WO2021227577A1 - 一种气体发生剂组合物、制备方法及其应用 - Google Patents

一种气体发生剂组合物、制备方法及其应用 Download PDF

Info

Publication number
WO2021227577A1
WO2021227577A1 PCT/CN2021/075533 CN2021075533W WO2021227577A1 WO 2021227577 A1 WO2021227577 A1 WO 2021227577A1 CN 2021075533 W CN2021075533 W CN 2021075533W WO 2021227577 A1 WO2021227577 A1 WO 2021227577A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas generating
generating agent
nitrate
composition according
zirconate
Prior art date
Application number
PCT/CN2021/075533
Other languages
English (en)
French (fr)
Inventor
罗运强
任响宁
杜涛
张俊
沈晓琛
Original Assignee
湖北航鹏化学动力科技有限责任公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 湖北航鹏化学动力科技有限责任公司 filed Critical 湖北航鹏化学动力科技有限责任公司
Priority to EP21737332.3A priority Critical patent/EP3936495A4/en
Priority to US17/478,013 priority patent/US20220009853A1/en
Publication of WO2021227577A1 publication Critical patent/WO2021227577A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
    • B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
    • B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
    • B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
    • B60R21/264—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic
    • B60R21/2644—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic using only solid reacting substances, e.g. pellets, powder
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt

Definitions

  • the invention relates to a gas generating agent composition, a preparation method and application thereof, and belongs to the technical field of automobile safety airbag gas generators.
  • the car airbag gas generating agent is used as a gas-producing agent to be loaded into the gas generator, which is triggered when needed to produce a large amount of gas.
  • the airbag consists of a gas generator and an air bag. Generally, when the collision exceeds the preset intensity, the gas generator is activated and triggered to start burning the internal gas generating agent to generate gas, inflate the air bag, and form a cushion air cushion between the interior and the human body to protect the human body from injury.
  • the early stage of the gas generating agent is mainly the sodium azide type gas generating agent formula.
  • This formula has many advantages such as stable combustion, low combustion temperature, easy ignition, low internal pressure, high gas production rate, and less residue.
  • the mainstream gas generating agents worldwide are guanidine nitrate and basic copper nitrate gas generating agents, with guanidine nitrate as the main fuel and basic copper nitrate as the main oxidant.
  • the combustion temperature of this type of gas generating agent is generally high.
  • basic copper nitrate mainly produces molten copper metal, which usually requires a multilayer metal filter to filter and cool it, leaving it inside the generator.
  • the increase in the weight of the metal filter will increase the cost and the weight of the generator; on the other hand, even if the multi-layer filter is used, all the residues cannot be filtered. A small part of the residue can burn the air bag through the filter, and more serious will cause burns. human body.
  • the solution is generally: 1. Reduce the amount of basic copper nitrate used, thereby reducing the molten copper residue formed after the combustion of the gas generating agent composition; 2. Add a form-retaining agent to the composition formula.
  • the form-retaining agent is generally a high-melting substance, which functions to increase the viscosity of the molten residue and maintain its shape as a tablet matrix.
  • Strontium titanate is a metal compound with a high melting point. It has also been used in the field of airbag gas generating agents.
  • the patent CN105801326A is a gas generating agent formula mainly containing guanidine nitrate, basic copper nitrate, and titanate.
  • titanate as a form-retaining agent, which does not have a significant effect on the form-maintaining effect, and cannot play a good role in maintaining the combustion form, especially for basic copper nitrate content greater than 40%, and guanidine nitrate content greater than 40%
  • the gas generating agent can not play a good role in maintaining the combustion form, and the gas generating agent formula is not easy to be ignited.
  • patent CN100376515C discloses a gas generating composition, including guanidine nitrate, basic copper nitrate, auxiliary oxidizing agent sodium nitrate, copper oxide and iron oxide, and ignition modifiers (aluminum trioxide, copper chloride, copper chromate, Potassium chromate), the use of ignition modifier makes the gas generating composition easier to ignite, and the ignition delay period is short, but aluminum oxide is generally used for residue agglomeration and has little effect on ignition improvement; copper chloride is a weak oxidant for ignition The improvement effect is not great; copper chromate and potassium chromate are strong copper-containing oxidants, which can play a certain ignition improvement effect, but both will increase the residue content. Copper chromate increases the insoluble residue content, and potassium chromate can increase the content of residues. The content of dissolved residue and the burning of substances containing alkali metal potassium will form soluble aerosol particles, which is not good for residue agglomeration.
  • ignition modifiers aluminum trioxid
  • the patent US5827996A discloses a gas generating agent for airbags, including the use of azoles or metal salts, oxidizers, combustion catalysts, combustion control agents and slagging agents for fuel, azoles and metal salts for fuels, and solidification of the slagging agent.
  • Additive to the combustion residue of the gas generating agent which is beneficial to the filter in the airbag to remove the residue.
  • the patent is applicable to the formulation of azoles as fuel. This type of formulation has a higher combustion temperature than the basic copper nitrate type of guanidine nitrate. Many, even if the slag forming agent is added, the form of the tablet cannot be maintained well.
  • the patent CN101952227B discloses a method for preparing a gas generating agent, adding guanidine nitrate, basic copper nitrate, auxiliary oxidants (such as potassium nitrate, strontium nitrate and sodium nitrate), burning rate regulator (potassium perchlorate), slag promoting Agent (silica, zinc oxide, ammonium oxide, aluminum oxide), tablet release aid and shape retention synergistic aid B (graphite, molybdenum disulfide, tungsten disulfide, boron nitride), the granulation used in this patent The method is spray granulation. Compared with wet granulation, spray granulation has higher energy consumption.
  • the slag accelerator used in this patent mainly comes from metal oxides, such as silica, alumina, zinc oxide, and cerium oxide.
  • metal oxide can play a certain role in promoting slag agglomeration, but it is not obvious for maintaining the shape of the tablet.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a gas generating agent composition which adopts zirconate, silicate or a mixture of zirconate and silicate as slag-forming
  • the tablets can condense and agglomerate in the filter after burning, and maintain their pre-combustion form very well, completely avoiding the melting and splashing of the tablets after burning to burn the air bag, and causing the gas generating agent composition to burn during the combustion period. Slagging is increased by at least 50%.
  • Another object of the present invention is to provide a method for improving the slag-forming ability of a gas generating agent composition.
  • the method includes basic copper nitrate, guanidine nitrate, strontium nitrate, and AP gas generating agent composition with high The melting point of the material is pickaxe and silicate slag forming agent components.
  • Another object of the present invention is to provide a method for preparing a gas generating agent composition and its application.
  • a gas generating agent composition comprising guanidine nitrate, basic copper nitrate, strontium nitrate and ammonium perchlorate, characterized in that it further comprises a slag-forming agent and a lubricant, and the slag-forming agent is at least one zirconate , Or at least one silicate, or a mixture of at least one zirconate and at least one silicate;
  • the mass percentage content of each component is as follows:
  • the zirconate is one or a combination of strontium zirconate, barium zirconate, or calcium zirconate.
  • the silicate is one or a combination of zirconium silicate or calcium silicate.
  • the slag-forming agent is a mixture of at least one zirconate and at least one silicate, and the mass ratio of zirconate to silicate is 1:0.5-3; preferably 1: 0.8-2.
  • the slag-forming agent is a mixture of strontium zirconate, zirconium silicate and calcium silicate, and the mass ratio of the three is 1:0.2 ⁇ 1.5:0.3 ⁇ 1.5, preferably 1:0.3 ⁇ 1: 0.5 to 1.
  • the slag-forming agent is a mixture of strontium zirconate and barium zirconate, and the mass ratio of the two is 1:0.5-3, preferably 1:0.8-2.
  • the lubricant is one or a combination of talc, graphite, calcium stearate, magnesium stearate, molybdenum disulfide or boron nitride.
  • the particle size D90 of the ammonium perchlorate is not greater than 20 ⁇ m; the particle size D90 of the slag-forming agent is not greater than 5 ⁇ m.
  • the particle size D90 of the basic copper nitrate and the lubricant is not greater than 5 ⁇ m.
  • the sum of the water content of each component of the gas generant composition is not more than 1% of the total mass of each component.
  • the gas generant composition has a circular or elliptical sheet structure, a circular or elliptical columnar structure, a special-shaped sheet or columnar structure, a circular or elliptical single hole after being formed. Structure, round or oval porous structure, special-shaped single hole or porous structure.
  • the diameter of the circular sheet-like structure is 3-15mm and the height is 2-5mm; the diameter of the circular columnar structure is 3-15mm and the height is 5-15mm; the circular single hole
  • the inner diameter of the structure is 0.5 ⁇ 2.5mm, the outer diameter is 3-15mm, and the height is 3-15mm; the inner diameter of the oval single-hole structure is 0.5 ⁇ 2.5mm, the long diameter is 3-20mm, the short diameter is 2-12mm, and the height is 3-15mm.
  • the above-mentioned preparation method of the gas generant composition adopts wet granulation, spray granulation or dry granulation to prepare the gas generant composition;
  • the specific preparation method of the wet granulation includes the following steps:
  • the first material is obtained after mixing guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate and a slag-forming agent;
  • guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate and slag-forming agent are mixed in a mixing device to obtain the first material, Mixing time ⁇ 5min.
  • the time of wet mixing in the step (2) is 20-60 minutes; the wet mixing equipment is a kneader or a mixer.
  • the above-mentioned preparation method of the gas generant composition adopts wet granulation to prepare the gas generant composition, and the specific preparation method includes the following steps:
  • the fourth material is formed into material.
  • guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate, slagging agent and lubricant are mixed in a mixing device to obtain the first One material, mixing time ⁇ 5min.
  • the time of wet mixing in the step (2) is 20-60 minutes; the wet mixing equipment is a kneader or a mixer.
  • a gas generator adopts the above-mentioned gas generating agent composition.
  • the present invention has the following beneficial effects:
  • the present invention uses zirconate, silicate or a mixture of zirconate and silicate as the slag-forming agent of the gas generating agent for the first time.
  • the combination of ammonium and mold release agent enables the tablet to maintain its pre-combustion form after burning, completely avoids the melting of the tablet after burning and burns the air bag, and significantly reduces the molten copper residue formed after the combustion and decomposition of basic copper nitrate.
  • the low-temperature ignition performance of the composition is improved while the burning speed is increased, so that the slagging during the combustion of the gas generating agent composition is increased by at least 50%.
  • the gas generating agent composition When the gas generating agent composition is combusted, it can collect all the solid combustion product agglomerates together to make the gas
  • the generator maintains its original shape after combustion; a large number of experiments show that the zirconate, silicate or the mixture of the two used in the present invention can form good condensation on the metallic copper melt formed after the decomposition of basic copper nitrate It can further reduce the molten copper residue, increase the viscosity of the molten residue and maintain its shape as a tablet skeleton, resulting in a significant effect of coagulation and slagging.
  • the present invention uses zirconate, silicate or a mixture of zirconate and silicate as the slag-forming agent of the gas generating agent for the first time, so that the gas is generated under the condition that the burning rate of the gas generating agent remains unchanged.
  • the slag formation during the combustion of the agent composition is increased by at least 50%.
  • the total content of insoluble and water-soluble matters is far less than 1g (USCAR industry requirements), and the total content is about 0.4g about.
  • the present invention uses a certain amount of ammonium perchlorate and strontium nitrate as auxiliary oxidants, which are used in conjunction with other components, and zirconate, silicate or a mixture of zirconate and silicate is added as a gas generation
  • the slag-forming agent can improve the low-temperature ignition performance of the composition and increase the combustion speed at the same time, and meet the requirements of the USCAR standard.
  • the present invention optimizes the design of the wet granulation process and process conditions to make the preparation process simple and easy to realize.
  • the release agent in the preparation method of the present invention can be mixed with the rest of the components before being wet. Method, you can also add talc at the end, the preparation method is more flexible.
  • Figure 1 is a diagram of the residue morphology of the gas generant composition tablet after combustion in Comparative Example 1 of the present invention
  • Example 2 is a morphological diagram of the residue after combustion of the gas generant composition tablet in Example 1 of the present invention
  • Example 4 is a morphological diagram of the residue after combustion of the gas generating agent composition tablet in Example 2 of the present invention.
  • Fig. 6 is a morphological diagram of the residue after combustion of the gas generant composition tablet in Example 3 of the present invention.
  • Fig. 7 is a morphological diagram of the residue after combustion of the gas generant composition tablet in Example 4 of the present invention.
  • Fig. 8 is a morphological diagram of the residue after combustion of the gas generant composition tablet in Example 5 of the present invention.
  • Fig. 9 is a morphological diagram of the residue after combustion of the gas generant composition tablet in Example 6 of the present invention.
  • the invention discloses a gas generating agent composition
  • a gas generating agent composition comprising guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate, a slag-forming agent and a lubricant
  • the slag-forming agent is at least one zirconate, or at least one A silicate, or a mixture of at least one zirconate and at least one silicate
  • the lubricant is selected from talc, graphite, calcium stearate, magnesium stearate, molybdenum disulfide or boron nitride At least one
  • the mass percentage content of each component is as follows:
  • the above-mentioned zirconate is one or a combination of strontium zirconate, barium zirconate or calcium zirconate.
  • the above-mentioned silicate is one or a combination of zirconium silicate or calcium silicate.
  • the slag-forming agent is a mixture of at least one zirconate and at least one silicate, and the mass ratio of zirconate to silicate is 1:0.5-3.
  • the slag-forming agent is a mixture of strontium zirconate, zirconium silicate and calcium silicate, and the mass ratio of the three is 1:0.5-3:0.5-3.
  • the slag-forming agent is a mixture of strontium zirconate and barium zirconate, and the mass ratio of the two is 1:0.5-3.
  • the particle size D90 of the above-mentioned ammonium perchlorate is not greater than 20 ⁇ m.
  • the particle size D90 of the above-mentioned slag-forming agent is not greater than 5 ⁇ m.
  • the particle size D90 of the above-mentioned basic copper nitrate and lubricant/release agent is not greater than 5 ⁇ m.
  • the sum of the water content of each component of the above-mentioned gas generating agent composition is not more than 1% of the total mass of each component.
  • the gas generating agent composition is formed into a circular or elliptical sheet structure, a circular or elliptical columnar structure, a special-shaped sheet or columnar structure, a circular or elliptical single-hole structure, Round or oval porous structure, special-shaped single-hole or porous structure.
  • the diameter of the circular sheet structure is 3-15mm and the height is 2-5mm; the diameter of the circular columnar structure is 3-15mm and the height is 5-15mm; the inner diameter of the circular single-hole structure is 0.5-2.5mm, and the outer diameter
  • the elliptical single-hole structure has an inner diameter of 0.5 to 2.5 mm, a long diameter of 3 to 20 mm, a short diameter of 2 to 12 mm, and a height of 3 to 15 mm.
  • the preparation method of the gas generating agent composition of the present invention can be prepared by wet granulation, spray granulation or dry granulation. Among them, spray granulation or dry granulation can adopt traditional granulation technology.
  • the specific preparation method of wet granulation includes the following steps:
  • 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 drying equipment can be an electric heating oven, oil Bath oven, steam oven, double cone oven, vibrating fluidized bed or belt vacuum dryer.
  • the molding equipment can be a hydraulic press, a rotary tablet press or a powder molding machine. After molding, it can be round or elliptical sheet structure, round or elliptical column structure, special-shaped sheet or column structure, round or elliptical single-hole structure, round or elliptical porous structure, special-shaped single-hole or porous structure.
  • the diameter of the circular sheet structure is 3-15mm and the height is 2-5mm; the diameter of the circular columnar structure is 3-15mm and the height is 5-15mm; the circular single-hole structure
  • the inner diameter is 0.5-2.5mm, the outer diameter is 3-15mm, and the height is 3-15mm; the inner diameter of the oval single-hole structure is 0.5-2.5mm, the long diameter is 3-20mm, the short diameter is 2-12mm, and the height is 3-15mm.
  • Another specific preparation method of wet granulation includes the following steps:
  • 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 drying equipment can be an electric heating oven, oil Bath oven, steam oven, double cone oven, vibrating fluidized bed or belt vacuum dryer.
  • the fourth material is formed into material.
  • the molding equipment can be a hydraulic press, a rotary tablet press or a powder molding machine.
  • the above-mentioned gas generating agent composition of the present invention is used in a gas generator of an automobile airbag.
  • zirconate, silicate or a mixture of zirconate and silicate is added as a slag-forming agent of the gas generating agent for the first time, so that the molten Copper metal can condense and agglomerate into lumps.
  • the melting point is about 2500K, which is much higher than the melting point of metallic copper.
  • the zirconate, silicate or the mixture of the two of the present invention can form a good coagulation effect on the metallic copper melt formed after the decomposition of basic copper nitrate, and further reduce the molten copper residue. It can increase the viscosity of the molten residue and maintain its shape as a tablet skeleton, resulting in a significant effect of coagulation and slagging.
  • the mixing equipment used in the following embodiments is a three-dimensional multi-motion mixer (or ultra-efficient mixer), the kneader is a horizontal kneader, the drying equipment is a vacuum oven, and the molding equipment is a rotary tablet press.
  • the gas generating agent composition contains the following components in mass percentage content:
  • the specific preparation method is: guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate
  • the first material is obtained; the first material is added to 15% distilled water for wet kneading for 60 minutes to obtain the second material, and the second material is passed through a 40-mesh screen to obtain the third material; The three materials are dried until the moisture 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 again; talc powder is added to the fourth material, and the material is formed by a rotary tablet press.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 1 shows the morphology of the residue after combustion of the gas generant composition tablet in Comparative Example 1 of the present invention
  • Table 1 shows the soluble residue and insoluble residue of the gas generant composition tablet in the present invention after combustion.
  • Statistics of weight and low-temperature ignition delay time from Figure 1 and Table 1, it can be seen that the tablet is in the form of a sheet, which is close to the inner wall of the filter, and its density is poor. Falling into the air bag may ablate the air bag and bring potential danger to the human body. Its low temperature ignition time meets the requirement of less than 7ms.
  • the gas generating agent composition contains the following components in mass percentage content:
  • the specific preparation method is: guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate
  • the first material is mixed with barium zirconate through mixing equipment; the first material is added to 15% distilled water for wet kneading for 60 minutes to obtain the second material, and the second material is passed through a 40-mesh screen to obtain the third material; The three materials are dried until the moisture 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 again; talc powder is added to the fourth material, and the material is formed by a rotary tablet press.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 2 shows the morphology of the residue after combustion of the gas generant composition tablet in Example 1 of the present invention
  • Table 2 below shows the soluble residue and insoluble residue of the gas generant composition tablet in Example 1 of the present invention after combustion.
  • Weight and low-temperature ignition delay time statistics from Figure 2 and Table 2, it can be seen that the shape of the tablet after high-temperature combustion is the original tablet shape. And it has harder strength and higher density to support it to maintain its original appearance. Its low temperature ignition time meets the requirement of less than 7ms.
  • barium zirconate was added as a slag-forming agent
  • basic copper nitrate was used as the main oxidant
  • guanidine nitrate was used as the fuel
  • AP and strontium nitrate were used as auxiliary oxidants
  • talc was used as a lubricant and mold release agent.
  • the gas generating agent composition contains the following components in mass percentage content:
  • the specific preparation method is: guanidine nitrate, basic copper nitrate and strontium titanate are mixed by mixing equipment Afterwards, the first material is obtained; the first material is added to 10% distilled water for wet kneading for 50 minutes to obtain the second material, and the second material is passed through a 35 mesh screen to obtain the third material; the third material is dried and dried Until the water content is less than 0.5% of the total mass of the third material, the fourth material is obtained through a 35-mesh screen again; talc powder is added to the fourth material, and the material is formed by a rotary tablet press.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 3 shows the morphology of the residue after combustion of the gas generant composition tablet in Comparative Example 2 of the present invention
  • Table 3 below shows the soluble residue and insoluble residue of the gas generant composition tablet in the present invention after combustion.
  • Weight and low-temperature ignition delay time statistics from Figure 3 and Table 3, it can be seen that the tablets are in the form of flakes and part of powder, which are close to the inner wall of the filter, and their density is poor, which will easily cause them to fly out of the generator filter and fall on the airbag In the medium, it may ablate the air bag and bring potential danger to the human body. Its low temperature ignition time meets the requirement of less than 7ms.
  • the gas generating agent composition contains the following components in mass percentage content:
  • the specific preparation method is: guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate
  • the first material is obtained; the first material is added to 10% distilled water for wet kneading for 50 minutes to obtain the second material, and the second material is passed through a 35-mesh screen to obtain the third material ; Dry the third material until the moisture content is less than 0.5% of the total mass of the third material, and then pass through a 35-mesh screen to obtain the fourth material; add talc to the fourth material and use a rotary tablet press Material shaping.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 4 shows the morphology of the residue after combustion of the gas generant composition tablet in Example 2 of the present invention
  • Table 4 below shows the soluble residue and insoluble residue of the gas generant composition tablet in Example 2 of the present invention after combustion.
  • the residue is close to the inner wall of the filter. Very good original morphology, with harder strength and higher density to support it to maintain its original morphology. Its low temperature ignition time meets the requirement of less than 7ms.
  • strontium zirconate was added as a slag-forming agent
  • basic copper nitrate was used as the main oxidant
  • guanidine nitrate was used as fuel
  • AP and strontium nitrate were used as auxiliary oxidants
  • talc was used as a lubricant and release agent.
  • the gas generating agent composition contains the following components in mass percentage content:
  • the specific preparation method is: guanidine nitrate, basic copper nitrate, copper oxide, potassium perchlorate, and two Silicon oxide and calcium stearate are mixed through mixing equipment to obtain the first material; the first material is added to 10% distilled water for wet kneading for 50 minutes to obtain the second material, and the second material is passed through a 30-mesh screen to obtain the third material ; Dry the third material until the moisture content is less than 0.5% of the total mass of the third material, and then pass through a 30-mesh screen to obtain the fourth material; add talcum powder to the fourth material and proceed through a rotary tablet press Material shaping.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 5 shows the morphology of the residue after combustion of the gas generant composition tablet in Comparative Example 3 of the present invention
  • Table 5 below shows the soluble residue and insoluble residue of the gas generant composition tablet in the present invention after combustion.
  • Weight and low-temperature ignition delay time statistics from Figure 5 and Table 5, it can be seen that agglomeration occurs after the tablet is burned, and a large amount of metallic copper is tinned out, which is attached to the inner wall of the filter. It is easy to fly out of the generator filter and fall into the air bag, which may ablate the air bag and bring potential danger to the human body. Its low temperature ignition time meets the requirement of less than 7ms.
  • the gas generating agent composition contains the following components in mass percentage content:
  • guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate, Calcium zirconate and calcium stearate are mixed through mixing equipment to obtain the first material; add the first material to 10% distilled water for wet kneading for 50 minutes to obtain the second material, and pass the second material through a 30-mesh screen to obtain the third material. Material; Dry the third material until the moisture content is less than 0.5% of the total mass of the third material, and pass through a 30-mesh screen again to obtain the fourth material; Add talc to the fourth material and pass through a rotary tablet press Carry out material shaping.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 6 shows the morphology of the residue after combustion of the gas generant composition tablet in Example 3 of the present invention
  • Table 6 below shows the soluble residue and insoluble residue of the gas generant composition tablet in Example 3 of the present invention after combustion.
  • Weight and low-temperature ignition delay time statistics from Figure 6 and Table 6, it can be seen that the form of the tablet after high-temperature combustion is the original tablet shape, which has a significant coagulation effect. Very good original morphology, with harder strength and higher density to support it to maintain its original morphology. Its low temperature ignition time meets the requirement of less than 7ms.
  • calcium zirconate is added as a slag-forming agent
  • basic copper nitrate is used as the main oxidant
  • guanidine nitrate is used as fuel
  • AP and strontium nitrate are used as auxiliary oxidants
  • calcium stearate is used as a lubricant and mold release agent.
  • the gas generating agent composition contains the following components in mass percentage content:
  • guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate, Strontium zirconate, barium zirconate, and magnesium stearate are mixed by mixing equipment to obtain the first material; add 10% distilled water to the first material for wet kneading for 60 minutes to obtain the second material, and pass the second material through a 40-mesh sieve Net to obtain the third material; dry the third material until the moisture content is less than 0.5% of the total mass of the third material, pass through a 40-mesh screen again to obtain the fourth material; add talc powder to the fourth material, pass Rotary tablet press for material forming.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 7 shows the morphology of the residue after combustion of the gas generant composition tablet in Example 4 of the present invention
  • Table 7 below shows the soluble residue and insoluble residue of the gas generant composition tablet in Example 4 of the present invention after combustion.
  • Weight and low-temperature ignition delay time statistics from Figure 7 and Table 7, it can be seen that the tablets are in the form of original tablets after high-temperature combustion, and have a significant coagulation effect. Very good original morphology, with harder strength and higher density to support it to maintain its original morphology. Its low temperature ignition time meets the requirement of less than 7ms.
  • strontium zirconate and barium zirconate are added as slag-forming agents
  • basic copper nitrate is used as the main oxidant
  • guanidine nitrate is used as fuel
  • AP and strontium nitrate are used as auxiliary oxidants
  • magnesium stearate is used as lubricant and mold release agent.
  • the gas generating agent composition contains the following components in mass percentage content:
  • guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate, Zirconium silicate and talc powder are mixed through mixing equipment to obtain the first material; add the first material to 10% distilled water for wet kneading for 55 minutes to obtain the second material, and pass the second material through a 35-mesh screen to obtain the third material; Dry the third material until the moisture content is less than 0.5% of the total mass of the third material, and pass through a 35-mesh screen again to obtain the fourth material; add talc to the fourth material, and pass the material through a rotary tablet press forming.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 8 shows the morphology of the residue after combustion of the gas generant composition tablet in Example 5 of the present invention
  • Table 8 below shows the soluble and insoluble residues of the gas generant composition tablet in Example 5 of the present invention after combustion.
  • Statistics of weight and low-temperature ignition delay time; from Figure 8 and Table 8 we can see that the tablets are in the form of original tablets after high-temperature combustion, and have a significant coagulation effect. Very good original morphology, with harder strength and higher density to support it to maintain its original morphology. Its low temperature ignition time meets the requirement of less than 7ms.
  • zirconium silicate was added as a slag-forming agent
  • basic copper nitrate was used as the main oxidant
  • guanidine nitrate was used as fuel
  • AP and strontium nitrate were used as auxiliary oxidants
  • talc was used as a lubricant and release agent.
  • the gas generating agent composition contains the following components in mass percentage content:
  • the specific preparation methods are: guanidine nitrate, basic copper nitrate, strontium nitrate, ammonium perchlorate, Strontium zirconate, zirconium silicate and talc powder are mixed through mixing equipment to obtain the first material; add the first material to 10% distilled water for wet kneading for 60 minutes to obtain the second material, and pass the second material through a 40-mesh screen The third material; the third material is dried until the moisture 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 again; the fourth material is added with talcum powder and passed through rotary pressing The tablet machine performs material forming.
  • the prepared discs are loaded into the test generator, and the ignition and combustion test is carried out. After the test, the generator was dissected and the shape of the tablet after burning was observed.
  • Figure 9 shows the morphology of the residue after combustion of the gas generant composition tablet in Example 6 of the present invention
  • Table 9 below shows the soluble residue and insoluble residue of the gas generant composition tablet in Example 6 of the present invention after combustion.
  • strontium zirconate and zirconium silicate are used as slag-forming agents
  • basic copper nitrate is used as the main oxidant
  • guanidine nitrate is used as fuel
  • AP and strontium nitrate are used as auxiliary oxidants
  • talc is used as lubricant and mold release agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Mechanical Engineering (AREA)
  • Air Bags (AREA)

Abstract

本发明涉及一种气体发生剂组合物、制备方法及包含该组合物的气体发生器，该气体发生剂组合物包括如下质量百分比含量的组分：硝酸胍40％～60％；碱式硝酸铜25％～60％；硝酸锶1％～20％；高氯酸铵1％～10％；成渣剂1％～10％；脱模剂/润滑剂0.6％～10％，该气体发生剂组合物通过使用成渣剂作为形态保持剂，使药片燃烧后能够很好的保持燃烧前的形态，避免燃烧后药片熔融飞溅烧伤气袋，并且通过采用硝酸锶和高氯酸铵作为辅助氧化剂，降低碱式硝酸铜的使用量，减少熔融铜残渣，该气体发生剂组合物主要用于汽车安全气囊气体发生器。

Description

一种气体发生剂组合物、制备方法及其应用
本申请要求于2020年5月15日提交中国专利局、申请号为202010414327.9、发明名称为“一种气体发生剂组合物、制备方法及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种气体发生剂组合物、制备方法及其应用，属于汽车安全气囊气体发生器技术领域。
背景技术
汽车安全气囊气体发生剂是作为一种产气药剂装入气体发生器中，需要的时候引发，产生大量的气体。安全气囊由气体发生器和气袋组成。一般碰撞超出预设强度时，气体发生器被激活触发，开始燃烧内部的气体发生剂产生气体，向气袋充气，在内饰和人体之间形成一个缓冲气垫，保护人体免受伤害。
气体发生剂前期主要是叠氮化钠类型的气体发生剂配方，此配方具有燃烧稳定、燃温低、易点火、内压低、产气率高、残渣少等很多优点。但是由于环保、对于人体健康安全方面的问题，现在很少用在汽车安全气囊方面。
目前世界范围内主流的气体发生剂为硝酸胍和碱式硝酸铜类气体发生剂，硝酸胍作为主要燃料，碱式硝酸铜作为主要氧化剂。这类气体发生剂的燃温普遍较高，燃烧后碱式硝酸铜主要生成熔融的铜金属，这导致通常需要多层金属过滤网对其进行过滤和降温，将其留在发生器内部。一方面金属过滤网重量增加会导致成本增加和发生器重量增大；另外一方面，即使使用多层过滤网也不能过滤所有残渣，少部分残渣可以通过过滤网烫伤气袋，更严重的会烫伤人体。
所以解决方式一般为：1.减少碱式硝酸铜的使用量，从而减少气体发生剂组合物燃烧后形成的熔融铜残渣；2.在组合物配方中加入形态保持剂。形态保持剂一般为高熔点物质，起到增大熔融残渣粘度和作为药片骨架维持自身形状的作用。
钛酸锶是一种高熔点的金属化合物。之前在安全气囊气体发生剂领域也有使用，例如专利CN105801326A就是主要含有硝酸胍、碱式硝酸铜、钛酸盐的气体发生剂配方。但是该专利使用钛酸盐作为形态保持剂，对形态保持作用并不明显，不能起到很好的燃烧形态保持作用，尤其是对于碱式硝酸铜含量大于40％，硝酸胍含量大于40％的气体发生剂更不能起到很好的燃烧形态保持作用，并且该气体发生剂配方不容易被点燃。
例如专利CN100376515C公开了一种产气组合物，包括硝酸胍、碱式硝酸铜、辅助氧化剂硝酸钠、氧化铜及氧化铁，以及点火改良剂(三氧化二铝、氯化铜、铬酸铜、铬酸钾)，采用点火改良剂使的产气组合物更易于点火，点火延迟期短，但是三氧化二铝一般用于残渣结团，对于点火改良作用不大；氯化铜为弱氧化剂点火改良作用不大；铬酸铜、铬酸钾都是含铜类的强氧化剂，能起到一定的点火改良作用，但是均会增加残渣含量，铬酸铜增加不溶残渣含量，铬酸钾增加可溶残渣含量，且含碱金属钾类的物质燃烧后会形成可溶性的气溶胶微粒，对残渣结团不利。
再例如专利US5827996A公开了一种气囊用气体发生剂，包括燃料采用唑类或其金属盐，氧化剂，燃烧催化剂，控制燃烧剂和造渣剂，燃料采用唑类和金属盐，造渣剂是固化气体发生剂的燃烧残留物的添加剂，从而有利于气囊中的过滤器除去残留物，但是该专利适用于唑类作为燃料的配方，该类配方燃温比硝酸胍碱式硝酸铜类型配方高的多，即使加入造渣剂药片形态也不能很好保持。
此外专利CN101952227B公开了一种制备气体发生剂的方法，添加了硝酸胍、碱式硝酸铜、辅助氧化剂(例如硝酸钾、硝酸锶和硝酸钠)、燃速 调节剂(高氯酸钾)、熔渣促进剂(二氧化硅、氧化锌、氧化铵、氧化铝)、压片脱模助剂兼形态保持协同助剂B(石墨、二硫化钼、二硫化钨、氮化硼)，该专利所用制粒方式为喷雾制粒方式，喷雾制粒与湿法制粒相比能耗较高；另外，该专利所用熔渣促进剂主要来之金属氧化物，如二氧化硅、氧化铝、氧化锌、氧化铈，金属氧化物作为熔渣促进剂可以起到一定的促进熔渣结团作用，但是对于药片形态保持作用并不明显。
申请号为CN107698415A的在先申请公开了组成为硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、钛酸锶，滑石粉的气体发生剂，该申请加入钛酸锶虽然具有成渣效果，但是在以BCN/GN为体系的配方中，其成渣效果并不显著，实际应用中发现其成渣效果不能满足需要，并且大量试验表明，药片燃烧后其密度较差，手一碰则易碎，将易导致飞出发生器过滤网，落在气囊中，有可能烧蚀气袋，给人体带来潜在的危险。
发明内容
本发明的目的在于克服现有技术的上述不足，提供一种气体发生剂组合物，该气体发生剂组合物通过采用锆酸盐、硅酸盐或者锆酸盐与硅酸盐的混合物作为成渣剂，与其余组份配合，使药片燃烧后能够凝结、团聚在过滤网内，非常好的保持燃烧前的形态，完全避免燃烧后药片熔融飞溅烧伤气袋，使气体发生剂组合物燃烧期间的造渣提高了至少50％。
本发明的另外一个目的在于提供了一种气体发生剂组合物提高成渣能力的方法，所述的方法包括碱式硝酸铜，硝酸胍，硝酸锶，AP的气体发生剂组合物中引入了高熔点的物质镐酸盐和硅酸盐的造渣剂组分。
本发明的另外一个目的在于提供一种气体发生剂组合物的制备方法及其应用。
本发明的上述目的主要是通过如下技术方案予以实现的：
一种气体发生剂组合物，包括硝酸胍、碱式硝酸铜、硝酸锶以及高氯酸铵，其特征在于：还包括成渣剂和润滑剂，所述成渣剂为至少一种锆酸 盐，或至少一种硅酸盐，或至少一种锆酸盐与至少一种硅酸盐的混合物；
各组分的质量百分比含量如下：
Figure PCTCN2021075533-appb-000001
在上述气体发生剂组合物中，所述锆酸盐为锆酸锶、锆酸钡或锆酸钙中的一种或组合。
在上述气体发生剂组合物中，所述硅酸盐为硅酸锆或硅酸钙中的一种或组合。
在上述气体发生剂组合物中，所述成渣剂为至少一种锆酸盐与至少一种硅酸盐的混合物中，锆酸盐与硅酸盐的质量比为1：0.5～3；优选1：0.8～2。
在上述气体发生剂组合物中，所述成渣剂为锆酸锶、硅酸锆与硅酸钙的混合物，三者的质量比为1：0.2～1.5：0.3～1.5，优选1：0.3～1：0.5～1。
在上述气体发生剂组合物中，所述成渣剂为锆酸锶与锆酸钡的混合物，二者的质量比为1：0.5～3，优选1：0.8～2。
在上述气体发生剂组合物中，所述润滑剂为滑石粉、石墨、硬脂酸钙、硬脂酸镁、二硫化钼或氮化硼中的一种或组合。
在上述气体发生剂组合物中，所述高氯酸铵粒径D90不大于20μm；所述成渣剂的粒径D90不大于5μm。
在上述气体发生剂组合物中，所述碱式硝酸铜和润滑剂的粒径D90均不大于5μm。
在上述气体发生剂组合物中，所述气体发生剂组合物的各组分含水量之和不大于各组分总质量的1％。
在上述气体发生剂组合物中，所述气体发生剂组合物成型后为圆形或椭圆形片状结构、圆形或椭圆形柱状结构、异形片状或柱状结构、圆形或椭圆形单孔结构、圆形或椭圆形多孔结构、异形单孔或多孔结构。
在上述气体发生剂组合物中，所述圆形片状结构的直径为3～15mm，高度为2～5mm；圆形柱状结构的直径为3～15mm，高度为5～15mm；圆形单孔结构的内径0.5～2.5mm，外径为3～15mm，高度为3～15mm；椭圆形单孔结构的内径0.5～2.5mm，长径3～20mm，短直径2～12mm，高度为3～15mm。
上述气体发生剂组合物的制备方法，采用湿法制粒、喷雾制粒或干法制粒制备气体发生剂组合物；所述湿法制粒的具体制备方法包括如下步骤：
(1)、将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和成渣剂混合后得到第一物料；
(2)、将第一物料加水进行湿法混合，得到第二物料，其中加水量为第一物料总质量的5％～15％；
(3)、将第二物料通过10～40目的筛网得到第三物料；
(4)、将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过10～40目的筛网得到第四物料；
(5)、将第四物料中加入润滑剂，进行物料成型。
在上述气体发生剂组合物的制备方法中，所述步骤(1)中将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和成渣剂在混合设备中进行混合得到第一物料，混合时间≥5min。
在上述气体发生剂组合物的制备方法中，所述步骤(2)中湿法混合的时间为20min～60min；湿法混合的设备为捏合机或混合机。
上述气体发生剂组合物的制备方法，采用湿法制粒的方式制备气体发生剂组合物，具体制备方法包括如下步骤：
(1)、将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、成渣剂和润滑剂混 合后得到第一物料；
(2)、将第一物料加水进行湿法混合，得到第二物料，其中加水量为第一物料总质量的5％～15％；
(3)、将第二物料通过10～40目的筛网得到第三物料；
(4)、将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过10～40目的筛网得到第四物料；
(5)、将第四物料进行物料成型。
在上述气体发生剂组合物的制备方法中，所述步骤(1)中将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、结渣剂和润滑剂在混合设备中进行混合得到第一物料，混合时间≥5min。
在上述气体发生剂组合物的制备方法中，所述步骤(2)中湿法混合的时间为20min～60min；湿法混合的设备为捏合机或混合机。
上述气体发生剂组合物的应用，所述气体发生剂组合物用于汽车安全气囊气体发生器。
一种气体发生器，采用上述气体发生剂组合物。
本发明与现有技术相比具有如下有益效果：
(1)、本发明首次采用锆酸盐、硅酸盐或者锆酸盐与硅酸盐的混合物作为气体发生剂的成渣剂，通过与硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵以及脱模剂的配合，使得药片燃烧后能够非常好的保持燃烧前的形态，完全避免燃烧后药片熔融飞溅烧伤气袋，显著减少碱式硝酸铜燃烧分解后形成的熔融铜残渣，在显著提高组合物的低温点火性能同时提高了燃烧速度，使气体发生剂组合物燃烧期间的造渣提高了至少50％。
(2)、本发明以碱式硝酸铜和硝酸胍为体系的气体发生剂配方中，首次加入锆酸盐、硅酸盐或者锆酸盐与硅酸盐的混合物作为气体发生剂的成渣剂，使熔融的铜金属能够凝结团聚成块状，熔点为2500K左右，该成渣剂不容易燃烧，在气体发生剂组合物燃烧时，能将全部固体燃烧产物附聚物 收集在一起，使气体发生剂在燃烧后保持其原有的形状；大量试验表明本发明采用的锆酸盐、硅酸盐或二者的混合物可以对碱式硝酸铜分解后形成的金属铜熔液形成很好的凝结作用，进一步减少熔融铜残渣，能够起到增大熔融残渣粘度和作为药片骨架维持自身形状的作用，得到了显著的凝聚结渣的效果。
(3)、本发明首次采用锆酸盐、硅酸盐或者锆酸盐与硅酸盐的混合物作为气体发生剂的成渣剂，在保证气体发生剂燃速不变的情况下，使气体发生剂组合物燃烧期间的造渣提高了至少50％，发生器在做过TANKWASH残渣实验后，其不溶物和水溶物的总含量远远小于1g(USCAR的行业要求)，总含量大约在0.4g左右。
(4)、本发明采用一定量的高氯酸铵和硝酸锶作为辅助氧化剂，与其它各组份配合使用，加入锆酸盐、硅酸盐或者锆酸盐与硅酸盐的混合物作为气体发生剂的成渣剂，提高组合物的低温点火性能同时提高了燃烧速度，且达到USCAR标准的要求。
(5)、本发明对湿法制粒的工艺过程及工艺条件进行优化设计，使得制备工艺简单、易于实现，同时本发明制备方法中脱模剂可以在制备之前同其余组份一起混合后进行湿法制备，也可以在最后加入滑石粉，制备方法更加灵活。
附图说明
图1为本发明对比例1中气体发生剂组合物药片燃烧后残渣形态图；
图2为本发明实施例1中气体发生剂组合物药片燃烧后残渣形态图；
图3为本发明对比例2中气体发生剂组合物药片燃烧后残渣形态图；
图4为本发明实施例2中气体发生剂组合物药片燃烧后残渣形态图；
图5为本发明对比例3中气体发生剂组合物药片燃烧后残渣形态图；
图6为本发明实施例3中气体发生剂组合物药片燃烧后残渣形态图；
图7为本发明实施例4中气体发生剂组合物药片燃烧后残渣形态图；
图8为本发明实施例5中气体发生剂组合物药片燃烧后残渣形态图；
图9为本发明实施例6中气体发生剂组合物药片燃烧后残渣形态图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细的描述：
本发明公开一种气体发生剂组合物，包括硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、成渣剂和润滑剂，其中成渣剂为至少一种锆酸盐，或至少一种硅酸盐，或至少一种锆酸盐与至少一种硅酸盐的混合物，润滑剂选自滑石粉、石墨、硬脂酸钙、硬脂酸镁、二硫化钼或氮化硼中的至少一种；
各组分的质量百分比含量如下：
Figure PCTCN2021075533-appb-000002
上述锆酸盐为锆酸锶、锆酸钡或锆酸钙中的一种或组合。
上述硅酸盐为硅酸锆或硅酸钙中的一种或组合。
上述成渣剂为至少一种锆酸盐与至少一种硅酸盐的混合物中，锆酸盐与硅酸盐的质量比为1：0.5～3。
本发明一可选实施例中，成渣剂为锆酸锶、硅酸锆与硅酸钙的混合物，三者的质量比为1：0.5～3：0.5～3。
本发明一可选实施例中，成渣剂为锆酸锶与锆酸钡的混合物，二者的质量比为1：0.5～3。
上述高氯酸铵粒径D90不大于20μm。
上述成渣剂的粒径D90不大于5μm。
上述碱式硝酸铜和润滑剂/脱模剂的粒径D90均不大于5μm。
上述气体发生剂组合物的各组分含水量之和不大于各组分总质量的1％。
本发明一可选实施例中，气体发生剂组合物成型后为圆形或椭圆形片状结构、圆形或椭圆形柱状结构、异形片状或柱状结构、圆形或椭圆形单孔结构、圆形或椭圆形多孔结构、异形单孔或多孔结构。其中圆形片状结构的直径为3～15mm，高度为2～5mm；圆形柱状结构的直径为3～15mm，高度为5～15mm；圆形单孔结构的内径0.5～2.5mm，外径为3～15mm，高度为3～15mm；椭圆形单孔结构的内径0.5～2.5mm，长径3～20mm，短直径2～12mm，高度为3～15mm。
本发明气体发生剂组合物的制备方法，可以采用湿法制粒、喷雾制粒或干法制粒方法制备。其中喷雾制粒或干法制粒可以采用传统制粒工艺方法。
其中湿法制粒的具体制备方法包括如下步骤：
(1)、将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和成渣剂混合后得到第一物料；在混合设备中进行混合，混合时间≥5min；混合设备可以为气动混合机、V型混合机、三维多向运动混合机、自动提升料斗混合机、振动磨、螺带混合机或声共振混合机。
(2)、将第一物料加水进行湿法混合，得到第二物料，湿法混合的时间为20min～60min；其中加水量为第一物料总质量的5％～15％；优选采用加入蒸馏水。湿法混合的设备为捏合机或混合机，例如可以选择卧式捏合机、立式捏合机、螺带混合机或声共振混合机。
(3)、将第二物料通过10～40目的筛网得到第三物料；
(4)、将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过10～40目的筛网得到第四物料；烘干设备可以为电加热烘箱、油浴烘箱、蒸汽烘箱、双锥烘箱、振动流化床或带式真空干燥机。
(5)、将第四物料中加入润滑剂，进行物料成型。成型设备可以为油压 机、旋转压片机或粉末成型机。成型后可以为圆形或椭圆形片状结构、圆形或椭圆形柱状结构、异形片状或柱状结构、圆形或椭圆形单孔结构、圆形或椭圆形多孔结构、异形单孔或多孔结构。本发明一可选实施例中，圆形片状结构的直径为3～15mm，高度为2～5mm；圆形柱状结构的直径为3～15mm，高度为5～15mm；圆形单孔结构的内径0.5～2.5mm，外径为3～15mm，高度为3～15mm；椭圆形单孔结构的内径0.5～2.5mm，长径3～20mm，短直径2～12mm，高度为3～15mm。。
另一种湿法制粒的具体制备方法包括如下步骤：
(1)、将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、成渣剂和润滑剂混合后得到第一物料；在混合设备中进行混合，混合时间≥5min；混合设备可以为V型混合机、三维多向运动混合机、自动提升料斗混合机、振动磨、螺带混合机或声共振混合机。
(2)、将第一物料加水进行湿法混合，得到第二物料，湿法混合的时间为20min～60min；其中加水量为第一物料总质量的5％～15％；优选采用加入蒸馏水。湿法混合的设备为捏合机或混合机，例如可以选择卧式捏合机、立式捏合机、螺带混合机或声共振混合机。
(3)、将第二物料通过10～40目的筛网得到第三物料；
(4)、将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过10～40目的筛网得到第四物料；烘干设备可以为电加热烘箱、油浴烘箱、蒸汽烘箱、双锥烘箱、振动流化床或带式真空干燥机。
(5)、将第四物料进行物料成型。成型设备可以为油压机、旋转压片机或粉末成型机。
本发明上述气体发生剂组合物用于汽车安全气囊气体发生器。
本发明以碱式硝酸铜和硝酸胍为体系的气体发生剂配方中，首次加入锆酸盐、硅酸盐或者锆酸盐与硅酸盐的混合物作为气体发生剂的成渣剂，使熔融的铜金属能够凝结团聚成块状，熔点为2500K左右，远远大于金属铜 的熔点，大量试验表明，该成渣剂不容易燃烧，在气体发生剂组合物燃烧时，能将全部固体燃烧产物附聚物收集在一起，使气体发生剂在燃烧后保持其原有的形状。本发明锆酸盐、硅酸盐或二者的混合物可以对碱式硝酸铜分解后形成的金属铜熔液形成很好的凝结作用，进一步减少熔融铜残渣。能够起到增大熔融残渣粘度和作为药片骨架维持自身形状的作用，得到了显著的凝聚结渣的效果。
以下实施例中采用的混合设备为三维多项运动混合机(或超高效混合机)、捏合机为卧式捏合机，烘干设备为真空烘箱，成型设备为旋转压片机。
对比例1
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍40％
碱式硝酸铜40％
硝酸锶12.75％
高氯酸铵1％
钛酸锶5.5％
滑石粉0.75％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和钛酸锶通过混合设备混合后得到第一物料；将第一物料加入15％的蒸馏水进行湿法捏合60min，得到第二物料，将第二物料通过40目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过40目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图1所示为本发明对比例1中气体发生剂组合物药片燃烧后残渣形 态图；如下表1为本发明对比例1中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图1和表1可知药片形态为片状，紧贴在过滤网的内壁，其密度较差，手一碰则易碎，易导致飞出发生器过滤网，落在气囊中，有可能烧蚀气袋，给人体带来潜在的危险。其低温点火时间满足小于7ms的要求。
表1
Figure PCTCN2021075533-appb-000003
实施例1
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍40％
碱式硝酸铜42.75％
硝酸锶8％
高氯酸铵3％
锆酸钡5.5％
滑石粉0.75％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和锆酸钡通过混合设备混合后得到第一物料；将第一物料加入15％的蒸馏水进行湿法捏合60min，得到第二物料，将第二物料通过40目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过40目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图2所示为本发明实施例1中气体发生剂组合物药片燃烧后残渣形态图；如下表2为本发明实施例1中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图2和表2可知药片在高温燃烧后形态为原药片状，紧贴在过滤网的内壁，其密度较大，药片保持了非常好的原形貌，且有较硬的强度和较高的密度支撑其维持其原来的形貌。其低温点火时间满足小于7ms的要求。
表2
Figure PCTCN2021075533-appb-000004
本实施例中加入锆酸钡作为成渣剂，以碱式硝酸铜为主氧化剂，硝酸胍为燃料，AP和硝酸锶作为辅助氧化剂，滑石粉作为润滑剂和脱模剂，在进行安全气囊发生器试验后，药片保持了非常好的原形貌，TANKWASH试验测试后，水溶物重量和不溶物重量减少显著。同时组合物燃烧速度提高，点火延迟满足USCAR的严格要求。
对比例2
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍52％
碱式硝酸铜44％
钛酸锶4％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：将硝酸胍、碱式硝酸铜和钛酸锶通过混合设备混合后得到第一物料；将第一物料加入10％的蒸馏水进行湿法捏 合50min，得到第二物料，将第二物料通过35目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过35目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图3所示为本发明对比例2中气体发生剂组合物药片燃烧后残渣形态图；如下表3为本发明对比例2中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图3和表3可知药片形态为片状和部分粉状，紧贴在过滤网的内壁，其密度较差，易导致飞出发生器过滤网，落在气囊中，有可能烧蚀气袋，给人体带来潜在的危险。其低温点火时间满足小于7ms的要求。
表3
Figure PCTCN2021075533-appb-000005
实施例2
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍50％
碱式硝酸铜41.5％
硝酸锶1.5％
高氯酸铵2％
锆酸锶4％
滑石粉1％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和锆酸锶、滑石粉通过混合设备混合后得到第一物料；将第一物料加入10％的蒸馏水进行湿法捏合50min，得到第二物料，将第二物料通过35目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过35目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图4所示为本发明实施例2中气体发生剂组合物药片燃烧后残渣形态图；如下表4为本发明实施例2中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图4和表4可知药片在高温燃烧后形态为原药片状，有着显著的凝结效果，残渣紧贴在过滤网的内壁，其密度较大，药片保持了非常好的原形貌，且有较硬的强度和较高的密度支撑其维持其原来的形貌。其低温点火时间满足小于7ms的要求。
表4
Figure PCTCN2021075533-appb-000006
本实施例中加入锆酸锶作为成渣剂，以碱式硝酸铜为主氧化剂，硝酸胍为燃料，AP和硝酸锶作为辅助氧化剂，滑石粉作为润滑剂和脱模剂，在进行安全气囊发生器试验后，药片保持了非常好的原形貌，TANKWASH试验测试后，水溶物重量和不溶物重量减少显著。同时组合物燃烧速度提高，点火延迟满足USCAR的严格要求。
对比例3
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍45％
碱式硝酸铜40％
高氯酸钾5％
氧化铜4％
二氧化硅5％
硬脂酸钙1％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：将硝酸胍、碱式硝酸铜、氧化铜、高氯酸钾、二氧化硅和硬脂酸钙通过混合设备混合后得到第一物料；将第一物料加入10％的蒸馏水进行湿法捏合50min，得到第二物料，将第二物料通过30目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过30目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图5所示为本发明对比例3中气体发生剂组合物药片燃烧后残渣形态图；如下表5为本发明对比例3中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图5和表5可知药片燃烧后出现凝聚，锡出大量的金属铜，贴在过滤网的内壁，并没有凝聚成理相想的片状，这样将导致残渣易飞出发生器过滤网，落在气囊中，有可能烧蚀气袋，给人体带来潜在的危险。其低温点火时间满足小于7ms的要求。
表5
Figure PCTCN2021075533-appb-000007
实施例3
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍45％
碱式硝酸铜40％
硝酸锶4％
高氯酸铵5％
锆酸钙5％
硬脂酸钙1％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、锆酸钙和硬脂酸钙通过混合设备混合后得到第一物料；将第一物料加入10％的蒸馏水进行湿法捏合50min，得到第二物料，将第二物料通过30目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过30目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图6所示为本发明实施例3中气体发生剂组合物药片燃烧后残渣形态图；如下表6为本发明实施例3中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图6和表6可知药片在高温燃烧后形态为原药片状，有着显著的凝结效果，残渣紧贴在过滤 网的内壁，其密度较大，药片保持了非常好的原形貌，且有较硬的强度和较高的密度支撑其维持其原来的形貌。其低温点火时间满足小于7ms的要求。
表6
Figure PCTCN2021075533-appb-000008
本实施例中加入锆酸钙作为成渣剂，以碱式硝酸铜为主氧化剂，硝酸胍为燃料，AP和硝酸锶作为辅助氧化剂，硬脂酸钙作为润滑剂和脱模剂，在进行安全气囊发生器试验后，药片保持了非常好的原形貌，TANKWASH试验测试后，水溶物重量和不溶物重量减少显著。同时组合物燃烧速度提高，点火延迟满足USCAR的严格要求。
实施例4
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍51.5％
碱式硝酸铜35％
硝酸锶6％
高氯酸铵3％
锆酸锶2％
锆酸钡2％
硬脂酸镁0.5％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、锆酸锶、锆酸钡和硬脂酸镁通过混合设备混合后得到第一物料；将第一物料加入10％的蒸馏水进行湿法捏合60min，得到第二物料，将第二 物料通过40目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过40目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图7所示为本发明实施例4中气体发生剂组合物药片燃烧后残渣形态图；如下表7为本发明实施例4中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图7和表7可知药片在高温燃烧后形态为原药片状，有着显著的凝结效果，残渣紧贴在过滤网的内壁，其密度较大，药片保持了非常好的原形貌，且有较硬的强度和较高的密度支撑其维持其原来的形貌。其低温点火时间满足小于7ms的要求。
表7
Figure PCTCN2021075533-appb-000009
本实施例中加入锆酸锶和锆酸钡作为成渣剂，以碱式硝酸铜为主氧化剂，硝酸胍为燃料，AP和硝酸锶作为辅助氧化剂，硬脂酸镁作为润滑剂和脱模剂，在进行安全气囊发生器试验后，药片保持了非常好的原形貌，TANKWASH试验测试后，水溶物重量和不溶物重量减少显著。同时组合物燃烧速度提高，点火延迟满足USCAR的严格要求。
实施例5
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍55％
碱式硝酸铜28％
硝酸锶4％
高氯酸铵7％
硅酸锆4％
滑石粉2％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、硅酸锆和滑石粉通过混合设备混合后得到第一物料；将第一物料加入10％的蒸馏水进行湿法捏合55min，得到第二物料，将第二物料通过35目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过35目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图8所示为本发明实施例5中气体发生剂组合物药片燃烧后残渣形态图；如下表8为本发明实施例5中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图8和表8可知药片在高温燃烧后形态为原药片状，有着显著的凝结效果，残渣紧贴在过滤网的内壁，其密度较大，药片保持了非常好的原形貌，且有较硬的强度和较高的密度支撑其维持其原来的形貌。其低温点火时间满足小于7ms的要求。
表8
Figure PCTCN2021075533-appb-000010
本实施例中加入硅酸锆作为成渣剂，以碱式硝酸铜为主氧化剂，硝酸胍为燃料，AP和硝酸锶作为辅助氧化剂，滑石粉作为润滑剂和脱模剂，在进行安全气囊发生器试验后，药片保持了非常好的原形貌，TANKWASH试验测试后，水溶物重量和不溶物重量减少显著。同时组合物燃烧速度提高，点火延迟满足USCAR的严格要求。
实施例6
气体发生剂组合物包含如下质量百分比含量的组份：
硝酸胍48％
碱式硝酸铜42％
硝酸锶2.5％
高氯酸铵3％
锆酸锶1.5％
硅酸锆2.5％
滑石粉0.5％
这些组分被称量后，通过湿法制粒和旋转压片机压制成直径5mm，厚度1.9mm的圆片，具体制备方法为：硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、锆酸锶、硅酸锆和滑石粉通过混合设备混合后得到第一物料；将第一物料加入10％的蒸馏水进行湿法捏合60min，得到第二物料，将第二物料通过40目的筛网得到第三物料；将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过40目的筛网得到第四物料；将第四物料中加入滑石粉，通过旋转压片机进行物料成型。
将制备的圆片装入试验发生器中，进行点火燃烧试验。试验后将发生器解剖，观察药片燃烧后的形态。
如图9所示为本发明实施例6中气体发生剂组合物药片燃烧后残渣形态图；如下表9为本发明实施例6中气体发生剂组合物药片燃烧后排出物可溶残渣与不溶残渣重量及低温点火延迟时间统计；由图9和表9可知药 片在高温燃烧后形态为原药片状，有着显著的凝结效果，残渣紧贴在过滤网的内壁，其密度较大，药片保持了非常好的原形貌，且有较硬的强度和较高的密度支撑其维持其原来的形貌。其低温点火时间满足小于7ms的要求。
表9
Figure PCTCN2021075533-appb-000011
本实施例中加入锆酸锶和硅酸锆共同作为成渣剂，以碱式硝酸铜为主氧化剂，硝酸胍为燃料，AP和硝酸锶作为辅助氧化剂，滑石粉作为润滑剂和脱模剂，在进行安全气囊发生器试验后，药片保持了非常好的原形貌，TANKWASH试验测试后，水溶物重量和不溶物重量减少显著。同时组合物燃烧速度提高，点火延迟满足USCAR的严格要求。
本发明上述对比例及实施例中均作了三组平行试验并取平均值。
以上所述，仅为本发明最佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。
本发明说明书中未作详细描述的内容属于本领域专业技术人员的公知技术。

Claims (20)

  1. 一种气体发生剂组合物，包括硝酸胍、碱式硝酸铜、硝酸锶以及高氯酸铵，其特征在于：还包括成渣剂和润滑剂，所述成渣剂为至少一种锆酸盐，或至少一种硅酸盐，或至少一种锆酸盐与至少一种硅酸盐的混合物；
    各组分的质量百分比含量如下：
    Figure PCTCN2021075533-appb-100001
  2. 根据权利要求1所述的气体发生剂组合物，其特征在于：所述锆酸盐为锆酸锶、锆酸钡或锆酸钙中的一种或组合。
  3. 根据权利要求1所述的气体发生剂组合物，其特征在于：所述硅酸盐为硅酸锆或硅酸钙中的一种或组合。
  4. 根据权利要求1～3之一所述的气体发生剂组合物，其特征在于：所述成渣剂为至少一种锆酸盐与至少一种硅酸盐的混合物中，锆酸盐与硅酸盐的质量比为1：0.5～3；优选1：0.8～2。
  5. 根据权利要求4所述的气体发生剂组合物，其特征在于：所述成渣剂为锆酸锶、硅酸锆与硅酸钙的混合物，三者的质量比为1：0.2～1.5：0.3～1.5，优选1：0.3～1：0.5～1。
  6. 根据权利要求1或2所述的气体发生剂组合物，其特征在于：所述成渣剂为锆酸锶与锆酸钡的混合物，二者的质量比为1：0.5～3，优选1：0.8～2。
  7. 根据权利要求1～3之一所述的气体发生剂组合物，其特征在于：所述润滑剂为滑石粉、石墨、硬脂酸钙、硬脂酸镁、二硫化钼或氮化硼中的 一种或组合。
  8. 根据权利要求1～3之一所述的气体发生剂组合物，其特征在于：所述高氯酸铵粒径D90不大于20μm；所述成渣剂的粒径D90不大于5μm。
  9. 根据权利要求1～3之一所述的气体发生剂组合物，其特征在于：所述碱式硝酸铜和润滑剂的粒径D90均不大于5μm。
  10. 根据权利要求1～3之一所述的气体发生剂组合物，其特征在于：所述气体发生剂组合物的各组分含水量之和不大于各组分总质量的1％。
  11. 根据权利要求1～3之一所述的气体发生剂组合物，其特征在于：所述气体发生剂组合物成型后为圆形或椭圆形片状结构、圆形或椭圆形柱状结构、异形片状或柱状结构、圆形或椭圆形单孔结构、圆形或椭圆形多孔结构、异形单孔或多孔结构。
  12. 根据权利要求11所述的气体发生剂组合物，其特征在于：所述圆形片状结构的直径为3～15mm，高度为2～5mm；圆形柱状结构的直径为3～15mm，高度为5～15mm；圆形单孔结构的内径0.5～2.5mm，外径为3～15mm，高度为3～15mm；椭圆形单孔结构的内径0.5～2.5mm，长径3～20mm，短直径2～12mm，高度为3～15mm。
  13. 权利要求1～12之一所述的气体发生剂组合物的制备方法，其特征在于：采用湿法制粒、喷雾制粒或干法制粒制备气体发生剂组合物；所述湿法制粒的具体制备方法包括如下步骤：
    (1)、将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和成渣剂混合后得到第一物料；
    (2)、将第一物料加水进行湿法混合，得到第二物料，其中加水量为第一物料总质量的5％～15％；
    (3)、将第二物料通过10～40目的筛网得到第三物料；
    (4)、将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过10～40目的筛网得到第四物料；
    (5)、将第四物料中加入润滑剂，进行物料成型。
  14. 根据权利要求13所述的气体发生剂组合物的制备方法，其特征在于：所述步骤(1)中将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵和成渣剂在混合设备中进行混合得到第一物料，混合时间≥5min。
  15. 根据权利要求13所述的气体发生剂组合物的制备方法，其特征在于：所述步骤(2)中湿法混合的时间为20min～60min；湿法混合的设备为捏合机或混合机。
  16. 权利要求1～12之一所述的气体发生剂组合物的制备方法，其特征在于：采用湿法制粒的方式制备气体发生剂组合物，具体制备方法包括如下步骤：
    (1)、将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、成渣剂和润滑剂混合后得到第一物料；
    (2)、将第一物料加水进行湿法混合，得到第二物料，其中加水量为第一物料总质量的5％～15％；
    (3)、将第二物料通过10～40目的筛网得到第三物料；
    (4)、将第三物料进行烘干，烘干至含水量小于第三物料总质量的0.5％，再次通过10～40目的筛网得到第四物料；
    (5)、将第四物料进行物料成型。
  17. 根据权利要求16所述的气体发生剂组合物的制备方法，其特征在于：所述步骤(1)中将硝酸胍、碱式硝酸铜、硝酸锶、高氯酸铵、结渣剂和润滑剂在混合设备中进行混合得到第一物料，混合时间≥5min。
  18. 根据权利要求16所述的气体发生剂组合物的制备方法，其特征在于：所述步骤(2)中湿法混合的时间为20min～60min；湿法混合的设备为捏合机或混合机。
  19. 权利要求1～12之一所述的气体发生剂组合物的应用，其特征在于：所述气体发生剂组合物用于汽车安全气囊气体发生器。
  20. 一种气体发生器，其特征在于：采用权利要求1～12之一所述的气体发生剂组合物。
PCT/CN2021/075533 2020-05-15 2021-02-05 一种气体发生剂组合物、制备方法及其应用 WO2021227577A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP21737332.3A EP3936495A4 (en) 2020-05-15 2021-02-05 GAS GENERATING AGENT COMPOSITION, METHOD FOR PREPARING IT AND ITS APPLICATION
US17/478,013 US20220009853A1 (en) 2020-05-15 2021-09-17 Gas generant composition, preparation method therefor, and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010414327.9 2020-05-15
CN202010414327.9A CN111675589B (zh) 2020-05-15 2020-05-15 一种气体发生剂组合物、制备方法及其应用

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/478,013 Continuation-In-Part US20220009853A1 (en) 2020-05-15 2021-09-17 Gas generant composition, preparation method therefor, and use thereof

Publications (1)

Publication Number Publication Date
WO2021227577A1 true WO2021227577A1 (zh) 2021-11-18

Family

ID=72452456

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/075533 WO2021227577A1 (zh) 2020-05-15 2021-02-05 一种气体发生剂组合物、制备方法及其应用

Country Status (4)

Country Link
US (1) US20220009853A1 (zh)
EP (1) EP3936495A4 (zh)
CN (1) CN111675589B (zh)
WO (1) WO2021227577A1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210061729A1 (en) * 2019-08-29 2021-03-04 Autoliv Asp, Inc. Alkaline earth metal zirconium oxide additive useful for improving ballistic performance of gas generating compositions
CN111548242B (zh) * 2020-05-15 2021-09-03 湖北航鹏化学动力科技有限责任公司 气体发生器
CN111675589B (zh) * 2020-05-15 2021-08-06 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、制备方法及其应用
CN114044729A (zh) * 2021-11-16 2022-02-15 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、气体发生剂及制备方法与应用
CN115974632A (zh) * 2022-12-27 2023-04-18 河北东方久乐瑞丰汽车安全部件有限公司 汽车安全气囊气体发生器用产气药及其制备工艺
CN116514615A (zh) * 2023-04-26 2023-08-01 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、气体发生剂及制备方法和应用

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4296084A (en) * 1979-10-29 1981-10-20 Thiokol Corporation Method of and apparatus for gas generation
WO1996025375A1 (en) * 1995-02-16 1996-08-22 Royal Ordnance Plc Vehicle occupant restraint systems powered by gas generating compositions
CN1132501A (zh) * 1993-10-06 1996-10-02 尼古化学股份公司 气体发生器的推进剂
CN1150794A (zh) * 1995-04-14 1997-05-28 汽车系统实验室公司 具有内在催化剂的非叠氮化物气体发生组合物
US5827996A (en) 1995-09-29 1998-10-27 Otsuka Kagaku Kabushiki Kaish Air bag gas generating composition
US6143102A (en) * 1999-05-06 2000-11-07 Autoliv Asp, Inc. Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods
CN1277598A (zh) * 1998-09-14 2000-12-20 大赛璐化学工业株式会社 产气组合物
US20020148542A1 (en) * 1999-05-06 2002-10-17 Taylor Robert D. Gas generant compositions containing copper ethylenediamine dinitrate and associated methods
CN1714059A (zh) * 2002-11-22 2005-12-28 日本化药株式会社 气体发生剂及其制造方法以及气囊用气体发生器
CN100376515C (zh) 2005-03-28 2008-03-26 东方久乐汽车安全气囊有限公司 一种产气组合物及其制备方法
CN101234943A (zh) * 2008-03-03 2008-08-06 烟台安泰德汽车安全系统有限公司 一种汽车安全气囊用气体发生剂及其制备方法
CN101415659A (zh) * 2006-04-04 2009-04-22 Snpe巨能材料公司 大尺寸的烟火颗粒及其制造和用途
WO2009126182A1 (en) * 2008-04-10 2009-10-15 Autoliv Asp, Inc. Monolithic gas generants containing perchlorate-based oxidizers and methods for manufacture thereof
CN101952227A (zh) 2008-04-10 2011-01-19 奥托里夫Asp股份有限公司 高性能气体发生组合物
CN102423805A (zh) * 2011-11-23 2012-04-25 西安理工大学 一种低铬含量的CuCr合金粉末的制备方法
CN105358507A (zh) * 2013-05-21 2016-02-24 有限会社三松 充气机固体排出量减少的气体发生剂组合物
CN105801326A (zh) 2011-05-09 2016-07-27 海瑞克里兹 产气烟火复合物
CN107501018A (zh) * 2017-08-08 2017-12-22 成都银河动力有限公司 一种用于化学能板材破拆装备的专用药剂
CN107698415A (zh) 2017-10-24 2018-02-16 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、制备方法、应用及气体发生器
CN107840772A (zh) * 2017-03-02 2018-03-27 湖北航天化学技术研究所 一种高燃速气体发生剂及其制粒工艺
CN108218648A (zh) * 2017-12-20 2018-06-29 湖北航鹏化学动力科技有限责任公司 一种气体发生器
CN111548242A (zh) * 2020-05-15 2020-08-18 湖北航鹏化学动力科技有限责任公司 气体发生器
CN111675589A (zh) * 2020-05-15 2020-09-18 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、制备方法及其应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO180189C (no) * 1994-03-30 1997-03-05 Elkem Materials Fremgangsmåte for opparbeiding av silisiumrike, uopplöste rester fra utluting av kobberholdige residuer fra organoklorsilansyntese
US6527886B1 (en) * 1996-07-22 2003-03-04 Daicel Chemical Industries, Ltd. Gas generant for air bag
CN100441550C (zh) * 1996-07-22 2008-12-10 大赛璐化学工业株式会社 用于气囊的产气剂
JP2000103692A (ja) * 1998-09-30 2000-04-11 Daicel Chem Ind Ltd エアバッグ用ガス発生剤組成物成型体
JP4641130B2 (ja) * 2000-10-10 2011-03-02 日本化薬株式会社 ガス発生剤組成物およびそれを使用したガス発生器
JP4302442B2 (ja) * 2002-09-12 2009-07-29 ダイセル化学工業株式会社 ガス発生剤組成物
JP2009137821A (ja) * 2007-12-11 2009-06-25 Daicel Chem Ind Ltd ガス発生剤組成物
US8808476B2 (en) * 2008-11-12 2014-08-19 Autoliv Asp, Inc. Gas generating compositions having glass fibers
CN104289828B (zh) * 2014-10-08 2016-05-04 山东大学 一种降低飞溅率的活性绞线焊丝

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4296084A (en) * 1979-10-29 1981-10-20 Thiokol Corporation Method of and apparatus for gas generation
CN1132501A (zh) * 1993-10-06 1996-10-02 尼古化学股份公司 气体发生器的推进剂
WO1996025375A1 (en) * 1995-02-16 1996-08-22 Royal Ordnance Plc Vehicle occupant restraint systems powered by gas generating compositions
CN1150794A (zh) * 1995-04-14 1997-05-28 汽车系统实验室公司 具有内在催化剂的非叠氮化物气体发生组合物
US5827996A (en) 1995-09-29 1998-10-27 Otsuka Kagaku Kabushiki Kaish Air bag gas generating composition
CN1277598A (zh) * 1998-09-14 2000-12-20 大赛璐化学工业株式会社 产气组合物
US6143102A (en) * 1999-05-06 2000-11-07 Autoliv Asp, Inc. Burn rate-enhanced basic copper nitrate-containing gas generant compositions and methods
US20020148542A1 (en) * 1999-05-06 2002-10-17 Taylor Robert D. Gas generant compositions containing copper ethylenediamine dinitrate and associated methods
CN1714059A (zh) * 2002-11-22 2005-12-28 日本化药株式会社 气体发生剂及其制造方法以及气囊用气体发生器
CN100376515C (zh) 2005-03-28 2008-03-26 东方久乐汽车安全气囊有限公司 一种产气组合物及其制备方法
CN101415659A (zh) * 2006-04-04 2009-04-22 Snpe巨能材料公司 大尺寸的烟火颗粒及其制造和用途
CN101234943A (zh) * 2008-03-03 2008-08-06 烟台安泰德汽车安全系统有限公司 一种汽车安全气囊用气体发生剂及其制备方法
WO2009126182A1 (en) * 2008-04-10 2009-10-15 Autoliv Asp, Inc. Monolithic gas generants containing perchlorate-based oxidizers and methods for manufacture thereof
CN101952227A (zh) 2008-04-10 2011-01-19 奥托里夫Asp股份有限公司 高性能气体发生组合物
CN105801326A (zh) 2011-05-09 2016-07-27 海瑞克里兹 产气烟火复合物
CN102423805A (zh) * 2011-11-23 2012-04-25 西安理工大学 一种低铬含量的CuCr合金粉末的制备方法
CN105358507A (zh) * 2013-05-21 2016-02-24 有限会社三松 充气机固体排出量减少的气体发生剂组合物
CN107840772A (zh) * 2017-03-02 2018-03-27 湖北航天化学技术研究所 一种高燃速气体发生剂及其制粒工艺
CN107501018A (zh) * 2017-08-08 2017-12-22 成都银河动力有限公司 一种用于化学能板材破拆装备的专用药剂
CN107698415A (zh) 2017-10-24 2018-02-16 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、制备方法、应用及气体发生器
CN108218648A (zh) * 2017-12-20 2018-06-29 湖北航鹏化学动力科技有限责任公司 一种气体发生器
CN111548242A (zh) * 2020-05-15 2020-08-18 湖北航鹏化学动力科技有限责任公司 气体发生器
CN111675589A (zh) * 2020-05-15 2020-09-18 湖北航鹏化学动力科技有限责任公司 一种气体发生剂组合物、制备方法及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3936495A4

Also Published As

Publication number Publication date
US20220009853A1 (en) 2022-01-13
EP3936495A1 (en) 2022-01-12
EP3936495A4 (en) 2022-04-13
CN111675589A (zh) 2020-09-18
CN111675589B (zh) 2021-08-06

Similar Documents

Publication Publication Date Title
WO2021227577A1 (zh) 一种气体发生剂组合物、制备方法及其应用
WO2021227578A1 (zh) 气体发生器
WO2019119762A1 (zh) 一种气体发生器
KR101899028B1 (ko) 가스 발생 점화 화합물
JP2009511411A (ja) 高速ガス発生剤及びその製造方法
CN101990526B (zh) 气体发生剂组合物
WO2019080395A1 (zh) 一种气体发生剂组合物、制备方法、应用及气体发生器
JPH07206568A (ja) 点火薬造粒物の製造方法
CN105294370B (zh) 一种气体发生器用超细硝酸胍及其制备工艺
CN104418676A (zh) 一种气体发生器用气体发生剂及制造方法
CN102173973B (zh) 安全气囊气体发生器用传火药剂及其制备方法
WO2019153624A1 (zh) 降低燃温保持形貌的气体发生剂组合物、制备方法、应用及气体发生器
CN101234943A (zh) 一种汽车安全气囊用气体发生剂及其制备方法
CN108863691B (zh) 一种安全气囊用气体发生剂药粒及其压制制备工艺
WO2023087570A1 (zh) 一种气体发生剂组合物、气体发生剂及制备方法与应用
JPH10130086A (ja) エアバッグ用ガス発生剤
WO2019080396A1 (zh) 气体发生剂组合物、制备方法、应用及气体发生器
CN108911936A (zh) 一种安全气囊气体发生器的点火药及其制备方法
CN109809954B (zh) 一种多孔产气剂模压制品及其制备工艺
JP4006835B2 (ja) 点火薬組成物
CN111978136B (zh) 一种改进的气体发生剂及其制备方法
JP7054126B2 (ja) ガス発生剤組成物およびその成形体ならびにそれを用いたガス発生器
CN116514615A (zh) 一种气体发生剂组合物、气体发生剂及制备方法和应用
JP4318238B2 (ja) ガス発生剤組成物
CN116891218A (zh) 一种延迟启动平稳放氧的氧烛及其制备方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021737332

Country of ref document: EP

Effective date: 20210715

NENP Non-entry into the national phase

Ref country code: DE