EP3724153A1 - Long unsaturated aliphatic chains as stabilisers for nitrate esters and nitrocellulose-based applications - Google Patents
Long unsaturated aliphatic chains as stabilisers for nitrate esters and nitrocellulose-based applicationsInfo
- Publication number
- EP3724153A1 EP3724153A1 EP17817712.7A EP17817712A EP3724153A1 EP 3724153 A1 EP3724153 A1 EP 3724153A1 EP 17817712 A EP17817712 A EP 17817712A EP 3724153 A1 EP3724153 A1 EP 3724153A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitrocellulose
- substituted
- alkyl
- stabiliser
- based composition
- 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.)
- Withdrawn
Links
- 239000003381 stabilizer Substances 0.000 title claims abstract description 80
- 239000000020 Nitrocellulose Substances 0.000 title claims abstract description 68
- 229920001220 nitrocellulos Polymers 0.000 title claims abstract description 68
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 12
- 150000002823 nitrates Chemical class 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 79
- -1 nitrate ester Chemical class 0.000 claims abstract description 60
- 239000003380 propellant Substances 0.000 claims abstract description 56
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 239000011630 iodine Substances 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229960003711 glyceryl trinitrate Drugs 0.000 claims description 16
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 16
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 13
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 12
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005422 blasting Methods 0.000 claims description 12
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- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 claims description 11
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims description 11
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- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 claims description 11
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 10
- 241000894007 species Species 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
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- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
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- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 6
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- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 6
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- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 6
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- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 claims description 5
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- 229940114079 arachidonic acid Drugs 0.000 claims description 5
- 235000021342 arachidonic acid Nutrition 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- OAIJSZIZWZSQBC-GYZMGTAESA-N lycopene Chemical compound CC(C)=CCC\C(C)=C\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C=C(/C)CCC=C(C)C OAIJSZIZWZSQBC-GYZMGTAESA-N 0.000 claims description 5
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 235000007586 terpenes Nutrition 0.000 claims description 4
- UNSRRHDPHVZAHH-YOILPLPUSA-N (5Z,8Z,11Z)-icosatrienoic acid Chemical compound CCCCCCCC\C=C/C\C=C/C\C=C/CCCC(O)=O UNSRRHDPHVZAHH-YOILPLPUSA-N 0.000 claims description 3
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- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 claims description 3
- UNSRRHDPHVZAHH-UHFFFAOYSA-N 6beta,11alpha-Dihydroxy-3alpha,5alpha-cyclopregnan-20-on Natural products CCCCCCCCC=CCC=CCC=CCCCC(O)=O UNSRRHDPHVZAHH-UHFFFAOYSA-N 0.000 claims description 3
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 3
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
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- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 45
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- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-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
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/006—Stabilisers (e.g. thermal stabilisers)
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
- C06B25/20—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with a non-explosive or a non-explosive or a non-thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
- C06B25/24—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine
- C06B25/26—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine with an organic non-explosive or an organic non-thermic component
Definitions
- the present invention relates to stabilised nitrate ester-based combustible 5 compositions for use as propellants and combustible items.
- it concerns nitrocellulose-based compositions stabilised with a novel stabiliser producing little to no carcinogenic and mutagenic by-products.
- Nitrocellulose is the most widely used nitrate ester for the production of energetic 0 materials such as propellants, combustible items, nitro-films or components inherent to these applications. Nitrocellulose is obtained by using nitric acid to convert cellulose into cellulose nitrate and water according to a general reaction:
- Nitrocellulose-based propellants are subsequently obtained by treating the hitherto obtained 5 nitrocellulose by extrusion, spherical or mechanical granulation, with or without solvent, three techniques that are well known to the persons skilled in the art.
- Combustible items such as modular charges or combustible cases are made using the blistering technique, also well known to the persons skilled in the art.
- nitrocellulose propellants are referred to as single-base propellants, and double- and triple-base propellants refer to compositions comprising nitrocellulose and one or two additional energetic bases, respectively; typically blasting oils such as nitroglycerine, nitroguanidine, or secondary5 explosives.
- Degradation usually leads to gas emissions, heat generation and reduction of molecular mass negatively affecting the material structure and ballistic properties.
- nitrate esters usually starts with a bond scission or hydrolysis, generating alkoxy radicals and nitrogen oxide (NOx) species (cf. Figure 1 ).
- the radicals further 0 react, generating more radicals, speeding up the degradation process, and ultimately leading to chain scission accompanied by heat generation.
- stabilisers are added to the energetic mixture to scavenge these radical species and slow down the degradation pattern.
- Most conventional stabilisers used to date for nitrocellulose-based propellants and 5 combustible items belong to (a) aromatic amines (e.g., diphenylamine, 4-nitro-N- methylamine) or (b) aromatic urea derivatives (e.g., akardite, centralite). They are/or produce toxic and/or potentially carcinogenic species at some point during a propellant’s lifetime.
- aromatic amines e.g., diphenylamine, 4-nitro-N- methylamine
- aromatic urea derivatives e.g., akardite, centralite
- the most widely used stabilisers to date are diphenylamine, Akardite, and centralite. These compounds, however, form carcinogenic derivatives such as N-nitrosodiphenylamine0 (cf. Figure 2) or N-nitrosoethylphenylamine.
- Flindered amines such as triphenylamine, reduce the formation of N-NO groups, but fail to stabilise nitrate esters satisfactorily.
- Conventional hindered phenols used in the plastics industry have been tested and for short amounts of time stabilise nitrocellulose with little to no N-NO formation.
- the phenols are able to trap the alkoxy radicals generated during the5 degradation of nitrocellulose and thus form new, relatively stable alkoxy radicals, by delocalisation of an electron at the foot of electron-rich, hindered groups.
- Long term stability B is, however, not always guaranteed, probably due to rapid phenol depletion and relative stability of the newly formed alkoxy radicals.
- the present invention concerns a nitrocellulose-based composition for use as a propellant or as a combustible item, said nitrocellulose-based composition comprising:
- the compound having a molecular weight of at least 1 20 and an iodine number of at least 25.
- the nitrate ester-based component consists of5 nitrocellulose alone thus defining a single base composition.
- the nitrate ester-based component consists of a mixture comprising nitrocellulose in combination with at least a blasting oil and/or at least one energetic additive, thus defining a double or higher base composition.
- the blasting oil can comprise at least a nitrated polyol, which is obtained by nitration of a polyol selected from a group consisting of glycerol, glycol, diethylene glycol, triethylene glycol and metriol, preferably glycerol.
- At least one energetic additive can be an 5 energetic plasticizer selected from the group of nitramines, such as butyl-NENA, dinitrodiazaalkane (DNDA), or is an explosive such as RDX, HMX, FOX-7, FOX-1 2, CL20, SMX.
- the nitrate ester-based component may comprise up to 60 wt.% nitroglycerine, such as between 5 and 45 wt.%, preferably between 7 and 22 wt.% nitroglycerine, with respect to the total weight of nitrate-ester based propellant.
- the stabiliser be a component capable of reacting with both degradation products of the nitrate ester, namely alkoxy radicals and NOx, mainly by hydrogen abstraction of one labile proton of the stabiliser, located in the alpha-position of an unsaturation generating another free radical species able, e.g. to further react with the NOx counterpart.
- the stabiliser can be selected from one or more of the following 5 components and their derivatives:
- terpenes or terpenoids including squalene, farnesol, myrcene, thymol, citral, limonene, lycopene,
- omega 3-6-9 unsaturated fatty acids including one or more of arachidonic acid,0 linolenic acid, mead acid, herring acid
- triglycerides i.e. oils
- fatty acids including linseed oil
- the stabiliser preferably consists of a component selected from a group consisting of polybutadiene, polyisoprene, squalene, farnesol, limonene, myrcene, lycopene and citral, preferably the stabiliser is polybutadiene.
- the stabiliser is preferably present in the composition in an amount comprised between 0.1 and 5.0 wt. %, preferably between 0.2 and 2.0 wt. %>, more preferably between 0.5 and 1 .0 wt. %, with respect to the total weight of the composition.
- the nitrocellulose-based com position may comprise one or more complementary stabilisers.
- the complementary stabiliser can be selected from one or more of the following components:
- R 6 represents: (i) H, (ii) alkyl substituted or not, or (iii) an al koxy group; and R 7 and R 8 are same or different, and represent (i) alkyl substituted or not, or (ii) alkoxy group;
- R 9 , R 1 0 and R 1 1 are same or different and represent C1 -5 alkyl unsubstituted or substituted with an alkoxy group;
- R 14 represents, H, alkyl-substituted or not, or OR 18 ;
- R 1 5 represents, alkyl-substituted or not, aromatic ring-substituted or not, or OR 18 ;
- R 16 represents, alkyl-substituted or not, aromatic ring-substituted or not, or OR 19 ;
- R 1 7 represents, aromatic ring-substituted or not;
- 0 R 18 represents, alkyl-substituted or not, or aromatic ring-substituted;
- R 19 represents, alkyl-substituted or not, or aromatic ring-substituted.
- R 20 , R 21 and R 22 are the same or different and represent: (i) alkyl-substituted or not, (ii) alkoxy group.
- R 20 , R 21 and R 22 are the same or different and represent: (i) alkyl-substituted or not, (ii) alkoxy group.
- the nitrocellulose-based composition may also comprise one or more of the following additives:
- a potassium salt preferably potassium nitrate (KNC ), and more preferably in an amount comprised between 0.001 and 1 .5 wt. %;
- combustion moderators such as phthalates, Cl and citrate derivatives, preferably in an amount comprised between 1 .0 and 1 0.0 wt. %
- the nitrocellulose-based composition according to the present invention preferably has a stability measured according to STANAC 4582 (Ed. 1 ) at a temperature of 90 C without heat generation above 350 pW/g of at least 3.43 days, preferably of at least 5 days, more preferably of at least 1 0 days.
- the present invention also concerns the use of a component (I) consisting of a long aliphatic chain having at least two unsaturation sites for stabilising a nitrate-ester based composition comprising nitrocellulose for applications including propellants and combustible items.
- a component (I) consisting of a long aliphatic chain having at least two unsaturation sites for stabilising a nitrate-ester based composition comprising nitrocellulose for applications including propellants and combustible items.
- Figure 1 shows a reaction of spontaneous decomposition of nitrocellulose with formation of free radicals and NOx.
- Figure 2 shows the assumed stabilisation mechanisms of akardite (Akll) and diphenylamine 0 (DPA) (prior art).
- the fine dashed lines represent the minimum requirements of STANAC 4582.
- FIG. 4 shows the normalised heat flow expressed in pW / g generated by propellant compositions stabilised with various stabilisers of the present invention: polybutadiene (la), polyisoprene (lb) and polystyrene (lc), as well as the conventional stabiliser DPA (prior art) for double base nitrocellulose / nitroglycerine (60 / 40 wt.%) propellants at 90°C.
- various stabilisers of the present invention polybutadiene (la), polyisoprene (lb) and polystyrene (lc), as well as the conventional stabiliser DPA (prior art) for double base nitrocellulose / nitroglycerine (60 / 40 wt.%) propellants at 90°C.
- Figure 5 shows the normalised heat flow expressed in pW / g generated by propellant0 compositions stabilised with 1 wt.% of various terpenoid stabilisers: squalene (Id) and limonene (le), for double base nitrocellulose / nitroglycerine (90 / 1 0 wt.%) propellants.
- Figure 6 illustrates the chemical pathways of (a) a 1 ,5-diene moiety (e.g. squalene, polybutadiene) and (b) of a 1 ,4-diene moiety (e.g., arachidonic acid). 5 Detailed description of the invention
- diphenylamine (DPA) 5 stabilises a propellant composition by the following mechanism.
- a free radical alkoxy group generated by the propellant abstracts the hydrogen of the amine group of DPA 5 to form a stable compound (ROFI, 9) (cf. reaction (C) of Figure 2(b)).
- the radical formed on the amine 8 can react with a NOx to form stable N-nitrosodiphenylamine 10 (cf. reaction (D) of Figure 2(b)).
- the NNO group of N-nitrosodiphenylamine 10 is, however, carcinogenic and should be avoided for safety reasons.
- Triphenylamine has been tested in the past in order to prevent formation of NNO groups, but with little success in stabilisation properties. Flindered phenols effectively react with free oxide radicals (R-O ) but form stable components which are unlikely to further react with NOx. The efficiency of such stabilisers is limited to short periods of time only because of rapid phenol depletion.
- a nitrocellulose-based composition according to the present invention can be used as a propellant or as a combustible item, such as modular charges or combustible cases.
- the composition comprises a nitrate ester-based component comprising nitrocellulose, and a stabiliser (I) which does not produce carcinogenic components.
- the stabiliser (I) as used in the present invention is a compound presenting a long aliphatic chain having at least two unsaturation sites, the compound having a molecular weight of at least 1 20 and an iodine number of at least 25.
- the iodine number is determined according to ISO 3961 :201 3, as follows: mass of iodine in grams that is consumed by 1 00 grams of the tested chemical substance and is used to determine the amount of unsaturation of that chemical substance.
- the nitrate ester-based component may consist of nitrocellulose alone thus defining a single base composition, or of a mixture comprising nitrocellulose in combination with at least 5 a blasting oil and/or at least one energetic additive, thus defining a double or higher base composition.
- the blasting oil may comprise at least a nitrated polyol, which is obtained by nitration of a polyol selected from a group consisting of glycerol, glycol, diethylene glycol, triethylene glycol and metriol, preferably glycerol, and wherein the at least one energetic additive is an energetic plasticizer selected from the group of nitramines, such as butyl-NENA, 0 dinitrodiazaalkane (DNDA), or is an explosive such as RDX, HMX, FOX-7, FOX-1 2, CL20, SMX.
- nitramines such as butyl-NENA, 0 dinitrodiazaalkane (DNDA)
- DNDA 0 dinitrodiazaalkane
- Nitroglycerol is a particularly preferred blasting oil for forming a double base composition.
- a double base propellant composition according to the present invention preferably comprises not more than 60 wt.% blasting oil (such as nitroglycerine) or energetic additive with respect to the total weight of nitrate ester based propellant. More preferably, it 5 comprises between 5 and 45 wt.%, most preferably between 7 and 22 wt.% blasting oil or energetic additive, with respect to the total weight of nitrate ester-based propellant.
- a preferred blasting oil is nitroglycerine (NCL).
- STANAC 4582 requires that a propellant composition yields a stability defined by a generation of energy not exceeding 350 pW / g during at least 3.43 days at a temperature of0 90°C.
- Figure 3 illustrates the stability of a single base (1 B, dashed line) and a double base (2B, solid line) propellant compositions without any stabiliser at a temperature of 90°C.
- the fine dashed lines illustrate the minimum requirements of STANAC 4582.
- Preferred examples of aliphatic, unsaturated stabilisers (I) according to the present invention include: terpenes/terpenoids such as squalene, farnesol, myrcene, thymol, citral, limonene, and the like,
- omega 3-6-9 unsaturated fatty acids such as arachidonic acid, linolenic acid, mead acid, herring acid, and the like) and their derivatives (oils e.g. linseed oil or condensed products)
- polymeric compounds such as polyenes, unsaturated polyester resins and particularly0 preferred polymeric compounds include homopolymers or copolymers of butadiene, isoprene, pentadiene, and the like
- the stabiliser is preferably a component capable of reacting with both degradation products of the nitrate ester, namely alkoxy radicals and NOx, mainly by hydrogen abstraction5 of one labile proton of the stabiliser, located in the alpha-position of an unsaturation.
- This reaction converts, for example, the unstable alkoxy nitrocellulose derivative into a stable alcohol compound (and therefore terminating the degradation process of the nitrocellulose) and a first by-product able to trap the NOx species or delocalise its free radical using the adjacent double bond.
- a stabiliser (I), as defined in the present invention works by repetitive sequences of H-abstractions of labile hydrogen in the alpha positions of unsaturations of the stabiliser by unstable alkoxy radicals generated during the degradation of the nitrate ester (cf. Figure 1 , molecule 2) and subsequent 5 recombinations either with other carbon-based free-radicals generated similarly or NOx species (cf. Figure 1 , molecule 3) arising from the ageing of the nitrate ester.
- This series of reactions converts unstable alkoxy nitrocellulose 2 derivatives into stable alcohol compounds and converts NOx species 3 into stable nitrated compounds and thus preventing the unwanted decomposition process of the nitrocellulose.
- the successive by-products thus formed are0 capable of further reacting with the degradation products of the nitrate ester, following the hitherto described scheme, producing no harmful NNO groups and providing a good chemical stability of the energetic material.
- polymeric stabilisers such as polybutadiene or polyisoprene.
- Figure 6(a) illustrates the5 chemical pathways of a 1 ,5-diene moiety (e.g. squalene, polybutadiene) and Figure 6(b) illustrate the pathways of a 1 ,4-diene moiety (e.g., arachidonic acid).
- R can take any value and can be same or different at both ends of a chain.
- the nature of the final products depends on the nature of the substituents (e.g. an electron-withdrawing group would favour the hydrogen abstraction whilst a bulky substituent would rather favour the delocalisation of0 the charge).
- the unstable alkoxy nitrocellulose 2 derivative abstracts the labile hydrogen of the stabiliser (I) converting it into a stable alcohol compound (and therefore preventing the unwanted decomposition process of the nitrocellulose) and a first by-product 1 2 , able to trap the NOx species generating 1 7, or delocalise its free radical using the adjacent double bond, yielding 1 3. It can subsequently5 react with e.g.
- the successive by-products 12 to 24 illustrated in Figure 6(a)&(b) are capable of reacting with more NOx and alkoxy radicals from the degradation of the nitrate ester 1 , and 5 thus substantially increase the efficiency of the stabiliser function. Since no harmful NNO groups are formed due to the lack of nitrogen atoms in compound (I) structure, the stabiliser according to the present invention produces little to no carcinogenic and mutagenic N-nitroso by-products.
- the stabiliser is selected from a group consisting of0 polybutadiene, polyisoprene, squalene, farnesol, limonene, myrcene, lycopene, citral, polystyrene.
- a preferred stabiliser is polybutadiene (la) (any type/combination)
- Another preferred stabiliser is polyisoprene (lb)
- Another preferred stabiliser is polystyrene (lc):
- Another preferred stabiliser is squalene (Id):
- a propellant composition according to the present invention comprises a stabiliser (I), in the form of a long aliphatic chain having at least two unsaturation sites, the compound having a molecular weight of at least 1 20 and an iodine number of at least 25.
- the stabiliser 5 is preferably present in an amount comprised between 0.1 and 5.0 wt.%, more preferably between 0.2 and 2.0 wt.%, most preferably between 0.5 and 1 .5 wt.%, with respect to the total weight of the composition.
- Figure 4 illustrates the stability of a double base propellant composition (60 wt.% nitrocellulose and 40 wt.% NCL) stabilised with 1 wt.% of various polymeric stabilisers (I) according to the present invention: polybutadiene (la), polyisoprene 0 (lb) and polystyrene (lc), as well as the conventional stabiliser DPA (prior art).
- polybutadiene la
- polyisoprene 0 polyisoprene 0
- lc polystyrene
- DPA conventional stabiliser
- Figures 5 illustrates the stability of a double base propellant composition (90 wt.% nitrocellulose and 1 0 wt.% NCL) stabilised with 1 wt.% of various terpene stabilisers (I) according to the present invention: squalene (Id) and limonene (le).
- a double base propellant composition stabilised with 1 wt.% of a stabiliser of according to the present invention maintains the level of energy released at 90°C perfectly stable below 200 pW / g for 9 days and longer.
- Double base propellants compositions containing nitroglycerine (NCL) are particularly 5 less stable than single base propellants.
- NCL nitroglycerine
- a double base propellant not containing any stabiliser enters into autocatalysis after only 2 days.
- the stabilising properties of a stabiliser according to the present invention are at least as good -and often substantially better- than those of DPA, without forming any carcinogenic NNO- components.
- a double base propellant composition stabilised0 with a stabiliser (I) according to the present invention has a stability measured according to STANAC 4582 (Ed. 1 ) at a temperature of 90°C without heat generation above 350 pW/g of at least 3.43 days, preferably of at least 5 days, more preferably of at least 1 0 days, and more.
- a stabiliser (I) according to the present invention with a complementary stabiliser in the form of an aromatic compound.
- This second stabiliser has a different, complementary stabilisation mechanism and is believed to provide a synergistic effect.
- the complementary stabiliser is preferably selected from the following group:
- R 6 represents: (i) H, (ii) alkyl substituted or not, or (iii) an alkoxy group; and R 7 and0 R 8 are same or different, and represent (i) alkyl substituted or not, or (ii) alkoxy group;
- R 9 , R 10 and R 1 1 are same or different and represent C1-5 alkyl unsubstituted or substituted with an alkoxy group;
- R 14 represents, H, alkyl-substituted or not, or OR 18 ;
- R 1 5 represents, alkyl-substituted or not, aromatic ring-substituted or not, or OR 18 ;
- R 16 represents, alkyl-substituted or not, aromatic ring-substituted or not, or OR 19 ;
- R 1 7 represents, aromatic ring-substituted or not
- R 18 represents, alkyl-substituted or not, or aromatic ring-substituted
- R 19 represents, alkyl-substituted or not, or aromatic ring-substituted.
- R 12 represents C1 -5 alkyl-substituted or not, preferably CH3; further, it is preferred that R 13 represents:
- R28 represents H, alkyl-substituted or not, or aromatic ring, substituted or not.
- eugenol (4-111) or isoeugenol (4-IV) are suitable complementary stabilisers
- composition according to the present invention comprises a curcumin derivative of formula (4-11) as a complementary stabiliser, wherein
- R 12 and R 29 are the same or different and represent alkyl substituted or not, preferably C1-5, more preferably CH3;
- R 14 and R 30 are the same or different and represent H or alkyl substituted or not (e.g., C1-5 alkyl), wherein each of R 12 and R 29 , and R 14 and R 30 , are preferably the same, and more preferably both are H.
- R 20 , R 21 and R 22 are the same or different and represent: (i) alkyl-substituted or not, (ii) alkoxy group.
- R 23 , R 24 , R 25 and R 26 are the same or different and represent: (i) alkyl-substituted or not, (ii) alkoxy group.
- a propellant composition according to the present invention may comprise additives.
- it may comprise one or more of the following additives: (a) a potassium salt, such as potassium nitrate (KNO3) or sulphate (K2SO4),
- combustion moderants to slow the burning rate of the propellant, such as
- wt.% are expressed in terms of the total weight of the propellant composition.
- Table 1 typical propellant compositions according to the present invention
- STANAC 4582 (Ed. 1 ) of March 9, 2007 entitled “Explosives, nitrocellulose based propellants, stability test procedure and requirements using heat flow calorimetry”, defi nes an accelerated stability test procedure for single-, double-, and triple-base propellants using0 heat flow calorimetry (HFC). The test is based on the measurement of the heat generated by a propellant composition at a high temperature. Fulfilment of the STANAC 4582 (Ed. l ) test qualifies a propellant composition for a 1 0 year stability at 25°C.
- a sample of propellant composition is enclosed in a hermetically sealed vial and positioned in a heat flow calorimeter having a measuring range corresponding to 1 0 to 5 500 pW/g.
- the sample is heated and maintained at a constant temperature of 90°C for the whole duration of the test and the heat flow is measured and recorded.
- a heat flow not exceeding 350 pW / g for a period of 3.43 days at 90°C is considered to be equivalent to at least 1 0 years of safe storage at 25°C.
- the graphs of Figures 3, 4 and 5 show the stability of compositions as a function of time measured as defined above over a period of 9 days.
- the 0 fine horizontal dashed line corresponds to a value of 350 pW / g not to be exceeded according to STANAC 4582 (Ed. l ), and the fine vertical dashed line indicates 3.43 days.
- the initial heat flow peaks of graphs of Figures 3, 4 and 5 are ignored as they are not representative of any specific reaction or phase transformation of the propellant composition, provided they do not exceed an exotherm of 5 J. 5 [0043]
- Figure 3 shows the stability of unstabilised single base (1 B) and double base (2B) compositions. After two days at 90°C a double base composition comprising 1 0 wt.% NCL becomes unstable and goes to autocatalysis.
- Figures 4 and 5 show the results of the stability tests carried out on double base nitrocellulose based propellants comprising 40 wt.% and 1 0 wt.% nitroglycerine, respectively, and stabilised with 1 wt.% of a0 stabiliser (la-e)) according to the present invention. It can be seen that the heat flow never exceeds 200 pW / g for 9 days, when STANAC 4582 (Ed. l ) requires to maintain the heat flow below 350 pW / g for 3.43 days.
- Figure 4 also shows the stability of a corresponding composition stabilised with 1 wt.% of a state of the art diphenylamine (DPA) stabiliser. The composition remains stable for a week and becomes unstable. 5 [0044] As can be seen in Figure 4, both DPA and stabiliser (I) fulfil the requirements of
- Stabiliser (I) according to the present invention is, however, advantageous over DPA and Akardite because, (a) there is significant increase in performance and therefore a longer use and storage in safety: DPA curve (solid line) shows a thermal runaway for a double base propellant containing 40% of nitroglycerine after less than 7 days where stabilisers according to the present invention (la, lb and lc remain below 200 pW / g for over 9 days, as shown in Figure 4.
- the propellant compositions of the present invention consolidates the development and use of a new generation of stabilisers which can be referred to as “green or environmentally-friendly stabilisers,” which combine efficient, long term stability of nitrocellulose-based propellants without the formation of any detectable amounts of carcinogenic or mutagenic by-products.
Abstract
Description
Claims
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PCT/EP2017/082359 WO2019114930A1 (en) | 2017-12-12 | 2017-12-12 | Long unsaturated aliphatic chains as stabilisers for nitrate esters and nitrocellulose-based applications |
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EP (1) | EP3724153A1 (en) |
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US1651459A (en) * | 1926-07-27 | 1927-12-06 | Charles H Keck | Propellant powder |
US2357989A (en) * | 1942-04-01 | 1944-09-12 | Hercules Powder Co Ltd | Smokeless powder |
US3186882A (en) * | 1962-01-12 | 1965-06-01 | Holt Erich Von | Nitrocellulose containing explosive compositions and methods of preparing same |
US3726729A (en) * | 1965-06-30 | 1973-04-10 | Us Army | Solid propellant compositions having a nitrocellulose-hydroxyl-terminated polybutadiene binder and method of preparing the same |
US5180747A (en) * | 1989-02-28 | 1993-01-19 | Nisshin Flour Milling Co., Ltd. | Stabilized fat-soluble vitamin compositions |
US5682009A (en) * | 1994-07-21 | 1997-10-28 | Primex Technologies, Inc. | Propellant containing a thermoplatic burn rate modifer |
US8641842B2 (en) * | 2011-08-31 | 2014-02-04 | Alliant Techsystems Inc. | Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same |
DE102010020776B4 (en) * | 2010-05-18 | 2015-03-05 | Diehl Bgt Defence Gmbh & Co. Kg | Propellant charge and method for its production |
GB201317423D0 (en) * | 2013-10-02 | 2014-09-17 | Pb Clermont Sa | Stabilized nitrocellulose based propellant composition |
GB201317421D0 (en) | 2013-10-02 | 2013-11-13 | Pb Clermont Sa | Nitrocellulose based propellant composition stabilized with a trialkoxy benzene stabilizer |
GB201317420D0 (en) | 2013-10-02 | 2013-11-13 | Pb Clermont Sa | Nitrocellulose based propellant composition stabilized with a substituted phenol stabilizer |
WO2016135227A1 (en) | 2015-02-25 | 2016-09-01 | P.B. Clermont | Ionone stabilisers for nitrocellulose-based propellants |
US10414697B2 (en) | 2015-02-25 | 2019-09-17 | Pb Clermont | Tocopherol stabilisers for nitrocellulose-based propellants |
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2017
- 2017-12-12 CA CA3076850A patent/CA3076850A1/en active Pending
- 2017-12-12 WO PCT/EP2017/082359 patent/WO2019114930A1/en unknown
- 2017-12-12 US US16/768,922 patent/US20210221752A1/en not_active Abandoned
- 2017-12-12 EP EP17817712.7A patent/EP3724153A1/en not_active Withdrawn
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