JP2017538648A - その組成中に鉛を含まない高性能複合火工製品及びその製造方法 - Google Patents
その組成中に鉛を含まない高性能複合火工製品及びその製造方法 Download PDFInfo
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- 238000005266 casting Methods 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
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- 238000007872 degassing Methods 0.000 description 2
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- 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 2
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 2
- MZRUFMBFIKGOAL-UHFFFAOYSA-N 5-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=CC=NN1 MZRUFMBFIKGOAL-UHFFFAOYSA-N 0.000 description 1
- KEJFAGMNOBNFJR-QMTHXVAHSA-N Isophorene Natural products S=C(NC[C@]1(C)C[C@H](NC(=S)NC)CC(C)(C)C1)NC KEJFAGMNOBNFJR-QMTHXVAHSA-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
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- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- VAALVBPLSFRYMJ-XXMNONFOSA-N O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 Chemical compound O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 VAALVBPLSFRYMJ-XXMNONFOSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
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- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- AKAJRKUSJKGVFT-UHFFFAOYSA-K bismuth 2-carboxy-5-hydroxyphenolate Chemical compound [Bi+3].Oc1ccc(C([O-])=O)c(O)c1.Oc1ccc(C([O-])=O)c(O)c1.Oc1ccc(C([O-])=O)c(O)c1 AKAJRKUSJKGVFT-UHFFFAOYSA-K 0.000 description 1
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- GRBFCEINWFRDOG-UHFFFAOYSA-K di(octadecanoyloxy)bismuthanyl octadecanoate Chemical compound [Bi+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GRBFCEINWFRDOG-UHFFFAOYSA-K 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical group [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- HMZSDLABZPPSEM-UHFFFAOYSA-N ethene 2-(2-hydroxyethoxy)ethanol Chemical group C=C.C=C.C=C.OCCOCCO HMZSDLABZPPSEM-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KUNXCAIGAVGORW-UHFFFAOYSA-N n-ethyl-n-[[ethyl(nitro)amino]methyl]nitramide Chemical compound CCN([N+]([O-])=O)CN(CC)[N+]([O-])=O KUNXCAIGAVGORW-UHFFFAOYSA-N 0.000 description 1
- NQPFICHAHMRTNV-UHFFFAOYSA-N n-ethyl-n-[[methyl(nitro)amino]methyl]nitramide Chemical compound CCN([N+]([O-])=O)CN(C)[N+]([O-])=O NQPFICHAHMRTNV-UHFFFAOYSA-N 0.000 description 1
- XIFJZJPMHNUGRA-UHFFFAOYSA-N n-methyl-4-nitroaniline Chemical compound CNC1=CC=C([N+]([O-])=O)C=C1 XIFJZJPMHNUGRA-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
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- 229920000151 polyglycol Polymers 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-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
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
・ 前記硬化エネルギーポリマーは、数平均分子量(Mn)が700グラム/モル(g/mol)〜3000g/molの範囲であるグリシジルアジドポリマー(GAP)からなり、そのヒドロキシル末端官能基を介して少なくとも1種のポリイソシアネート型硬化剤を用いて硬化され、及び
・ 前記燃焼触媒はクエン酸ビスマスからなる。
・ 50%〜70%、有利には55%〜65%の有機エネルギー装薬、
・ 10%〜14%のエネルギーポリマー(そのヒドロキシ末端官能基を介して、少なくとも1種のポリイソシアネートにより硬化されるヒドロキシテレケリックGAPタイプ)、
・ 10%〜30%、有利には15%〜25%の少なくとも1種のエネルギー可塑剤、
・ 1%〜6%、有利には3%〜5%のクエン酸ビスマス、及び
・ 0%〜4%、有利には0.1%〜4%の少なくとも1つの添加剤。
・ a)35℃〜55℃の範囲の温度で、適切なグリシジルアジドポリマー(上記で特定した数平均分子量を示すヒドロキシテレケリックGAP)中に、攪拌しながら、少なくとも1種のエネルギー可塑剤、有機エネルギー装薬、及び所望の複合火工製品(特定の燃焼触媒であるクエン酸ビスマスを含む)を構成する他の成分を取り込み、但し硬化剤や硬化触媒は取り込まず、及び
b)得られた混合物を、部分真空下で35℃〜55℃の範囲の温度(有利には前記温度)で攪拌する、ことにより均一なペーストを調製する工程と、
・ 部分真空下で、35℃〜55℃の範囲の温度(有利には前記温度)で、前記得られた均一なペースト中に、前記少なくとも1種の硬化剤、及び場合により少なくとも1種の硬化触媒を取り込み、次に得られた混合物を攪拌する工程と、
・ 前記得られた攪拌混合物(=得られた混合物)を少なくとも1つの構造に投入する工程と、
・ 前記少なくとも1つの構造に投入された前記得られた攪拌混合物(攪拌された混合物)を熱処理する工程。
以下をミキサーに導入した:バインダー前駆体ポリマーとしてグリシジルアジドポリマー(GAP)、次に可塑剤(BTTN/TMETN)、及び前記可塑剤の安定剤(MMA/2−NDPA)。混合物を40℃の温度で15分間混合した。
こうして調製した各推進薬ペーストの試料を取って、ポットライフを決定した。
ポットライフは、当該推進薬ペースト(硬化剤と硬化触媒とを含む)の粘度を、Brookfield粘度計(1回転/分(rpm)で回転する3番のボディ(モバイルC)を使用)を使用して40℃の温度で、経時的に測定することにより決定した。粘度が15kPoに達するまでの時間を測定して、推進薬が工業化の基準を満たすかどうか、すなわち測定された時間が15時間より大きいかどうかを調べた。
予測されたように、弾道触媒を含まない(例A)か又はクエン酸鉛を弾道触媒としてクエン酸鉛を含む(例B1及びB2)参照推進薬のペーストは、24時間より後に15kPoの粘度値に達し、工業的注型性の基準を満足した。
表2はまた、弾道触媒(燃焼触媒)すなわちクエン酸ビスマスが、圧力の関数として、参照推進薬A(その組成中に弾道触媒を含まない)の燃焼速度よりはるかに大きく、燃焼触媒としてクエン酸鉛(毒性製品)を含む組成の推進薬B1とB2の燃焼速度に近い燃焼速度を、本発明の推進薬に付与することを示す。
Claims (9)
- 硬化エネルギーポリマーと少なくとも1種のエネルギー可塑剤とを含む可塑化バインダー中に有機エネルギー装薬と燃焼触媒とを含有する複合火工製品であって、
・ 該硬化エネルギーポリマーが、数平均分子量(Mn)が700g/mol〜3000g/molの範囲であるグリシジルアジドポリマー(GAP)からなり、そのヒドロキシル末端官能基を介して少なくとも1種のポリイソシアネート型硬化剤を用いて硬化されており、及び
・ 該燃焼触媒がクエン酸ビスマスからなる、
ことを特徴とする、複合火工製品。 - 該グリシジルアジドポリマー(GAP)が、1700g/mol〜2300g/molの範囲の数平均分子量(Mn)を有することを特徴とする、請求項1に記載の複合火工製品。
- 該少なくとも1種のエネルギー可塑剤が、硝酸塩型及び/又はニトラミン型であることを特徴とする、請求項1又は請求項2に記載の複合火工製品。
- 該有機エネルギー装薬が、ヘキソーゲン、オクトーゲン、ヘキサニトロヘキサアザイソブルツジタン、ニトログアニジン、エチレンジニトラミン、N−グアニル尿素ジニトラミド、1,1−ジアミノ−2,2−ジニトロエチレン、ビス(トリアミノグアニジニウム)−5,5’−アゾテトラゾレート、ジヒドラジニウム5,5’−アゾテトラゾレート、5,5’−ビス(テトラゾリル)ヒドラジン、ビス(2,2−ジニトロプロピル)ニトラミン、及びニトロピラゾール装薬、及びこのような装薬の混合物から選択されることを特徴とする、請求項1〜3のいずれか1項に記載の複合火工製品。
- 1重量%〜6重量%、有利には3重量%〜5重量%の上記クエン酸ビスマスを含有することを特徴とする、請求項1〜4のいずれか1項に記載の複合火工製品。
- 少なくとも1種の添加剤を更に含むことを特徴とする、請求項1〜5のいずれか1項に記載の複合火工製品。
- 該少なくとも1種の添加剤が、少なくとも1種の硬化触媒、及び/又は該少なくとも1種のエネルギー可塑剤用の少なくとも1種の安定剤を含むことを特徴とする、請求項6に記載の複合火工製品。
- その組成が以下(重量%で示される):
・ 50%〜70%、有利には55%〜65%の該有機エネルギー装薬、
・ 10%〜14%の該硬化エネルギーポリマー、
・ 10%〜30%、有利には15%〜25%の該少なくとも1種のエネルギー可塑剤、
・ 1%〜6%、有利には3%〜5%の該クエン酸ビスマス、及び
・ 0%〜4%、有利には0.1%〜4%の少なくとも1種の添加剤、
を含むことを特徴とする、請求項1〜7のいずれか1項に記載の複合火工製品。 - 請求項1〜8のいずれか1項に記載の複合火工製品の製造方法であって、
・ a)35℃〜55℃の範囲の温度で、グリシジルアジドポリマー中に、少なくとも1種のエネルギー可塑剤、有機エネルギー装薬、及び所望の複合火工製品を構成する他の成分を取り込み、但し硬化剤や硬化触媒は取り込まず、及び
b)得られた混合物を、部分真空下で35℃〜55℃の範囲の温度で攪拌する、ことにより均一なペーストを調製する工程と、
・ 部分真空下で、35℃〜55℃の範囲の温度で、得られた均一なペースト中に、少なくとも1種の硬化剤、及び場合により少なくとも1種の硬化触媒を取り込み、次に得られた混合物を攪拌する工程と、
・ 得られた攪拌混合物を少なくとも1つの構造に投入する工程と、
・ 少なくとも1つの構造中の投入された攪拌された得られた混合物を熱処理する工程と、
を含む、方法。
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FR1402431 | 2014-10-28 | ||
FR1402431A FR3027597B1 (fr) | 2014-10-28 | 2014-10-28 | Produit pyrotechnique composite performant sans pb dans sa composition et sa preparation |
PCT/FR2015/052888 WO2016066945A1 (fr) | 2014-10-28 | 2015-10-27 | PRODUIT PYROTECHNIQUE COMPOSITE PERFORMANT SANS Pb DANS SA COMPOSITION ET SA PREPARATION |
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JP7024134B1 (ja) * | 2020-12-02 | 2022-02-22 | 湖北航天化学技術研究所 | 温度感受性時間変化型高エネルギー固体推進剤 |
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FR3056583B1 (fr) * | 2016-09-26 | 2018-10-19 | Airbus Safran Launchers Sas | Produit pyrotechnique composite renfermant un agent anti-lueur de type sel de potassium |
FR3090629B1 (fr) * | 2018-12-20 | 2021-07-23 | Arianegroup Sas | Procédé de préparation de produits pyrotechniques composites |
FR3096680B1 (fr) | 2019-06-03 | 2021-09-24 | Arianegroup Sas | produit pyrotechnique composite |
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FR3027597A1 (fr) | 2016-04-29 |
IL251766B (en) | 2020-04-30 |
US20180290945A1 (en) | 2018-10-11 |
PL3212594T3 (pl) | 2019-01-31 |
IL251766A0 (en) | 2017-06-29 |
EP3212594B1 (fr) | 2018-07-18 |
EP3212594A1 (fr) | 2017-09-06 |
WO2016066945A1 (fr) | 2016-05-06 |
KR20170101897A (ko) | 2017-09-06 |
KR102621576B1 (ko) | 2024-01-05 |
FR3027597B1 (fr) | 2016-12-09 |
JP6510640B2 (ja) | 2019-05-08 |
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