CN113248340B - High-pressure-strength-index low-combustion-temperature gas generating agent and preparation method thereof - Google Patents

High-pressure-strength-index low-combustion-temperature gas generating agent and preparation method thereof Download PDF

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CN113248340B
CN113248340B CN202110483981.XA CN202110483981A CN113248340B CN 113248340 B CN113248340 B CN 113248340B CN 202110483981 A CN202110483981 A CN 202110483981A CN 113248340 B CN113248340 B CN 113248340B
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combustion
gas generating
generating agent
pressure
temperature gas
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CN113248340A (en
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占明明
祝世杰
王文博
安百强
鲁国林
王业腾
张运刚
佘飞云
刘芳
王锐
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Hubei Institute of Aerospace Chemical Technology
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Hubei Institute of Aerospace Chemical Technology
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    • 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
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0058—Shaping the mixture by casting a curable composition, e.g. of the plastisol type

Abstract

The invention relates to a high pressure strength index low combustion temperature gas generating agent and a preparation method thereof, which obtains the gas generating agent with the pressure strength index more than or equal to 0.60 and the combustion temperature less than or equal to 1200 ℃ by selecting each component and adjusting the proportion, in particular by matching a main oxidant and a performance regulator and adjusting the proportion of the combustion temperature regulator.

Description

High-pressure-strength-index low-combustion-temperature gas generating agent and preparation method thereof
Technical Field
The invention relates to a high-pressure-strength-index low-combustion-temperature gas generating agent for a gas generator and other gas generators and a preparation method thereof, belonging to the field of composite solid propellant gas generating agents.
Background
The gas generating agent is a branch of the composite solid propellant, and the gas generated by combustion is used as a working medium for driving an auxiliary power device to convert chemical energy into mechanical energy or electric energy. Because the gas generator has simple structure, light weight and convenient use, the gas generator is widely applied to the fields of liquid rocket turbine starters, superchargers, servo systems for thrust vector control of solid rocket missiles, projectile body and projectile head rolling control, ejection devices, standing devices of launching vehicles, last boosting, turbine motors, steering engine control and the like.
The development of advanced missile weapons and aerospace power control systems puts new technical requirements on the combustion performance of a gas propellant, and flexible energy control and release technologies become important directions for the development of control-type gas generators. On the premise of keeping the advantages of simple structure, small volume, easy storage, convenient maneuvering deployment, high reserve rate, fast reaction, convenient use and maintenance and the like of the solid gas generator, the thrust adjusting technology of the gas generator is developed, the random controllability of the thrust is realized, and the energy of the gas generating agent can be more reasonably distributed.
The gas generating agent with high burning speed and pressure index can make the thrust regulating range of the engine larger. The combustion chamber pressure change is very large as long as the section of the spray pipe has small change by adopting the combustion gas generating agent with large positive combustion speed pressure index. By adopting a propellant technology with a high combustion speed pressure index, the thrust regulating ratio of a fuel gas generator can be more than 10 and even can reach 100, so that the method has important significance for further improving the maneuverability and the prevention capability of the missile and is a subject to be solved urgently by the development of an advanced tactical missile control system.
The typical formula of the existing low-combustion-temperature gas generating agent technology comprises the following components: the adhesive system is HTPB/DOS/TDI-IPDI, the oxidant is AP, the combustion temperature regulator is hydroxylammonium oxalate, nitroguanidine or dihydroxyglyoxime, the combustion rate catalyst is a ferrocene substance, the pressure index level of the ferrocene substance is generally between 0.1 and 0.45, the requirement of an advanced tactical missile control system cannot be met, and in the prior art, although the development of a high-pressure-intensity-index high-combustion-temperature gas generating agent is involved, relevant reports aiming at a high-pressure-intensity-index low-combustion-temperature gas generating agent are not seen, and the invention fills the gap in the technical field.
Disclosure of Invention
The invention aims to overcome the defects and provides a high-pressure-intensity-index low-combustion-temperature gas generating agent and a preparation method thereof, the gas generating agent with the pressure intensity index of more than or equal to 0.60 and the combustion temperature of less than or equal to 1200 ℃ is obtained by selecting various components and adjusting the proportion, and meanwhile, the gas generating agent has the advantages of no metal powder, low residue and easy adjustment of performance, can be used for a gas generator with adjustable thrust, and can greatly improve the maneuverability and the penetration resistance of missiles.
In order to achieve the above purpose, the invention provides the following technical scheme:
a high-pressure-intensity-index low-combustion-temperature gas generating agent comprises the following components in percentage by mass:
Figure BDA0003050143990000021
the main oxidant is one or more of 5,5 '-bistetrazole-1, 1' -dioxygen dihydroxy ammonium salt, cyclotrimethylenetrinitramine and triaminoguanidine nitrate;
the performance regulator is one or more of ferric polyacrylate, copper chromite, N-octyl ferrocene, tert-butyl ferrocene, triphenyl bismuth, iron acetylacetonate, carbon black, tris [1, - (2-methyl aziridine) ] phosphine oxide, triethanolamine or N, N-diphenyl p-phenylenediamine.
Further, the high-pressure-intensity-index low-combustion-temperature gas generating agent comprises the following components in percentage by mass:
Figure BDA0003050143990000022
Figure BDA0003050143990000031
further, the adhesive system comprises an adhesive, a curing agent and a plasticizer;
the adhesive is hydroxyl-terminated polybutadiene; the curing agent is one or the combination of more than one of toluene diisocyanate, isophorone diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate; the plasticizer is one or more of dioctyl sebacate, acetyl triethyl citrate or triethyl glycerol tricarbonate.
Further, the auxiliary oxidant is ammonium perchlorate.
Further, the combustion temperature regulator is one or more of oxamide, ammonium oxalate or dihydroxy glyoxime.
Further, the combustion speed regulator is ferric oxide.
Further, the performance regulator is ferric polyacrylate, or a combination of ferric polyacrylate and one or more of copper chromite, N-octyl ferrocene, tert-butyl ferrocene, triphenyl bismuth, ferric acetylacetonate, carbon black, tris [1, - (2-methylaziridine) ] phosphine oxide, triethanolamine or N, N-diphenyl-p-phenylenediamine.
Furthermore, the pressure index of the high-pressure-intensity-index low-combustion-temperature gas generating agent is more than or equal to 0.60, and the combustion temperature is less than or equal to 1200 ℃.
The preparation method of the high-pressure-intensity-index low-combustion-temperature gas generating agent comprises the following steps of:
(1) sequentially adding the components into a mixer, mixing uniformly and then discharging;
(2) and (2) carrying out vacuum pouring on the slurry obtained in the step (1), and curing to obtain the high-pressure-intensity-index low-combustion-temperature gas generating agent.
Further, in the step (1), the mixing temperature is 40-60 ℃, and the mixing time is 50-80 min;
in the step (2), the curing condition is that the curing is carried out for 5-8 days in a drying environment at 50-70 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a high-pressure-strength-index low-combustion-temperature gas generating agent, which adopts 5,5 '-bistetrazole-1, 1' -dioxygen dihydroxy ammonium salt, cyclotrimethylenetrinitramine and triaminoguanidine nitrate with larger difference of decomposition speeds under high and low pressure as main oxidants, and the high decomposition speed of the oxidants under high pressure is favorable for improving the pressure index of the obtained gas generating agent;
(2) the invention relates to a high-pressure-intensity-index low-combustion-temperature gas generating agent, which selects the types of performance regulators, particularly introduces a novel high-molecular high-efficiency catalyst ferric polyacrylate as the performance regulators, can further improve the decomposition speed of an oxidant under high pressure, improves the pressure intensity index, enables a formula to have the characteristic of the high-pressure-intensity index, and obtains the gas generating agent with the pressure intensity index as high as 0.75, which is the level of the high-pressure-intensity index which cannot be reached by the existing low-combustion-temperature gas generating agent technology;
(3) the invention relates to a high-pressure-intensity-index low-combustion-temperature gas generating agent, which can control the combustion temperature of the gas generating agent at a lower level by adjusting the proportion of a combustion temperature regulator and matching with an oxidant with high nitrogen content and high gas production rate, and the combustion temperature of the gas generating agent is kept below 1200 ℃ in a standard state;
(4) the invention relates to a high-pressure-index low-combustion-temperature gas generating agent, which comprises the following components of organic matters easy to decompose and generate gas except a small amount of special regulator, and the propellant has clean combustion products, less condensed phases and less residues.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
A high-pressure-intensity-index low-combustion-temperature gas generating agent comprises the following components in percentage by mass:
Figure BDA0003050143990000041
the main oxidant is one or more of 5,5 '-bitetrazole-1, 1' -dioxygen dihydroxy ammonium salt (TKX-50), cyclotrimethyltrinitroamine (RDX) and triaminoguanidine nitrate (TAGN);
the performance regulator is one or more of ferric Polyacrylate (PAAF), Copper Chromite (CC), N-Octyl Ferrocene (OFC), tert-butyl ferrocene (TBFC), triphenyl bismuth (TPB), ferric acetylacetonate (FeAA), carbon black (C), tris [1, - (2-methyl aziridine) ] phosphine oxide (MAPO), Triethanolamine (TEA) or N, N-diphenyl p-phenylenediamine (anti-aging agent DPPD).
Further, the high-pressure-intensity-index low-combustion-temperature gas generating agent comprises the following components in percentage by mass:
Figure BDA0003050143990000051
further, the adhesive system includes an adhesive, a curing agent, and a plasticizer.
Further, the binder is hydroxyl-terminated polybutadiene (HTPB);
the curing agent is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) or 4, 4' -dicyclohexyl methane diisocyanate (HMDI);
the plasticizer is one or more of dioctyl sebacate (DOS), Acetyl Triethyl Citrate (ATC) or triethyl Triglycerate (TGEA).
Further, the auxiliary oxidant is ammonium perchlorate.
Further, the combustion temperature regulator is one or more of Oxamide (OAM), ammonium oxalate (AMO) or dihydroxy glyoxime (DHG).
Further, the combustion speed regulator is ferric oxide (Fe)2O3)。
Further, the performance regulator is ferric polyacrylate, or a combination of ferric polyacrylate and one or more of copper chromite, N-octyl ferrocene, tert-butyl ferrocene, triphenyl bismuth, ferric acetylacetonate, carbon black, tris [1, - (2-methylaziridine) ] phosphine oxide, triethanolamine or N, N-diphenyl-p-phenylenediamine.
Further, the pressure intensity index of the high-pressure-intensity-index low-combustion-temperature gas generating agent is more than or equal to 0.60, and the combustion temperature is less than or equal to 1200 ℃.
The preparation method of the high-pressure-intensity-index low-combustion-temperature gas generating agent comprises the following steps of:
(1) accurately weighing the components in a dry environment, sequentially adding the components into a mixer, uniformly mixing, and discharging;
(2) and (2) carrying out vacuum pouring on the slurry obtained in the step (1), and curing to obtain the high-pressure-intensity-index low-combustion-temperature gas generating agent.
Further, in the step (1), the mixing temperature is 40-60 ℃, and the mixing time is 50-80 min;
in the step (2), the curing condition is that the curing is carried out for 5-8 days in a drying environment at 50-70 ℃.
Example 1
Table 1 example 1 propellant composition
Figure BDA0003050143990000061
Table 2 example 1 gas generant performance
Figure BDA0003050143990000062
Figure BDA0003050143990000071
Example 2
Table 3 example 2 propellant composition
Figure BDA0003050143990000072
Table 4 example 2 gas generant performance
Figure BDA0003050143990000073
Example 3
Table 5 example 3 propellant composition
Figure BDA0003050143990000074
Figure BDA0003050143990000081
TABLE 6 example 3 gas generant Performance
Figure BDA0003050143990000082
Example 4
Table 7 example 4 propellant composition
Figure BDA0003050143990000083
Table 8 example 4 gas generant performance
Figure BDA0003050143990000084
Figure BDA0003050143990000091
The performance of the fuel gas generating agent obtained in the above embodiments 1 to 4 can be obtained, and the low-combustion-temperature fuel gas generating agent with the high pressure intensity index has a higher pressure intensity index than the low-combustion-temperature fuel gas generating agent in the prior art, and has a good application prospect in the field of development of advanced tactical missile control systems.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.

Claims (6)

1. The high-pressure-intensity-index low-combustion-temperature gas generating agent is characterized by comprising the following components in percentage by mass:
Figure FDA0003569113640000011
the main oxidant is one or more of 5,5 '-bistetrazole-1, 1' -dioxygen dihydroxy ammonium salt, cyclotrimethylenetrinitramine and triaminoguanidine nitrate;
the performance regulator is one or more of ferric polyacrylate, copper chromite, N-octyl ferrocene, tert-butyl ferrocene, triphenyl bismuth, iron acetylacetonate, carbon black, tris [1, - (2-methyl aziridine) ] phosphine oxide, triethanolamine or N, N-diphenyl p-phenylenediamine;
the combustion temperature regulator is one or the combination of more than one of oxamide, ammonium oxalate or dihydroxy glyoxime;
the performance regulator is ferric polyacrylate, or the combination of ferric polyacrylate and one or more of copper chromite, N-octyl ferrocene, tert-butyl ferrocene, triphenyl bismuth, iron acetylacetonate, carbon black, tris [1, - (2-methyl aziridine) ] phosphine oxide, triethanolamine or N, N-diphenyl p-phenylenediamine;
the pressure index of the high-pressure-index low-combustion-temperature gas generating agent is more than or equal to 0.60, and the combustion temperature is less than or equal to 1200 ℃.
2. The high pressure index low firing temperature gas generant of claim 1 wherein the binder system comprises a binder, a curing agent and a plasticizer;
the adhesive is hydroxyl-terminated polybutadiene; the curing agent is one or the combination of more than one of toluene diisocyanate, isophorone diisocyanate or 4, 4' -dicyclohexylmethane diisocyanate; the plasticizer is one or more of dioctyl sebacate, acetyl triethyl citrate or triethyl glycerol tricarbonate.
3. The hAN _ SNs-low temperature fuel gas generator of claim 1, wherein the supplemental oxidizer is ammonium perchlorate.
4. The high pressure index low combustion temperature gas generating agent as claimed in claim 1, wherein the combustion speed modifier is ferric oxide.
5. The method for preparing a high pressure-index low combustion temperature gas generating agent as claimed in any one of claims 1 to 4, comprising the steps of:
(1) sequentially adding the components into a mixer, mixing uniformly and then discharging;
(2) and (2) carrying out vacuum pouring on the slurry obtained in the step (1), and curing to obtain the high-pressure-intensity-index low-combustion-temperature gas generating agent.
6. The method for preparing a high pressure index low combustion temperature gas generating agent as claimed in claim 5, wherein in the step (1), the mixing temperature is 40 ℃ to 60 ℃, and the mixing time is 50min to 80 min;
in the step (2), the curing condition is that the curing is carried out for 5-8 days in a drying environment at 50-70 ℃.
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