CN113956121A - High-energy low-characteristic signal propellant and preparation method thereof - Google Patents

Abstract

The invention provides a high-energy low-characteristic signal propellant and a preparation method thereof, wherein the propellant is prepared from the following raw material components in parts by mass: polyazide glycidyl ether adhesive: 8 to 12 percent; plasticizer: 10% -22.5%; oxidizing agent: 62 to 75 percent; curing agent: 0.5 to 2 percent; additive: 1% -4%; aluminum powder (Al): 0 to 5 percent; wherein the oxidizer contains 5,5 '-bitetrazole-1, 1' -dioxygen dihydroxy ammonium salt (TKX-50), the mass content of TKX-50 in the propellant is not less than 48%, and the mass percentage content of Ammonium Perchlorate (AP) in the oxidizer is not more than 10% of the total mass of the propellant; the additive is selected from at least one of a stabilizer, a bonding agent or a curing catalyst; the sum of the mass percentages of the high-energy low-characteristic signal propellant is 100%. The propellant provided by the invention has standard theoretical specific impulse of more than 255s, low plume characteristic signal, high safety performance and good comprehensive performance.

Description

High-energy low-characteristic signal propellant and preparation method thereof

Technical Field

The invention belongs to the technical field of propellants, relates to a high-energy low-characteristic signal propellant and a preparation method thereof, and particularly relates to a novel high-energy low-characteristic signal propellant for a future new generation of small maneuvering strategic tactical missile with high requirement on the energy of the propellant and good safety performance.

Background

With the development of missile defense systems, the viability of missile weapon models in various countries is greatly challenged. In order to improve the survivability and the penetration capability of missile weapons, the main technical approaches are various, and the engines of the weapon systems mainly have two aspects:

(1) the energy of the propellant is improved, namely, a high-energy propellant is adopted.

In the development history of solid propellants, the energy performance of the solid propellants is gradually improved to 255-260 s of polyether high-energy solid propellants (NEPE) plasticized by nitrate by continuously improving and selecting materials with high generated heat, low average molecular weight of combustion products and large heat release, such as energetic oxidants, energetic plasticizers, novel combustion agents, novel catalysts and the like. The synthesis process of the oxidant ammonium nitrate compound (CL-20) in the formula is complex, a noble metal catalyst Pd is needed, the synthesis cost is high, the safety performance is poor, the requirements of a new generation of maneuvering strategy tactical missile on the solid propellant cannot be met, and the formula of a high-energy solid propellant containing a novel high-energy density insensitive oxidant is urgently required to be developed so as to meet the performance requirements of a new generation of weapon models.

(2) The probability of missile detection is reduced by using low-characteristic signal propellant technology.

The common double-base and modified double-base propellants have small plume signal characteristics (the transmission rates of middle and far infrared rays, visible light and laser are more than or equal to 90 percent), but the energy is too low (between 220s and 230 s); the energy of the butylated Hydroxytoluene (HTPB) propellant meets the requirement (240s (standard theoretical specific impulse)) but the plume signal does not meet the requirement (the transmission rates of middle and far infrared rays, visible light and laser light are more than or equal to 40%).

Therefore, the development of a high-energy low-characteristic signal solid propellant which has a higher specific impulse, a lower plume characteristic signal and good comprehensive performance is urgently needed.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides the propellant with standard theoretical specific impulse of more than 255s, low plume characteristic signal, high safety performance and good comprehensive performance.

The technical scheme provided by the invention is as follows:

in a first aspect, the high-energy low-characteristic signal propellant is prepared from the following raw material components in parts by mass:

polyazide glycidyl ether adhesive: 8 to 12 percent;

plasticizer: 10% -22.5%;

oxidizing agent: 62 to 75 percent;

curing agent: 0.5 to 2 percent;

additive: 1% -4%;

aluminum powder (Al): 0 to 5 percent;

wherein the oxidizer contains 5,5 '-bitetrazole-1, 1' -dioxygen dihydroxy ammonium salt (TKX-50), the mass content of TKX-50 in the propellant is not less than 48%, and the mass percentage content of Ammonium Perchlorate (AP) in the oxidizer is not more than 10% of the total mass of the propellant;

the additive is selected from at least one of a stabilizer, a bonding agent or a curing catalyst;

the sum of the mass percentages of the high-energy low-characteristic signal propellant is 100%.

In a second aspect, a method of making a high energy, low signature signal propellant, for use in making the propellant of the first aspect, comprises the steps of:

premixing the additive, the fuel aluminum powder and part of the binder/plasticizer before mixing;

adding the premixed material into a mixing container, and then sequentially adding an oxidant, a curing agent and the rest of the adhesive/plasticizer; after being uniformly mixed, the slurry is poured into an engine shell or various molds by using a vacuum pouring system and is cured in an oven.

The high-energy low-characteristic signal propellant and the preparation method thereof provided by the invention have the following beneficial effects:

(1) the invention provides a high-energy low-characteristic signal propellant and a preparation method thereof, wherein the high-energy low-characteristic signal propellant is characterized in that: by introducing TKX-50, the standard theoretical specific impulse of the propellant is more than 255s under 6.86 MPa;

(2) the invention provides a high-energy low-characteristic signal propellant and a preparation method thereof, wherein the fuel gas plume characteristic signal is low: by reducing the content of Al and AP in the propellant, the transmission rates of far infrared light, visible light and laser in the propellant plume are all more than 70 percent;

(3) the high-energy low-characteristic signal propellant and the preparation method thereof provided by the invention have good safety performance: the safety performance and the dangerous characteristic of the formula are equivalent to those of the existing mature propellant;

(4) according to the high-energy low-characteristic signal propellant and the preparation method thereof, the oxidant TKX-50 is low in synthesis process difficulty and low in cost, and other components in the formula are high in maturity, so that the high-energy low-characteristic signal propellant is easy to popularize and apply; the TKX-50-containing high-energy low-characteristic signal propellant has excellent comprehensive performance, can greatly improve the missile range, greatly reduce the signal characteristics of the missile and obviously improve the survival capability and the penetration capability of the missile after being applied to weapon models.

Detailed Description

The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.

According to a first aspect of the invention, a high-energy low-characteristic signal propellant is provided, which is prepared from the following raw material components in parts by mass:

polyazide glycidyl ether adhesive: 8 to 12 percent;

plasticizer: 10% -22.5%;

oxidizing agent: 62 to 75 percent;

curing agent: 0.5 to 2 percent;

additive: 1% -4%;

aluminum powder (Al): 0 to 5 percent;

wherein the oxidizer contains 5,5 '-bitetrazole-1, 1' -dioxygen dihydroxy ammonium salt (TKX-50), the mass content of TKX-50 in the propellant is not less than 48%, and the mass percentage content of Ammonium Perchlorate (AP) in the oxidizer is not more than 10% of the total mass of the propellant;

the additive is selected from at least one of a stabilizer, a bonding agent or a curing catalyst;

the sum of the mass percentages of the high-energy low-characteristic signal propellant is 100%.

In a preferred embodiment, the plasticizer is selected from at least one of Nitroglycerin (NG), butanetriol trinitrate (BTTN), triethylene glycol dinitrate (TEGDN), trimethylolethane trinitrate (TMETN), or diethylene glycol dinitrate (DEGDN).

Further, the mass ratio of the plasticizer to the azido polyether adhesive (GAP) is (1.0-3.0): 1.

In a preferred embodiment, the oxidizing agent is selected from any one of the following:

a combination of 5,5 '-bitetrazole-1, 1' -dioxygenated diammonium salt (TKX-50), Ammonium Perchlorate (AP), cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (HMX) and hexanitrohexaazaisowurtzitane (CL-20);

② a combination of TKX-50, AP, RDX and CL-20;

③ the combination of TKX-50, AP, HMX and CL-20;

a combination of TKX-50, AP and HMX;

TKX-50, AP and CL-20;

sixthly, the combination of TKX-50 and CL-20;

seventy, a combination of TKX-50 and HMX;

combining the TKX-50 and the AP;

⑨TKX-50。

the research of the inventor finds that the TKX-50 has the characteristics of high energy and low sensitivity (friction and impact sensitivity), and has a good application prospect in the field of solid propellants. At present, the synthesis research and related properties of 5,5 '-bistetrazole-1, 1' -dioxygenated diammonium TKX-50 are reported in J.Mater.chem.,2012,22, 20418-one 20422. A national defense patent 5,5 '-bitetrazole-1, 1' -dioxygen dihydroxy ammonium salt synthesis method (patent acceptance number: 2013102886012) applied in China develops a new synthesis method, reduces the variety of reaction solvents, shortens the synthesis period, reduces the difficulty and cost of the production process, and improves the reaction efficiency and the product yield, but the TKX-50 is not applied to NEPE high-energy solid propellant at present. According to the invention, the specific content of TKX-50 is introduced, so that the high-energy low-sensitivity propellant is high, and the standard theoretical specific impulse of the propellant is larger than 255s under 6.86 MPa.

In a preferred embodiment, the curing agent is an isocyanate compound selected from at least one of Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), polyfunctional isocyanate N-100, isophorone diisocyanate (IPDI).

In a preferred embodiment, the stabilizer is selected from at least one of N, N-dimethylaniline (NN), N-methylaniline or diphenylamine; the bonding agent is neutral polymer bonding agent NPBA, and at least one of various types can be selected from commercially available bonding agents; the curing catalyst is at least one selected from dicumyl peroxide (DCP), dibutyl tin dilaurate and the like.

In a preferred embodiment, the standard theoretical specific impulse of the propellant is 2579 Ns/kg (6.86 MPa); the visible light transmittance of the plume is more than or equal to 82 percent, the laser transmittance is more than or equal to 75 percent, and the middle and far infrared transmittances are more than or equal to 75 percent.

According to a second aspect of the present invention there is provided a high energy low signature signal propellant comprising the steps of:

premixing the additive, the fuel aluminum powder and part of the binder/plasticizer before mixing;

adding the premixed material into a mixing container, and then sequentially adding an oxidant, a curing agent and the rest of the adhesive/plasticizer; after being uniformly mixed, the slurry is poured into an engine shell or various molds by using a vacuum pouring system and is cured in an oven. The propellant formulation is preferably mixed homogeneously using a vertical mixer.

Examples

Example 1

(1) Propellant composition

(2) The preparation method comprises the following steps:

premixing the additive, the fuel aluminum powder and part of the binder/plasticizer before mixing;

adding the premixed material into a mixing pot, and then sequentially adding an oxidant, a curing agent and the rest of adhesive/plasticizer; and uniformly mixing by using a vertical mixer, and pouring the slurry into the engine shell by using a vacuum pouring system. The propellant preparation method in the following examples is the same as in example 1.

(3) Performance of propellant

Standard theoretical specific impulse: 2606.5N · s/kg (6.86 MPa).

Density: 1.800g/cm³。

Combustion performance: r (6.86MPa) is 20mm/s, and n is 0.54 (3-9 MPa).

Characteristic signals: the propellant plume has the visible light transmittance of 82.5 percent, the laser transmittance of 78.5 percent and the middle and far infrared transmittance of 77.7 percent.

Mechanical properties: maximum elongation epsilon at 70 DEG C_m≥45％；

Maximum tensile strength sigma at 25 DEG C_m≥0.82MPa，ε_m≥52％；

-40℃，ε_m≥62％。

Example 2

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2636.8N · s/kg (6.86 MPa).

Density: 1.793g/cm³。

Combustion performance: r (6.86MPa) is 16mm/s, and n is 0.57 (3-9 MPa).

Characteristic signals: the propellant plume has the visible light transmittance of 85.0 percent, the laser transmittance of 80.0 percent and the middle and far infrared transmittances of 79 percent.

Mechanical properties: at 70 ℃ of e_m≥45％；

25℃，σ_m≥0.78MPa，ε_m≥48％；

-40℃，ε_m≥55％。

Example 3

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2593.5N · s/kg (6.86 MPa).

Density: 1.791g/cm³。

Combustion performance: r (6.86MPa) is 12mm/s, and n is 0.58 (3-9 MPa).

Characteristic signals: the propellant plume visible light transmittance is 90%, the laser transmittance is 85%, and the middle and far infrared transmittance is 84%.

Mechanical properties: at 70 ℃ of e_m≥40％；

25℃，σ_m≥0.70MPa，ε_m≥45％；

-40℃，ε_m≥50％。

Example 4

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2598.8N · s/kg (6.86 MPa).

Density: 1.803g/cm³。

Combustion performance: r (6.86MPa) is 21.5mm/s, and n is 0.55 (3-9 MPa).

Characteristic signals: the propellant plume has the visible light transmittance of 82.9 percent, the laser transmittance of 78.3 percent and the middle and far infrared transmittance of 78 percent.

Mechanical properties: at 70 ℃ of e_m≥45％；

25℃，σ_m≥0.85MPa，ε_m≥52％；

-40℃，ε_m≥62％。

Example 5

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2641.0N · s/kg (6.86 MPa).

Density: 1.800g/cm³。

Combustion performance: r (6.86MPa) is 23mm/s, and n is 0.57 (3-9 MPa).

Characteristic signals: the propellant plume has the visible light transmittance of 85 percent, the laser transmittance of 77.5 percent and the middle and far infrared transmittance of 78 percent.

Mechanical properties: at 70 ℃ of e_m≥38％；

25℃，σ_m≥0.78MPa，ε_m≥55％；

-40℃，ε_m≥43％。

Example 6

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2638.2N · s/kg (6.86 MPa).

Density: 1.800g/cm³。

Combustion performance: r (6.86MPa) is 24mm/s, and n is 0.59 (3-9 MPa).

Characteristic signals: propellant plume visible light transmittance of 84.5%, laser transmittance of 76%, and middle and far infrared transmittance of 76%.

Mechanical properties: at 70 ℃ of e_m≥48％；

25℃，σ_m≥0.80MPa，ε_m≥53％；

-40℃，ε_m≥51％。

Example 7

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2606.5N · s/kg (6.86 MPa).

Density: 1.800g/cm³。

Combustion performance: r (6.86MPa) is 24mm/s, and n is 0.56 (3-9 MPa).

Characteristic signals: the propellant plume has a visible light transmittance of 84%, a laser transmittance of 75.5% and a middle and far infrared transmittance of 75%.

Mechanical properties: at 70 ℃ of e_m≥49％；

25℃，σ_m≥0.77MPa，ε_m≥51％；

-40℃，ε_m≥55％。

Example 8

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2596.2N · s/kg (6.86 MPa).

Density: 1.800g/cm³。

Combustion performance: r (6.86MPa) is 25mm/s, and n is 0.57 (3-9 MPa).

Characteristic signals: the propellant plume visible light transmittance is 89%, the laser transmittance is 93%, and the middle and far infrared transmittance is 89%.

Mechanical properties: at 70 ℃ of e_m≥46％；

25，σ_m≥0.73MPa，ε_m≥48％；

-40℃，ε_m≥50％。

Example 9

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2600.0N · s/kg (6.86 MPa).

Density: 1.795g/cm³。

Combustion performance: r (6.86MPa) is 14mm/s, and n is 0.6 (3-9 MPa).

Characteristic signals: the propellant plume has 88 percent of visible light transmittance, 93 percent of laser transmittance and 90 percent of middle and far infrared transmittance.

Mechanical properties: at 70 ℃ of e_m≥36％；

25℃，σ_m≥0.62MPa，ε_m≥50％；

-40℃，ε_m≥41％。

Example 10

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2599.1N · s/kg (6.86 MPa).

Density: 1.820g/cm³。

Combustion performance: r (6.86MPa) is 17 mm/s.

Characteristic signals: the propellant plume visible light transmittance is 89%, the laser transmittance is 94%, and the middle and far infrared transmittance is 93%.

Mechanical properties: at 70 ℃ of e_m≥38％；

25℃，σ_m≥0.65MPa，ε_m≥52％；

-40℃，ε_m≥43％。

Example 11

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2622.2N · s/kg (6.86 MPa).

Density: 1.850g/cm³。

Combustion performance: r (6.86MPa) is 30 mm/s.

Characteristic signals: the propellant plume visible light transmittance is 90%, the laser transmittance is 92%, and the middle and far infrared transmittance is 95%.

Mechanical properties: at 70 ℃ of e_m≥35％；

25℃，σ_m≥0.60MPa，ε_m≥45％；

-40℃，ε_m≥40％。

Example 12

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2579.3N · s/kg (6.86 MPa).

Density: 1.805g/cm³。

Combustion performance: r (6.86MPa) is 27mm/s, and n is 0.58 (3-9 MPa).

Characteristic signals: the propellant plume has the visible light transmittance of 85 percent, the laser transmittance of 75.5 percent and the middle and far infrared transmittance of 77 percent.

Mechanical properties: at 70 ℃ of e_m≥40％；

25℃，σ_m≥0.80MPa，ε_m≥47％；

-40℃，ε_m≥50％。

Example 13

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2602.2N · s/kg (6.86 MPa).

Density: 1.803g/cm³。

Combustion performance: r (6.86MPa) is 15 mm/s.

Characteristic signals: the propellant plume visible light transmittance is 89%, the laser transmittance is 94%, and the middle and far infrared transmittance is 93%.

Mechanical properties: at 70 ℃ of e_m≥35％；

25℃，σ_m≥0.61MPa，ε_m≥48％；

-40℃，ε_m≥40％。

Example 14

(1) Propellant composition

(2) Performance of propellant

Standard theoretical specific impulse: 2600.4N · s/kg (6.86 MPa).

Density: 1.828g/cm³。

Combustion performance: r (6.86MPa) is 28 mm/s.

Characteristic signals: the propellant plume visible light transmittance is 90%, the laser transmittance is 92%, and the middle and far infrared transmittance is 95%.

Mechanical properties: at 70 ℃ of e_m≥37％；

25℃，σ_m≥0.61MPa，ε_m≥49％；

-40℃，ε_m≥42％。

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 technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present 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 (8)

1. The high-energy low-characteristic signal propellant is characterized by being prepared from the following raw material components in parts by mass:

polyazide glycidyl ether adhesive: 8 to 12 percent;

plasticizer: 10% -22.5%;

oxidizing agent: 62 to 75 percent;

curing agent: 0.5 to 2 percent;

additive: 1% -4%;

aluminum powder (Al): 0 to 5 percent;

wherein the oxidizer contains 5,5 '-bitetrazole-1, 1' -dioxygen dihydroxy ammonium salt (TKX-50), the mass content of TKX-50 in the propellant is not less than 48%, and the mass percentage content of Ammonium Perchlorate (AP) in the oxidizer is not more than 10% of the total mass of the propellant;

the additive is selected from at least one of a stabilizer, a bonding agent or a curing catalyst;

the sum of the mass percentages of the raw material components of the high-energy low-characteristic signal propellant is 100%.

2. The high energy, low signature propellant as claimed in claim 1 wherein the plasticizer is selected from at least one of Nitroglycerin (NG), butanetriol trinitrate (BTTN), triethylene glycol dinitrate (TEGDN), trimethylolethane trinitrate (TMETN) or diethylene glycol dinitrate (DEGDN).

3. The high energy, low signature propellant as claimed in claim 2 wherein the mass ratio of plasticizer to azido polyether binder (GAP) is (1.0-3.0): 1.

4. the high energy, low signature propellant as claimed in claim 1 wherein said oxidizer is selected from any one of the following:

a combination of 5,5 '-bitetrazole-1, 1' -dioxygenated diammonium salt (TKX-50), Ammonium Perchlorate (AP), cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (HMX) and hexanitrohexaazaisowurtzitane (CL-20); ② a combination of TKX-50, AP, RDX and CL-20; ③ the combination of TKX-50, AP, HMX and CL-20; a combination of TKX-50, AP and HMX; TKX-50, AP and CL-20; sixthly, the combination of TKX-50 and CL-20; seventy, a combination of TKX-50 and HMX; combining the TKX-50 and the AP; ninthly TKX-50; preferably a combination of TKX-50 and HMX, or TKX-50.

5. The propellant of claim 1 wherein the curing agent is an isocyanate compound selected from at least one of Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), polyfunctional isocyanate N-100 or isophorone diisocyanate (IPDI).

6. The high energy, low signature propellant as claimed in claim 1 wherein the stabilizer is selected from at least one of N, N-dimethylaniline (NN), N-methylaniline or diphenylamine; the bonding agent is a neutral polymer bonding agent NPBA; the curing catalyst is at least one selected from dicumyl peroxide (DCP) or dibutyl tin dilaurate.

7. The high energy, low signature propellant of claim 1 wherein the standard theoretical specific impulse of the propellant is at least 2579 ns/kg (6.86 MPa); the visible light transmittance of the plume is more than or equal to 82 percent, the laser transmittance is more than or equal to 75 percent, and the middle and far infrared transmittances are more than or equal to 75 percent.

8. A high energy, low signature propellant for use in the preparation of a propellant as claimed in any one of claims 1 to 7 comprising the steps of:

premixing the additive, the fuel aluminum powder and part of the binder/plasticizer before mixing;

adding the premixed material into a mixing container, and then sequentially adding an oxidant, a curing agent and the rest of the adhesive/plasticizer; after being uniformly mixed, the slurry is poured into an engine shell or various molds by using a vacuum pouring system and is cured in an oven.