JPH04164887A - High energy-containing cdb propellant - Google Patents

Abstract

PURPOSE:To provide the subject propellant improved in combustion performance, stability, etc., by including a hydroxyl groupterminated methyl azide group- containing polyether and an aliphatic plasticizer having ester and ether bonds in respective specific amounts in the propellant. CONSTITUTION:A physical property improver is produced by mixing (A) 70-95wt.% hydroxyl group-terminated methyl azide group-containing polyether (e.g. formula I) with (B) 30-5wt.% aliphatic plasticizer (e.g. formula II) having ester and ether bonds. The resultant physical property improver is then mixed with nitroglycerin, nitrocellulose, nitramine, a stabilizer (e.g. diphenylamine), a hardener (e.g. hexamethylene diisocyanate), a hardening catalyst, etc., to produce a high-energy-containing composite double base(CDB) propellant. Furthermore, the component (A) has improving action on combustion performance and the component (B) has enhancing action on compatibility of the component (A) with the nitroglycerin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to pace grain slurry CDB propellants. Specifically, the present invention relates to a high-energy polymer containing an azide group as a physical property improver, and a high-energy CDB propellant using a plasticizer to improve the compatibility between the polymer and NG (Troglycerin).

[Prior Art] Solid propellants have advantages over liquid fuels in that they can be stored for a long time and can be launched immediately, and are used in military rockets and missiles.

Solid propellants include hybrid composite propellants, which are made by mixing oxidizer and fuel components, and double-base propellants, which are explosives whose main components are nitroglycerin and nitrocellulose and use non-volatile solvents. It is broadly divided into

Ammonium perchlorate, nitramine, ammonium nitrate, etc. are used as oxidizers used in composite propellants, polybutadiene, polyurethane, etc. are used as fuel (binder), and aluminum powder etc. are used as combustion improvers. There is.

Furthermore, in order to take advantage of the characteristics of composite propellants and double base propellants, we have created a composition in which a binder, which is a component of composite propellants, is added to a slurry cast type double base whose main components are fine nitrocellulose or base grains and nitroglycerin. CDB (composite double base) propellants have been developed.

Improvement in combustion performance can be achieved by improving and improving the combustion characteristics of each of these components.

However, at present, propellants made of the above substances have already achieved approximately 95% of the theoretically expected combustion performance, and there is little room for further performance improvement. Applications of high-energy materials are being considered.

Due to stability and safety constraints, oxidizing agents and combustion improvers are sometimes limited to the above-mentioned substances in practical terms, and research is being carried out on propellants in which the prepolymer itself, which is the main component of the binder, has a high energy content. There is.

US Pat. No. 4,268,450 discloses a polyether with a terminal hydroxyl group containing an azide group as a prepolymer, and its general formula is as follows: expressed.

This polyether has the following advantages by containing an azide group to improve the performance of the propellant.

One is that the specific impulse of the propellant is improved by increasing the heat of formation, and similarly, increasing the density also leads to an improvement of the specific impulse. Furthermore, by increasing the amount of nitrogen gas due to the decomposition of the azide group and increasing the amount of nitrogen in the binder, carbon,
This leads to a lower hydrogen ratio, which reduces the amount of oxidizing agent in the propellant, making it possible to lower sensitivity and improve safety.

Due to these characteristics, various applications are being considered.

Pace grain slurry type CDB propellant is produced by mixing and defoaming an NG solution in which BG (pace grain) and nitramine are dissolved as main solid components, and physical property improvers, curing agents, stabilizers, etc. as liquid components. CDB propellant is a double-base propellant whose mechanical properties are improved by controlling the reaction between CDB and a hardening agent using a catalyst, and the raw materials for CDB propellant produced by the base grain slurry method are as follows.

Main component) Nitrocellulose (Os Hr O2) (OH)3o-, (ONO
2) 8, Nitroglycerin C3H3 (ONO2) 3, HMX, (CH2) 4 (NNO2) 4, RD
X, (CH2) 3 (NNO2) 3 stabilizer) 2-nitrodiphenylamine CGH5NHC6H4NO2, diphenylamine (C6Is) 2 Nll physical property improver) polyester polyol HO-HCl2) b CO2 (CH2) 4 CO
r+-1←CHz) b O) 1° Hardening agent) Hexamethylene diisocyanate (CI+2) h (NCO) 2° Others) Lead salicylate, lead stearate, dibutyltin acetate.

The manufacturing flow is as shown in FIG.

[Problems to be Solved by the Invention] In order to improve the combustion performance of CDB propellants, replacing the polyester polyol currently used as a physical property improver with an azide group-containing polyether polyol will improve the propellant combustion performance. It is valid.

As shown in the previous manufacturing flow, there was an initial failure.

In the process of adding stabilizers, physical property improvers, and if necessary nitramine, and performing mixed dehydration, what is important is the ability to dissolve NG, which is an extremely sensitive substance, with other substances and handle it safely. It is to have the

It is known that by suppressing the purity of NG to 80% or less, it becomes less than half-explosion in the 22gv steel pipe test specified in the Industrial Explosives Association standard agitation detonation test method, and can be handled fairly safely. There is. In order to impart this property, it was necessary to uniformly dissolve the physical property improver and stabilizer in the NG.

Furthermore, when storing the product, it is usually mixed with NG, a stabilizer, and a physical property improver to impart stability before storage.

However, azide group-containing polyether polyols, which are introduced to improve the combustion performance of propellants, have poor compatibility with NG, and when left to stand after mixing, NG separates into the lower layer, causing problems during operation and storage. It was very problematic.

Under these circumstances, the present invention provides a high-energy-containing carbonaceous substance that has improved combustion performance and improved compatibility with azide group-containing polyether polyols to enhance safety during storage and handling.
The purpose is to provide DB propellant.

[Means for Solving the Problems] The present inventors took the above-mentioned problems into consideration and, as a result of intensive research, found that by using an aliphatic plasticizer having an ester bond and an ether bond, NG and azide groups can be reduced. The present invention was completed based on the discovery of the property that the compatibility with the boriether polyol contained therein can be improved.

That is, the present invention relates to a high energy-containing CDB propellant characterized by containing 70 to 95% by weight of a polyether containing a terminal hydroxyl group and a methyl azide group and 30 to 5% by weight of an aliphatic plasticizer having an ester bond and an ether bond.

The azide group-containing polyether polyol used in the present invention is +1O-C4Hs +0-C-C-C+ OH1
Particularly preferred are those obtained by polymerizing an azidomethylmethyloxetane monomer, such as 11n HCl13 8 (n-10 to 50), but any polyether with a terminal hydroxyl group containing a methyl azide group may be used.

Further, examples of aliphatic plasticizers having an ester bond and an ether bond include CH2CH2COOC2H40C2H40C4H9CH
Like 2CH2COOC2H40C2H40C4H*,
There are no restrictions as long as the ester bond and ether bond are present in the same molecule.

The amount of plasticizer is required to be 5% by weight or more based on the polyether containing a terminal hydroxyl group and methyl azide group in order to make it compatible with NG. Furthermore, addition of a large amount of plasticizer hinders the improvement in the combustion performance of the propellant due to the inclusion of an azide group, so the addition is preferably 30% by weight or less.

[Example] Hereinafter, the present invention will be specifically explained using comparative examples and examples.

A polyether containing a terminal hydroxyl group and a methyl azide group, the main component of which is azidomethylmethyloxetane, was produced as follows.

In order to polymerize 3-azidomethyl-3-methyloxetane, 1 sol of 1,4-butanediol was kept at 0°C or below, and a mixture of BF3 ether complex 4 O1 in dichloromethane was added dropwise, and after stirring, 3- A mixture of azidomethyl-3-methyloxetane and dichloromethane is added dropwise and stirred at 10°C or lower.

After the reaction was completed, a saturated NaCl solution was added with a stirring bar, and then a dichloromethane layer was collected using a separating funnel and poured into methanol to obtain a precipitate.

The dried precipitate is found to be polyethyl containing a terminal hydroxyl group and a methyl azide group, which has a main structure of C112N3i-40-CH2-C-CH2+ nlls, based on analysis results using a nuclear magnetic resonance apparatus.

Comparative Example 1 Obtained polyether containing terminal hydroxyl group methyl azide group 2
1 part by weight of 5i and 75 parts by weight of NG were mixed gently without applying impact, and then allowed to stand still.

After several minutes, observation revealed that it was separated into two layers. Looking at the volume ratio after separation, the upper layer is 22 and the lower layer is about 47.
Since the specific gravity is 1.59 (NG) for polyether containing terminal hydroxyl group and methyl azide group, respectively, it can be seen that they are separated without dissolving in each other.

Similarly, polyether 30 containing terminal hydroxyl group methyl azide group
Parts by weight and 70 parts by weight of NG were also prepared.

Comparative Example 2 5 parts by weight of the following plasticizer was mixed with 20 parts by weight of the polyether containing terminal hydroxyl and methyl azide groups used in Comparative Example 1, and then mixed with 75 parts by weight of NG using the same method as in Comparative Example 1, and then left to stand. did.

In all cases, turbidity or separation was confirmed.

1) Triacetylglycerin) 12C-OCOC
H2 HC-OCOCl+2 112 C-OC0Ct12 (C112)4 \ COOCs Hrt 3) Isodecyl pelargonate CH3 (CH2) r C00C1oH21 Example 1 20 parts by weight of the terminal hydroxyl methyl azide group-containing polyether shown in Comparative Example 1 and the following A mixture of 5 parts by weight of di(butyl diglycol) adipate of the formula
Parts by weight were mixed in the same manner as in Comparative Example 1, and then left to stand. This system did not separate and became a homogeneous solution.

CH2CH2C-0-C2H40C2H40C4HsC
H2CH2C-0-C2H40C2Ha HC4H1
Example 2 In order to handle and compare the safety of the samples obtained in Comparative Example 1 and Example 1, 22 polymers specified by the Industrial Explosives Association standard fanning and detonation test method (1); Ether From these results, it can be said that stability is increased by using the plasticizer of the present invention.

Furthermore, it is highly dangerous to use separated NG.

[Effects of the Invention] As explained above, the present invention improves the combustion performance of a propellant by using a polyether containing a terminal hydroxyl group and a methyl azide group, and also improves the combustion performance of a propellant by using a plasticizer having an ester bond and an ether bond. By using CD
It is possible to improve the compatibility with NGOs used in H and improve safety during storage and handling.

[Brief explanation of drawings]

Figure 1 is a diagram of the manufacturing process for pace grain slurry type CDB propellant. Patent applicant Asahi Kasei Industries Co., Ltd. agent Patent attorney Hide Komatsu

Claims (2)

[Claims] (1) Polyether 70 containing terminal hydroxyl group and methyl azide group
A high energy-containing CDB propellant, characterized in that it comprises ~95% by weight and 30-5% by weight of an aliphatic plasticizer having ester and ether bonds. (2) It is characterized by containing 70 to 95% by weight of a polyether containing a terminal hydroxyl group and a methylazide group, the main component of which is azidomethylmethyloxetane, and 30 to 5% by weight of an aliphatic plasticizer having an ester bond and an ether bond. High energy content CDB propellant.