JPH08259366A - Solid propellant containing azido group and nitrato group - Google Patents
Solid propellant containing azido group and nitrato groupInfo
- Publication number
- JPH08259366A JPH08259366A JP5729895A JP5729895A JPH08259366A JP H08259366 A JPH08259366 A JP H08259366A JP 5729895 A JP5729895 A JP 5729895A JP 5729895 A JP5729895 A JP 5729895A JP H08259366 A JPH08259366 A JP H08259366A
- Authority
- JP
- Japan
- Prior art keywords
- group
- solid propellant
- nitrato
- propellant
- solid
- 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.)
- Granted
Links
- 239000004449 solid propellant Substances 0.000 title claims abstract description 17
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 title abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 claims abstract description 5
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 claims abstract description 5
- IXYHLWZRPFVFON-UHFFFAOYSA-N (3-methyloxetan-3-yl)methyl nitrate Chemical compound [O-][N+](=O)OCC1(C)COC1 IXYHLWZRPFVFON-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 claims abstract description 3
- GOPVUFFWLXPUBM-UHFFFAOYSA-N 3,3-bis(azidomethyl)oxetane Chemical compound [N-]=[N+]=NCC1(CN=[N+]=[N-])COC1 GOPVUFFWLXPUBM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000003380 propellant Substances 0.000 claims description 19
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 9
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 10
- 238000013329 compounding Methods 0.000 abstract 2
- 229910004679 ONO2 Inorganic materials 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 14
- -1 nitramine compound Chemical class 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001120 nichrome Inorganic materials 0.000 description 3
- XVLDLRUWOGLKIT-UHFFFAOYSA-N 3-(azidomethyl)-3-methyloxetane Chemical compound [N-]=[N+]=NCC1(C)COC1 XVLDLRUWOGLKIT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- KINVDIZXFAZMTE-UHFFFAOYSA-N 1,1-diphenylpentane-2,4-dione Chemical compound C=1C=CC=CC=1C(C(=O)CC(=O)C)C1=CC=CC=C1 KINVDIZXFAZMTE-UHFFFAOYSA-N 0.000 description 1
- UQWZRRLLGFKAHC-UHFFFAOYSA-N 2-(2-butoxy-2-oxoethoxy)acetic acid Chemical compound CCCCOC(=O)COCC(O)=O UQWZRRLLGFKAHC-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical group 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical group CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
- C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Air Bags (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、アジド基を含有する高
エネルギ−化されたプレポリマ−を用い、これに触媒を
配合することにより燃焼特性を改良した固体推進薬に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid propellant having an energetic prepolymer containing an azide group and having a catalyst incorporated therein to improve combustion characteristics.
【0002】[0002]
【従来の技術】従来の固体推進薬は、酸化剤と燃料成分
からなるコンポジット推進薬と、ニトログリセリンとニ
トロセルロ−スを主成分とするダブルベ−ス推進薬とに
大別される。2. Description of the Related Art Conventional solid propellants are roughly classified into composite propellants consisting of an oxidizer and a fuel component, and double-base propellants consisting mainly of nitroglycerin and nitrocellulose.
【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硝酸アンモニウム等が
使用され、燃料兼結合剤としては、ポリウレタン、ポリ
ブタジエン等が使用され、その他金属燃料としては、ア
ルミ粉末等が用いられる。このコンポジット推進薬は、
ダブルベ−ス推進薬に比べ高い比推力を有することか
ら、広く利用されている。Ammonium perchlorate, ammonium nitrate, etc. are used as the oxidizer used in the composite propellant, polyurethane, polybutadiene, etc. are used as the fuel / binder, and aluminum powder etc. are used as the other metal fuel. Is used. This composite propellant
It is widely used because it has a higher specific thrust than double-base propellants.
【0004】しかし、この中で最も広く使用されている
過塩素酸アンモニウムを酸化剤とするコンポジット推進
薬は、燃焼時に生成する塩化水素の問題から、酸化剤と
して分子内に塩素を含まないニトラミン化合物を用いた
無煙性コンポジット推進薬の研究が近年盛んに行われて
いる。However, the most widely used composite propellant using ammonium perchlorate as an oxidant is a nitramine compound containing no chlorine in the molecule as an oxidant because of the problem of hydrogen chloride produced during combustion. Recently, research on smokeless composite propellants has been actively conducted.
【0005】さらに、ニトラミン化合物の酸素不足を補
い燃焼性能を向上させるために、燃料成分いわゆるバイ
ンダ−を高エネルギ−化したものが用いられるようにな
った。そのバインダ−として現在研究されているものと
して、熱分解により窒素分子を生成して多量の反応熱を
放出するアジド基を有するポリマ−や、分子内に酸素を
多量にもち、熱分解によって発生ガス量が多いニトラト
基を有するポリマ−が注目されている。Further, in order to supplement the oxygen deficiency of the nitramine compound and improve the combustion performance, a fuel component with a high energy has been used as a so-called binder. Polymers having azide groups that generate a large amount of heat of reaction by generating nitrogen molecules by thermal decomposition, and those that have a large amount of oxygen in the molecule and gas generated by thermal decomposition are currently being researched as the binder. Polymers having a large amount of nitrato groups have received attention.
【0006】[0006]
【発明が解決しようとする課題】ニトラミンを酸化剤、
バインダ−にアジド基及びニトラト基を有するポリマ−
を用いた推進薬は、燃焼性能のうち圧力指数が極めて高
いという問題があった。一般的に燃焼速度rは r=aPn a:定数 P:圧力 n:圧力指数 の関係が成立することが経験的に知られている。この意
味するところは、燃焼圧力を増加することにより燃焼速
度が増大するということであるが、nが大きい場合、わ
ずかの圧力上昇で燃焼速度が大きく変わることを意味す
る。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Polymer having azide group and nitrato group in binder
The propellant using is problematic in that it has a very high pressure index in combustion performance. It is empirically known that the combustion speed r generally satisfies the following relationship: r = aP n a: constant P: pressure n: pressure index. This means that the combustion speed increases as the combustion pressure increases, but when n is large, it means that the combustion speed changes significantly with a slight pressure increase.
【0007】従って、燃焼圧力の変動を押さえるため燃
焼面積及びノズルスロ−ト面積を極めて正確に維持しな
ければ、信頼性の高いロケットは得られにくい。これを
避けるため、圧力指数nは一般に1.0以下が好まし
く、現状0.5以下が固体推進薬として用いられてい
る。Therefore, it is difficult to obtain a highly reliable rocket unless the combustion area and the nozzle slot area are maintained extremely accurately in order to suppress fluctuations in combustion pressure. In order to avoid this, the pressure index n is generally preferably 1.0 or less, and currently 0.5 or less is used as a solid propellant.
【0008】本発明は、こうした実情の下に、比推力及
び燃焼速度が大きく、且つアジド基及びニトラト基含有
ポリマ−を用いた固体推進薬の圧力指数を低下させた固
体推進薬を提供することを目的とするものである。Under the circumstances, the present invention provides a solid propellant having a large specific thrust and a high burning rate and a reduced pressure index of the solid propellant using a polymer containing an azide group and a nitrato group. The purpose is.
【0009】[0009]
【課題を解決するための手段】本発明者らは、前記の問
題点を考慮し鋭意研究した結果、燃料結合剤の主成分が
アジド基及びニトラト基を含有するプレポリマ−、好ま
しくは3,3−ビス(アジドメチル)オキセタンと3−
ニトラトメチル−3−メチルオキセタンである燃料結合
剤に酸化剤としてシクロ−1,3,5−トリメチレン−
2,4,6−トリニトラミン(RDX)、シクロ−1,
3,5,7−テトラメチレン−2,4,6,8−テトラ
ニトラミン(HMX)の様なニトラミンにクエン酸鉛、
ステアリン酸鉛、2エチルヘキサン酸鉛の様な有機鉛化
合物及びカ−ボンを配合することにより無煙性で高エネ
ルギ−をもち且つ圧力指数を低下できるという特性を見
いだし、本発明を完成するに至った。DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors in view of the above problems, a prepolymer whose main component of a fuel binder contains an azide group and a nitrato group, preferably 3,3. -Bis (azidomethyl) oxetane and 3-
Nitratomethyl-3-methyloxetane as a fuel binder with cyclo-1,3,5-trimethylene-
2,4,6-trinitramine (RDX), cyclo-1,
Lead citrate on nitramine such as 3,5,7-tetramethylene-2,4,6,8-tetranitramine (HMX),
By blending lead stearate, an organic lead compound such as lead ethylhexanoate, and carbon, it has been found that smokeless, high energy and pressure index can be lowered, and the present invention has been completed. It was
【0010】本発明において使用されるアジド基含有プ
レポリマ−としては、アジド基を含有するポリマ−であ
れば、特に制限はなく例えば、3−アジドメチル−3−
メチルオキセタン(AMMO)、グリシジルアジドポリ
マー(GAP)、3,3−ビス(アジドメチル)オキセ
タン(BAMO)等が一般的である。The azido group-containing prepolymer used in the present invention is not particularly limited as long as it is an azide group-containing polymer, and for example, 3-azidomethyl-3-
Methyloxetane (AMMO), glycidyl azide polymer (GAP), 3,3-bis (azidomethyl) oxetane (BAMO) and the like are common.
【0011】また、ニトラト基含有プレポリマ−として
は、3−ニトラトメチル−3−メチルオキセタン(NM
MO)、3,3−ビス(ニトラトメチル)オキセタン
(BNMO)等が一般的である。As the nitrato group-containing prepolymer, 3-nitratomethyl-3-methyloxetane (NM
MO), 3,3-bis (nitratomethyl) oxetane (BNMO) and the like are common.
【0012】この中で、BAMOはアジド基の含有量が
最も多く、従ってエネルギ−が大きいがこのポリマ−
は、常温で固体である。従って、下記(1)式で表され
る如きニトラト基含有のNMMOと共重合することによ
り、常温で液状にすることができる(USP 5099
042)ため推進薬としての燃料結合剤として使用可能
となる。Of these, BAMO has the highest content of azide groups and therefore has a high energy, but this polymer is
Is a solid at room temperature. Therefore, it can be liquefied at room temperature by copolymerizing with NMMO containing a nitrato group as represented by the following formula (1) (USP 5099).
042) can be used as a fuel binder as a propellant.
【0013】[0013]
【化1】 Embedded image
【0014】注:上記は、ブロックコポリマ−及びラン
ダムコポリマ−を含む。Note: The above includes block copolymers and random copolymers.
【0015】なお、このプレポリマ−共重合体にオキセ
タンやテトラヒドロフラン等の第3成分を加えて共重合
することもでき、この様な第3成分を加えたものでも良
い。これらのプレポリマ−は末端水酸基をもち、これを
主成分とするバインダ−とするため、硬化剤は水酸基と
反応するイソシアネ−ト化合物、例えばトリレンジイソ
シアネ−ト、イソホロンジイソシアネ−ト、ヘキサメチ
レンジイソシアネ−トジフェニルメタンジイソシアネ−
ト、トリフェニルジメチレントリイソシアネ−ト、トリ
フェニルメタントリイソシアネ−ト等を用いる。The prepolymer copolymer may be copolymerized by adding a third component such as oxetane or tetrahydrofuran, or such a third component may be added. Since these prepolymers have a terminal hydroxyl group and are used as a binder containing these as a main component, the curing agent is an isocyanate compound that reacts with the hydroxyl group, such as tolylene diisocyanate, isophorone diisocyanate, and hexa. Methylene diisocyanate-diphenylmethane diisocyanate
, Triphenyldimethylene triisocyanate, triphenylmethane triisocyanate and the like are used.
【0016】架橋剤は、多官能の水酸基をもつ化合物、
例えばトリメチロ−ルエタン、トリメチロ−ルプロパ
ン、グリセリン、ヘキサントリオ−ル、ジグリセリン等
や、多官能イソシアネ−トが用いられる。The crosslinking agent is a compound having a polyfunctional hydroxyl group,
For example, trimethylolethane, trimethylolpropane, glycerin, hexanetriol, diglycerin and the like, and polyfunctional isocyanates are used.
【0017】可塑剤は、ジオクチルアジペ−ト、ジエチ
ルフタレ−ト等のエステル系や、ジ(ブチルジグリコ−
ル)アジペ−トのようなエ−テルとエステル結合をもっ
た化合物等、プレポリマ−と相溶性が良好なものを用い
る。The plasticizer may be an ester type such as dioctyl adipate or diethyl phthalate, or di (butyl diglycolate).
(L) A compound having a good compatibility with the prepolymer such as a compound having an ester bond with an ether such as adipate is used.
【0018】硬化触媒は、ブチルチントリクロライド、
ジブチルチンジアセテ−ト、ジブチルチンジラウレ−ト
等の有機錫化合物や、フェリックアセチルアセトン、フ
ェリックジフェニルアセチルアセトン等の有機鉄化合物
等を用いる。The curing catalyst is butyltin trichloride,
Organotin compounds such as dibutyltin diacetate and dibutyltin dilaurate, and organic iron compounds such as ferric acetylacetone and ferric diphenylacetylacetone are used.
【0019】添加する鉛化合物は、クエン酸鉛、ステア
リン酸鉛、2エチルヘキサン酸鉛の様な有機鉛化合物が
用いられる。その際、カ−ボンの添加が必要であり、鉛
化合物だけでは、効果を示さない。特に、鉛化合物の中
でクエン酸鉛が最も好ましい。As the lead compound to be added, an organic lead compound such as lead citrate, lead stearate or lead 2-ethylhexanoate is used. At that time, it is necessary to add carbon, and the lead compound alone does not show the effect. Particularly, lead citrate is most preferable among the lead compounds.
【0020】その添加量は、固体推進薬に対して外割で
0.5〜5%、好ましくは2〜4%であり、この時の圧
力指数が最も低い値を示しこれ以下では効果を現さず、
また、それ以上添加しても効果がなく、エネルギ−も低
下する。また、カ−ボンの添加量は、固体推進薬に対し
て外割で0.1〜3%、好ましくは0.3〜0.8%と
する。また、3%より多いと推進薬の粘度が上昇し製造
性が悪く、0.1%より少ないと効果が現れない。The added amount is 0.5 to 5%, preferably 2 to 4%, based on the solid propellant, and the pressure index at this time shows the lowest value, and below this, the effect is not exhibited. No
Further, if it is added more than that, there is no effect and the energy is lowered. The amount of carbon added is 0.1 to 3%, preferably 0.3 to 0.8%, based on the solid propellant. If it is more than 3%, the viscosity of the propellant increases and the manufacturability is poor, and if it is less than 0.1%, the effect is not exhibited.
【0021】[0021]
【実施例】以下に、本発明を実施例によって具体的に説
明する。EXAMPLES The present invention will be specifically described below with reference to examples.
【0022】表1に示す組成により各種推進薬を製造し
た。アジド基及びニトラト基含有プレポリマ−として
は、BAMO/NMMOをモル比で7対3の共重合体を
用いた。まず、プレポリマ−と硬化触媒、架橋剤、可塑
剤及び硬化剤を加温で混合し、その中に燃焼触媒を添加
し、さらに過塩素酸アンモニウムを投入したのち混合・
脱泡した。 硬化は、60℃で約7日間行った。Various propellants having the compositions shown in Table 1 were produced. As the azide group- and nitrato group-containing prepolymer, a BAMO / NMMO copolymer having a molar ratio of 7: 3 was used. First, a prepolymer, a curing catalyst, a cross-linking agent, a plasticizer and a curing agent are heated and mixed, a combustion catalyst is added thereto, and ammonium perchlorate is further added, followed by mixing and mixing.
Defoamed. Curing was carried out at 60 ° C. for about 7 days.
【0023】[0023]
【表1】 [Table 1]
【0024】表1に示す各種推進薬を用いて、以下の方
法により燃焼速度等を調べた。Using various propellants shown in Table 1, the burning rate and the like were examined by the following method.
【0025】固体推進薬を外径7mm角、長さ70mm
の円柱に切り出し円柱状の側面に、約1mm厚さの樹脂
層(燃焼制御層)を形成し、試料を作製した。このよう
な試料は、ストランド推進薬と一般に呼ばれる。ストラ
ンド推進薬の一端より約10mmの所に点火用のニクロ
ム線を通し、また一端から20mmと60mmの箇所に
ヒュ−ズ線を通した。ストランド推進薬を圧力容器内に
密閉し加圧下でニクロム線によりニクロム線に通電し着
火燃焼させ、2本のヒュ−ズ線が切断した時間差でヒュ
−ズ線間(ここでは、40mm)を除した値として、燃
焼速度とする。この測定は加圧下で行うが、燃焼容器と
ストランド推進薬燃焼中に一定圧に保つために十分な容
量をもつ蓄圧器とが連結されたストランド燃焼器を用
い、燃焼容器中にストランド推進薬をセットし、所定圧
に窒素ガスで加圧したのち着火するものとする。Solid propellant with an outer diameter of 7 mm square and a length of 70 mm
A resin layer (combustion control layer) having a thickness of about 1 mm was formed on the side surface of the column, which was cut out into a cylinder, to prepare a sample. Such samples are commonly referred to as strand propellants. A nichrome wire for ignition was passed through about 10 mm from one end of the strand propellant, and a fuse wire was passed through 20 mm and 60 mm from one end. The strand propellant was sealed in a pressure vessel, and the nichrome wire was energized and ignited by burning with the nichrome wire under pressure to remove the space between the fuse wires (here, 40 mm) by the time difference between the two fuse wires. The burning velocity is defined as the value. This measurement is performed under pressure, but using a strand combustor in which a combustion container and a pressure accumulator having a sufficient capacity to maintain a constant pressure during combustion of the strand propellant are connected, Set, pressurize to a predetermined pressure with nitrogen gas, and then ignite.
【0026】この様な方法で、加圧圧力を変えて繰り返
し燃焼速度を、測定した。In this way, the burning rate was measured repeatedly while changing the pressure applied.
【0027】得られた各種推進薬の燃焼速度を表2に示
す。The burning rates of the various propellants obtained are shown in Table 2.
【0028】[0028]
【表2】 [Table 2]
【0029】[0029]
【発明の効果】以上説明したように、燃料結合剤の主成
分がアジド基及びニトラト基を含有するポリマ−である
固体推進薬において、成分として鉛化合物及びカ−ボン
を含むことにより以下の特長を有することが判明した。As described above, in the solid propellant in which the main component of the fuel binder is a polymer containing an azide group and a nitrato group, the following characteristics are obtained by including a lead compound and carbon as components. Was found to have.
【0030】1.圧力指数が、従来の値に比べ極めて低
くロケットモ−タの設計が容易となり、信頼性の高いロ
ケットモ−タのための推進薬を得た。1. The pressure index is much lower than the conventional value, which facilitates the design of rocket motors and provides a highly reliable propellant for rocket motors.
【0031】2.燃焼速度についても、低圧側で約2倍
に増加しており固体推進薬の利用範囲を拡大することが
できた。2. The burning rate also doubled on the low pressure side, and the range of application of the solid propellant could be expanded.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 阿南 敏行 大分県大分市大字里2620番地 旭化成工業 株式会社内 (72)発明者 甲斐 竜己 大分県大分市大字里2620番地 旭化成工業 株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Anan 2620 Oji-ri, Oita-shi, Oita Prefecture Asahi Kasei Kogyo Co., Ltd.
Claims (3)
トラト基を含有するプレポリマ−であり、酸化剤がニト
ラミンである組成物に鉛化合物及びカ−ボンを配合する
ことを特徴とする固体推進薬。1. A solid comprising a prepolymer containing an azide group and a nitrato group as a main component of a fuel binder, and a lead compound and a carbon compounded in a composition in which the oxidant is nitramine. Propellant.
メチル)オキセタンと3−ニトラトメチル−3−メチル
オキセタンの共重合体であることを特徴とする請求項1
記載の固体推進薬。2. The prepolymer is a copolymer of 3,3-bis (azidomethyl) oxetane and 3-nitratomethyl-3-methyloxetane.
The solid propellant described.
鉛等の有機鉛化合物であり、固体推進薬に対して1〜3
重量%含有することを特徴とする請求項1記載の固体推
進薬。3. The lead compound is an organic lead compound such as lead citrate and lead stearate, and is 1 to 3 relative to the solid propellant.
The solid propellant according to claim 1, wherein the solid propellant is contained in a weight percentage.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP7057298A JP2981592B2 (en) | 1995-03-16 | 1995-03-16 | Azide and nitrato group-containing solid propellants |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7057298A JP2981592B2 (en) | 1995-03-16 | 1995-03-16 | Azide and nitrato group-containing solid propellants |
Publications (2)
Publication Number | Publication Date |
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JPH08259366A true JPH08259366A (en) | 1996-10-08 |
JP2981592B2 JP2981592B2 (en) | 1999-11-22 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008513593A (en) * | 2004-09-23 | 2008-05-01 | イギリス国 | New energy polyphosphazene |
CN111704516A (en) * | 2020-05-20 | 2020-09-25 | 湖北三江航天江河化工科技有限公司 | Hydroxyl-terminated aluminum-free propellant and preparation method thereof |
-
1995
- 1995-03-16 JP JP7057298A patent/JP2981592B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008513593A (en) * | 2004-09-23 | 2008-05-01 | イギリス国 | New energy polyphosphazene |
CN111704516A (en) * | 2020-05-20 | 2020-09-25 | 湖北三江航天江河化工科技有限公司 | Hydroxyl-terminated aluminum-free propellant and preparation method thereof |
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Publication number | Publication date |
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