US2716056A - Blasting explosive and process of producing same - Google Patents
Blasting explosive and process of producing same Download PDFInfo
- Publication number
- US2716056A US2716056A US277058A US27705852A US2716056A US 2716056 A US2716056 A US 2716056A US 277058 A US277058 A US 277058A US 27705852 A US27705852 A US 27705852A US 2716056 A US2716056 A US 2716056A
- Authority
- US
- United States
- Prior art keywords
- explosive
- ester
- proportion
- liquid
- nitrocellulose
- 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 - Lifetime
Links
- 239000002360 explosive Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 19
- 238000005422 blasting Methods 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 150000002148 esters Chemical class 0.000 claims description 22
- 239000000020 Nitrocellulose Substances 0.000 claims description 14
- 229920001220 nitrocellulos Polymers 0.000 claims description 14
- 235000011007 phosphoric acid Nutrition 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 150000005691 triesters Chemical class 0.000 claims description 8
- 229910001959 inorganic nitrate Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- -1 aromatic nitro compound Chemical class 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 7
- 229960003711 glyceryl trinitrate Drugs 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 235000015110 jellies Nutrition 0.000 description 7
- 239000008274 jelly Substances 0.000 description 7
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 239000001828 Gelatine Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 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
- C06B23/009—Wetting agents, hydrophobing agents, dehydrating agents, antistatic additives, viscosity improvers, antiagglomerating agents, grinding agents and other additives for working up
-
- 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
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
- C06B31/38—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the nitrated compound being an aromatic
- C06B31/40—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the nitrated compound being an aromatic with an organic non-explosive or an organic non-thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
- C06B31/44—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the compound being nitroglycerine
- C06B31/48—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound the compound being nitroglycerine with other explosive or thermic component
Definitions
- the present invention is concerned with improvements in or relating to gelatine blasting explosives containing a major proportion of crystalline salts and if desired other solid ingredients distributed through a lesser proportion of a viscous solution or jelly of nitrocellulose in a solvent comprising at least one explosive liquid nitric ester and more especially atleast one explosive liquid nitric ester and an aromatic nitro compound.
- nitroglycerine is one of the most expensive constituents in gelatine blasting explosives, whenever the blasting performance of the explosive permits, it is the practice to include a high proportion of crystalline salts, especially ammonium nitrate or other power producing salts in the composition, and other salts such as flamequenching salts, oxidising salts, and plant tissue materials are frequently present also, but the extent to which the proportion of the nitroglycerine in the explosive composition can be minimised has hitherto been limited in practice more by the difiiculty of maintaining a suitably plastic consistency sufficient for the extrusion of the composition for cartridging purposes than by the diminution in sensitiveness to initiation of the explosive, and obviously the higher the proportion of the salts and other solid ingredients the more important it is to maintain sufiicient plasticity to enable the explosive to be extruded. To a certain extent economy in nitroglycerine can also be effected by partially replacing it by a liquid aromatic nitro compound, in particular a liquid nitrotol
- the amount of the aforesaid compound of polyethylene glycol ether structure used is stated to be from 0.02 to 0.5% of the weight of the whole composition.
- the said para-tertiary-octyl-aryl group is preferably a para-tertiary-octyl-phenyl group or nuclearly substituted alkyl derivative thereof, preferably a methyl derivative.
- para-tertiary-octyl-aryl dialkyl esters of phosphoric acid effective for the purposes of the invention include Para-tertiary-octyl-phenyl (ii-methyl phosphate Para-tertiary-octyl-phenyl di-ethyl phosphate Para-tertiary-octyl-phenyl di-n-propyl phosphate
- the amount of the aforesaid tri ester of phosphoric acid employed may advantageously be in practice from 0.15 to 0.5% of the Weight of the whole explosive cornposition.
- esters of phosphoric acid are powerful surface active agents and it is found that by their use the percentage of nitroglycerine in the explosive composition may be quite substantially reduced even when a nitroaromatic compound is present in the liquid explosive solvent for the nitrocellulose without adversely affecting the extrudability of the composition.
- ester of phosphoric acid may be conveniently added to the aromatic nitro compound and the latter may then be dissolved in the nitroglycerine whereupon the nitrocell lose may be mixed with the resulting explosive liquid an the remainder of the ingredients introduced in known manner.
- the required surface active tri active esters of phosphoric acid may be obtained from para-tertiary-octyl-aryl phosphoryl dichloride by reaction with a monohydric aliphatic alcohol in a quantity sufficient to react with both chlorine atoms or vwth a quantity sufficient to react with one chlorine atom and thereafter with another of said alcohols in a quantity sufiicient to react with the other chlorine atom.
- Example 1 of this application sets forth a paratertiary-octyl-phenoxy-phosphoryl dichloride and indicates that the same has a boiling point of 142 C. at 0.8 mm. pressure and a boiling point of 190-192 C. at 10 mm. pressure.
- the reaction is preferably carried out in the absence of moisture at raised temperature and results in the evolution of hydrogen chloride. In some cases better yields are obtained by effecting the reaction in presence of a tertiary nitrogen base as an acceptor for hydrogen chloride at ordinary or only slightly raised temperatures. Pyridine may be used for this purpose.
- the aromatic nitro compound may be, for example, orthonitrotoluene or a mixture of nitrotoluenes or dinitrotoluenes that Will not crystallise out from solution in the liquid explosive nitric ester, for example a dinitrotoluene oil.
- the liquid explosive nitric ester may if desired include in admixture with trinitroglycerol other liquid explosive nitric esters, for example, ethylene glycol dinitrate, as is commonly the case in the manufacture of low-freezing explosives.
- Example 1 0.20 part para-tertiary-octylphenyl di-ethyl phosphate are mixed with 3 parts ortho-nitrotoluene and the resulting liquid is dissolved in 21 parts of a nitrated mixture of glycerol and ethylene glycol in the proportions 80-20. 1.1 parts of nitrocellulose are mixed with the resulting liquid and when gelatinisation is substantially completed there is incorporated a mixture of the following ingredients in known manner:
- the ingredients are mixed in a McRoberts mixer.
- the product is a gelatine explosive that can be extruded satisfactorily through an ordinary cartridging machine as used for cartridging explosives.
- Example 2 The para-tertiary-octyl-phenyl di-ethyl phosphate included in the composition produced in accordance with Example 1 is replaced by 0.2 part of para-tertiary-octyh phenyl-di-isopropyl phosphate.
- the resulting composition has the same plastic and extrusion properties as the composition of Example 1.
- the explosive compositions of Examples 1 and 2 also have substantially the same consistency and the same sensitivity to initiation and capability for transmitting their initiation with cartridges separated in file (as determined by a double cartridge test) as the following composition free from phosphoric esters and containing 30 parts of a liquid mixture consisting of 26 parts of a nitrated mixture of glycerine and ethylene glycol in the ratio of :20 and 4 parts ortho-nitrotoluene.
- the nitrocellulose used in Examples 1 and 2 is the variety known as blasting soluble nitrocellulose which is the product of nitration of purified cotton cops by the pot process to a nitrogen content of 11.95 to 12.2%.
- the product is at least soluble in ether alcohol solution and has a viscosity of l00-1300 CGS. units in solution of 3 grams in millilitres acetone (95% at 20 C).
- a method for the production of blasting explosives of the kind comprising a preponderating proportion of freely water-soluble inorganic nitrates distributed in a lesser proportion of a viscous solution of nitrocellulose in a solvent comprising a liquid explosive nitric ester which comprises forming a mixture of said freely water-soluble inorganic nitrates and said viscous solution in the presence of tri-ester of ortho-phosphoric acid having the general formula:
- R and R1 are alkyl radicals containing up to 12 carbon atoms and R2 is a radical selected from the group consisting of hydrogen and alkyl radicals.
- a method as claimed in claim 2 wherein the aromatic nitro compound is ortho-nitrotoluene.
- R2 is an alkyl radical
- Blasting explosives of the kind comprising a preponderating proportion of freely Water-soluble inorganic nitrates distributed in a lesser proportion of a viscous solution of nitrocellulose in a solvent comprising a liquid explosive nitric ester which explosives include a tri-ester of ortho-phosphoric acid having the general formula:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Jellies, Jams, And Syrups (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB14372/51A GB713758A (en) | 1951-06-18 | 1951-06-18 | Improvements in or relating to gelatine blasting explosives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2716056A true US2716056A (en) | 1955-08-23 |
Family
ID=10040022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US277058A Expired - Lifetime US2716056A (en) | 1951-06-18 | 1952-03-17 | Blasting explosive and process of producing same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US2716056A (en)) |
| BE (1) | BE512162A (en)) |
| CH (1) | CH307001A (en)) |
| ES (1) | ES202886A1 (en)) |
| GB (1) | GB713758A (en)) |
| NL (2) | NL79962C (en)) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2911431A (en) * | 1958-02-28 | 1959-11-03 | Ethyl Corp | Dimethyl-(methylphenyl)-phosphates |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2071017A (en) * | 1936-07-13 | 1937-02-16 | Dow Chemical Co | Aryl phosphoric acid halides |
-
0
- BE BE512162D patent/BE512162A/xx unknown
- NL NL7209610.A patent/NL168374B/xx unknown
- NL NL79962D patent/NL79962C/xx active
-
1951
- 1951-06-18 GB GB14372/51A patent/GB713758A/en not_active Expired
-
1952
- 1952-03-17 US US277058A patent/US2716056A/en not_active Expired - Lifetime
- 1952-04-08 ES ES0202886A patent/ES202886A1/es not_active Expired
- 1952-05-21 CH CH307001D patent/CH307001A/de unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2071017A (en) * | 1936-07-13 | 1937-02-16 | Dow Chemical Co | Aryl phosphoric acid halides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2911431A (en) * | 1958-02-28 | 1959-11-03 | Ethyl Corp | Dimethyl-(methylphenyl)-phosphates |
Also Published As
| Publication number | Publication date |
|---|---|
| BE512162A (en)) | |
| ES202886A1 (es) | 1954-03-16 |
| NL168374B (nl) | |
| CH307001A (de) | 1955-05-15 |
| GB713758A (en) | 1954-08-18 |
| NL79962C (en)) |
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