GB2200626A - Explosive composition - Google Patents
Explosive composition Download PDFInfo
- Publication number
- GB2200626A GB2200626A GB08800926A GB8800926A GB2200626A GB 2200626 A GB2200626 A GB 2200626A GB 08800926 A GB08800926 A GB 08800926A GB 8800926 A GB8800926 A GB 8800926A GB 2200626 A GB2200626 A GB 2200626A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polymer
- emulsion explosive
- emulsion
- group
- acid
- 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
- 239000000203 mixture Substances 0.000 title claims description 155
- 239000002360 explosive Substances 0.000 title claims description 94
- 239000000839 emulsion Substances 0.000 claims description 113
- 229920000642 polymer Polymers 0.000 claims description 80
- -1 amine salts Chemical class 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 27
- 239000012074 organic phase Substances 0.000 claims description 27
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 24
- 239000012071 phase Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000002334 glycols Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000295 fuel oil Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 4
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000000787 lecithin Substances 0.000 claims description 4
- 235000010445 lecithin Nutrition 0.000 claims description 4
- 229940067606 lecithin Drugs 0.000 claims description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 239000010775 animal oil Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229940013317 fish oils Drugs 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002462 imidazolines Chemical class 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000003738 xylenes Chemical class 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 2
- MVYVKSBVZFBBPL-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical class OS(=O)(=O)CC(C)NC(=O)C=C MVYVKSBVZFBBPL-UHFFFAOYSA-N 0.000 claims 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 239000004816 latex Substances 0.000 description 10
- 229920000126 latex Polymers 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- APZBIEHZUCEYNW-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazol-2-ylmethanol Chemical compound OCC1=NCCO1 APZBIEHZUCEYNW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- ZCYXFITUYVYSJW-UHFFFAOYSA-N 1-ethenylisoquinoline Chemical class C1=CC=C2C(C=C)=NC=CC2=C1 ZCYXFITUYVYSJW-UHFFFAOYSA-N 0.000 description 1
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- APLNAFMUEHKRLM-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(3,4,6,7-tetrahydroimidazo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)N=CN2 APLNAFMUEHKRLM-UHFFFAOYSA-N 0.000 description 1
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical class C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- XLHFQWCMIWOPGG-UHFFFAOYSA-N 2-ethenylquinoxaline Chemical class C1=CC=CC2=NC(C=C)=CN=C21 XLHFQWCMIWOPGG-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical class C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- ZXWNFKKVGPYFRR-UHFFFAOYSA-N 3-ethenyl-2-methylpyridine Chemical class CC1=NC=CC=C1C=C ZXWNFKKVGPYFRR-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 101100126167 Escherichia coli (strain K12) intD gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 241000589634 Xanthomonas Species 0.000 description 1
- 241000589636 Xanthomonas campestris Species 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000003857 carboxamides Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- UXJXCZLHRLBCLF-UHFFFAOYSA-N n-ethylethanamine;ethyl 2-methylprop-2-enoate Chemical compound CCNCC.CCOC(=O)C(C)=C UXJXCZLHRLBCLF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229960004321 pentaerithrityl tetranitrate Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 244000000003 plant pathogen Species 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-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
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
- C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Colloid Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
1 1, p 2ZO 0 6 2 6 - 1 EXPLOSIVE COMPOSITION The invention relates to
emulsion explosive compositions having a discontinuous phase comprising an oxygen- releasing salt and a continuous liquid organic phase and in partic ular to emulsion explosives compositions containing an oil-soluble polymer having associative groups.
Emulsion explosive pompositions-have been widely accepted in the explosives industry because of their excellent explosive properties and ease of handling. The emulsion explosive compositions now in common use in the industry are of the water-in-oil type first disclosed byBluhm in US Patent No. 3 447 978 and comprise as components:
(a) a discontinuous aqueous phase comprising 1 2 - (b) (C) discrete droplets of an aqueous solution of inorganic oxygen- releasing salts; a continuous water- immi s c JILble organic phase throughout which the droplets are dispersed; and an emulsifier which forms an emulsion of the droplets of oxidizer salt solution throughout the continuous organic phase.
For some applications, water content of the oxidizer phase of the emulsion may be eliminated or reduced to a low level, for example, to less than 4% by weight of the total emulsion composition. Sch compositions are conveniently referred to as melt-in-oil or melt-in-fuel emulsion explosives and have been described, for example, in US Patent 4 24 8 644. The term "emulsion explosiVe is used herein.to embrace compositions of both.the water-in-oil and the melt-in-oil types. 20 Emulsion explosives may be handled in bulk and are easily loaded into boreholes for large-scale blasting operations. A particular problem however arises where boreholes contain water, for example, after rain. In such cases, and in particular where boreholes become completely or -partially filled with water,, the explosive performance of emulsion explosives is severely reduced. This is a particular problem when using blends of emulsion explosive and a solid adjuvant such as ammonium nitrate prills or ANFO.
i 1 Indeed, in many cases it is difficult to detonate an emulsion explosive charge which has been loaded into a borehole containing water.
Due to these problems it has generally been the practice to drain water from a borehole before loading the explosive. This is both time consuming and labour intensive.- If emulsion explosives are carefully loaded into the bottom of a borehole via a hose, it is sometimes possible to displace water from the bore-hole. However, this again is a time consuming procedure and unsatisfactory for deep boreholes.
We have now developed an emulsion explosive composition which is highly elastic and which may be loaded into wet boreholes without using such procedures.
Further advantages of the composition of the present invention will become evident on considering the physical properties of the emulsion explosive composition.
Accordingly we provide an emulsion explosive composition comprising a discontinuous phase comprising at least one oxygen-releasing salt; a continuous organic phase; an emulsifying agent; and at least one polymer soluble in the organic phase and wherein the polymer comprises associative functional groups.
-Generally the associative functional groups are polar groups capable of entering into specific association with other associative groups.
Examples of associative functional group may be selected f rom a group of: ionmeric functional groups; functional groups which are I.
1 - 4 capable of protolytic reactions; and groups capable forming hydrogen bonds.
Examples of functional groups capab le of association through hydrogen bond formation may 5 be selected from the group consisting of hydroxyl, carboxyl and carboxamide functional groups.
Examples of ionomeric functional groups include those selected from the groups of salts of sulphonic and carboxylic acids such as metal and ammonium ion salts thereof, and quaternary ammonium salts.
Examples of groups capable of undergoing protolytic reaction include acid groups such as carboxylic, sulphonic and phosphoric acid groups and basic groups such as nitrogen-containing basic groups.
Examples of nitrogen-containing basic groups may be chosen from the groups of formula I I where R 1 and R 2 may be aryl, aralkyl,alkyl cycloalkyl or hydrogen and R 1 and R 2 may together form a 5 or 6 membered heteocyclic ring by a linking group of 4 or 5 members; and nitrogen containing heteroaromatic group such as pyridyl, picolinyl, quinolinyl, isoquinolinyl and quinoxalinyl groups and the salts thereof. Preferred acid and basic groups include the carboxylic acid group, sulphonic acid group and pyridyl group.
1 1 W Examples of the group of formula I 1 2 1 wherein R and R form a heterocycle include pyrazolinyl, pyrrolidinyl, peperazinyl and morpholinyl.
The said polymer may comprise more than one type of functional group. For example said polymer may comprise a plurality of different monomers capable of undergoing dipole-dipole interaction or protolytic reaction with one another.
Polymers suitable for use in preparation of compositions of the invention may be prepared by conventional polymerization techniques. Suitable polymers may be.prepared by addition polymerization reactions using at least one main monoethylenically unsaturated monomer and at least one associative monomer comprising a functional group chosen from associative functional groups as hereinbefore described, and groups capable of conversion to said associative functional groups.
Examples of main monoethylenically unsaturated monomers (hereinafter referred to as main monomer) may be selected from the group consisting of: alkenes, preferably comprising from 2 to 6.carbon atoms such-as ethylene and propylene; higher alkyl acrylates and methacrylates, in which the alkyl group contains from 4 to 18 carbon atoms, for example 2-ethyl hexylacrylate, stearyl methacrylate and lauryl 30 methacrylate; styrenes; alkyl styrenes in which the alkyl group contains from 1 to 12 carbon atoms, for example tertiarybutyl styrene; and vinyl esters of fatty acids, such as vinyl stearate.
Particularly preferred main monome'rs are lauryl methacrylate, styrene and tertbutylstyrene.
6 Examples of associative monomers may be chosen from the groups consisting of: vinyl substituted nitiogen containing heteroaromatic compounds such as vinyl pyridines, 5 vinylpicolines, vinyl quinolines, vinylisoquinolines and vinyl quinoxalines, hydroxy(C 1 to C 6)alkyl acrylates and methacrylates, such as hydroxyethyl acrylate and hydroxy propyl methacrylate; acrylic acid, methacrylic acid and their metal or amine salts; acrylamide; methacrylamide; acids selected from the group of styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamides, propane sulfonic acid, acrylic acid, methacrylic acid; and the metal salts of these acids; halide salts of quaternary ammonium compounds selected from the group consisting of dimethylanmonium methacrylate, diethylammonium. ethyl-methacrylate; diethylammonium ethyl -methacrylate; and precursors of these monomers. Particularly preferred associative monomers are methacrylic acid and metal and amine salts thereof, and vinylpyridines such as 2-vinylpyridine and 4- vinylpyridine. 25 Where the associative monomer comprises an associative group precursor, the precursor will be capable of conversion to an associative group following polymerization. For example, dienes such as norbornene and butadiene may be used in the preparations of polymers, and the monomeric units derived therefrom may be converted to sulfonic acids and thence to salts of sulfonic acids by procedures known to those in the art.
R 61 1 I- Emulsion polymerization is a particula::ly convenient teChnfque for preparation of copolyiiers for use in the present composition However, the method of preparation is.not narrowly critical and the skilled artisan will be well acquainted with a wide variety of techniques for preparation of suitable polymers.
The polymers can conveniently be obtained by.aqueous emulsion copolymerisation of the constituent monomers employing if necessary a minor proportion of a water-miscible organic co-solvent, such as acetone, in order to enhance the solubility of the monomer mixture in the aqueous continuous phase (the main monomers described above will inherently have very low solubilities in water and a measurable degree of solubility inthe continuous phase is necessary if the polymerisation is to proceed at an acceptable rate). The polymerisation is generally carried out at a temperature in the range 0 - 70 0 C. preferably 10 - 60 0 C. in an inert gas atmosphere and in the presence of a water-soluble free radical initiator system, such as ammonium persulphate or potassium persulphate in combination with sodium dithionite optimally, sodium sulphite, sodium thiosulphate or ascorbic acid. There may be added to the polymerisation mixture water-soluble surfactants such as sodium dodecylbenzenesulphonate, sodium dioctylsulpho succinate. sodium lauryl sulphate or salts of sulphated nonylphenol-ethylene oxide condensates.
The amount of initiator (or initiator combination) used may typically lie in the range 0.05% to 1%, and the amount of surfactant in the range 1% to 15%# based on the weight of the monomer mixture. The polymerisation may be effected by a "one-shot" procedure, in which all the monomer required is introduced intD the reaction mixture at onc(--, or by a "seed and feed" procedure in which a small proportion of the total monomer mixture is polymerised initially to form a "seed" polymer dispersion and the remainder of the monomer is then added gradually. Chain transfer agents, such as n-octyl mercaptan, dodecyl mercaptan or chloroform, may also be added during the course of the polymerisation, especially in the later stages when more than 75% of the monomer has been polymerised, in order to regulate the formation of the polymer.
Typically, the polymers are prepared using 0.001 to 30% associative monomer by weight of total monomer and preferably 0.01 to 20% w/w.
Typically, the total amount of said polymer will comprise in the range of 0.001 to 10% by weight of the emulsion composition.
However, we have found that particularly good resul_s are obtained by using in the range of 0.01 to 2% of the total emulsion composition.
Generally, the amount of polymer will be in the range of 0.001 to 20% w/w based on the organic phase and preferably in the range 0.1 to 10%.
However, higher or lower quantities may be used if desired, the amount of polymer being determined without undue experimentation based on the required properties of the emulsion.
As hereinbefore stated the polymer is soluble in the organic phase. Generally, the polymer will be soluble in the organic phase at the polymer/organic phase weight ratio to be used in the emulsion explosive.
4 Q 1 Hence the polymer will generally be soluble in the organic phase at 6 concentration of at least 0.001% w/w and preferablY at least 0.1% w/w.
One polymer particularly useful for the preparation of composition of the invention is a polymer of styrene, lauryl methacrylate and methacrylic acid.
An example of such a polymer may be derived by emulsion polymerization from a mixture of 10-80% w/w styrene,, 10-80% w/w lauryl methacrylate and 0.1-10 % w/w methacrylic acid. A particularly preferred composition comprises 50-60% lauryl methacrylate, 40-50% styrene and is 1-4% methacrylic acid.
As hereinbefore discussed, the emulsion explosive compositions of the present invention have advantages over conventional explosives, making them more suitable for loading in wet boreholes.
Without wishing to be bound by theory, we believe that the better wet borehole performance of the emulsions of the invention may be due to their elastic and cohesive nature.
Unlike conventional emulsion explosives which tend to break upwhen loaded into water, the emulsions of the present invention pass easily through water. The cohesive properties and resilience also make the emulsion explosive composition particularly useful in packaged products. Emulsion explosives of the invention typically have an elastic modulus in the range 100-1000 Pa at 200C. Typically, the viscosity is 35 in the range 120,000 to 800,,000 cp at 20 0 C.
The advantages of the emulsion explosive compositions axe parti.Cularly apparent when the polymer has an average weight molecular weight of at least 1 x 10 Preferably the polymer has an average molecular weight in the range 5 X 10 5 to 7 6 7 1 X 10, more preferably 1 x 10 to 1 x 10. This is particularly surprising as it was expected that the bulk of high molecular weight polymer molecules may disrupt the stability of an emulsion explosive.
For example, in the case of water-in-oil emulsion explosives, it is generally believed that droplets of oxidizer solution in an emulsion explosive are separated by bilayers of oil phase which are 5 to 20 nm thick, hence bulky polymer 6 molecules of molecular weight 1 x 10 and higher that are typically100 to 200 rim in diameter were not expected to be compatible with an emulsion explosive.
Suitable oxygen-releasing salts for use in the discontinuous phase component of the composition of the present invention include the alkali and alkaline earth metal nitrates, chlorates and perchlorates, ammonium nitrate, ammonium chlorate,, ammonium perchlorate and mixtures thereof. The preferred oxygen-releasing salts include ammonium nitrate, sodium nitrate and calcium nitrate. More preferably, the oxygen-releasing salt comprises ammonium nitrate or a mixture of ammonium nitrate and sodium or calcium nitrates.
Typically, the oxygen-releasing salt component of the compcsitions of the present invention comprises from 45 to 95% and preferably from 60 to 90% by weight of the total cl 4 C.
composition. In compositions wherein the oxygen-releasing salt comprises. a mixture of w.-monium nitrate and sodium nitrate, the preferred composition range for such a blend is from 5 to 80 parts of sodium nitrate for every 100 parts of ammonium nitrate. Therefore,, in the preferred compositions of the present invention, the oxygen-releasing salt component comprises from 45 to 90% by weight (of the total composition) ammonium nitrate from 0 to 40% by weight (of the total composition) sodium or calcium nitrates.
The discontinuous phase may be entirely devoid of water, in the.case of a melt-in-oil emulsion or may contain water in the case of a water-in-oil emulsion. In the latter case, the amount of water employed in the compositions of the present invention is typically in the range of from 1 to 30% by weight of- the total composition. Preferably the amount employed is from 5 to 25%, and more preferably from 6 to 20%, by weight of the total composition.
The organic phase component of the composition of the present invention comprises the continuous "oil" phase of the emulsion explosive and is a fuel. Preferably the organic phase is water-immiscible. Suitable organic fuels include aliphatic, alicyclic and aromatic compounds and mixtures thereof which are in the liquid state at the formulation temperature. Suitable organic fuels may be chosen from fuel oil, diesel oil, distillate, kerosene, naphtha, waxes, (eg. microcrystalline wax), paraffin oils, benzene, toluene, xylenes, asphaltic materials, 4 t polymeric oils such as the low molecular weight polymers of olefins,, animal oils,, fish oils, and other mineral. hydrocarbon or fatty oils. and mixtures thereof. Preferred organic fuels are liquid hydrocarbons generally referred to as petroleum distillates such as gasoline, kerosene, fuel oils andparaffin oils.
Typically, the organic fuel or continuous phase of the emulsion explosive composition of the present invention comprises from 2 to 15% by weight and preferably 3 to 10% by weight of the total composition.
The emulsifying agent component of the composition of the present invention may be chosen from the wide range of emulsifying agents known in the art for the preparation of-emulsion explosive compositions. Examples of such emulsifying agents include alcohol alkoxylates, phenol alkoxylates, poly(oxyalkylene) glycols, poly(oxyalkylene) fatty acid esters, amine alkoxylates, fatty acd esters of sorbitol and glycerol, fatty acid salts, sorbitan esters. poly(oxyalkylene) sorbitan esters. fatty amine alkoxylates, poly(oxyalkylene) glycol esters. fatty acid amides, fatty acid amide alkoxylates, fatty amines, quaternary anines, alkyloxazolines, alkenyloxazolines, imidazolines, alkylsulfonates, alkanoylsulfonates, allkylsulfosuccinates, alkylphosphates, alkenylphosphates, phosphate esters, lecithin, copolymers of poly(oxyalkylene) glycols and- poly(12-hydroxystearic acid) polyalkylene succinic acid and derivatives thereof, and mixtures thereof. Among the preferred emulsifying agents are the 2-alkyl- A 1 -I p and 2-alkenyl-4,4'-bis (hydroxymethyl) oxazoline, the fatty acid esters of sorbitol. lecithin, copolymers of poly(oxyalkylene) glycols and poly(12-hydroxystearic acid). and mixtures thereof, and particularly sorbitan mono-oleate., sorbitan sesquioleate, 2- oleyl- 4.41-bis (hydroxymethyl) oxazolines mixture of sorbitan sesquioleate, lecithin and a copolymer of poly(oxyalkylene glycol and poly (12-hydroxystearic acid), polyisobutylene succinic acid and derivatives thereof, and mixtures thereof.
Typically, the emulsifying agent component of the composition of the present invention comprises up to 5% by weight of the total composition. Higher proportions of the emulsifying agent may be used and may serve As a supplemental fuel for the composition but in general it is not necessary to add more than 5% by weight of emulsifying agent to achieve the desired effect. one of the advantages of the compositions of the present invention is that stable emulsions can be formed using relatively low levels of emulsifying agent, andfor reasons of economy it is preferable to keep to amount of emulsifying agent in the range from 0.1 to 2.0% by weight of the total composition.
If desired. other optional fuel materials, hereinafter referred to as secondary fuels, may be incorporated into the compositions of the,present invention in addition to the water-immiscible organic fuel phase. Examples of such secondary fuels include finely- divided solids. and water-miscible organic liquids which can be used to partially replace water as a e solvent for the oxygen-releasing salts or to extend the aqueous solvent for the oxygen-releasing salts. Examples of solid secondary fuels include finely divided materials such as: sulfur; aluminum; and carbonaceous materials such as.gilsonite, comminuted coke or charcoal, carbon black, resin acids such as abietic acid, sugars such as glucose or dextrose and other vegetable products such as starch, nut meal, grain meal and wood pulp. Examples of water-miscible organic liquids include alcohols such as methanol, glycols such as ethylene glycol, amides such as formamide, and amines such as methylamine, Typically, the optional secondary fuel component of the compositions of the present invention comprise from 0 to 30% by weight of the total composition. It lies within the invention-that there may also be incorporated.into the emulsion explosive compositions hereinbefore described other substances or mixtures of substances which are oxygen-releasing salts or which are themselves suitable as explosive materials. As a typical example of such a modified emulsion explosive composition, reference is made to compositions wherein there is added to and mixed with an emulsion explosive composition as hereinbefore described up to 90% w/w of a solid oxidizing salt such as ammonium nitrate or an explosive composition comprising a mixture of a solid oxidizing salt such as ammonium nitrate and fuel oil and commonly referred to by those skilled in the art as "Anfo". The compositions Z 1 - is- - Q; Cl of "Anfo" are well known and have been described at length in the literature relating to explosives.
Mixtures of solid ammonium nitrate or "Anfo" and the emulsion explosive of the invention are suized to use in wet bore holes and water containing bore holes, Mixtures of 'Anfo" (or solid ammonium nitrate) and conventional emulsion explosive generally give poor performance when loaded into bore holes containing water. The mixture tends to break up on impact with water and this tends to result in the dissolution of the ammonium nitrate. In contrast, mixtures of "Anfo" with the emulsion explosive of the present invention may be used in bore holes containing water without significant loss of performance.
Accordingly there is provided an explosive composition comprising a emulsion as hereinbefore described and up to 90% w/w of a composition comprising an ammonium nitrate fuel oil mixture.
Typically, the proportion of ammonium nitrate or "Anfo" in such compositions will be in the range 20-80% wlw.
It also lies within the invention to have as a further explosive component of the composition well known explosive materials comprisi ng one or more of. for example.
trinitrotoluene. nitroglycerine or pentaerythritol tetranitrate.
Accordingly there is provided an explosive composition comprising as a first component an emulsion explosive- composition as hereinbefore described and as a second component an amount of material which is an oxidizing salt or which is in Its own right an explosive material.
1 Generally it is not necessary to use thickening agents in the discontinuous phase ofi the present composition as the amount of polymor may be varied according to the properties desired. However, if desired, the discontinuous phase of the compositions of the present invention may comprise thickgning agents which optionally may be cross-linked. The thickening agents, when used in the compositions of the present invention. are suitably polymeric materials, especially gum materials typified by the galactomannan gums such as locust bean gum or guar gum or derivatives thereof such as hydroxypropyl guar.gum. Other useful but less preferred gums are the so-called biopolymeric gums such as the heteropolysaccharides prepared by the microbial transformation of carbohydrate material. for example the treatment of glucose with a plant pathogen of the genus Xanthomonas typified by Xanthomonas campestris.
Typically, where used, the optional thickening agent component of the compositions of the present invention comprises from 0 to 2% by weight of the total composition.
As indicated above, when used in the compositions of the present invention, the thickening agent optionally may be cross-linked. It is convenient f or this purpose to use conventional cross-linking agents such as zinc chromate or dichromate either as a separate entity or as a component of a conventional redox system such as a mixture of potassium dichromate and potassium antimony tartrate.
Typically, the optional cross-linking agent component of the compositions of the present invention comprises from 0 to 0.5% and preferably from 0 to 0.1% by weight of the total composition.
:I Qi c W The emulsion explosive compositions of the present invention may additionally comprise a discontinuous gaseous component.
The methods of incorporating a gaseous component and the enhancedsensitivity of emulsion explosive compositions comprising such gaseous components have been previously reported. Typically, where used the said gaseous component will be present in an amount required to reduce the density of the composition to with in the range 0.8 to 1.4 gm/cc.
The gaseous component may, for example, be incorporated into the composition of the present invention as fine gas bubbles dispersed through the composition, as hollow particles which are often referred to as microballoons or microspheres, as porous particles, or as mixtures thereof.
A discontinuous phase of fine gas bubbles may be incorporated into the compositions of the present invention by mechanical agitation, injection or bubbl-ing the gas through the composition, or by chemical generation of the gas in situ.
Suitable chemicals for the in situ generation of gas bubbles include peroxides, such as hydrogen peroxide, peroxide nitrates, such as sodium nitrite, nitros-oamines, such as N, N'-dinitrosopentamethylene tetramine, alkali metal borohydrides, such as sodium borohyride, and carbonatesi such as sodium carbonate. Catalytic agents such as thiocyanate or thiourea may be used to accelerate the decomposition of a nitrite gassing agent. Suitable small hollow particles include small hollow microspheres of 1 is - glass or resinous materials, such as phenol- f orma idehyde and urea - f ormaldehyde. Suitable porous materials include expanded minerals, such as perlite.
Where used, the gaseous agent is preferably added during cooling. after preparation of the emulsion, and typically comprises 0.05 to 50% by volume of the total emulsion explosive composition at ambient temperature and pressure. More preferably, where used, the gaseous component is present in the range 10 to 30% by volume of the emulsion explosive composition and preferably the bubble size of the occluded gas is below 200 um. More preferably,at least 50% of the gas component will be in the form of bubbles or microspheres of 20 to 90 um internal diameter.
The pH of the emulsion explosive compositions of the present invention is not narrowly critical. However. in general the pH is between 0 and 8, preferably between 0.5 and 6.
- The emulsion explosive composition of the present invention may be prepared by a number of methods.
The polymer may be mixed with the oil phase before preparation of the emulsion. Alternatively, it may be more convenient to prepare the emulsion composition of the invention by mixing of a composition comprising at least one polymer with an emulsion explosive composition comprisipg: a discontinuous phase comprising at least one oxygen releasing salt; a continuous organic phase; and an emulsifying agent.
ti v k.
0 1 If desired. the polymermay be added using both methods, that is adding the polymer to the oil ph,ase before preparation of the emulsion and also to the emulsion once prepared---.
When a composition comprising the polymer is added to the prepared emulsionr the polymer may, for example,, be in the form of a solid such As a powder. a solution in a suitable solvent such as a hydrocarbon solvent or as an aqueous dispersion.
- Aqueous dispersions of polymer may be prepared by methods well known to those ikilled in the art. For example, such a dispersion may be formed by mixing a fine powder of polymer with an aqueous composition in the presence of a surfactant.
In a particularly preferred embodiment of the process of the invention we therefore provide a process comprising mixing an aqueous dispersion of said polymer with an explosive com-position comprising (a) an emulsion explosive comprising a discontinuous aqueous phase comprising an oxygen releasing salt, a continuous organic phase and an emulsifying agent and optionally (b) solid ammonium nitrate or a mixture of solid ammonium nitrate and fuel oil.
Generally. the composition is mixed for a period following additive of the polymer so as to facilitate dispersion within the emulsion explosive.
One preferred method of preparing suitable polymers Involves an emulsion polymerization technique which produces a latex of the product (i.e.i an aqueous dispersion of small polymer particles). We have found it to be particularly convenient in many instances to use such composition in preparation of the emulsion explosive composition of present invention 20 In an embodiment of the invention there is thus provided a process for the preparation of an emulsion explosive composition, the process comprising:
dissolving said oxygen-releasing salt in water at a temperature above the fudge.point of the salt solution, preferably at a temperature in the range of 25 to 110 0 C, to give an aqueous salt solution; optionally mixing said polymer with said water immiscible organic phase;.
combining said salt solution, said water-immiscible organic phase, said water-in-oil emulsifying agent. Mixing until the emulsion is uniform and if said polymer has not been
added, adding a said polymer.
The invention is now demonstrated by but in no way limited to the following examples in which all proportions are on a weight basis unless otherwise specified.
Example 1
A high molecular weight (average molecular weight in excess of 1 x 10 6) copolymer of tert-butyl styrene and 4-vinyl pyridine (97:3 by weight) was prepared by emulsion polymerization.
A i Emulsion Polymerization Method - (preparation of polymer latex) The surfactant AEROSOL OT (AEROSOL is a trade mark) (available from American Cyanamid), (0.3 g) and initiator ammonium persulfate,, (0.10 g) were dissolved in acetone'(10.0 g) and water (50.0 g) the monomers (tert- bUtyl styrene, and 4-vinylpyridine; 20 g) were added, and the mixture emulsified by stirring. The mixture was flushed with nitrogen for ten minutes, sealed, and the temperature raised to 50 0 C and maintained at-that temperature for 24 hours, with gentle stirring. The resulting product was a latex of polymer. The polymer was found to have an average molular weight of approx. 1.19 x 106 g mol- 1. Powder To prepare the polymer as a powder a small amount of latex (10 g) was added dropwise to a large excess of methanol (100 g)i and the polymer isolated by filtration. The polymer was dried in air and ground to.a fine powder.
Examples 2 and 3 and Comparative Example A These examples demonstrate the effect on the viscosity of an emulsion explosive composition of the addition of a polymer powder prepared according to Example 1.
Example 2
A diesel solution for use as the organic phase was prepared by dissolving copolymer powder prepared according to Example 1 In diesel oil at a temperature of 800C to give a concentration of 1% w/w of diesel solution.
7 An emulsion composition was then prepared using the following components Parts w/w Ammonium nitrate (chemically pure) Calcium nitrate distilled water diesel solution (1% w/w copolymer) emulsifier - sorbitan monooleate The method used was as follows:
84.06 75.02 25.30 13.02 2.60 The ammonium nitrate and -calcium nitrate were dissolved in'the water at a temperature of about 80 0 C to give the oxidizer phase. The oxidizer phase was combined with a mixture of the diesel solution and emulsifier and the resulting mixture was stirred rapidly to form an emulsion.
Exam-ple 3 The procedure of Example 2 was repeated except that the diesel solution was prepared using 2% w/w of copolymer prepared according to Example 1.
Comparative Example A The procedure of Example 2 was repeated except that copolymer was not used in the organic phase.
The viscosities of the emulsions of Examples 2,, 3 and Comparative Example A were measured at room temperature (200C) with a BROOKFIELD instrument using spindle #7 on speed 5 rpm and the results are shown in the Table 1 below.
1 1 'I 1 e TABLE 1
COP.Olymer viscosity concentration (cp) (% w/w of organic phase) Comparative Example A/ Example 2 Example 3 1 2 Exami:)1e 4 and Comarative ExamDle B 48,000 75j200 122,400 This example dem9nstrates Q' method of preparation of an emulsion of the invention by addition of a polymer powder to a preformed emulsion. An emulsion having the following components was prepared according to Example 2, the organic phase not containing dissolved polymer., Prilled ammonium nitrate ("Nitropril") Calcium nitrate 75.02 Distilled water 25.30 Distillate oil 13.02 Emulsifier 84.06 2.60 The emulsifier wad a 1:1 molar condensate of poly(isobutylene) succinic anhydride and ethanolamine and had an average molecular weight in the range of 800 to 1200.
A sample of the composition was set aside for comparison (Comparative Example B). NITROPRIL is a trade mark.
- 24 Example 4
To a sample of the prepared emdlsion (200 g) at 80 0 C was added polymer powder (0.24 g, 2% w/w on dieselY prepared according to Example 1. rhe composition was heated at 80 0 for four hours with occasional stirring, then allowed to cool. The composition was stored at room temperature overnight.
TABLE 2
Copolymer Viscosity % w/w diesel (cp) Comparative Example B 0 Example 4
2% 91,400 244,800 Examples 5 to 7 and Comparative Examples C and D The following examples demonstrate the highly viscoelastic nature of the explosives of the invention. Comparative Example C An emulsion composition having the following components was prepared according to Example 2, the organic phase being f ree of polymer.
Parts w/w Chemically pure ammonium nitrate 84.06 Calcium nitrate 75.02 Distilled water 25.30 Distillate oil 13.02 Emulsifier 2.60 The emulsifier was a 1:1 molor condensate of poly(isobutylene)succinic anhydride and ethanolamine and had an average molecular weight In the range 800 to 1200.
1 In Q t z is 1 v 1 A, sample of emulsion was set aside for comparison and the bulk of the amulsion was used in preparation of the following compositions. ' Exam21es 5 to 7 1 To three samples of emulsion prepared above were added polymer latexes prepared according to the procedure of example 1 using the monomer compositions shown in Table 3 below (numbers in brackets show the proportion of each monomer based on the total mdnomer composition). The average molecular weight of polymers used in Examples 6 and 7 was measured and found to be 1.23 x 16 6 g mol -1 for example 6 6 -1 and 0.82 x 10 g mol for example'7.
In each case the appropriate latex was added to the emulsion to give a polymer concentration of approx. 6% w1w on the organic phase and the latex was thoroughly mixed with the emulsion.
Comparative Example D An emulsion explosive composition was prepared using the above procedure except that the polymer added in Examples 5 to was'omitted.
T he viscosity of the emulsion compositions was measured at room temperature using a BROOKFIELD instrument spindle #7 at speed. S.
The yield stress and elastic modulus of the compositions was measured using a B01MIN Rheometer.
1 1 A - 26 TABLE 3
Example Main Monomer Associative Viscosity Yield Stress Elastic Elongation W/W) Monomer (20 0 C) CP (20 0 C) (Pa) Modulus (cm) (% W/W) (20 0) 5. (PA) CEA 21,600 0.26 9.2 0.2 TBS ( 97%) VP (3%) 232,000 87 841 A 6 TBS ( 97%) MA (3%) 440,000 36 11;6 15 7 STY C47%) + MA (3%) 616,800 20 LMA ( 50%) 4 CED TBS STY LMA is VP MA TBS (100%) tert-butylstyrene Styrene Lauryl methacrylate 4-Vinyl pyridine Methacrylic acid 104,600 .v 1 A 1 it k.
27 - Elongation i:; a comparative measure of viscoelasticity of the emulsion compositions and was determined using the following method:- is A spatula having a'l cm, width blade was inserted into a bulk sample of emulsion at an angle of about 45 0 to the surface to a depth of about 1 cm. The spatula was raised vertically from the emulsion at a rate of about 1 cm'S-1 until the thread of emulsion between the spatula and bulk sample broke or became Iess than 1 mm in thickness. The height of the spatula above the bulk emulsion was measured at this stage.
Compositions of the invention typically have an elongation in the range 2 to 30 cm (preferably 4 to 20 cm).
Examples 8 to 10 and Comparative Example E These examples demonstrate the advantage of using explosives of the present invention when loading into wet boreholes.
Comparative Example E An emulsion explosive prepared according to Comparative Example C (7.5 kg) was mixed with "ANFO" (ammonium nitrate fuel oil mixture) (7.5 kg). The mixture was gassed using an in-situ nitrite gassing agent.
Example 8
An emulsion explosive prepared according to Comparative Example C was (7. 5 kg) was throughly mixed with polymer latex (37.5 g latex containing 9.38 g of polymer) to give a polymer concentration of 0.13% w/w on total emulsion. This emulsion mixture was combined and mixed with 7.5 kg of "ANFOu and the composition was gassed using an in-situ nitrite gassing agent.
Example 9
An emulsion/ANFO mix was prepared according to Example 8 except that 75 g of latex containing 18.75 g polymer was added.
The polymer latex used in Examples 8 and 9 was prepared according to the procedure of Example 1 using the monomers styrene (47%), lauryl methacrylate (50%) and methacrylic acid (3%) [percentages based on w1w of total monomerl 1^ 17 4 I 1 W k Y i> Example 10
An emulc;ion/ANFO mix was prepared according to Example 8 except that the quantity ofLatex was adjusted to provide-a polymer concentration of 0.5% w/w on total emulsion prior to addition of ANFO.
The performance of the explosives prepared in Examples 8, 9 and Comparative Example E on loading into wet boreholes was 10 tested using the following procedure:- The explosive sample was dropped 3 metres into water 2 metres deep. The explosive was allowed to settle and was then removed from the water. After 2 hours the total detonation energy of the explosive was tested.
Results of the tests are shown in Table 4.
TABLE 4
Example 'No. Tests Polymer Energy conc. % w/w W Kg-1 of emulsion CE E 2 0.38 + 8 3 0.13 1.09 + 9 2 0.26 1.12 + 2 0.50 1.50 The above results clearly show the 25 superiority in performance of the compositions of the present invention over corresponding compositions devoid of polymer.
i
Claims (1)
1. An emulsion explosive composition comprising a discontinuous phase comprising at least one oxygen-releasing. salt; a continuous organic phase; an emulsifying agent; and at least one polymer soluble In the organic phase and wherein the polymer comprises associative functional groups.
2. An emulsion explosive composition according to claim 1 wherein said associative functional groups.are selected from the group consisting of ionomeric functional groups, functional groups which are capable of protolytic reactions and groups capable of forming hydrogen bonds.
3. An emulsion explosive composition according to claim 1 or claim 2 wherein said associative functional groups are selected from one or more of the members of the group consisting of carboxylic acid group, sulphonic acid group, phosphoric acid group, nitrogen containing basic groups of formula I ' -N I,' R 1 ",-% R 2 I wherein R1 and R2 are independently selected from aryl, aralkyl, alkyl, cycloalkyl and hydrogen and R 1 and R 2 may together form a 5 or 6 membered heterocycle by a linking group of 4 or 5 constituent members; and nitrogen containing heteroaromatic groups.
i 1 1 W f j q t, 4. - An emulsion explosive according to any one of claims 1 to 3 wherein thb polymer is a copolymer of at least One monomer selected from the group consisting of C to C alkenes, (C to 2 6 4 C 19 alkyl) acrylates, styrenes, (C 1 to C 18 alkyl)styrenes, and vinyl esters of fatty acids with at least one comonomer selected from the group consisting of vinyl substituted nitrogen containing heteromatic compounds, hydroxy(C 1 to C6 alkyl) acrylates, hydroxy(C 1 to C 6 alkyl)methacrylates, acrylic acid, methacrylic acid, the metal and amine salts of acrylic and methacrylic acid, styrene sulphonic acid, vinyl sulfonic acid, 2-acrylamidopropane sulphonic acid, and the halid-salts of quaternary ammonium compounds selected from the group consisting'of dime thylammonium methacrylate and diethylammonium, ethylmethacrylate.
5. An' emulsion explosive composition according to claim 4 wherein said polymer is a copolymer of at least one monomer selected from the group consisting of styrene, (C 1 to C 6 alkyl)styrene, (C 4 to C 18 alkyl)acrylates and (C 4 to C 18 a_lkyl)methacrylates with at least one comonomer selected from the group consisting of vinyl pyridines, acrylic acid and methacrylic acid.
6.. An emulsion explosive according to claim 4 or claim 5 wherein said polymer is a copolymer of 10 to 86oby weight styrene,, 10-80% by weight lauryl methacrylate and 0.1 to 10% by weight methacrylic acid.
7. An emulsion explosive according to claim 4 or claim 5 wherein said polymer comprises In the range of 0.01 to 20% w/w of said comonomer.
1 1 1 1; 3 1 i 8. An emulsion explosive according to any one of claims 1 to 3 inclusive wherein the average molecular weight of said polymer is in the range of from 5 x 10 5 to 1,x 10 7.
g. An emulsion explosive according to any one of claims 1 to 3 wherein the average molecular weight is in the range of from 1 x 10 6 7 to 1 X 10 10. An emulsion explosive composition according to any one of claim 1 to 9 comprising in the range of from 0.01 to 10% by weight of said polymer.
11. An emulsion explo;ive composition according to claim 10 comprising in the range of from 0.01 to 2% by weight of said polymer.
12. An emulsion explosive according to.claim 1 wherein said discontinuous phase comprises an aqueous solution of said oxygen-releasing salt.
13. An emulsion explosive according to any one of claims 1 to 12 whereinthe oxygen -releasing salt component of said emulsion explosive comprises one or more of the salts selected from the group of ammonium.nitrate, sodium nitrate and calcium nitrate.
14., An emulsion explosive according to any one of claim 1 to 13 wherein the organic phase comprises a fuel selected from the group consisting of fuel oilt diesel oil. distillate, kerosene, naphtha. waxesi paraffin oils, benzene toluene, xylenes, asphattic materials, polymers of olefins, animal oils and fish oils.
1 1 i 1 . 1 1.1 15. An emulsion explosive according to any one of claim 1 to 14 wherein the emulsify.Lnr agent component comprises at least one emulsifying agent selected from the group consisting of alcohol alkoXYlates, phenol alkoxylates, poly(oxyalkylene)glycols, (polyoxyalkylene)fatty,acid e. sters,, amine alkoxylates, fatty acid esters of sorbitol and glycerol, fatty acid salts, sorbitan esters., poly(oxyjalkylehe)sorbitan esters, fatty amine alkoxylates, poly(oxyalkylene) glycol esters., fatty acid amides. fatty acid amide alkoxylates. fatty amines. quaternary aminds,, alkoxazolines, alkenyloxazolines, imidazolines, alkyl sulfonates, alkanoylsulfonates, allylsulfosuccinates alkylphosphates, alkenylphosphates, phosphate esters. lecithin, polymers of poly(oxyalkylene) glycols and pol-y(12-hydroxystearic acid), polyisobutylene succinic acid and derivatives thereof.
16. An emulsion explosive composition according to any one of claims 1 to 15 comprising 60 to 90% w/w of oxygen-releasing salt. 5 to 25% w/w water. 3 to 10% w/w of organic fuel,, and TA to 2% w/w of emulsifying agent.
17. An explosive composition comprising an emulsion explosive composition according to any one of claims 1 to 16 inclusive and in the range of from 20 to 80% wiw the total composition of either solid ammonium nitrate or a solid anmonium nitratelfuel oil mixture.
18. A process for preparing an emulsion -explosive according to any one of claims 1 to 17 comprising mixing a composition comprising said polymer with an explosive.composition comprising (a) an emulsion explosive comprising a.. discontinuous aqueous phase comprising an oxygen releasing salt, a continuous organic phase and an emulsifying agent and optionally (b) solid ammonium nitrate or a mixture of solid ammonium nitrate and fuel oil.
19. A process according to claim 18 wherein the composition comprising said polymer is an aqueous dispersion 9f said polymer.
2o. A process for preparing an emulsion explosive composition according to any one claim 1 to 17 the process comprising dissolving said oxygen releasing salt in water at a temperature in the range of from 25 to 110 0 C to form an aqueous salt solution; combining said salt solution said organic phase, said emulsifying agent and optionally said polymer; mixing until a unif orm emulsion is formed; and if said polymer. has not been added mixing said polymer with said emulsion.
1 21. An emulsion explosive composition substantially as described herein with reference to any one of Examples 2 to 10 inclusive.
22. A process for preparing an emulsion explosive substantially as described herein with reference to any one of Examples 2-10 inclusive.
Published 1988 at The Patent Office, State House, 66'71 High Holborn, Lopdon WC1R 4TP. Further copies may be Obtained from The Patent Office, Wes Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St MarY CraY, Kent- Con, 1/87.
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GB2224501A (en) * | 1988-11-07 | 1990-05-09 | Canadian Ind | Aromatic hydrocarbon-based emulsion explosive composition. |
WO2017103635A1 (en) * | 2015-12-16 | 2017-06-22 | Rhodia Poliamida E Especialidades Ltda | Emulsifier system for explosive emulsions |
WO2020118367A1 (en) * | 2018-12-11 | 2020-06-18 | Michael Cechanski | A water-based explosive |
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GB9003613D0 (en) * | 1990-02-16 | 1990-04-11 | Explosives Tech Eti | Method of reducing the overloading of a borehole and explosive composition used therefor |
ES2052453B1 (en) * | 1992-12-29 | 1995-02-16 | Espanola Explosivos | EXPLOSIVE IN WATER-IN-OIL EMULSION. |
FR2701942B1 (en) * | 1993-02-24 | 1995-05-19 | Prod Ind Cfpi Franc | Internal additive and process for the preparation of certain crystallized forms of ammonium nitrate and industrial applications thereof. |
FR2701860A1 (en) * | 1993-02-24 | 1994-09-02 | Francais Prod Ind Cfpi | Internal additive and process for the preparation of some crystalline forms of ammonium nitrate and industrial applications thereof |
US5401341A (en) * | 1993-04-14 | 1995-03-28 | The Lubrizol Corporation | Cross-linked emulsion explosive composition |
GB9511701D0 (en) * | 1995-06-09 | 1995-08-02 | Burwood Corp The Ltd | Composition |
WO1997042141A1 (en) * | 1996-05-08 | 1997-11-13 | Rhone-Poulenc Inc. | Waterproof oxidizing salt/emulsion blend explosives |
AUPO679297A0 (en) * | 1997-05-15 | 1997-06-05 | Ici Australia Operations Proprietary Limited | Rheology modification and modifiers |
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GB9914400D0 (en) * | 1999-06-22 | 1999-08-18 | Ciba Spec Chem Water Treat Ltd | Oil based drilling fluid |
AU2002239707B2 (en) * | 2000-11-02 | 2007-01-11 | The Lubrizol Corporation | Thickened water in oil emulsion composition |
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WO2014019011A1 (en) * | 2011-11-14 | 2014-02-06 | Croda Singapore Pte Limited | Emulsion composition |
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- 1988-01-06 NZ NZ223084A patent/NZ223084A/en unknown
- 1988-01-07 ZA ZA8898A patent/ZA8898B/en unknown
- 1988-01-08 CA CA000556163A patent/CA1330395C/en not_active Expired - Fee Related
- 1988-01-11 ZW ZW4/88A patent/ZW488A1/en unknown
- 1988-01-15 EP EP88300342A patent/EP0276934A3/en not_active Withdrawn
- 1988-01-15 CN CN88100209A patent/CN1043755C/en not_active Expired - Fee Related
- 1988-01-15 GB GB8800926A patent/GB2200626B/en not_active Expired - Lifetime
- 1988-01-29 NO NO880393A patent/NO880393L/en unknown
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GB2224501A (en) * | 1988-11-07 | 1990-05-09 | Canadian Ind | Aromatic hydrocarbon-based emulsion explosive composition. |
WO2017103635A1 (en) * | 2015-12-16 | 2017-06-22 | Rhodia Poliamida E Especialidades Ltda | Emulsifier system for explosive emulsions |
WO2020118367A1 (en) * | 2018-12-11 | 2020-06-18 | Michael Cechanski | A water-based explosive |
US11565981B2 (en) | 2018-12-11 | 2023-01-31 | STT-Surfex Technology & Trading Pty Ltd | Water-based explosive |
Also Published As
Publication number | Publication date |
---|---|
NO880393D0 (en) | 1988-01-29 |
ZA8898B (en) | 1989-02-22 |
GB8800926D0 (en) | 1988-02-17 |
EP0276934A2 (en) | 1988-08-03 |
NO880393L (en) | 1988-08-01 |
CN1043755C (en) | 1999-06-23 |
CA1330395C (en) | 1994-06-28 |
CN88100209A (en) | 1988-08-10 |
ZW488A1 (en) | 1989-08-16 |
GB2200626B (en) | 1990-05-02 |
EP0276934A3 (en) | 1989-07-26 |
NZ223084A (en) | 1991-01-29 |
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Legal Events
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PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940115 |