KR101850395B1 - Composite for solid propellant and manufacturing method of the same - Google Patents

Abstract

The present invention relates to a solid propellant composition and a method for producing a solid propellant using the solid propellant composition, wherein the solid propellant composition comprises 9 to 71% by weight of a prepolymer, 0 to 81% by weight of a combustion catalyst comprising a lead compound or a bismuth compound, By weight, carbon black: 5 to 31% by weight, and diisocyanate: 0 to 10% by weight.

Description

Technical Field [0001] The present invention relates to a solid propellant composition and a method for manufacturing a solid propellant using the solid propellant composition,

The present invention relates to solid propellant compositions for improving combustion characteristics.

Propellants using ammonium perchlorate (AP) as an oxidizing agent can control the combustion characteristics according to the particle size of AP and metal oxides such as Fe ₂ O ₃ are used as combustion catalyst to realize various combustion characteristics.

However, since minimum smoke NEPE propellants using RDX, HMX and HNIW as energy fillers, BTTN, TMETN, DEGDN, BuNENA, TEGDN and BDNPA / F as energy plasticizers are not easy to control combustion characteristics, It is known to control the combustion characteristics by using the lead compound or the bismuth compound when the AP is not used.

The molecular weight of the prepolymer for solid propellant is generally in the range of 3000-5000 g / mol in consideration of the mechanical strength of the propellant and the processability of the propellant. In order to increase the energy of the propellant, the energy plasticizer is preferably 3 to 4 times The viscosity of the binder is low. The above-mentioned combustion catalysts have a better effect as the particles are thinner, but they are difficult to disperse evenly in a propellant having a low viscosity of the binder, so that it is hard to see the effect thereof.

The present invention is directed to solving the above-mentioned problems and other problems. Another object is to provide a paste composition for increasing dispersibility in solid propellants.

According to an aspect of the present invention, there is provided a fuel cell comprising: 0 to 81% by weight of a combustion catalyst comprising 9 to 71% by weight of a prepolymer, a lead compound or a bismuth compound, 5 to 31% by weight, and diisocyanate: 0 to 10% by weight based on the total weight of the solid propellant composition.

According to one aspect of the present invention, the prepolymer is selected from the group consisting of HTPB, HTPE, PEG, PPG, PCP, and GAP ≪ / RTI >

According to one aspect of the present invention, the lead compound is selected from the group consisting of lead citrate, lead acetate, lead acetylacetonate, lead carbonate, lead cyanamide, Lead nitrate, lead oxide, lead salicylate, lead subacetate, lead sulfate, lead sulfide, and lead thiocyanate lead thiocyanate), or a mixture of two or more thereof.

According to one aspect of the present invention, the bismuth compound is selected from the group consisting of bismuth acetate, bismuth citrate, bismuth nitrate, bithmuth subnitrate, bithmuth pentahydrate, And may be composed of one or a mixture of two or more selected from bismuth oxide, bismuth phosphate, bismuth salicylate, bismuth subsalicylate, and bismuth sulfide.

According to one aspect of the present invention, the molecular weight of the HTPB, HTPE, PEG, PPG, and PCP may be less than 1000.

According to an aspect of the present invention, the molecular weight of the GAP may be 500-3000.

According to one aspect of the present invention, there is provided a continuous catalyst comprising 0 to 81 wt% of a continuous catalyst comprising 9 to 71 wt% of a prepolymer, a lead compound or a bismuth compound, 5 to 31 wt% of carbon black, : 0 to 10% by weight of a paste by using a 3 roll mill; Adding a curing agent to the paste and vacuum mixing the paste; And a step of curing the paste.

According to one aspect of the present invention, the curing agent is selected from the group consisting of dimer diisocyanate (DDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and hydrogenated diphenylmethane Diisocyanate (hydrogenated diphenylmethane diisocyanate, H ₁₂ MDI), or a mixture of two or more thereof.

The effect of the solid propellant composition according to one embodiment of the present invention will be described as follows.

According to one embodiment of the present invention, a solid propellant of a lead compound or a bismuth compound may be dispersed in advance in an arbitrary composition in order to increase the dispersibility, and then the paste may be added to the propellant mixing process to improve the effect of the catalyst particles There are advantages.

In addition, according to one embodiment of the present invention, the molecular weight of the prepolymer used in the paste is lowered, thereby improving the processability of the solid propellant and enhancing the mechanical properties.

In addition, according to one embodiment of the present invention, when the paste composition is added during the production of the NEPE (Nitrate Ester Plasticized Polyether) propellant, the burning rate of the propellant increases, the pressure index decreases and the tensile property improves, There is an advantage that reliability is improved as well as improvement.

Further scope of applicability of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and specific examples, such as the preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art.

1 is a flow chart of a method of manufacturing a solid propellant according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein like or similar components are denoted by the same reference numerals, and redundant explanations thereof will be omitted. The suffix "module" and " part "for the components used in the following description are given or mixed in consideration of ease of specification, and do not have their own meaning or role. In the following description of the embodiments of the present invention, a detailed description of related arts will be omitted when it is determined that the gist of the embodiments disclosed herein may be blurred. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. , ≪ / RTI > equivalents, and alternatives.

Terms including ordinals, such as first, second, etc., may be used to describe various elements, but the elements are not limited to these terms. The terms are used only for the purpose of distinguishing one component from another.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between.

The singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

In an embodiment of the present invention, in order to achieve the above object, a lead compound or a bismuth compound having a very small particle size using PEG (having a molecular weight of 600 or less) and diisocyanate, which are liquid at room temperature, Black was used to make paste by using a 3 roll mill and the amount required for the propellant was added to drastically improve the combustion characteristics, fairness and mechanical properties.

The additive composition according to an embodiment of the present invention may include a prepolymer: 9 to 71% by weight, a combustion catalyst containing 0 to 81% by weight of a lead compound or a bismuth compound, 5 to 31% , And diisocyanate: 0 to 10% by weight.

At this time, if the weight of the prepolymer is 9 wt% or less, the viscosity is not enough to form a paste. If the weight of the prepolymer is 71 wt% or more, a problem that the catalyst compound is not dispersed well in the paste may occur. The prepolymer in the examples is limited to 9 to 71% by weight. Incidentally, although there is no need to include the combustion catalyst, it is preferable to include it in order to achieve the effect of the present invention. At this time, when the amount of the continuous catalyst is 81 wt% or more, the amount of the prepolymer is relatively small, and the catalyst compounds are not well dispersed in the prepolymer and are easily aggregated.

In an embodiment of the present invention, the content of the carbon black is limited to 5 to 31% by weight. When the content is less than 5% by weight, the catalyst compound is not well dispersed due to a small interaction with the prepolymer. The carbon black aggregates with each other and is not well dispersed. Therefore, it is limited to the above range.

When the content of the diisocyanate is 10% by weight or more, the paste is cured by the curing reaction with the prepolymer in the paste before the injection of the paste in the propellant, and the content of isocyanate to be finally added to the propellant is reduced, , The content of the diisocyanate in one embodiment of the present invention is limited to 10% by weight.

The prepolymer may be selected from the group consisting of hydroxy-terminated polybutadiene (HTPB), hydroxy-terminated polyether (HTPE), polyethylene glycol (PEG), polypropylene glycol (Poly caprolactone polymer), and GAP (Glycidyl azide polymer), or a mixture of two or more thereof. According to one embodiment of the present invention, the molecular weight of the HTPB, HTPE, PEG, PPG, and PCP is limited to less than 1000, since the polymer is liquid, If the molecular weight of the GAP is less than 500, the viscosity of the propellant is too low to produce a viscous phase. When the molecular weight of the GAP is more than 3,000, the prepolymer There is a problem that the paste itself is difficult to be manufactured because of its high viscosity. Therefore, the molecular weight of GAP in one embodiment of the present invention is limited to 500-3000.

In this case, the curing agent in one embodiment of the present invention may include dimer diisocyanate (DDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and hydrogenated diphenyl Hydrogenated diphenylmethane diisocyanate (H ₁₂ MDI) (to be confirmed), or a mixture of two or more thereof.

The lead compound may be selected from the group consisting of lead citrate, lead acetate, lead acetylacetonate, lead carbonate, lead cyanamide, lead nitrate, One or more selected from lead oxide, lead salicylate, lead subacetate, lead sulfate, lead sulfide, and lead thiocyanate. 2 or more.

The bismuth compound may be at least one selected from the group consisting of bismuth acetate, bismuth citrate, bismuth nitrate, bithmuth subnitrate, bithmuth pentahydrate, bismuth oxide, It is composed of one or a mixture of two or more selected from bismuth phosphate, bismuth salicylate, bismuth subsalicylate, and bismuth sulfide.

Example

Hereinafter, the present invention will be described in more detail by way of examples.

A prepolymer, a combustion catalyst, a carbon black, and a diisocyanate were weighed into a suitable size container using the composition shown in the following [Table 1], and a paste composition for use in the production of a propellant was manufactured using a three roll mill (S110) do.

Example Paste composition (% by weight) PEG600 Combustion catalyst CB IPDI One 70.0 - 30.0 2 40.0 Pb Citrate
60.0 - 3 50.4 Pb Citrate
30.0 10.0 9.6 4 20.0 Bi2O3
80.0 - 5 50.0 Pb Citrate
37.5 12.5 6 65.0 Bismuth subsalicylate
35 -

In Table 2, propellant compositions using the same were prepared as follows.

First, the necessary raw materials are weighed and the necessary paste is quantitatively added. Subsequently, the mixture is thoroughly vacuum-mixed (S120) at 50 to 60 ° C. for 60 to 120 minutes using a vertical mixer, and the curing agent and the curing catalyst are charged. After mixing, the mixture was cured in an oven at 50 to 60 ° C for more than 7 days (S130) to prepare a propellant sample.

Example Propellant composition (% by weight) PEG
3350 BTTN / TMETN HMX IPDI /
N-100 Combustion catalyst paste NMA /
2NDPA /
ZrC /
NC / 7 6.646 30.933 59.00 1.021 Pb Citrate
2.50 CB
0.30 - - 2.4
8 3.137 30.933 57.00 1.530 - - Example 3
5.0 -
"
9 2.403 26.133 63.00 1.899 - - Example 2
2.5 Example 1
1.665 "
10 3.140 26.133 63.25 1.745 - - Example 2
2.5 Example 1
0.833 "
11 1.656 26.133 62.25 2.146 - - Example 2
3.75 Example 1
1.665 "
12 3.516 26.133 63.67 1.618 - - Example 5
2.666 - "
13 2.607 26.133 63.00 1.860 - - Example 5
4.00 - "
14 2.607 26.133 63.00 1.860 - - Example 5
4.00 - "
15 1.678 26.133 62.33 2.123 - - Example 5
5.333 - "
16 0.828 26.133 61.67 2.305 - - Example 5
6.667 - "
17 2.752 26.933 62.00 1.915 - - Example 5
5.333 - "

The pastes used in Examples 1 to 3 and 5 in Table 1 were used as the paste composition.

The examples in the above table are examples of the composition of the solid propellant to which the actual paste is applied. PEG 3350 with molecular weight of 3350 g / mol was used as prepolymer of propellant. Butane trioltrinitrate (BTTN) and trimethylol trinitrate (TMETN) were used as energy plasticizers. HMX (Cyclotetramethylene tetranitramine) was used as the propellant energy enhancer and oxidizer, and IPDI (Isophorone diisocyanate) and N-100 (Desmodur N-100) were used as the hardening agent. N (N-methyl aniline) and 2-NDPA (2-Nitrodiphenyl amine) were used as stabilizers and NC (Nitrocellulose) as a binding agent to increase the strength of the propellant. Finally, ZrC (Zirconium carbide) was used as a combustion stabilizer. Table 2 shows the characteristics of each of the above-mentioned pastes added with the pastes of each kind shown in Table 1, and the results are compared and analyzed.

Table 3 shows the burning rate and tensile strength test results of the propellant specimens prepared with the composition of [Table 2].

Example Combustion characteristic Mechanical properties R Burning rate
(mm / s@6.89 MPa) a
(a constant) Pressure Index The tensile strength
(Bar) Strain rate
(%) Modulus of elasticity
(Bar) Hardness 7 0.9987 4.96 0.00051 0.8603 3.3 285 3.3 10 8 0.9915 11.97 0.04970 0.3257 6.4 180 10.7 27 9 0.9924 9.34 0.02306 0.4009 4.7 186 8.6 24 10 0.9919 7.75 0.00382 0.6342 7.9 148 16.6 39 11 0.9964 11.95 0.15373 0.1619 4.1 185 7.5 21 12 0.9951 12.28 0.00726 0.6078 8.5 180 19.0 40 13 0.9956 12.57 0.09167 0.2441 7.9 143 16.7 41 14 0.9933 11.19 0.05022 0.3144 4.6 123 14.6 38 15 0.9971 12.63 0.02515 0.4320 6.5 124 13.3 37 16 0.9954 11.32 0.04628 0.3278 5.1 119 9.5 32 17 0.9918 12.48 0.05054 0.3293 6.6 147 13.6 36

In Table 3, R means a linear factor.

Example 7 of the above examples is a propellant prepared without putting the required amount of lead citrate and carbon black into paste, and Examples 8 to 17 are propellants prepared according to various paste compositions. The burning rate was increased by as much as 57% (Example 10), the combustion rate was increased by about 153% (Example 15), and the pressure index was 19% of that before the paste application (Example 7) 11) level. This is very low in hybrid propellants. The tensile strength, the elastic modulus and the hardness were also improved more than those of Example 7, and the overall stiffness was enhanced.

 The foregoing detailed description should not be construed in all aspects as limiting and should be considered illustrative. The scope of the present invention should be determined by rational interpretation of the appended claims, and all changes within the scope of equivalents of the present invention are included in the scope of the present invention.

Claims (8)

1.633 to 1.739 wt% of PEG having a molecular weight of 3350 g / mol, 1.631 to 1.748 wt% of the first paste, 2.4 to 2.6 wt% of the second paste, 26.133 to 27.440 wt% of butane trioltrinitrate, 62 to 63.67 wt% of cyclotetramethylene %, Isophorone diisocyanate / Desmodur N-100: 2.103-2.189% by weight and additive: 2.4% by weight,
The first paste is composed of 69 to 71% by weight of PEG having a molecular weight of 600 g / mol and 29 to 31% by weight of carbon black,
The second paste is composed of 39 to 41% by weight of PEG having a molecular weight of 600 g / mol and 59 to 61% by weight of Pb Citrate,
Wherein the additive is a mixture of N-methyl aniline, 2-Nitrodiphenyl amine, Nitrocellulose and Zirconium carbide. delete delete delete delete delete 69 to 71% by weight of PEG having a molecular weight of 600 g / mol and 29 to 31% by weight of carbon black to prepare a first paste;
Preparing a second paste comprising 39 to 41% by weight of PEG having a molecular weight of 600 g / mol and 59 to 61% by weight of Pb Citrate;
1.633 to 1.739 wt% of PEG having a molecular weight of 3350 g / mol, 1.631 to 1.748 wt% of the first paste, 2.4 to 2.6 wt% of the second paste, 26.133 to 27.440 wt% of butane trioltrinitrate, 62 to 63.67 wt% of cyclotetramethylene %, 2.103-2.189% by weight of Isophorone diisocyanate / Desmodur N-100 and 2.4% by weight of an additive, followed by vacuum mixing;
Curing the vacuum mixed mixture,
Wherein the additive is a mixture of N-methyl aniline, 2-Nitrodiphenyl amine, Nitrocellulose and Zirconium carbide. delete

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