Gas generating agent with wide burning rate adjustment range, preparation method and application thereof

Abstract

The present application belongs to the field of composite solid propellant manufacturing, and specifically discloses a gas generating agent with a wide burning rate adjusting range, a preparation method and application thereof, which comprises the following raw materials in parts by weight: binder: 10-15%; plasticizer: 3.4-8.4%; curing agent: 1.0-1.5%; oxidizer: 30-65%; cooling agent: 10-45%; burning rate catalyst: 0.5-6.0%; bonding agent: 0.1-0.3%; wherein the oxidizer is mixed in an arbitrary ratio of 100-400 μm coarse particles and 10 μm or less fine particles to achieve the adjustment of the burning rate range. The gas generating agent uses polyether or azide polyether as the binder, high-oxygen-content inert ester as the plasticizer, and modified borate or alcohol amine as the bonding agent, and has a wide formula burning rate adjusting range, can be adjusted to 2.5 mm / s-35 mm / s, the normal temperature mechanical strength is adjusted to 1.0 MPa-1.8 MPa, and the elongation is greater than 60%.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite solid propellant, and particularly relates to a gas generating agent with a wide burning rate adjustment range and a preparation method and application thereof. BACKGROUND

[0002] The gas generating agent is a low-temperature slow-burning propellant, which mainly provides power source for various gas generators of rocket missiles, space shuttles and the like. It can also be used as a gas source of an expansion device on an airplane emergency system ejection device, a marine emergency inflatable raft, an inflatable garment, a safety inflatable bag on a car and the like. However, the gas generating agent with a wide burning rate adjustment range at present is mostly an ammonium perchlorate (AP) type gas generating agent, which adopts hydroxyl-terminated polybutadiene (HTPB) and carboxyl-terminated polybutadiene (CTPB) as the binder, diisooctyl sebacate (DOS) and diisooctyl adipate (DOA) as the plasticizer, and has a large amount of residue (about 10% to 20%). The gas generating agent prepared by using a polyether binder and an energetic plasticizer has a residue of 2.5% to 3.5% when the combustion temperature adjustment range is 1000℃ to 2000℃, but the burning rate adjustment range is only 2.5 mm / s to 8.0 mm / s (7 MPa), and there are problems such as a narrow burning rate adjustment range. SUMMARY

[0003] The present application provides a gas generating agent with a wide burning rate adjustment range and a preparation method and application thereof, which has a large adjustable range of burning rate, and can meet the characteristics of low burning temperature and low residue while adjusting the low burning rate.

[0004] In order to achieve the above-mentioned target, the present application adopts the following technical scheme: a gas generating agent with a wide burning rate adjustment range, which comprises the following raw materials in parts by weight: a binder: 10% to 15%; a plasticizer: 3.4% to 8.4%; a curing agent: 1.0% to 1.5%; an oxidizing agent: 30% to 65%; a temperature reducing agent: 10% to 45%; a burning rate catalyst: 0.5% to 6.0%; and a bonding agent: 0.1 to 0.3%, wherein the oxidizing agent is mixed in an arbitrary ratio to achieve the adjustment of the burning rate range, and the oxidizing agent is in a coarse particle size of 100 to 400 μm and a fine particle size of 10 μm or less.

[0005] Further, the binder is one of a polyether binder or an azide binder or a combination of the two; the polyether binder is a copolyether of ethylene oxide and tetrahydrofuran (PET / HTPE), and the azide binder is a glycidyl azide polymer (GAP / PBT).

[0006] Further, the plasticizer is one or a combination of several of acetyl tri-butyl citrate (ATBC), dibutyl phthalate (DBP), diisooctyl sebacate (DOS) and diisooctyl adipate (DOA).

[0007] Further, the curing agent is one or a combination of toluene diisocyanate, isophorone diisocyanate, and polymethyl polyisocyanate.

[0008] Further, the oxidizing agent is one or a combination of ammonium perchlorate (AP), nitramine oxidizing agent (RDX / HMX), and 5,5'-tetrazine-1,1'-dioxymonohydrate (TKX-50).

[0009] Further, the cooling agent is one or a combination of ammonium oxalate, dihydroxyglyoxime, and azobisformamide.

[0010] Further, the bonding agent is one or a combination of modified borate ester bonding agent and alcohol amine bonding agent.

[0011] Further, the burning rate catalyst is one or a combination of 2',2-bis(ethylferrocenyl)propane, bis(ethylferrocenyl)methane, octylferrocene, copper chromite, iron oxide, and cobalt sesquioxide.

[0012] The present application also relates to a preparation method of the gas generating agent, and the specific steps are as follows:

[0013] S1, the binder, the plasticizer, the bonding agent, and the burning rate catalyst are uniformly mixed, and then the mixture is kept at 50-60 DEG C for 20-30 minutes;

[0014] S2, the slurry obtained in S1 is uniformly mixed, the cooling agent and the oxidizing agent are added and uniformly mixed, and finally the curing agent is added and uniformly mixed;

[0015] S3, the slurry obtained in S2 is poured and solidified to form the gas generating agent.

[0016] The present application also relates to the application of the gas generating agent in a gas generator.

[0017] The present application has the following beneficial effects:

[0018] (1) The present application uses oxidizing agents with different particle sizes, wherein the coarse particle size can reduce the burning rate, and the fine particle size can increase the burning rate, and the two can be used in combination to adjust the burning rate of the gas generating agent as needed; the burning rate catalyst added at the same time helps to increase the burning rate, and the cooling agent added helps to reduce the burning rate, and through the synergistic use of multiple raw materials, the burning rate of 2.5mm / s-35mm / s (7MPa) can be adjusted.

[0019] (2) The azobisformamide in the cooling agent of the present application can significantly reduce the burning rate and the burning temperature, but it can easily cause ignition difficulty, and by adding dihydroxyglyoxime for compounding use, low burning temperature, low burning rate, and stable ignition can be achieved, and the burning temperature can be adjusted to 900 DEG C-2000 DEG C.

[0020] (3) The adhesive and plasticizer with high oxygen content are used in combination in the present application, and the formula has the characteristics of low residue, with residue ≤3.0%.

[0021] (4) The gas generating agent provided by the present application has excellent mechanical properties, with adjustable tensile strength at room temperature of 1.0 MPa-1.8 MPa and elongation ≥60%. DETAILED DESCRIPTION

[0022] The embodiments of the present application will be described in detail below with reference to the examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application.

[0023] Example 1

[0024] (1) Composition of the gas generating agent

[0025] Formulation composition Percentage / % Ethylene oxide tetrahydrofuran copolyether 14.404 Isophorone diisocyanate 1.196 Dibutyl phthalate (DBP) 6.2 Ammonium oxalate / dihydroxyglyoxime 15 / 20 Ammonium perchlorate (100~400 μm / 10 μm below) 41（32 / 9） Triethanolamine 0.2 2,2-bis(ethylferrocenyl)propane 2

[0026] (2) Performance of the gas generating agent (performance test refers to GJB770B)

[0027] Average molecular weight of gas, g / mol 21.55 Burning rate (7 MPa), mm / s 4.52 Pressure exponent (2 MPa~20 MPa) 0.35 Burning temperature (℃) 920 Residue (%) 1.05 Mechanical strength (MPa), elongation (%) 1.345,80.5

[0028] Example 2

[0029] (1) Composition of the gas generating agent

[0030] Formulation composition Percentage / % Ethylene oxide tetrahydrofuran copolyether 14.57 Toluene diisocyanate / multi-methyl polyisocyanate 0.979 / 0.086 Dibutyl phthalate 8.165 Ammonium oxalate 10 RDX / AP (100~400 μm / 10 μm below) 10 / 52（15 / 37） Triethanolamine 0.2 Copper chromite / iron oxide 2.0 / 2.0

[0031] (2) Performance of the gas generating agent

[0032] Average molecular weight of gas, g / mol 21.62 Burning rate (7 MPa), mm / s 22.65 Pressure exponent (2 MPa~20 MPa) 0.45 Burning temperature (℃) 1820 Residue (%) 2.2 Mechanical strength (MPa), elongation (%) 1.256,90.3

[0033] Example 3

[0034] (1) Composition of the gas generating agent

[0035] Formulation composition Percentage / % Ethylene oxide tetrahydrofuran copolyether 13.444 Toluene diisocyanate 1.056 Acetyl tributyl citrate 3.4 Azodicarbonamide 20 5,5'-diazidetetrazol-1,1'-dioxymonohydrate salt / AP (100~400 μm / 10 μm below) 10 / 46（10 / 36） Triethanolamine 0.1 Octylferrocene 6

[0036] (2) Performance of the gas generating agent

[0037] Average molecular weight of gas, g / mol 20.16 Burning rate (7 MPa), mm / s 17.64 Pressure exponent (2 MPa~20 MPa) 0.45 Burning temperature (℃) 1109 Residue (%) 2.96 Mechanical strength (MPa), elongation (%) 1.764,76.3

[0038] Example 4

[0039] (1) Composition of the gas generating agent

[0040] Formulation composition Percentage / % Ethylene oxide tetrahydrofuran copolyether 14.191 Toluene diisocyanate 1.109 Diisooctyl sebacate 3.4 Dihydroxyglyoxime 30 AP (100~400 μm / 10 μm below) 45（10 / 35） Triethanolamine 0.3 2,2-bis(ethylferrocenyl)methane 6

[0041] (2) Performance of the gas generating agent

[0042] Average molecular weight of gas, g / mol 20.79 Burning rate (7 MPa), mm / s 28.76 Pressure exponent (2 MPa~20 MPa) 0.35 Burning temperature (℃) 1150 Residue (%) 2.76 Mechanical strength (MPa), elongation (%) 1.863,89.4

[0043] Example 5

[0044] (1) Gas generating agent composition

[0045] Formulation composition Percentage / % Ethylene oxide tetrahydrofuran copolyether 14.404 Toluene diisocyanate 1.196 Dibutyl phthalate (DBP) 6.2 Dihydroxyglyoxime / azodicarbonamide 15 / 20 Ammonium perchlorate (100~400 μm / 10 μm below) 41（32 / 9） Triethanolamine 0.2 2,2-bis(ethylferrocenyl)propane 2

[0046] (2) Gas generating agent performance

[0047] Average molecular weight of gas, g / mol 21.43 Burning rate (7 MPa), mm / s 3.02 Pressure exponent (2 MPa~20 MPa) 0.37 Burning temperature (℃) 900 Residue (%) 1.0 Mechanical strength (MPa), elongation (%) 1.734,86

[0048] The above examples describe the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all belong to the protection scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.

Claims

1. A gas generating agent having a wide range of fuel velocity adjustment, characterized by comprising: It comprises the following raw materials by weight parts: Binder: 10%~15%; plasticizer: 3.4%~8.4%; Curing agent: 1.0%~1.5%; Oxidizing agent: 30%~65%; cooling agent: 10%~45%; burning rate catalyst: 0.5%~6.0%; bonding agent: 0.1~0.3%; wherein the oxidizing agent is mixed with 100~400μm coarse particles and fine particles below 10μm in any ratio to achieve the adjustment of burning rate range 2.5mm / s~35mm / s; the plasticizer is a combination of one or several of acetyl tri-butyl citrate, dibutyl phthalate, diisooctyl sebacate, diisooctyl adipate; the burning rate catalyst is 2',2-bis(ethyl ferrocene) propane and / or bis(ethyl ferrocene) methane.

2. The gas generating agent according to claim 1, characterized by: The binder is a combination of one or both of polyether binder or azide binder; wherein the polyether binder is copolyether of ethylene oxide and tetrahydrofuran, and the azide binder is glycidyl azide polymer.

3. The gas generating agent according to claim 1, characterized by: The curing agent is a combination of one or several of toluene diisocyanate, isophorone diisocyanate, and polymethyl polyisocyanate.

4. The gas generating agent according to claim 1, characterized by: The oxidizing agent is a combination of one or several of ammonium perchlorate, nitramine oxidizing agent, and 5,5'-tetrazolyl-1,1'-dioxymonohydrate.

5. The gas generant according to any one of claims 1 to 4, wherein: The cooling agent is a combination of one or several of ammonium oxalate, dihydroxyglyoxime, and azodicarbonamide.

6. The gas generant according to any one of claims 1 to 4, wherein: The bonding agent is a combination of one or several of modified borate bonding agent and alcohol amine bonding agent.

7. The method of producing the gas generating agent according to any one of claims 1 to 6, characterized by, The specific steps are: S1, first mix the binder, plasticizer, bonding agent and burning rate catalyst uniformly, and keep at 50~60℃ for 20min~30min; S2, mix the slurry obtained in S1, add the cooling agent and oxidizing agent, and mix uniformly, and finally add the curing agent and mix uniformly; S3, pour and cure the slurry obtained in S2 to form, and obtain the gas generating agent.

8. The application of the gas generating agent of any one of claims 1~6 in a gas generator.