reduce the strength requirements of the materials used, thereby reducing costs .

(3) Compared with ordinary round tablets, the molded product of the porous gas-generating agent of the present invention has a larger burning surface when the size is the same, so the formula with low burning rate and low burning temperature can be used; and the burning is more complete without leaving behind The unused tablets have a higher utilization rate of gas generating agents.

(4) The PT curve of the porous gas-generating agent molded product of the present invention in the gas generator is a smooth curve, the slope in the early stage is low, the slope in the middle stage is high and stable, the slope in the later stage is low and the decline is gentle, and the pressure retention time in the later stage can also be extended , Excellent performance.

(5) The molded product of the porous gas-generating agent of the present invention can achieve intelligent dual-stage or multi-stage combustion, that is, when one area of the tablet is completely burned, about 30% of the other area is still not burned out. Realize the function of some bipolar generators.

(6) Compared with the single-hole gas-generating agent, the molded product of the porous gas-generating agent of the present invention can maintain part of the drug form after combustion, and has the advantages of less residue after combustion, low internal pressure, and adjustable burning rate. Quantify.

(7) In the preparation process of the molded product of the porous gas generating agent of the present invention, the compression molding method is adopted, the preparation process is simple, efficient, easy to operate and control, and the output is high.

BRIEF DESCRIPTION

1 is a schematic diagram of the shape and hole layout of the porous gas generating agent molded product of the present invention, wherein FIG. 1a is a porous gas generating agent molded product with a cross-sectional shape of two holes with a full arc shape, and FIG. 1b is a cross-sectional shape with two circular arcs and a straight line. The porous porous gas generating agent molded product, Figure 1c is a three-hole porous gas generating agent molded product with an arc shape and a straight equilateral triangle in cross-sectional shape, and Figure 1d is a three-hole porous product with a rectangular cross-sectional shape and circular shape. Aerosol molded products;

Fig. 2 is a schematic diagram of arc connection of porous gas generating agent molded products of the present invention, wherein Fig. 2a is a front view of a porous gas generating agent molded product connected with a six-segment arc similar to a triangle, and Fig. 2b is similar to an eight segment arc connection Front view of molded product of porous gas generating agent in quadrilateral;

3 is a schematic view of a molding method of a porous gas generating agent molded product hole of the present invention, wherein FIG. 3a is a through hole, FIG. 3b is a non-through hole, and FIG. 3c is a part of the number of through holes and a part of the number of non-through holes;

4 is a schematic diagram of the pressing die of the present invention, wherein FIG. 4a is a combination of pressing dies when the core rod is extended from the lower punch, FIG. 4b is the lower punch, and FIG. 4c is the core rod with an increased diameter; where 4- 1 represents upper punch, 4-2 represents upper punch through hole, 4-3 represents upper punch discharge hole, 4-4 represents upper punch working end, 4-5 represents middle die, 4-6 represents middle die inner hole, 4 -7 represents the middle die fixing groove, 4-8 represents the down punch, 4-9 represents the core rod and core rod body as a whole, 4-9 represents the overall fixed end of the core rod, 4-11 represents the under punch through hole, 4 -12 represents the working end of the punch, 4-13 represents the core rod and its working end, 4-14 represents the part of the core rod that increases the diameter and increases the strength;

Figure 5 is the overall core rod assembled in the pressing mold of the present invention;

6 is a schematic diagram of a two-hole gas generating agent in Example 1, wherein FIG. 6a is a schematic view of a two-hole gas generating agent at a natural angle, and FIG. 6b is a front view of the two-hole gas generating agent;

7 is a schematic view of a triangular three-hole gas generating agent in Example 2, wherein FIG. 7a is a schematic view of a triangular three-hole gas generating agent at a natural angle, and FIG. 7b is a front view of the triangular three-hole gas generating agent and a cross-sectional line along FIG. 7a. Cutaway view

8 is a schematic view of a special-shaped three-hole gas-generating agent of Example 3, wherein FIG. 8a is a schematic view of a special-shaped three-hole gas-generating agent at a natural angle, and FIG. 8b is a front view of the special-shaped three-hole gas-generating agent and a cross-sectional view along the section line of FIG. 8a ;

9 is a schematic diagram of a rounded quadrilateral three-hole gas generating agent in Example 4, wherein FIG. 9a is a natural angle of the rounded quadrilateral three-hole gas generating agent, and FIG. 9b is a front view of the rounded quadrilateral three-hole gas generating agent;

10 is a P-T curve diagram of the compressed product of the gas generating agent in Example 1 and Example 2 in the gas generator;

11 is a P-T curve diagram of the compressed product of the gas generating agent in Example 3 and Example 4 in the gas generator;

FIG. 12 is a P-t curve chart of the comparative three-hole gas generating agent in Comparative Example 1 compared with the ordinary disk gas generating agent;

FIG. 13 is a P-t curve chart comparing the heterogeneous three-hole gas generating agent and the single-hole gas generating agent in Comparative Example 2;

Fig. 14 is a schematic diagram of a round-cone three-hole gas generating agent in Comparative Example 3 and a Pt curve chart comparing with a special-shaped three-hole gas generating agent, wherein Fig. 14a is a schematic view of a natural truncated three-hole gas generating agent, and Fig. 14b is the circle The front view of the mesa-shaped three-hole gas generating agent and the cross-sectional view along the section line of FIG. 14a, and FIG. 14c is the Pt curve of the contrast between the mesa-shaped three-hole gas generating agent and the shaped three-hole gas generating agent;

15 is a P-t curve chart of the comparison between the rounded quadrilateral three-hole gas generating agent and the ordinary disk gas generating agent in Comparative Example 4. FIG.

detailed description

The present invention will be described in further detail below with reference to the drawings and specific embodiments:

The preparation process of the porous gas generating agent includes the following steps:

(1) The raw material components containing at least fuel and oxidant are mixed to obtain the first material; the mixing is performed in a mixing device with a mixing time of 15 minutes. The mixing device may be a V-type mixer, a three-dimensional multidirectional motion mixer, Automatic lifting hopper mixer, ribbon mixer or acoustic resonance mixer; wherein, the fuel is guanidine nitrate, its content is 50%, the oxidant is basic copper nitrate, its content is 31.75%, the auxiliary oxidant It is ammonium perchlorate, the content of which is 2%; the form-retaining agents are strontium titanate and strontium nitrate, the contents of which are 5.5% and 9.75%; in addition, the first material also includes a functional aid to help demolding The agent is talc and graphite, and their contents are 0.75% and 0.25%, respectively.

(2) Wet mixing the first material with water, where the amount of water added is 10% of the total mass of the first material, the wet mixing time is 45 minutes to obtain the second material, and the wet mixing equipment is a kneader or mixer , For example, horizontal kneader, vertical kneader, ribbon mixer or acoustic resonance mixer.

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

(4) The third material is dried to a moisture content less than 0.5% of the total mass of the third material, and then passed through a 10-40 mesh screen to obtain the fourth material; the drying equipment can be an electric heating oven or an oil bath oven , Steam oven, double cone oven, vibrating fluidized bed or vacuum desiccant.

(5) Compression molding of the fourth material. The molding equipment may be a rotary tablet press or a powder molding machine. This application uses a rotary tablet press, which specifically includes the following steps:

(a) Add the fourth material to the rotary tablet press through the hopper;

(b) The fourth material is made into the prefabricated porous gas-generating agent under the upper and lower punching and pressing of the core rod of the rotary tablet press;

(c) The prefabricated porous gas-generating agent is ejected through an upward downward punch and collected.

(6) Dry the prefabricated porous gas generating agent at a drying temperature of 100° C. and a drying time of more than 8 hours to obtain a porous gas generating agent whose water content is not more than 0.15% of its total weight.

The shape of the porous gas-generating agent molded product prepared by the present application can be any columnar body, the maximum dimension D of the cross section of the columnar body is in the range of 2.0 to 20 mm, and the height H is in the range of 2.0 to 20 mm, and the porous is a through or non-through cylinder Shape, square, rectangle or any other shape, the diameter d of each hole of the porous is in the range of 0.5 to 5mm. The porous gas generating agent molded product prepared by the invention is mainly used for automobile airbag gas generators.

In the following examples, the maximum cross-sectional dimension of the columnar body is denoted as D, the maximum cross-sectional dimension of the hole is denoted as d, and the height of the columnar body is denoted as H.

Example 1

The real-time working capacity of the rotary tablet press is 8.0t. The cross-section and dimensions of the prepared two-hole gas-generating agent are shown in FIG. 6, D=8.62 mm, H=3 mm; the hole is a cylindrical hole penetrating the cylinder, and its diameter d=1.4 mm.

The two-hole gas-generating agent prepared above is loaded into a PAB test generator to perform P-t performance test. The test results are shown in Table 1, and the P-t test curve is shown in FIG. 10.

Table 1

As shown in Table 1 and Figure 10, the above two-hole gas generating agent is used in the PAB generator, the maximum pressure is 355KPa, the pressure is only 56KPa in 10ms, Slope1 (slope) is 6.43, Slope3 (slope) is 8.60, the data shows that the two The hole gas-generating medicine has a small impact force on the air bag when it is deployed, the gas-generating pressure is stable, and the air bag is not likely to be torn or damaged, and the design strength of the air bag module assembly is low, thereby reducing the design cost. The slope of the early P-t curve rises smoothly, indicating that the burning rate of the porous gas generating agent is stable.

Example 2

The real-time working capacity of the rotary tablet press is 7.5t. The cross-section and dimensions of the prepared three-hole gas generating agent are shown in FIG. 7, D=9.1 mm, H=3 mm; the hole is a cylindrical hole penetrating the cylinder, and its diameter d=1.4 mm.

Load the three-hole gas-generating agent prepared above into the PAB test generator and perform P-t performance test. The test results are shown in Table 2, and the P-t test curve is shown in Figure 10.

Table 2

As shown in Table 2 and FIG. 10, the above triangular three-hole gas generating agent is used in the PAB generator, the maximum pressure is 356KPa, the pressure is only 42kPa in 10ms, Slope1 (slope) is 5.00, Slope3 (slope) is 9.40, the early slope is low The impact force when the air bag is deployed is small, and the air bag is not easy to produce tearing and damage. The high slope in the later stage helps the air bag to expand and maintain a full state for a long time. The design strength of the air bag module assembly is low, which reduces the design. cost. The slope of the early P-t curve rises smoothly, indicating that the burning rate of the porous gas generating agent is stable.

Example 3

The real-time working capacity of the rotary tablet press is 8.2t. The shape and size of the prepared special-shaped three-hole gas generating agent are shown in FIG. 8, D=9.1 mm, H=3 mm; the hole is a cylindrical hole penetrating through the cylinder, and its diameter d=1.4 mm.

The three-hole gas-generating agent prepared above is loaded into a PAB test generator to perform P-t performance test. The test results are shown in Table 3, and the P-t test curve is shown in FIG. 11.

table 3

As shown in Table 3 and Figure 11, the above-mentioned special-shaped three-hole gas generating agent is used in the PAB generator, the maximum pressure is 373KPa, the pressure is only 44KPa in 10ms, Slope (slope) is 5.23, Slope3 (slope) is 9.90, the early slope is low The impact force when the air bag is deployed is small, the air bag is not easy to produce tearing and damage, and the high slope in the later period helps the air bag to expand and maintain a full state for a long time. The slope of the P-t curve in the early stage rises steadily, indicating that the burning rate of the shaped three-hole gas generating agent is stable.

Example 4

The real-time working capacity of the rotary tablet press is 9.1t. The shape and size of the prepared rounded quadrilateral three-hole gas-generating agent are shown in Fig. 9, D=9.93mm, H=4mm; the hole is a cylindrical hole penetrating the cylinder, and its diameter d=1.4mm.

The rounded quadrilateral three-hole gas-generating agent prepared above is loaded into a PAB test generator to perform P-t performance test. The test results are shown in Table 4, and the P-t test curve is shown in FIG. 11.

Table 4

As shown in Table 4 and Figure 11, the above-mentioned special-shaped three-hole gas generating agent is used in the PAB generator. The maximum pressure is 364KPa and the pressure is only 25KPa in 10ms. The low slope at the early stage has little impact on the deployment of the air bag, and the air bag is not easy to produce. For tearing and breakage, Slope (slope) is 3.01 and Slope3 (slope) is 11.90. The later slope is high, which helps the airbag to expand and maintain a full state for a long time.

Comparative Example 1

A disk-shaped gas generating agent was prepared using the same formula as in Example 3, with an outer diameter D of 5 mm and a thickness H of 1.9 mm.

The irregular-shaped three-hole gas generating agent prepared in Example 3 and the above-mentioned disk-shaped gas generating agent were loaded into a PAB test generator to perform Pt performance test. The external pressure test results are shown in Table 5, and the external pressure Pt curve is shown in FIG. 12 Show.

table 5

As shown in Table 5 and Figure 12, the three-hole gas-generating agent of the present invention has a pressure of 10 ms and a pressure of 20 ms lower than that of a common wafer gas-generating agent under the same charge amount. The disk-shaped gas-generating agent, and the P95 pressure of the three-hole gas-generating agent is higher than that of the disk-shaped gas-generating agent, indicating that the early output pressure of the three-hole gas generating agent is small, which is beneficial to the deployment of the airbag, and the later output pressure is large, which is beneficial to the airbag. Extension of hold time.

Comparative Example 2

Cylindrical single-hole tablets were prepared using the same formula and process as in Example 3. The prepared single-hole gas generating agent and the irregular-shaped three-hole gas generating agent prepared in Example 3 were loaded into a PAB test generator for Pt performance test. The external pressure test results are shown in Table 6, and the external pressure Pt curve is shown in Figure 13.

Table 6

As shown in Table 6 and FIG. 13, the three-hole gas-generating agent of the present invention compares with the single-hole gas-generating agent. Under the same charge amount, the porous gas-generating agent has a pressure of 10 ms and 20 ms lower than that of the single-hole gas-generating agent. It shows that the early output pressure is small, which is beneficial to the deployment of the airbag, and the later output pressure is large, which is beneficial to the extension of the airbag retention time.

Comparative Example 3

A round table-shaped three-hole medicinal gas-generating agent was prepared using the same formula and process as in Example 3, and the prepared round table-shaped three-hole medicinal gas-generating agent and the three-hole gas-generating agent prepared in Example 3 were loaded into a PAB test generator , Pt performance test, the external pressure test results are shown in Table 7, the external pressure Pt curve shown in Figure 14.

Table 7

As shown in Table 7 and FIG. 14, the heterogeneous three-hole gas-generating agent of the present invention is compared with the round-table three-hole gas-generating agent. Under the same charge amount, the heterogeneous three-hole gas-generating agent has a pressure of 10ms and 20ms lower than that of the round-table three. Hole gas generating agent, the pressure-shaped three-hole gas generating agent in the later 40ms is higher than that of the round table three-hole gas generating agent. It shows that the early output pressure is small, which is beneficial to the deployment of the airbag, and the later output pressure is large, which is beneficial to the extension of the airbag retention time.

Comparative Example 4

Using the same formula and process as in Example 4, an ordinary disk gas generating agent was prepared. The prepared ordinary disk gas generating agent and the rounded quadrilateral three-hole gas generating agent prepared in Example 4 were loaded into a PAB test generator. Carry out Pt performance test. The external pressure test results are shown in Table 8. The external pressure Pt curve is shown in Figure 15.

Table 8

As shown in Table 8 and Figure 15, the three-hole rounded quadrangular gas generating agent of the present invention is compared with the ordinary disk gas generating agent. Under the same charge amount, the three-hole rounded quadrangular gas generating agent has a pressure of 10ms and a pressure of 20ms It is lower than the ordinary disk gas generating agent, and the 40ms pressure three-hole rounded quadrilateral gas generating agent is higher than the ordinary disk gas generating agent in the later 40ms. It shows that the small output pressure in the early stage will not cause the air bag to tear, and the large output pressure in the later stage is beneficial to the deployment of the airbag and is beneficial to the extension of the airbag retention time.

The above is only the best specific embodiment of the present invention, but the scope of protection of the present invention is not limited to this, any person skilled in the art can easily think of changes or changes within the technical scope disclosed by the present invention. Replacement should be covered within the protection scope of the present invention.

The contents not described in detail in the specification of the present invention belong to the well-known technologies of those skilled in the art.

Claims (25)

1. A molded product of a porous gas generating agent, which is a columnar body with a plurality of holes inside in the height direction, wherein the ratio of the height of the columnar body to the maximum dimension of the cross-section is 0.3 to 1.8; and

   The ratio of the total cross-sectional area of the porous columnar body to the total cross-sectional area of the columnar body ranges from 0.03 to 0.15.
2. The porous gas-generating agent molded article according to claim 1, wherein the pores are randomly distributed inside the columnar body, preferably uniformly or symmetrically.
3. The porous gas generating agent molded article according to claim 1 or 2, wherein the maximum cross-sectional size of the columnar body is in the range of 2.0-20 mm, the height of the columnar body is in the range of 2.0-20 mm, and the maximum cross-sectional size of the hole In the range of 0.5 ~ 5mm.
4. The perforated gas-generating agent molded product according to claim 3, characterized in that, the largest dimension of the cross section of the columnar body is in the range of 3 to 15 mm, and the height is in the range of 2.0 to 10 mm, and the largest cross section of the hole The size is in the range of 0.8 to 4 mm; preferably, the maximum size of the cross section of the columnar body is in the range of 5 to 15 mm, the height is in the range of 2.0 to 10 mm, and the maximum size of the hole cross section is in the range of 0.8 to 4 mm; More preferably, the maximum cross-sectional size of the columnar body is in the range of 5-12 mm, the height is in the range of 2.0-8 mm, and the maximum cross-sectional size of the hole is in the range of 0.8-3 mm; most preferably, the columnar body The maximum size of the cross-section of the body is in the range of 8-10 mm, the height is in the range of 3.0-7.5 mm, and the maximum size of the cross-section of the hole is in the range of 0.8-2 mm.
5. The porous gas-generating agent molded article according to claim 1, wherein the cross section of the columnar body is selected from a circle, an equilateral triangle with rounded corners, a rounded quadrilateral, a clover shape, a four-leaf clover shape or a straight line , Curves or arcs of any closed shape.
6. The porous gas generating agent molded article according to claim 5, wherein the cross section of the columnar body is composed of a first arc, a second arc, a third arc, a fourth arc, a fifth circle The arc and the sixth arc are sequentially closed end-to-end in a clockwise direction, wherein the second arc is tangent to the first arc and the third arc, respectively, and the fourth arc and the third arc The arc and the fifth arc are tangent respectively, and the sixth arc is tangent to the first arc and the fifth arc; and

   The first circular arc, the third circular arc, and the fifth circular arc of the cross section of the columnar body are concentric with the corresponding holes respectively; and

   The opening directions of the first arc, the third arc, and the fifth arc are toward the inside of the closed shape, the center line is an equilateral triangle, the radius is R1, and the range of R1 is 1-10 mm; and

   The opening directions of the second arc, the fourth arc, and the sixth arc are toward the outside of the closed shape, and the center line of the arc is an equilateral triangle with a radius of R2. Among them, the second arc, the fourth arc, and the first arc The six arcs can be straight lines.
7. The porous gas generating agent molded article according to claim 5, wherein the cross section of the rounded quadrilateral columnar body includes a first arc, a second arc, a third arc, a fourth arc, The fifth circular arc, the sixth circular arc, the seventh circular arc, and the eighth circular arc are connected in a clockwise direction to form a closed shape, wherein the second circular arc is separated from the first circular arc and the third circular arc Tangent, the fourth arc is tangent to the third arc and the fifth arc, the sixth arc is tangent to the fifth arc and the seventh arc, the eighth arc is The first arc and the seventh arc are tangent respectively; and

   The first circular arc, the third circular arc, the fifth circular arc, and the seventh circular arc of the cross section of the columnar body are respectively concentric with the corresponding holes; and

   The opening directions of the first arc, the third arc, the fifth arc, and the seventh arc are toward the inside of the closed shape, the center line of the circle is a square, the radius is R1, and the range of R1 is 1-10 mm; and

   The opening directions of the second arc, the fourth arc, the sixth arc, and the eighth arc are outward of the closed shape, and the center line of the circle is a square, and the radius is R2, wherein the second arc, the fourth circle The arc, sixth arc, and eighth arc may be straight lines.
8. The porous gas-generating agent molded article according to claim 6 or 7, wherein the holes are arranged concentrically with the odd-numbered circular arcs of the corresponding columnar bodies in cross section.
9. The porous gas generating agent molded article according to claim 1, wherein the porous body penetrates the columnar body, and the cross section of the hole is any shape, preferably circular, square or rectangular.
10. The porous gas generating agent molded article according to claim 1, wherein the porous does not penetrate the columnar body, and the cross section of the hole is any shape, preferably a circle, a square, or a rectangle.
11. The preparation process of the porous gas generating agent molded product according to any one of claims 1-10, characterized in that the preparation process is: mixing a raw material component containing at least fuel and an oxidant to obtain a direct mixture, or After granulation to obtain the granulated material, the directly mixed material or the granulated material is loaded into a compression mold, and the compressed gas-forming agent molded product with holes is obtained by compression molding.
12. The preparation process according to claim 11, characterized in that, in the first material, the content of the fuel is 35% to 60%; the content of the oxidant is 25% to 58%; the fuel is selected from Guanidine nitrate, aminoguanidine nitrate, melamine cyanurate, melamine, nitroguanidine, 5-aminotetrazole, 3-nitro-1,2,4-triazol-5-one, amidinourea copper nitrate, ammonium nitrate , Bistetrazolium ammonium salt, bistetrazolium potassium salt, NTO, one or more of the new energetic materials FOX7, FOX12, TKX-50, LLM-105; the oxidant is selected from metal basic nitrate, metal One or more of basic carbonate, metal nitrate, ammonium perchlorate, metal perchlorate, chlorate; functional additives are metal titanate, titanium dioxide, strontium titanate, aluminum hydroxide , One or more of alumina, kaolin, copper phthalocyanine, boron nitride, silica, fumed silica, graphite, talc; catalysts are metal oxides, ferrocene and its derivatives, oxidation One or more organic compounds of cobalt organic lead compound and copper.
13. The preparation process according to claim 11, wherein the particle size of the granulated material is 10 to 200 mesh, and the particle packing density is 0.5 g/cm ³ to 2.0 g/cm ³ .
14. The preparation process according to claim 11, characterized in that the compression molding equipment is a rotary tablet press, the number of punching groups of the rotary tablet press ranges from 6 to 100 shots, and the compression capability of the rotary tablet press The range is 1 to 30t, and the rotation speed is 1 to 25 rpm.
15. A pressing die used in the preparation process according to any one of claims 11-14, which comprises an upper punch, a middle die, a lower punch, and a plurality of core rods, the middle die is provided with through holes inside; The upper punch, the lower punch and the movement of the core rod are compressed in the middle mold to make the porous gas generating agent molded product.
16. The pressing mold according to claim 15, wherein the number, shape, and size of the core rods correspond to the number, shape, and size of the holes inside the column; the shape of the through holes in the middle mold and The size corresponds to the external shape and size of the porous gas-generating agent molded product; the end faces of the upper punch and the lower punch correspond to the outer shapes of the upper and lower end faces of the columnar body, respectively.
17. The pressing die according to claim 15, wherein the upper punch and the lower punch have through holes corresponding to the number, shape, and size of the core rods, and the plurality of core rods extend from the bottom The through holes corresponding to the punching are extended, corresponding to the plurality of through holes punched upward, and a plurality of through holes are formed in the molded product of the gas generating agent; or

    The inside of the lower punch has through holes corresponding to the number of core rods, and the inside of the upper punch has fewer through holes than the number of core rods. By adjusting the length of the core rod and the forming position of the gas generating agent in the middle mold, the Multiple through and non-through holes are simultaneously formed in the molded product of the gas generating agent; or

    The lower punch has a through hole corresponding to the number of core rods, and the upper punch has no holes. By adjusting the length of the core rod and the forming position of the gas generating agent in the middle mold, many holes are formed in the molded product of the gas generating agent. A broken hole.
18. The pressing die according to claim 15, wherein the upper punch and the lower punch have through holes corresponding to the number, shape, and size of the core rods, and the plurality of core rods extend from the top The through holes corresponding to the punching are extended, corresponding to the multiple through holes punched down, and a plurality of through holes are formed in the molded product of the gas generating agent; or

    The upper punch has a through hole corresponding to the number of core rods, and the lower punch has a smaller number of through holes than the number of core rods. By adjusting the length of the core rod and the forming position of the gas generating agent in the middle mold, the Multiple through and non-through holes are simultaneously formed in the molded product of the gas generating agent; or

    The upper punch has through holes corresponding to the number of mandrels, and the lower punch has no holes. By adjusting the length of the mandrel and the forming position of the gas generating agent in the middle mold, many holes are formed in the molded product of the gas generating agent A broken hole.
19. The pressing die according to claim 15, wherein the upper punch and the lower punch have through holes corresponding to the number, shape, and size of the core rods, and the plurality of core rods extend from the top The through holes corresponding to the punch and the down punch are extended at the same time. By adjusting the length and position of the core rod and the forming position of the gas generating agent in the middle mold, a plurality of through holes or a plurality of non-through holes are formed in the gas generating agent molded product A plurality of through holes and non-through holes may be formed at the same time.
20. The pressing mold according to claim 15, wherein the working parts of the upper punch, the lower punch, the middle mold, and the core rod are provided with a plating layer, and the middle mold is composed of two materials, the outer material is low in hardness For internal material hardness.
21. The pressing mold according to claim 15, wherein a chamfer is provided at the connection between the outer side surface of the middle mold and the upper and lower end surfaces, and the opening edge of the through hole in the middle mold is provided with a chamfer.
22. The pressing mold according to any one of claims 15 to 21, wherein the plurality of core rods are fixedly arranged on the base body to form an integrated body; or the core rod is separated from the base body.
23. The pressing die according to claim 15, wherein the upper punch is provided with a discharge hole according to the number of core rods.
24. The pressing mold according to claim 15, wherein the upper punch, the lower punch, the middle die and the core rod are all provided with a positioning unit, and the positioning unit includes a positioning groove, a positioning hole or a positioning key.
25. The use of the porous gas generating agent molded product according to any one of claims 1-10, characterized in that the porous gas generating agent molded product is applied to a car airbag gas generator, fire extinguisher, solid oxygen generator or Lifeboat aerator and other systems.

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