JPH085735B2 - Solid propellant fuel - Google Patents
Solid propellant fuelInfo
- Publication number
- JPH085735B2 JPH085735B2 JP5868591A JP5868591A JPH085735B2 JP H085735 B2 JPH085735 B2 JP H085735B2 JP 5868591 A JP5868591 A JP 5868591A JP 5868591 A JP5868591 A JP 5868591A JP H085735 B2 JPH085735 B2 JP H085735B2
- Authority
- JP
- Japan
- Prior art keywords
- propellant
- azido group
- polymer
- containing polymer
- fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Solid Fuels And Fuel-Associated Substances (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は固体推進薬燃料に関す
る。詳しくは、アジト基を含有して高エネルギー化され
たポリマーに、他化合物を併用することにより、燃焼特
性を改良した固体推進薬燃料に関する。FIELD OF THE INVENTION This invention relates to solid propellant fuels. More specifically, the present invention relates to a solid propellant fuel having improved combustion characteristics by using another compound in combination with a polymer having a high energy by containing an azido group.
【０００２】[0002]
【従来の技術】固体推進薬は、液体燃料に比べ、長期保
存が可能であり、かつ、即時発射が可能であるという利
点を有し、軍用のロケット弾やミサイルに利用されてい
る。固体推進薬は、酸化剤と燃料の各成分を混合して成
型した混成質系のコンポジット推進薬と、ニトログリセ
リセリンとニトロセルロースを主成分とし、不揮発性溶
剤をもちいた火薬であるダブルベース推進薬とに大別さ
れる。2. Description of the Related Art Solid propellants have advantages over liquid fuels in that they can be stored for a long period of time and can be immediately launched, and are used in military rockets and missiles. Solid propellants are hybrid composite propellants that are molded by mixing oxidizer and fuel components, and double-base propellant, which is a explosive that uses nitroglycerin and nitrocellulose as the main components and uses a non-volatile solvent. It is roughly divided into medicine.
【０００３】コンポジット推進薬に使用される酸化剤と
しては、過塩素酸アンモニウムやニトラミン及び硝酸ア
ンモニウム等が使用され、燃料としてはポリブダジエ
ン、ポリウレタン等が使用され、助燃剤としてアルミニ
ウム粉末などが用いられている。燃料性能の改善は、こ
れら各成分の燃焼特性を改良、向上させることにより達
成できる。Ammonium perchlorate, nitramine, ammonium nitrate, etc. are used as the oxidizer used in the composite propellant, polybudadiene, polyurethane, etc. are used as the fuel, and aluminum powder etc. are used as the combustion improver. There is. The improvement of fuel performance can be achieved by improving and improving the combustion characteristics of each of these components.
【０００４】しかし、前記物質により構成された推進薬
は、現状では、すでに理論的に期待できる燃焼性能の約
９５％を達成されており、これ以上の性能向上の余地は
少なく、高性能化のためにいくつかの高エネルギー物質
の応用が検討されている。酸化剤や助燃剤は、安定性、
安全性の制約により、実用面では前記物質に限定される
こともあり、バインダー主成分となるプレポリマー自体
を高エネルギー化した推進薬の研究がなされている。米
国特許４２６８４５０号ではプレポリマーとして下記化
１式で表わされるアジド基を含有した末端水酸基ポリエ
ーテルが開示されている。However, at present, propellants composed of the above substances have already achieved about 95% of theoretically expected combustion performance, and there is little room for further improvement in performance, and the propellant cannot be improved in performance. Therefore, the application of some high-energy materials is being studied. Oxidizers and combustion improvers have stability,
Due to safety restrictions, it may be practically limited to the above substances, and studies have been made on propellants in which the prepolymer, which is a binder main component, itself has high energy. U.S. Pat. No. 4,268,450 discloses a terminal hydroxyl group polyether containing an azide group represented by the following chemical formula 1 as a prepolymer.
【０００５】[0005]
【化１】 Embedded image
【０００６】このポリエーテルは推進薬の性能向上のた
めアジド基を含有させることにより、下記の利点を得て
いる。一つには生成熱を高めることにより推進薬の比推
力の向上、又同様に密度が高まることも比推力の向上に
つながる。更にアジド基の分解に伴う窒素ガス量の増大
およびバインダー中の窒素量を高めることで、相対的に
炭素、水素の比率を下げることにつながり、推進薬中の
酸化剤の量を低減でき、感度を下げることが可能とな
り、安全性の向上がはかれる。This polyether has the following advantages by containing an azide group for improving the performance of the propellant. For one thing, the specific thrust of the propellant is improved by increasing the heat of formation, and similarly, the density is also increased, which leads to the improvement of the specific thrust. Furthermore, by increasing the amount of nitrogen gas accompanying the decomposition of the azido group and increasing the amount of nitrogen in the binder, the ratio of carbon and hydrogen can be relatively reduced, and the amount of oxidizer in the propellant can be reduced, thus increasing the sensitivity. It becomes possible to lower the safety and improve the safety.
【０００７】[0007]
【発明が解決しようとする課題】固体推進薬の燃焼性能
を向上させるため、現状用いられているポリマーをアジ
ド基含有ポリマーで置換することは推進薬燃焼性能向上
に有効である。ところが推進薬の燃焼性能向上のために
導入しようとするアジド基含有ポリマーは、温度感度が
高く、実用に供する場合に、非常に問題であった。In order to improve the combustion performance of solid propellants, it is effective to improve the combustion performance of propellants by substituting the polymer currently used with an azido group-containing polymer. However azido group-containing polymer to be introduced to the combustion performance improvement of propellant has a high temperature sensitivity is, when it is practically used was very problematic.
【０００８】固体推進薬の燃焼速度は燃焼時の圧力によ
って大きく変化するが、その初期温度（保存温度）によ
っても変化する。温度変化による燃焼速度の変化は圧力
一定とすると、温度感度（σp ）は下記式と定義され
る。The burning rate of the solid propellant greatly changes depending on the pressure at the time of burning, but also changes depending on its initial temperature (storage temperature). The temperature sensitivity (σ p ) is defined by the following equation, assuming that the change in the combustion speed due to the temperature change is constant.
【０００９】[0009]
【数１】 [Equation 1]
【００１０】温度感度が高いと温度によりγが大きく変
化することとなり、ロケットの推力制御上、好ましくな
い。本発明は、こうした実情の下に、燃焼性能が高く、
かつアジド基含有ポリマー温度感度を低下させた固体推
進薬用燃料を提供することを目的とするものである。If the temperature sensitivity is high, γ changes greatly depending on the temperature, which is not preferable in controlling the thrust of the rocket. Under the circumstances, the present invention has high combustion performance,
Moreover, it is an object of the present invention to provide a fuel for a solid propellant in which the temperature sensitivity of an azido group-containing polymer is lowered.
【００１１】[0011]
【課題を解決するための手段】本発明者らは前記の問題
点を考慮して鋭意研究した結果、りんをアジド基含有ポ
リマーに添加して使用することにより、温度感度を低下
できるという特性を見出し、本発明を完成するに至っ
た。即ち、本発明はアジド基含有ポリマー１００重量部
に対し、りんを０．０１〜１０重量部含むことを特徴と
する固体推進薬燃料である。Means for Solving the Problems As a result of intensive studies conducted by the present inventors in consideration of the above problems, it was found that the temperature sensitivity can be reduced by adding phosphorus to an azido group-containing polymer. Heading out, the present invention has been completed. That is, the present invention is a solid propellant fuel characterized by containing 0.01 to 10 parts by weight of phosphorus based on 100 parts by weight of an azido group-containing polymer.
【００１２】本発明において使用されるアジド基含有ポ
リマーとしては、下記〔化２〕式で表わされる如き、ア
ジドメチルメチルオセキタンモノマーを重合することに
より得られたものがとくに好ましいが、アジド基を含有
するポリマーであればよい。The azido group-containing polymer used in the present invention is particularly preferably one obtained by polymerizing an azidomethylmethyloxetane monomer as represented by the following formula [Chemical formula 2]. Any polymer may be included.
【００１３】[0013]
【化２】 Embedded image
【００１４】また、りんには種々の同素体があるが、こ
のうち赤りんが最も好ましい。りんの添加量は、アジド
基含有ポリマーに対して、有効な効果を発現させるため
には０．０１重量部以上必要である。多量の添加はアジ
ド基を含有させることによる推進薬の燃焼性能向上をさ
またげることになり、１０重量部以下が望ましい。アジ
ド基含有ポリマーにりんを共存させて用いることによ
り、温度感度が低下する理由は明らかでないが、アジド
基よりのＮ2 とリンＰとの相乗効果により、ポリマー分
解が抑制され、推進薬固体中での分解を少ならしめるた
め、推進薬表面での発熱が減少することによるものと推
測される。Although phosphorus has various allotropes, red phosphorus is the most preferable. The amount of phosphorus added is required to be 0.01 part by weight or more in order to exert an effective effect on the azido group-containing polymer. Addition of a large amount will hinder the improvement of the combustion performance of the propellant due to containing an azide group, so 10 parts by weight or less is desirable. It is not clear why the temperature sensitivity is lowered by using phosphorus together with the azido group-containing polymer, but the synergistic effect of N 2 and phosphorus P from the azido group suppresses the polymer decomposition, and the propellant solid It is presumed that this is due to the decrease in heat generation on the surface of the propellant in order to reduce the decomposition at.
【００１５】アジド基含有ポリマーの一般的な使い方と
しては、末端水酸基を有するメチルアジド基含有ポリマ
ーをプレポリマーとし、硬化に必要なイソシアネートお
よびトリオール等を必要量加え、加熱により硬化可能な
組成分とした液分をりんと混合した後、酸化剤成分を加
え、均一混合させ、推進薬組成分とし、所定時間加熱す
ることにより、硬化成形体を得、目的とする推進薬とす
ることができる。As a general usage of the azido group-containing polymer, a methyl azido group-containing polymer having a terminal hydroxyl group is used as a prepolymer, and a necessary amount of isocyanate and triol necessary for curing is added to obtain a composition curable by heating. After the liquid component is mixed with phosphorus, an oxidizer component is added and uniformly mixed to obtain a propellant composition, which is then heated for a predetermined time to obtain a cured molded article, and the desired propellant can be obtained.
【００１６】[0016]
【実施例】以下、本発明を実施例によって具体的に説明
する。 （アジド基含有ポリマーの合成）アジド基含有ポリマー
として、アジドメチルメチルオキセタンを主成分とする
ポリマーを以下のように製造した。EXAMPLES The present invention will be specifically described below with reference to examples. (Synthesis of Azido Group-Containing Polymer) As an azido group-containing polymer, a polymer containing azidomethylmethyloxetane as a main component was produced as follows.
【００１７】３−アジドメチル−３−メチルオキセタン
をポリマー化するために、１，４−ブタンジオール１ｍ
ｏｌを０℃以下に保ち、ＢＦ3 エーテル錯体４ｍｏｌを
ジクロルメタンに混合したものを滴下し、攪拌後、３−
アジドメチル−３−メチルオキセタンをジクロルメタン
と混合したものを滴下し、１０℃以下で攪拌を行う。反
応終了後、ＮａＣｌ飽和溶液を攪拌下投入したのち分液
ロートでジクロルメタン層を採取し、メタノール中に投
入し、液状沈殿物を得た。To polymerize 3-azidomethyl-3-methyloxetane, 1 m of 1,4-butanediol was used.
was kept at 0 ° C or lower, a mixture of 4 mol of BF 3 ether complex and dichloromethane was added dropwise, and after stirring, 3-
A mixture of azidomethyl-3-methyloxetane and dichloromethane was added dropwise, and the mixture was stirred at 10 ° C or lower. After the reaction was completed, a saturated NaCl solution was added under stirring, and then the dichloromethane layer was collected with a separating funnel and added into methanol to obtain a liquid precipitate.
【００１８】この液状物の揮発分を除去したものは、核
磁気共鳴装置による解析結果などから、主として下記
〔化３〕式で表わされる構造を含む末端水酸基メチルア
ジド基含有ポリエーテルであることがわかる。Those obtained by removing the volatile content of this liquid substance are mainly shown in the following from the analysis results by the nuclear magnetic resonance apparatus.
It can be seen that the terminal hydroxyl group-containing methyl azide group-containing polyether having the structure represented by the formula:
【００１９】[0019]
【化３】 [Chemical 3]
【００２０】このポリマーは、イソシアネート含有化合
物、３官能ＯＨ基含有化合物などと併用し、加熱するこ
とにより硬化でき、また適量の可塑剤を使用すること
で、硬化後の伸び、強度などの調整が可能であり、固体
推進薬用燃料として適するものである。得られたアジド
基含有ポリマーを、液状のまま、４ｍｍφのガラスチュ
ーブに入れ、上端にヒーター線をとりつけ、着火させ、
燃焼する様子を、加圧容器の外より、ビデオにより撮影
した。燃焼速度は、各左力下および、ガラスチューブ内
ポリマーの初期温度ごとに測定した結果、このアジド基
含有ポリマーの温度感度はσp ＝０．００５７／ｋであ
った。This polymer can be cured by heating in combination with an isocyanate-containing compound, a trifunctional OH group-containing compound, etc., and by using an appropriate amount of a plasticizer, the elongation and strength after curing can be adjusted. It is possible and suitable as a solid propellant fuel. The obtained azido group-containing polymer is put in a liquid state in a 4 mmφ glass tube, a heater wire is attached to the upper end and ignited.
The state of burning was photographed by a video from outside the pressure vessel. The burning rate was measured under each left force and at each initial temperature of the polymer in the glass tube. As a result, the temperature sensitivity of this azido group-containing polymer was σ p = 0.0057 / k.
【００２１】[0021]
【実施例１】合成例で用いたものと同一のポリマーに対
し、赤りん微粒子表面を樹脂コーティングしたノーパレ
ット（燐化学工業社製：微粒子赤りんの表面を樹脂コー
ティングした赤りん含有量８５重量％品）をポリマー１
００重量部に対し０．５、５、１０重量部混合したもの
を、前記と同様の方法により温度感度を測定した。表１
から明らかなように赤りん添加による温度感度の低減効
果があることがわかった。Example 1 The same polymer as used in the synthesis example was coated with red phosphorus fine particles on a resin-free palette (manufactured by Rin Kagaku Kogyo Co., Ltd .: fine red phosphorus surfaces were resin-coated with a red phosphorus content of 85% by weight). % Product) to polymer 1
A mixture of 0.5 parts by weight, 5 parts by weight and 10 parts by weight with respect to 00 parts by weight was measured for temperature sensitivity by the same method as described above. Table 1
It is clear from the results that the addition of red phosphorus has the effect of reducing the temperature sensitivity.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【発明の効果】以上説明したように、本発明は、アジド
基含有ポリマーを使用することにより、推進薬の燃料性
能を向上させるとともに、リンを含むことにより、温度
感度を低下させることを可能とし、推進薬の温度変化に
よる燃速変化を小とすることができ、固体推進薬運用上
大きな利点を有する。INDUSTRIAL APPLICABILITY As described above, the present invention makes it possible to improve the fuel performance of a propellant by using an azido group-containing polymer and, at the same time, reduce the temperature sensitivity by containing phosphorus. the fuel rate variation due to temperature change of the propellant can be small, it has significant advantages over solid propellant production.
Claims (1)
し、りんを０．０１〜１０重量部含むことを特徴とする
固体推進薬用燃料。1. A fuel for a solid propellant, which comprises 0.01 to 10 parts by weight of phosphorus based on 100 parts by weight of an azido group-containing polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5868591A JPH085735B2 (en) | 1991-03-22 | 1991-03-22 | Solid propellant fuel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5868591A JPH085735B2 (en) | 1991-03-22 | 1991-03-22 | Solid propellant fuel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04295085A JPH04295085A (en) | 1992-10-20 |
| JPH085735B2 true JPH085735B2 (en) | 1996-01-24 |
Family
ID=13091409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5868591A Expired - Fee Related JPH085735B2 (en) | 1991-03-22 | 1991-03-22 | Solid propellant fuel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085735B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008169073A (en) * | 2007-01-11 | 2008-07-24 | Technical Research & Development Institute Ministry Of Defence | Composite propellant |
-
1991
- 1991-03-22 JP JP5868591A patent/JPH085735B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008169073A (en) * | 2007-01-11 | 2008-07-24 | Technical Research & Development Institute Ministry Of Defence | Composite propellant |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04295085A (en) | 1992-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Menke et al. | Formulation and properties of ADN/GAP propellants | |
| US4379903A (en) | Propellant binders cure catalyst | |
| US4158583A (en) | High performance ammonium nitrate propellant | |
| JP3370118B2 (en) | Stable solid rocket propellant composition | |
| US3609115A (en) | Propellant binder | |
| Liu et al. | Application of 3D energetic metal-organic frameworks containing Cu as the combustion catalyst to composite solid propellant | |
| Gayathri et al. | Nitrato functionalized polymers for high energy propellants and explosives: recent advances | |
| US3362859A (en) | Gas-generating compositions and their preparation | |
| US3711343A (en) | Cellular nitrocellulose based composition and method of making | |
| EP0520104A1 (en) | Non-self-deflagrating fuel compositions for high regression rate hybrid rocket motor application | |
| US3255059A (en) | Fluoroalkyl acrylate polymeric propellant compositions | |
| Ou et al. | Development of energetic additives for propellants in China | |
| EP0997449B1 (en) | Solid rocket propellant | |
| US3923564A (en) | Double base propellant with thorium containing ballistic modifier | |
| US3726729A (en) | Solid propellant compositions having a nitrocellulose-hydroxyl-terminated polybutadiene binder and method of preparing the same | |
| JPH085735B2 (en) | Solid propellant fuel | |
| US3834956A (en) | Solid propellant composition containing lead and lead compounds | |
| US3383860A (en) | Low flame temperature gas generant containing ammonium iodate and methode of operatin a gas generator | |
| Simmons | Guidelines to higher energy gun propellants | |
| US3846195A (en) | Composite polyurethane propellants with negative pressure exponent of ammonium sulfate | |
| US6197135B1 (en) | Enhanced energetic composites | |
| JP2562501B2 (en) | Rocket solid propellant | |
| US3896865A (en) | Propellant with polymer containing nitramine moieties as binder | |
| JP2981592B2 (en) | Azide and nitrato group-containing solid propellants | |
| JPH0816038B2 (en) | Solid propellant containing azido group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19960814 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080124 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090124 Year of fee payment: 13 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090124 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100124 Year of fee payment: 14 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110124 Year of fee payment: 15 |
|
| LAPS | Cancellation because of no payment of annual fees |