CN111454113A - Hydroxyl-terminated aluminum-free propellant and preparation method thereof - Google Patents

Abstract

The invention discloses a butylated hydroxyanisole propellant and a preparation method thereof, wherein the butylated hydroxyanisole propellant comprises, by mass, 7.5-8.0% of an adhesive, 2.5-3.5% of a plasticizer, 0.5-1.0% of a curing agent, 63-74% of an oxidant, 10-20% of a nitramine explosive, 1.5-2.5% of a burning rate catalyst and 1.0-3.0% of a combustion stabilizer, and the raw materials further comprise 0.5-2% of a burning rate regulator, wherein the burning rate regulator is one or more of organic barium salt, an amantadine derivative and ferrocenyl quaternary ammonium salt. The hydroxyl-terminated aluminum-free propellant provided by the invention has less smoke and low characteristic signals, has a lower burning speed pressure index within the range of 16-24 MPa, and ensures the working stability of a high-pressure engine.

Description

Hydroxyl-terminated aluminum-free propellant and preparation method thereof

Technical Field

The invention relates to the technical field of composite solid propellants, in particular to a butylated hydroxyanisole aluminum-free propellant and a preparation method thereof.

Background

With the development of missile technology, high pressure, high acceleration and strong stealth flight capability have become the development direction of tactical missiles. The airborne air-ground missile generally adopts a single-chamber double-thrust engine, and the engine has high boosting stage thrust, high working pressure and short combustion time; the cruise stage has small thrust, low working pressure and long duration. Meanwhile, in order to enhance the environment adaptability of the airborne air-ground missile, the propellant has less smoke and low characteristic signals.

The exertion of the excellent performance of the airborne air-ground missile engine depends on the combustion performance and smoke signals of the solid propellant. The lower the burning speed and pressure index of the solid propellant is, the more stable the combustion is, and the safer and controllable the ballistic performance of the engine is; aluminum powder is not added into the solid propellant, and part of the oxidant is replaced by the nitramine explosive, so that the generation amount of smoke in the propellant combustion product can be greatly reduced, characteristic signals such as infrared light, visible light and the like are weakened, and the stealth capability of the missile is improved.

The solid propellant has high working pressure, does not contain aluminum powder and is added with nitramine explosive, so the problem of high burning rate pressure index exists, and the reliability of the normal work of the solid rocket engine can be seriously influenced.

In the prior art, a burning rate regulator such as ammonium oxalate, carbonate, nano aluminum powder, metal oxide and the like is usually added into a butylated hydroxytoluene propellant to reduce the burning rate pressure index of the propellant. However, such substances have a great negative effect on the propellant, for example, the working pressure exceeds 9MPa, the ammonium oxalate combustion rate reducing pressure index fails, and the carbonate is an inert material and can significantly reduce the energy performance of the propellant; the nanometer aluminum powder and the metal oxide can cause the technical performance of the propellant to be poor, and the smoke characteristic signal of the propellant is increased.

Disclosure of Invention

The invention provides a butylated hydroxyanisole aluminum-free propellant and a preparation method thereof, which can improve the performance of the butylated hydroxyanisole propellant and have the advantages of less smoke, low characteristics, low burning rate and pressure index and the like.

The technical scheme of the invention is that the hydroxyl-terminated aluminum-free propellant comprises the following raw materials in percentage by weight: 7.5 to 8.0 percent of adhesive, 2.5 to 3.5 percent of plasticizer, 0.5 to 1.0 percent of curing agent, 63 to 74 percent of oxidant, 10 to 20 percent of nitramine explosive, 1.0 to 3.0 percent of combustion stabilizer, 1.5 to 2.5 percent of burning rate catalyst and 0.5 to 2 percent of burning rate regulator; wherein the burning rate regulator is one or more of organic barium salt, amantadine derivative and ferrocenyl quaternary ammonium salt.

Furthermore, the adhesive is hydroxyl-terminated polybutadiene HTPB, the plasticizer is diisooctyl sebacate GZ, the curing agent is toluene diisocyanate TDI, and the oxidant is ammonium perchlorate AP.

Further, the nitramine explosive is hexogen RDX or octogen HMX.

Further, the burning rate catalyst is 2, 2-bisethylferrocene propane GFP or octylferrocene XMT

Further, the combustion stabilizer is zirconium carbide ZrC, magnesium oxide MgO and titanium dioxide TiO₂

Furthermore, the median particle size of the organic barium salt is 5-15 μm, the barium content is 39-41%, and the moisture content is not more than 0.1%.

Furthermore, the median particle size of the amantadine derivative is 5-15 μm, the carbon content is 67.8%, the hydrogen content is 10.9%, the oxygen content is 12%, the nitrogen content is 2.6%, the chlorine content is 6.7%, and the moisture content is not more than 0.1%.

Furthermore, the ferrocenyl quaternary ammonium salt has a median particle size of 5-15 μm, an iron content of 8.2-8.5% and a moisture content of not more than 0.1%.

The invention also relates to a preparation method of the hydroxyl-terminated aluminum-free propellant, which comprises the following steps:

(1) weighing the raw materials according to the proportion;

(2) mixing: stirring the weighed adhesive, plasticizer and burning rate catalyst for 20-30 min in a vertical mixer, uniformly mixing, then sequentially adding the weighed combustion stabilizer, burning rate regulator, nitramine explosive and oxidant, mixing for 70-80 min, finally adding the weighed curing agent, and continuously mixing for 20-30 min to obtain propellant slurry;

(3) pouring: the propellant slurry is cast by a vacuum casting method, and the residual pressure in a casting cylinder is less than or equal to 10 mmHg;

(4) and (3) curing: the mould poured with the propellant slurry and the engine shell are placed in a curing oven for heating and curing,

(5) demolding and shaping: and taking out the solidified engine, pulling out the core mold, and finishing the surface of the powder.

Further, the mixing temperature in the step 2) is controlled to be 45-50 ℃, and the pouring temperature in the step 3) is 50-55 ℃; in the step 4), the curing temperature is 70 ℃, and the curing time is 72-96 h.

The invention has the following beneficial effects:

1. the propellant is added with the organic barium salt, the amantadine derivative or the ferrocenyl quaternary ammonium salt combustion speed regulator, wherein the organic barium salt mainly contains N, C, H and other elements besides a certain amount of Ba, and the elements can generate heat through chemical reaction with oxygen in the propellant combustion process, thereby having certain contribution to the energy performance of the propellant. The ferrocenyl quaternary ammonium salt is solid, the burning rate pressure index of the propellant is reduced by the synergistic effect of the ferrocene and the quaternary ammonium salt, and the problems of migration phenomenon of liquid ferrocene compounds in the propellant and failure of high-pressure reduction index effect of ammonium oxalate are avoided. The amantadine derivative does not contain metal substances, smoke in the propellant can be effectively reduced, the cage-shaped structure of the amantadine can effectively absorb heat during combustion, and the burning rate pressure index of the propellant is reduced.

2. The addition amount of the combustion speed regulator in the propellant is 0.5-2.0%, the addition amount is small, the solid powder is solid powder, does not contain active groups, has good compatibility with all components of the propellant, has excellent pharmaceutical process performance, and has good effect of reducing the combustion speed pressure index of the propellant under the high-pressure condition.

3. The propellant does not contain aluminum powder, can effectively reduce the generation amount of primary smoke in the propellant, and has low characteristic signals.

4. The combustion stabilizer in the propellant is zirconium carbide ZrC, magnesium oxide MgO or titanium dioxide TiO₂The material has high melting point and strong heat conduction, and ensures the stable combustion of the hydroxyl-terminated aluminum-free propellant.

Drawings

FIG. 1 is a visual representation of the ground test smoke generation for an engine made with the reference propellant having an aluminum content of 8% in example 2.

FIG. 2 is a visual representation of the aerosol generation in a ground test of an engine made with the propellant of the invention of example 2.

FIG. 3 is a ground test operating condition curve of a full-scale engine of a certain airborne model, to which the propellant of the present invention of example 4 is applied.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.

In examples 1-6, the inventors designed reference propellants for comparison with the butylated hydroxyaluminum-free propellants of the present invention based on the composition and content range of common butylated hydroxyanisolpropellants. The combustion speed regulator in the butylated hydroxyaluminum-free propellant is purchased from Shanghai organic institute of Chinese academy of sciences, and other substances in the propellant can be obtained from a public way.

Example 1:

(1) the propellant composition (mass percent) is shown in table 1:

TABLE 1

(2) The propellant properties are shown in table 2:

TABLE 2

Example 2:

(1) the propellant composition (mass percent) is shown in table 3:

TABLE 3

(2) Propellant properties are shown in table 4:

TABLE 4

Wherein the ground test smoke generation of the engine prepared by the reference propellant and the propellant adopting the formula of the invention in the example 2 is shown in a visual chart in figures 1 and 2, and can be seen by comparing figures 1 to 2: the combustion smoke generation amount of the hydroxyl-terminated aluminum-free propellant is obviously less than that of a reference propellant with 8 percent of aluminum content.

Example 3

(1) The propellant composition (in mass%) is shown in table 5:

TABLE 5

(2) Propellant properties are shown in table 6:

TABLE 6

Example 4

(1) The propellant composition (in mass%) is shown in table 7:

TABLE 7

(2) Propellant properties are shown in table 8:

TABLE 8

The ground test operating curve of the propellant applied to a certain onboard model full-size engine in the embodiment 4 is shown in fig. 3 in particular, and can be seen from fig. 3: the hydroxyl-terminated aluminum-free propellant disclosed by the invention works stably under a high pressure (more than 20 MPa), which shows that the hydroxyl-terminated aluminum-free propellant has a low burning rate pressure index under the high pressure.

Example 5

(1) The propellant composition (in mass%) is shown in table 9:

TABLE 9

(2) Propellant properties are shown in table 10:

watch 10

Example 6

(1) The propellant composition (in mass%) is shown in table 11:

TABLE 11

(2) Propellant properties are shown in table 12:

TABLE 12

Claims (10)

1. The hydroxyl-terminated aluminum-free propellant is characterized by comprising the following raw materials in percentage by weight: 7.5 to 8.0 percent of adhesive, 2.5 to 3.5 percent of plasticizer, 0.5 to 1.0 percent of curing agent, 63 to 74 percent of oxidant, 10 to 20 percent of nitramine explosive, 1.0 to 3.0 percent of combustion stabilizer, 1.5 to 2.5 percent of burning rate catalyst and 0.5 to 2 percent of burning rate regulator; wherein the burning rate regulator is one or more of organic barium salt, amantadine derivative and ferrocenyl quaternary ammonium salt.

2. The aluminum-free butylated propellant of claim 1, wherein: the adhesive is hydroxyl-terminated polybutadiene HTPB, the plasticizer is diisooctyl sebacate GZ, the curing agent is toluene diisocyanate TDI, and the oxidant is ammonium perchlorate AP.

3. The aluminum-free butylated propellant of claim 1, wherein: the nitramine explosive is hexogen RDX or HMX.

4. The aluminum-free butylated propellant of claim 1, wherein: the burning rate catalyst is 2, 2-bisethylferrocene propane GFP or octylferrocene XMT.

5. The aluminum-free butylated propellant of claim 1, wherein: the combustion stabilizer is zirconium carbide ZrC, magnesium oxide MgO or titanium dioxide TiO₂。

6. The aluminum-free butylated propellant of claim 1, wherein: the median particle size of the organic barium salt is 5-15 mu m, the barium content is 39% -41%, and the water content is not more than 0.1%.

7. The aluminum-free butylated propellant of claim 1, wherein: the median particle size of the amantadine derivative is 5-15 mu m, the carbon content is 67.8%, the hydrogen content is 10.9%, the oxygen content is 12%, the nitrogen content is 2.6%, the chlorine content is 6.7%, and the water content is not more than 0.1%.

8. The aluminum-free butylated propellant of claim 1, wherein: the ferrocenyl quaternary ammonium salt has a median particle size of 5-15 mu m, an iron content of 8.2-8.5% and a water content of not more than 0.1%.

9. The method of making the aluminum-free butylated propellant of any one of claims 1 to 8, comprising the steps of:

(1) weighing the raw materials according to the proportion;

(2) mixing: stirring and uniformly mixing the weighed adhesive, plasticizer and burning rate catalyst for 20-30 min in a vertical mixer, then sequentially adding the weighed combustion stabilizer, burning rate regulator, nitramine explosive and oxidant, mixing for 70-80 min, finally adding the weighed curing agent, and continuously mixing for 20-30 min to obtain propellant slurry;

(3) pouring: the propellant slurry is cast by a vacuum casting method, and the residual pressure in a casting cylinder is less than or equal to 10 mmHg;

(4) and (3) curing: the mould poured with the propellant slurry and the engine shell are placed in a curing oven for heating and curing,

(5) demolding and shaping: and taking out the solidified engine, pulling out the core mold, and finishing the surface of the powder.

10. The method of claim 9, wherein: the mixing temperature in the step (2) is controlled to be 45-50 ℃, and the pouring temperature in the step (3) is 50-55 ℃; in the step (4), the curing temperature is 70 ℃, and the curing time is 72-96 h.

Images