US3533762A - Hydrocarbon fuels containing polyvalent metal hydrocarbyl pyrophosphate salts and amine adducts thereof - Google Patents
Hydrocarbon fuels containing polyvalent metal hydrocarbyl pyrophosphate salts and amine adducts thereof Download PDFInfo
- Publication number
- US3533762A US3533762A US668984A US3533762DA US3533762A US 3533762 A US3533762 A US 3533762A US 668984 A US668984 A US 668984A US 3533762D A US3533762D A US 3533762DA US 3533762 A US3533762 A US 3533762A
- Authority
- US
- United States
- Prior art keywords
- pyrophosphate
- mono
- monoacid
- metal
- hydrocarbyl
- 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
- -1 hydrocarbyl pyrophosphate salts Chemical class 0.000 title description 90
- 229910052751 metal Inorganic materials 0.000 title description 64
- 239000002184 metal Substances 0.000 title description 64
- 150000001412 amines Chemical class 0.000 title description 51
- 239000004215 Carbon black (E152) Substances 0.000 title description 16
- 229930195733 hydrocarbon Natural products 0.000 title description 16
- 150000002430 hydrocarbons Chemical class 0.000 title description 14
- 239000000446 fuel Substances 0.000 title description 9
- 235000011180 diphosphates Nutrition 0.000 description 193
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 160
- 125000001183 hydrocarbyl group Chemical group 0.000 description 43
- 239000000203 mixture Substances 0.000 description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 32
- 239000010936 titanium Substances 0.000 description 32
- 229910052719 titanium Inorganic materials 0.000 description 32
- 239000003502 gasoline Substances 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 239000002253 acid Substances 0.000 description 19
- 239000000654 additive Substances 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 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 description 10
- 125000000962 organic group Chemical group 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229910052735 hafnium Inorganic materials 0.000 description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 5
- 150000002440 hydroxy compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 5
- 125000000552 p-cresyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1O*)C([H])([H])[H] 0.000 description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 5
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000002704 decyl 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])* 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000003254 gasoline additive Substances 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229910052762 osmium Inorganic materials 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 125000003717 m-cresyl group Chemical group [H]C1=C([H])C(O*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 125000002960 margaryl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([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])[H] 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005645 linoleyl group Chemical group 0.000 description 2
- 239000003879 lubricant additive Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- TUFJPPAQOXUHRI-KTKRTIGZSA-N n'-[(z)-octadec-9-enyl]propane-1,3-diamine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCN TUFJPPAQOXUHRI-KTKRTIGZSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000002465 nonacosyl group Chemical group [H]C([*])([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])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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical compound C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GOLAKLHPPDDLST-HZJYTTRNSA-N (9z,12z)-octadeca-9,12-dien-1-amine Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCN GOLAKLHPPDDLST-HZJYTTRNSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
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- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- MGWAGIQQTULHGU-UHFFFAOYSA-O 2-ethylbutylazanium Chemical compound CCC(CC)C[NH3+] MGWAGIQQTULHGU-UHFFFAOYSA-O 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- AWGOHBMCPWUVAL-UHFFFAOYSA-N 2-propyldecan-1-amine Chemical compound CCCCCCCCC(CN)CCC AWGOHBMCPWUVAL-UHFFFAOYSA-N 0.000 description 1
- KOQDZLJGORGLNW-UHFFFAOYSA-N 5-phenylcyclohexa-2,4-diene-1,1-diamine Chemical compound C1=CC(N)(N)CC(C=2C=CC=CC=2)=C1 KOQDZLJGORGLNW-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- LJQFHDUFUVMPSP-UHFFFAOYSA-N 8-methylnonan-1-amine Chemical compound CC(C)CCCCCCCN LJQFHDUFUVMPSP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101150009724 CYBA gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 239000004440 Isodecyl alcohol Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([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])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])[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-O benzylaminium Chemical compound [NH3+]CC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-O 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- BUOSLGZEBFSUDD-BGPZCGNYSA-N bis[(1s,3s,4r,5r)-4-methoxycarbonyl-8-methyl-8-azabicyclo[3.2.1]octan-3-yl] 2,4-diphenylcyclobutane-1,3-dicarboxylate Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1C(C=2C=CC=CC=2)C(C(=O)O[C@@H]2[C@@H]([C@H]3CC[C@H](N3C)C2)C(=O)OC)C1C1=CC=CC=C1 BUOSLGZEBFSUDD-BGPZCGNYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
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- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-O dodecylazanium Chemical compound CCCCCCCCCCCC[NH3+] JRBPAEWTRLWTQC-UHFFFAOYSA-O 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002818 heptacosyl group Chemical group [H]C([*])([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])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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([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])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])[H] 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000002819 montanyl group Chemical group [H]C([*])([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])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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- UMKZVPUCHAKXME-UHFFFAOYSA-N n,n-dimethylaniline;n-methylaniline Chemical compound CNC1=CC=CC=C1.CN(C)C1=CC=CC=C1 UMKZVPUCHAKXME-UHFFFAOYSA-N 0.000 description 1
- SKLXFEQHEBALKG-UHFFFAOYSA-N n-hexyloctan-1-amine Chemical compound CCCCCCCCNCCCCCC SKLXFEQHEBALKG-UHFFFAOYSA-N 0.000 description 1
- LBTAXVIGKZQJMU-UHFFFAOYSA-N n-propyldecan-1-amine Chemical compound CCCCCCCCCCNCCC LBTAXVIGKZQJMU-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000000486 o-cresyl group Chemical group [H]C1=C([H])C(O*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([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])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-O propan-1-aminium Chemical compound CCC[NH3+] WGYKZJWCGVVSQN-UHFFFAOYSA-O 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- DMTMQVNOOBTJCV-UHFFFAOYSA-N tetra(propan-2-yl)plumbane Chemical compound CC(C)[Pb](C(C)C)(C(C)C)C(C)C DMTMQVNOOBTJCV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-O tridecylazanium Chemical compound CCCCCCCCCCCCC[NH3+] ABVVEAHYODGCLZ-UHFFFAOYSA-O 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/098—Esters of polyphosphoric acids or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2658—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) amine salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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- C—CHEMISTRY; METALLURGY
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- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C10M2223/04—Phosphate esters
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/02—Esters of silicic acids
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/08—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having metal-to-carbon bonds
- C10M2227/082—Pb compounds
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- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
Definitions
- a fuel composition comprising a liquid hydrocarbon fuel and a minor proportion of a compound having the wherein M is a polyvalent metal; n is an integer of from 0 to 4; n is an integer of from 0 to 2; the sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R" and R are hydrocarbyl groups having from 1 to about 30 carbon atoms and also amine adducts of said polyvalent metal compound wherein n is an integer of from 1 to 4 and n is an integer from 0 t0 1.
- This invention relates to novel metal organo pyrophosphates, and more particularly to metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates), and to hydrocarbon compositions containing such compounds.
- the invention relates to novel amine adducts of the metal (acid hydrocarbyl pyrophosphates) and to hydrocarbon compositions containing such amine adducts.
- liquid hydrocarbon products such as fuels and lubricating oils contain additives for improving their performance characteristics.
- additives are employed for improving various performance characteristics such as to assist in maintaining cleanliness of the carburetor, to resist surface ignition, and to inhibit rust and carburetor icing.
- Lubricating compositions contain various additives such as those for improving viscosity index and lubricity. The additives vary in effectiveness and it is often necessary to use a number of additives in a single composition.
- metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates) are beneficial for imparting carburetor and intake system detergency, rust suppression, reduction in octane requirement increase, resistance to surface ignition of liquid hydrocarbon fuels, and friction and wear reduction in mineral oil lubricants. It has been further found that reaction products of amines and these metal (acid hydrocarbyl pyrophosphates) are especially advantageous for these purposes. It is to be understood that the term metal as used herein is intended to include silicon, which is normally considered to be a non-metal.
- the metal organo pyrophosphates of the present invention may be generally represented by the formula:
- M is a polyvalent metal
- n is an integer of from 0 to 4
- n is an integer from O to 2 and the sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4
- R, R, R and R are hydrocarbyl groups having from 1 to about 30 carbon atoms.
- M in the above Formula I represents a polyvalent element having a valence of 2 to 4 and selected from the group consisting of manganese, chromium, molybdenum, copper, gold and silicon and the metals of Groups II, IV, and VIII of the Periodic Table.
- a suitable Periodic Table is shown on pp. 392393 of the Handbook of Chemistry and Physics, 35th ed. (1953).
- the metal organo pyrophosphates can have 0, l, 2, 3, or 4 acid groups (OH) per metal atom, but preferably contain at least one acid group.
- Particularly desirable compounds are the acid hydrocarbyl pyrophosphates of Group IV-B metals, namely titanium, zirconium and hafnium.
- R, R, R" and R may represent identical or different hydrocarbyl groups. While any hydrocarbyl groups having between 1 and about 30 carbon atoms and soluble to the required extent in gasoline may be used, the aliphatic hydrocarbyl groups, particularly branched-chain aliphatic hydrocarbyl groups of from 6 to about 22 carbon atoms are preferred. Such groups are generally more soluble in gasoline than other hydrocarbyl groups, thereby facilitating the use of the novel compounds as gasoline additives. Furthermore, the total number of carbon atoms per molecule of metal organo pyrophosphate can vary from about 2 to about 240, but preferably ranges from about 12 to about carbon atoms.
- Typical R, R, R and R groups may include, for instance, alkyl, alkenyl, aryl, alkylaryl, arylalkyl or alicyclic hydrocarbon radicals.
- suitable hydrocarbyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, 2,2,4- trimethylpentyl, Z-methylpentyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, heptyl, Z-methylhexyl, 3-methylhexyl, 3,3- dimethylpentyl, octyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, Z-ethylhexyl, Z-ethylbutyl, nonyl, decyl, undecyl,
- dodecyl tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,
- heptacosyl heptacosyl, octacosyl, nonacosyl, tricontyl, phenyl, naphthyl, benzyl, o-cresyl, p-cresyl, m-cresyl, dodecylphenyl, octaphenyl, ethylphenyl, diphenyl, pentadecyl, fl-pentylethyl, omegaphenylhexyl, cyclohexyl, cyclobutyl, cyclopentyl, butenyl, octenyl, 2,3-dimethylpentenyl, 2-ethylhexenyl, linoleyl, oleyl, etc.
- the componuds of Formula I above may be prepared, for instance, by reacting 1 mole of phosphorous pentoxide with 2 moles of a hydroxy compound, or a mixture of hydroxy compounds, in which the hydroxy group is attached to a hydrocarbyl radical of 1 to about 30 carbon atoms to form a dihydrocarbyl diacid pyrophosphate.
- the dihydrocarbyl diacid pyrophosphate so formed may then be reacted with a suitable amount of a halide of the desired metal dispersed or dissolved in an organic solvent.
- the metal tetrahalides may be reacted With dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2, 1:3 and 1:4 to form, respectively, metal (IV) bis [di(hydrocarbyl) pyrophosphate]; metal (IV) di [monoacid di (hydrocarbyl) pyrophosphate] mono [di (hydrocarbyl) pyrophosphate] and metal (IV) tetra [monoacid di (hydrocarbyl pyrophosphate].
- metal trihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2 and 1:3 to form, respectively, metal (III) mono [monoacid di (hydrocarbyl) pyrophosphate] mono [di (hydrocarbyl) pyrophosphate]; and metal (III) tri [monoacid di (hydrocarbyl) pyrophosphate).
- metal dihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:1 and 1:2 to form respectively, metal (II) mono [di (hydrocarbyl) pyrophosphate] and metal (II) bis [monoacid di (hydrocarbyl) pyrophosphate].
- the metal organo pyrophosphates of Formula I may be prepared by reacting together, in a single step, the metal halide, phosphorous pentoxide and the hydroxy compound in the same relative proportions as given above.
- the reactants may be combined in the proportions of 8 moles of hydroxy compound to 4 moles of phosphorous pentoxide to 1 mole of the metal tetrahalide.
- the reactants may be simply mixed together at a temperature from about 10 C. to about 120 C., in an inert solvent.
- the inert solvent is preferably a hydrocarbon such as an aliphatic or an aromatic hydrocarbon, e.g. benzene, toluene, heptane, octane, hexane, etc.
- the inert organic solvent need not be a hydrocarbon, but instead any inert organic solvent such as an ether or halogenated hydrocarbon, e.g. ethyl ether, tetrahydrofuran, carbon tetrachloride, chlorobenzene, etc., can be employed.
- identity of the hydrocarbyl groups present in the compounds represented by Formula I is determined by the identity of the hydrocarbyl groups present in the dihydrocarbyl diacid pyrophosphates or hydroxy compounds used as reactants.
- reaction mixtures resulting from the above-noted preparatory procedures may or may not contain minor quantities of additional compounds, not all of which have been entirely identified, in addition to the metal organo pyrophosphates represented by Formula I. Regardless of their identity, these extraneous compounds do not impair the effectiveness of the metal organo pyrophosphate compounds of the present invention as gasoline and lubricating oil additives, and, therefore, need not be separated therefrom. Furthermore, although generally desirable, it is not necessary to separate the compounds of the present invention from the solvent in which they are prepared prior to use.
- the metal organo pyrophosphates provided by the present invention are useful as gasoline and lubricant additives.
- particularly desirable metal organo pyrophosphates of the present invention are those which contain at least one acid group (OH) per metal atom, i.e. the metal [acid hydrocarbyl pyrophosphates].
- These metal [acid hydrocarbyl pyrophosphate] may be reacted with an organic amine to form amine adducts having exceptional properties as additives in liquid hydrocarbon compositions.
- the novel amine adducts of this invention are useful as lubricant additives, anticorrosion additives, detergents, anti-stall additives, and to reduce octane requirement increase.
- the amine adducts can be prepared by simply neutralizing the free acid group or groups of the metal [acid hydrocarbyl pyrophosphates]. Formation of the adduct takes place at a temperature between about 15 C. and 60 C. Preferably each of the acid groups of the pyrophosphate is neutralized with basic nitrogen of the amine reactant, although this is not essential. Neutralization can be accomplished by simply adding the amine to the metal [acid hydrocarbyl pyrophosphate] to raise the pH thereof to at least 6 or 7. Also, the neutralization can be accomplished by adding a stoichiometric quantity of the amine to the metal [acid hydrocarbyl pyrophosphate].
- the amine employed in preparing the amine adducts of the present invention can be any salt-forming amine having from 1 to about 30 carbon atoms.
- primary, secondary, tertiary, aliphatic, aromatic or alicyclic amines may be used.
- the cyclic amines can be carbocyclic or heterocyclic.
- the amine can also be a mono-, di-, tri-, or other polyamine.
- the amine may be a B-amine and may contain various substituent groups such as hydroxyl groups.
- Preferred amines useful in the practice of the invention are aliphatic, monoor polyamines containing 6 to 22 carbon atoms arranged in an alkyl or alkenyl chain.
- Suitable amines for preparing the amine adducts of the metal organo orthophosphates and pyrophosphates there can be mentioned: methylamine, ethylamine, diethylamine, propylamine, tripropylamine, isopropylamine, butylarnine, isobutylamine, hexylamine, 2- ethylhexylamine, octylamine, dodecylamine, 2-propyldecylamine, pentadecylamine, tetradecylamine, octadecylamine, 6-butyloctadecylamine, eicosamine, 6,6-dimethyli propyldecylamine, 8-hexyl-10-isobutyloctadecylamine, dioctylamine, tribenzylamine, hexadecylamine, decylamine, N-hexyloct
- the amines can also contain various 'substituent groups such as hydroxyl groups, e.g. alkanol amines, such as diethylanolamine, 3,3-hydroxydipropanolamine, isopropanolamine, and the like.
- 3- Amine such as octyl-fi-amine, can also be used.
- Mixtures of amines may also be used to prepare the amine adducts of the present invention. Fore instance, cocoamine, which is a mixture of amines prepared from coconut oil fatty acids and contains predominantly n-dodecylamine, and soya amine, which is a mixture of amines containing 16 to 18 carbon atoms, are especially useful.
- the amine adducts provided by the invention may be represented by the following formula:
- M is metal having a valence of 2 to 4 and particularly an element selected from the group consisting of manganese, chromium, molybdenum, copper, gold and silicon and the metals of Groups II, IV and VIII of the Periodic Table
- each of R, R, R" and R' are hydrocarbyl groups having from 1 to about 30 carbon atoms; 11 is an integer from 1 to 4; n is an integer from 0 to 1;
- n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and A is an amine containing from 1 to about 30 carbon atoms.
- Particularly preferred amine adducts for use in hydrocarbon compositions are those represented by Formula 11 above, wherein M is a Group IV-B metal (e.g. titanium), each R, R, R" and R' is a branched-chain hydrocarbyl radical having from 6 to 22 carbon atoms, (e.g. 2-ethylhexyl), n is 0, n is 4, and A is an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group, which may be alkyl or alkenyl.
- M is a Group IV-B metal (e.g. titanium)
- each R, R, R" and R' is a branched-chain hydrocarbyl radical having from 6 to 22 carbon atoms, (e.g. 2-ethylhexyl)
- n e.g. 2-ethylhexyl
- n e.g. 2-ethylhexyl
- n e.g
- the compositions of the present invention When used as gasoline additives, the compositions of the present invention, namely metal [hydrocarbyl pyrophosphates], metal [acid hydrocarbyl pyrophosphates] and amine salts of metal [acid hydrocarbyl pyrophosphate], are used in an amount between 10 and about 500 parts per million parts of gasoline by weight, preferably from 20 to about 250 p.p.m. and particularly from about 25 to 200 ppm.
- the gasoline composition can be either leaded or unleaded, although leaded gasoline is preferred.
- a gasoline composition is provided which comprises a major portion of leaded hydrocarbon base fuel boiling in the gasoline range and containing between 10 and 500 ppm.
- amine salts represented by Formula II above and particularly the salts obtained by reacting an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group with a metal ('IV-B) [monoacid di (branched-chain C to C hydrocarbyl) pyrophosphate].
- 'IV-B metal
- gasoline, hydrocarbon base boiling in a gasoline range and similar terms refer to a petroleum fraction boiling in the gasoline range (e.g. between 50 F. and about 450 F).
- leaded gasoline refers to gasoline to which there has been added a small amount, such as between 0.1 and about 6.0 ml. per gallon of metallo organic anti-knock compound such as tetraethyl lead (TEL), tetramethyl lead (TML), tetraisopropyl lead, etc.
- the gasoline compositions of this invention can also include, for instance, light hydrocarbon lubricating oils having viscosities at of between about 50 and about 200 Saybolt Universal seconds (SSU) and viscosity indexes of between about 30 and about 130. Such oils may be present in suitable amounts such as between about 0.1 and about 1.0% by weight of the gasoline composition.
- SSU Saybolt Universal seconds
- the additives provided by the present invention improve the boundary lubrication properties of the composition.
- lubricants containing the additives of this invention inhibit the stick-slip sliding tendencies that are often found in automatic transmission clutching surfaces.
- the amount of additive can vary over a wide range such as from 0.01% to about 3%, by weight, of the lubricant base material.
- the amine salts of the metal are particularly desirable lubricating oil additives.
- a wide variety of both mineral oil and synthetic base stock including mixtures of the same, can be used.
- Suitable mineral oil base materials include 100 and 200 neutral oils, light and heavy intermediate mineral oils, bright stock as well as combinations of the foregoing.
- a synthetic base material it can be that of diesters, polyesters, silicones, silicates, fluorocarbons, phosphates and the like.
- the additives of the present invention may also be used in other hydrocarbon compositions.
- they may be used in minor quantities of diesel fuel oil compositions to impart anti-rust activity, etc. to the composition.
- Titanium tetra [monoacid di (Z-ethylhexyl) pyrophosphate] is obtained by reacting phosphorous pentoxide, titanium tetrachloride and 2-ethyl-1-hexanol as shown below:
- the solution is homogeneous.
- the reactants are then heated under reflux at 88 C. to 100 C, and when evolution of hydrogen chloride moderates, dry air is passed through the solution to displace the acid gas more rapidly and to accelerate the reaction.
- evolution of hydrogen chloride ceases, as revealed by Congo red indicator, the n-heptane and any unreacted 2-ethyl-l-hexanol are removed by distillation in vacuo.
- the final temperature of the light yellow residual product in the reaction vessel is 125 C. at 6 mm.
- the product is very viscous and weighs 175 g. which is 96% of theory based on the metal halide. Upon analysis, the product is found to contain 2.98% titanium and 15.36% phosphorous, theory being 2.89% titanium and 14.99% phosphorous.
- EXAMPLE 2 In the manner described in Example 1, a mixture of 0.4 mole (56.8 g.) of P and 0.1 mole (23.3 g.) of ZrCl in 500 ml. of anhydrous n-heptane is reacted with 0.84 mole (133 g.) of isodecyl alcohol to form zirconium tetra [monacid di (isodecyl) pyrophosphate], which is represented by the following formula:
- R is isodecyl
- EXAMPLE 3 P 0 in the amount of 28.4 g. (0.2 mole), and GeC1 in the amount of 21.4 g. (0.1 mole), are dispersed in 500 ml. of toluene.
- a blend consisting of 33.2 g. (0.21 mole) of isodecanol and 43.3 g. (0.21 mole) of octylphenol, is added to the toluene dispersion in a manner described in Example 1.
- liberation of hydrogen chloride is completed upon heating the reaction solution at 90 C-100" C,. the solvent is removed by distillation at reduced pressure.
- the hydrocarbyl garmanium pyrophosphate can be represented by the following formula:
- EXAMPLE 4 A mixture of 0.2 mole (56.8 g.) of P 0 and 0.1 mole (27.2 g.) of cadmium bromide is finely dispersed by vigorous stirring in 400 ml. of a reaction medium consisting of equal volumes of n-heptane and toluene. Then 0.42 mole (55 g) of iso-octanol is added in the manner described in Example 1. The reactants are heated under reflux at 98 C.-105 C. until liberation of by-product HBr is completed. The solvent is removed by distillation at lower pressure to obtain as the residue cadmium bis [monoacid di (iso-octyl) pyrophosphate] as shown below:
- EXAMPLE 6 The titanium tetra [monoacid di (2-ethylhexyl) pyrophosphate] product of Example 1 is mixed with various amines to obtain products having a pH of 7. The reactants are thoroughly mixed at room temperature while protected from carbon dioxide in a vessel blanketed with air. The amounts of amines employed to obtain adducts of pH 7 are given in the following tabulation.
- EXAMPLE 8 A measure of the boundary lubricating ability of each of the amine adducts of titanium tetra [monoacid di (2- ethylhexyl) pyrophosphate] of Example 7 in lubricating oil, and consequently their eifectiveness in reducing wear, is obtained by means of a special apparatus used to access the boundary properties of lubricants in the 50 F.-350 F. range. The measurement is reported as Normal Lubricity Indices, NLI, and values of 200 and above are considered very good.
- One part by weight of the various amine adducts is blended with 99 parts by weight of a neutral oil having a viscosity of 100 SUS at 100 F.
- the NLI values are set forth in the following tabulation.
- Friction modifier Normal lubricity index None 100 Titanium tetra [cocoammonium di (2-ethylhexyl) pyrophosphate] 257 Titanium tetra [soya ammonium di (2-ethylhexyl) pyrophosphate] 315 Titanium tetra [oleylammonium di (2-ethy1- hexyl) pyrophosphate] 370 Amine adduct of N oleyl 1,3 propylene diamine and titanium tetra [monoacid di (2- ethylhexyl) pyrophosphate] 386
- the following example illustrates the use of the amine adducts of Example 7 as additives in gasoline compositions.
- EXAMPLE 9 Gasoline compositions are prepared by employing each of the previously-noted amine adducts of titanium tetra [monoacid di (Z-ethylhexyl) pyrophosphate] in an amount of 50 ppm. in a base gasoline having the following characteristics.
- ASTM rust tests are run at 75 F. with each of the additive-containing gasoline compositions using distilled water. Each of the compositions passed the test.
- a fuel composition comprising a major proportion of a liquid hydrocarbon fuel and a minor proportion sufficient to improve performance characteristics of an adduct of an amine containing from 1 to about 30 carbon atoms with a compound having the formula:
- R wherein M is a polyvalent metal; n is an integer of from 1 to 4; n is an integer of from 0 to 1; the sum of it plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R and R" are hydrocarbyl groups having from 1 to about 30 carbon atoms.
- a gasoline composition comprising a major proportion of gasoline and dissolved therein from about 10 to about 500 ppm. of an adduct of an amine containing from 1 to about 30 carbon atoms with a compound having the formula:
- M is a polyvalent metal
- n is an integer of from 1 to 4
- n is an integer of from 0 to 1
- the sum of n plus 211 is equal to the valence of the metal and is an integer from 2 to 4
- R, R, R are hydrocarbyl groups having from 1 to about 30 carbon atoms.
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Description
United States Patent Mar. 6, 1964. Divided and this application Aug. 17,
'1967, Ser. No. 668,984
Int. Cl. Ci 1/26 US. CI. 4468 6 Claims ABSTRACT OF THE DISCLOSURE A fuel composition comprising a liquid hydrocarbon fuel and a minor proportion of a compound having the wherein M is a polyvalent metal; n is an integer of from 0 to 4; n is an integer of from 0 to 2; the sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R" and R are hydrocarbyl groups having from 1 to about 30 carbon atoms and also amine adducts of said polyvalent metal compound wherein n is an integer of from 1 to 4 and n is an integer from 0 t0 1.
CROSS-REFERENCE TO RELATED APPLICATION This application is a division of application Ser. No. 459,089 filed May 26, 1965, now Pat. No. 3,354,189, which is in turn a continuation-in-part of my copending application Ser. No. 350,113 filed Mar. 6, 1964 now Pat. No. 3,401,184.
This invention relates to novel metal organo pyrophosphates, and more particularly to metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates), and to hydrocarbon compositions containing such compounds. In other aspects, the invention relates to novel amine adducts of the metal (acid hydrocarbyl pyrophosphates) and to hydrocarbon compositions containing such amine adducts.
Normally liquid hydrocarbon products such as fuels and lubricating oils contain additives for improving their performance characteristics. Thus, in fuels such as gasoline additives are employed for improving various performance characteristics such as to assist in maintaining cleanliness of the carburetor, to resist surface ignition, and to inhibit rust and carburetor icing. Lubricating compositions contain various additives such as those for improving viscosity index and lubricity. The additives vary in effectiveness and it is often necessary to use a number of additives in a single composition.
It has now been found that metal (hydrocarbyl pyrophosphates) and metal (acid hydrocarbyl pyrophosphates) are beneficial for imparting carburetor and intake system detergency, rust suppression, reduction in octane requirement increase, resistance to surface ignition of liquid hydrocarbon fuels, and friction and wear reduction in mineral oil lubricants. It has been further found that reaction products of amines and these metal (acid hydrocarbyl pyrophosphates) are especially advantageous for these purposes. It is to be understood that the term metal as used herein is intended to include silicon, which is normally considered to be a non-metal.
The metal organo pyrophosphates of the present invention may be generally represented by the formula:
wherein M is a polyvalent metal; n is an integer of from 0 to 4; n is an integer from O to 2 and the sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R and R are hydrocarbyl groups having from 1 to about 30 carbon atoms.
M in the above Formula I represents a polyvalent element having a valence of 2 to 4 and selected from the group consisting of manganese, chromium, molybdenum, copper, gold and silicon and the metals of Groups II, IV, and VIII of the Periodic Table. A suitable Periodic Table is shown on pp. 392393 of the Handbook of Chemistry and Physics, 35th ed. (1953). It can be seen from Formula I that the metal organo pyrophosphates can have 0, l, 2, 3, or 4 acid groups (OH) per metal atom, but preferably contain at least one acid group. Particularly desirable compounds are the acid hydrocarbyl pyrophosphates of Group IV-B metals, namely titanium, zirconium and hafnium. Compounds of this type are the metal (IV-B) di [monoacid di (hydrocarbyl) pyrophosphate] mono [di (hydrocarbyl) pyrophosphate], wherein n is 2 and n is l; and the metal (IV-B) tetra [monoacid di (hydrocarbyl) pyrophosphate], wherein n is 4 and n is 0.
In Formula I above R, R, R" and R may represent identical or different hydrocarbyl groups. While any hydrocarbyl groups having between 1 and about 30 carbon atoms and soluble to the required extent in gasoline may be used, the aliphatic hydrocarbyl groups, particularly branched-chain aliphatic hydrocarbyl groups of from 6 to about 22 carbon atoms are preferred. Such groups are generally more soluble in gasoline than other hydrocarbyl groups, thereby facilitating the use of the novel compounds as gasoline additives. Furthermore, the total number of carbon atoms per molecule of metal organo pyrophosphate can vary from about 2 to about 240, but preferably ranges from about 12 to about carbon atoms.
Typical R, R, R and R groups may include, for instance, alkyl, alkenyl, aryl, alkylaryl, arylalkyl or alicyclic hydrocarbon radicals. Exemplary of suitable hydrocarbyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, 2,2,4- trimethylpentyl, Z-methylpentyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, heptyl, Z-methylhexyl, 3-methylhexyl, 3,3- dimethylpentyl, octyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, Z-ethylhexyl, Z-ethylbutyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,
heptacosyl, octacosyl, nonacosyl, tricontyl, phenyl, naphthyl, benzyl, o-cresyl, p-cresyl, m-cresyl, dodecylphenyl, octaphenyl, ethylphenyl, diphenyl, pentadecyl, fl-pentylethyl, omegaphenylhexyl, cyclohexyl, cyclobutyl, cyclopentyl, butenyl, octenyl, 2,3-dimethylpentenyl, 2-ethylhexenyl, linoleyl, oleyl, etc.
The componuds of Formula I above may be prepared, for instance, by reacting 1 mole of phosphorous pentoxide with 2 moles of a hydroxy compound, or a mixture of hydroxy compounds, in which the hydroxy group is attached to a hydrocarbyl radical of 1 to about 30 carbon atoms to form a dihydrocarbyl diacid pyrophosphate. The dihydrocarbyl diacid pyrophosphate so formed may then be reacted with a suitable amount of a halide of the desired metal dispersed or dissolved in an organic solvent. For example, the metal tetrahalides may be reacted With dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2, 1:3 and 1:4 to form, respectively, metal (IV) bis [di(hydrocarbyl) pyrophosphate]; metal (IV) di [monoacid di (hydrocarbyl) pyrophosphate] mono [di (hydrocarbyl) pyrophosphate] and metal (IV) tetra [monoacid di (hydrocarbyl pyrophosphate]. Likewise, metal trihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:2 and 1:3 to form, respectively, metal (III) mono [monoacid di (hydrocarbyl) pyrophosphate] mono [di (hydrocarbyl) pyrophosphate]; and metal (III) tri [monoacid di (hydrocarbyl) pyrophosphate). Additionally, metal dihalides may be reacted with dihydrocarbyl diacid pyrophosphates in molar ratios of 1:1 and 1:2 to form respectively, metal (II) mono [di (hydrocarbyl) pyrophosphate] and metal (II) bis [monoacid di (hydrocarbyl) pyrophosphate].
Advantageously, the metal organo pyrophosphates of Formula I may be prepared by reacting together, in a single step, the metal halide, phosphorous pentoxide and the hydroxy compound in the same relative proportions as given above. For example, if it is desired to prepare a metal (IV) tetra [monoacid di (hydrocarbyl) pyrophosphate], the reactants may be combined in the proportions of 8 moles of hydroxy compound to 4 moles of phosphorous pentoxide to 1 mole of the metal tetrahalide. In a process of this type, the reactants may be simply mixed together at a temperature from about 10 C. to about 120 C., in an inert solvent. The inert solvent is preferably a hydrocarbon such as an aliphatic or an aromatic hydrocarbon, e.g. benzene, toluene, heptane, octane, hexane, etc. However, the inert organic solvent need not be a hydrocarbon, but instead any inert organic solvent such as an ether or halogenated hydrocarbon, e.g. ethyl ether, tetrahydrofuran, carbon tetrachloride, chlorobenzene, etc., can be employed.
In either method of preparation, identity of the hydrocarbyl groups present in the compounds represented by Formula I is determined by the identity of the hydrocarbyl groups present in the dihydrocarbyl diacid pyrophosphates or hydroxy compounds used as reactants.
The reaction mixtures resulting from the above-noted preparatory procedures may or may not contain minor quantities of additional compounds, not all of which have been entirely identified, in addition to the metal organo pyrophosphates represented by Formula I. Regardless of their identity, these extraneous compounds do not impair the effectiveness of the metal organo pyrophosphate compounds of the present invention as gasoline and lubricating oil additives, and, therefore, need not be separated therefrom. Furthermore, although generally desirable, it is not necessary to separate the compounds of the present invention from the solvent in which they are prepared prior to use.
Illustrative of the metal (II) organo pyrophosphates represented generically by Formula I, there can be mentioned.
calcium mono [di (propyl) pyrophosphate] beryllium bis [monoacid di (isooctyl) pyrophosphate] magnesium bis [monoacid di (isobutyl) pyrophosphate] barium bis [monoacid di (2,4-dimethylhexyl) pyrophosphate] zinc bis [monoacid di (2-ethy1hexyl) pyrophosphatel cadmium mono [mono (4-octylphenyl) mono (octyl) pyrophosphate] palladium mono. [di (Z-ethylhexyl) pyrophosphate] platinum mono [mono (Z-ethylhexyl) mono (3-methylhexyl) pyrophosphate] chromium bis [monoacid di (2,3-dimethylhexyl) pyrophosphate] osmium bis [monoacid di (2,4-dimethylhexyl) pyrophosphate] osmium bis [monoacid di (cyclohexyl) pyrophosphate] strontium mono [di (2-ethylhexenyl) pyrophosphate].
Illustrative of the metal (III) organo pyrophosphates represented generically by Formula I, there can be mentioned:
gold tri [monoacid di (Z-ethylhexyl) pyrophosphate] gold mono [monoacid di (ethyl) pyrophosphate] mono [di (isohexyl) pyrophosphate] iron tri [monoacid mono (ethylphenyl) mono (dodecylphenyl) pyrophosphate iron tri [monoacid di (3,3 dimethylpentyl) pyrophosphate] iron mono [monoacid di (eicosyl) pyrophosphate] mono [di (eicosyl) pyrophosphate] iron mono [monoacid di (2-ethylhexyl) pyrophosphate] mono [di (2-ethy1hexyl) pyrophosphate] iron mono [monoacid di (triconyl) pyrophosphate] mono [di (triaconyl) pyrophosphate] nickel mono [monoacid di (nonyl) pyrophosphate] mono [di (nonyl) pyrophosphate] nickel tri [monoacid di (isodecyl) pyrophosphate] nickel mono [monoacid mono (heptyl) mono (hexyl) pyrophosphate] mono [mono (heptyl) mono (hexyl) pyrophosphate] nickel mono [monoacid di (Z-ethylhexyl) pyrophosphate] mono [mono (2-ethylhexyl) mono (isooctyl) pyrophosphate] cobalt tri [monoacid di (2,2,4-trimethylpentyl) pyrophosphate] cobalt tri [monoacid di (diphenyl) pyrophosphate] cobalt mono [monoacid di (cyclopentyl) pyrophosphate] mono [di (cyclopentyl) pyrophosphate] cobalt mono [monoacid mono (pentyl) mono (tridecyl) pyrophosphate] mono [di (pentyl) pyrophosphate] cobalt mono [monoacid mono (hexyl) mono (triaconyl) pyrophosphate] mono [mono (hexyl) mono (triaconyl) pyrophosphate] ruthenium tri [monoacid di (2,2 dimethylbutyl) pyrophosphate] ruthenium tri [monoacid di (phenyl) pyrophosphate] ruthenium mono [monoacid di (Z-ethylhexyl) pyrophosphate] mono [di (2-ethylhexyl) pyrophosphate] osmium mono [monoacid di (dodecyl) pyrophosphate] mono [di (dodecyl) pyrophosphate] rhodium mono [monoacid di (tetracosyl) pyrophosphate] mono [di (ethyl) pyrophosphate] rhodium tri [monoacid di (benzyl) pyrophosphate] iridium mono [monoacid di (undecyl) pyrophosphate] mono [di (undecyl) pyrophosphate] iridium tri [monoacid di (isononylene) pyrophosphate] molybdenum mono [monoacid di (2,4-dimethylhexyl) pyrophosphate] mono [di (2,4 dimethylhexyl) pyrophosphate] molybdenum tri [monoacid di (heptadecyl) pyrophosphate] chromium tri [monoacid di (naphthyl) pyrophosphate] chromium mono [monoacid di (isoheptyl) pyrophosphate] mono [di (isoheptyl) pyrophosphate] chromium mono [monoacid di (ethylphenyl) pyrophosphate] mono [di (ethylphenyl) pyrophosphate] titanium tri [monoacid di (isodecyl) pyrophosphate] titanium mono [monoacid di (isodecyl) pyrophosphate] mono [di (isodecyl) pyrophosphate] titanium tri [monoacid di (2-ethylhexyl) pyrophosphate] titanium mono [monoacid di (Z-ethylhexyl) pyrophosphate] mono [di (2 ethylhexyl) pyrophosphatel titanium tri [monoacid di (hexadecyl) pyrophosphate] titanium mono [monoacid mono (propyl) mono (butyl) pyrophosphate] mono [mono (amyl) mono (hexyl) pyrophosphate] Illustrative of the metal (IV organo pyrophosphate represented generically by Formula I, there can be mentioned:
manganese bis [di (dodecylphenyl) pyrophosphate] manganese tetra [monoacid di (2-3-thylbutyl) pyrophosphate] molybdenum tetra [monoacid di (linoleyl) pyrophosphate] molybdenum bis [di (nonacosyl) pyrophosphate] titanium bis [di (2-ethylhexyl) pyrophosphate] titanium tetra [monoacid di (2 ethylhexyl) pyrophosphate] titanium di [monoacid di (Z-ethylhexyl) pyrophosphate] mono [di (2-ethylhexyl) pyrophosphate] titanium tetra [monoacid mono (hexyl) mono (heptyl) pyrophosphate] titanium tetra [monoacid di (isodecyl) pyrophosphate] titanium bis [di (isodecyl) pyrophosphate] hafnium bis [di (tertbutyl) pyrophosphate] hafnium di [monoacid di (p-cresyl) pyrophosphate] mono [di (p-cresyl) pyrophosphate] hafnium tetra [monoacid di (2-ethylhexyl) pyrophosphate] zirconium di [monoacid di (Z-methylhexyl) pyrophosphate] mono [di (methylhexyl) pyrophosphate] zirconium bis [di (docosyl) pyrophosphate] zirconium tetra [monoacid mono (2-ethylhexyl) mono (benzyl) pyrophosphate] ruthenium tetra [monoacid di (butyl) pyrophosphate] platinum bis [di (ethyl) pyrophosphate] platinum tetra [monoacid di (decyl) pyrophosphate] osmium di [monoacid di (beta-phenylethyl)' pyrophosphate] mono [di (hexyl) pyrophosphate] iridium di [monoacid di (hencosyl) pyrophosphate] mono [di (hencosyl) pyrophosphate] tin di [monoacid di (cyclohexyl) pyrophosphate] mono [di (hexyl) pyrophosphate] germanium di [monoacid di (m-cresyl) pyrophosphate] mono [di (m-cresyl) pyrophosphate] tin bis [di (2, B-dimethylpentenyl) pyrophosphate] lead his [di (Z-ethylhexyl) pyrophosphate] silicon tetra [monoacid di (Z-ethylbutyl) pyrophosphate].
The metal organo pyrophosphates provided by the present invention are useful as gasoline and lubricant additives. As previously noted, particularly desirable metal organo pyrophosphates of the present invention are those which contain at least one acid group (OH) per metal atom, i.e. the metal [acid hydrocarbyl pyrophosphates]. These metal [acid hydrocarbyl pyrophosphate] may be reacted with an organic amine to form amine adducts having exceptional properties as additives in liquid hydrocarbon compositions. Thus, the novel amine adducts of this invention are useful as lubricant additives, anticorrosion additives, detergents, anti-stall additives, and to reduce octane requirement increase.
The amine adducts can be prepared by simply neutralizing the free acid group or groups of the metal [acid hydrocarbyl pyrophosphates]. Formation of the adduct takes place at a temperature between about 15 C. and 60 C. Preferably each of the acid groups of the pyrophosphate is neutralized with basic nitrogen of the amine reactant, although this is not essential. Neutralization can be accomplished by simply adding the amine to the metal [acid hydrocarbyl pyrophosphate] to raise the pH thereof to at least 6 or 7. Also, the neutralization can be accomplished by adding a stoichiometric quantity of the amine to the metal [acid hydrocarbyl pyrophosphate].
The amine employed in preparing the amine adducts of the present invention can be any salt-forming amine having from 1 to about 30 carbon atoms. Thus, primary, secondary, tertiary, aliphatic, aromatic or alicyclic amines may be used. The cyclic amines can be carbocyclic or heterocyclic. The amine can also be a mono-, di-, tri-, or other polyamine. Furthermore, the amine may be a B-amine and may contain various substituent groups such as hydroxyl groups. Preferred amines useful in the practice of the invention are aliphatic, monoor polyamines containing 6 to 22 carbon atoms arranged in an alkyl or alkenyl chain.
Illustrative of suitable amines for preparing the amine adducts of the metal organo orthophosphates and pyrophosphates there can be mentioned: methylamine, ethylamine, diethylamine, propylamine, tripropylamine, isopropylamine, butylarnine, isobutylamine, hexylamine, 2- ethylhexylamine, octylamine, dodecylamine, 2-propyldecylamine, pentadecylamine, tetradecylamine, octadecylamine, 6-butyloctadecylamine, eicosamine, 6,6-dimethyli propyldecylamine, 8-hexyl-10-isobutyloctadecylamine, dioctylamine, tribenzylamine, hexadecylamine, decylamine, N-hexyloctylamine, N,N-dirnethyldodecylamine, oleylamine, linoleylamine, 1,IO-decamethylenediamine, ethylenediamine, 1,2 propylenediamine, 1,12 dodecamethylenediamine, tetramethylenediamine, 1,6 hexamethylenediamine, tetramethylenediamine, 1,6 hexamethylenediamine, triethylenetetramine, 1,2 phenylenediamine, benzylamine, 3,3 biphenyldiamine, biphenylamine, l-naphthylamine, l-fiuorenamine, aniline, N-methylaniline N,N-dimethylaniline, 2,3 phenylenediamine, piperazine, piperidine, furfurylamine, N cyclohexylheptylamine, and the like. The amines can also contain various 'substituent groups such as hydroxyl groups, e.g. alkanol amines, such as diethylanolamine, 3,3-hydroxydipropanolamine, isopropanolamine, and the like. 3- Amine, such as octyl-fi-amine, can also be used. Mixtures of amines may also be used to prepare the amine adducts of the present invention. Fore instance, cocoamine, which is a mixture of amines prepared from coconut oil fatty acids and contains predominantly n-dodecylamine, and soya amine, which is a mixture of amines containing 16 to 18 carbon atoms, are especially useful.
The amine adducts provided by the invention may be represented by the following formula:
wherein M is metal having a valence of 2 to 4 and particularly an element selected from the group consisting of manganese, chromium, molybdenum, copper, gold and silicon and the metals of Groups II, IV and VIII of the Periodic Table each of R, R, R" and R' are hydrocarbyl groups having from 1 to about 30 carbon atoms; 11 is an integer from 1 to 4; n is an integer from 0 to 1; the
sum of n plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and A is an amine containing from 1 to about 30 carbon atoms.
Representative of such amine addusts are:
beryllium bis [mono (cocoammonium) di (isooctyl) pyrophosphate] mangnesium bis [mono (oleylammonium) di (isoamyl) pyrophosphate] zinc bis [mono (propylammonium) di (2-ethy1hexyl) pyrophosphate] nickel bis [mono (cocoammonium) di (Z-ethylhexyl) pyrophosphate] iron bis [mono (dodecylammonium) mono (dodecyl) mono (heptadecyl) pyrophosphate] manganese bis [mono (linoleylammonium) mono (penyl) mono (Z-methylpentyl) pyrophosphate] chromium bis [mono (heptadecylammonium) di (2,3-
dimethylhexyl) pyrophosphate] gold tri [mono (decadienylammonium) di (2-ethylhexyl) pyrophosphate] iron tri [mono (cyclohexylammonium) mono (ethylphenyl) mono (dodecylphenyl) pyrophosphate] nickel mono [mono (nonylammonium) di (nonyl) pyrophosphate] mono [di (nonyl) pyrophosphate] cobalt mono [mono (tridecylammonium) mono (pentyl) mono (tridecyl) pyrophosphate] mono [di (pentyl) pyrophosphate] ruthenium tri [mono (tetradecylammonium) di (phenyl) pyrophosphate] rhodium tri [mono (benzylammonium) di (benzyl) pyrophosphate] molybdenum tri [mono (heptadecylammonium) di (heptadecyl) pyrophosphate] titanium tri [mono (6-butyloctyldecylammonium) di (isodecyl) pyrophosphate] titanium di [mono (isobutylamine) mono (propyl) mono (butyl) pyrophosphate] mono [mono (amyl) mono (hexyl) pyrophosphate] manganese tetra [mono (2-ethylbutylammonium) di (2- ethylbutyl) pyrophosphate] amine adduct of 1,6-tetrahexylenediamine and molybdenum tetra [monoacid di (octyl) pyrophosphate] titanium di [mono (oleylammonium) di (Z-ethylhexyl) pyrophosphate] mono [di (2-ethylhexyl) pyrophosphate] titanium tetra [mono (oleylammonium) di (2-ethylhexyl) pyrophosphate] titanium tetra [mono (cocoammonium) di (2-ethylhexyl) pyrophosphate] titanium di [mono (cocoammonium) di (2-ethylhexyl) pyrophosphate] mono [di (2-ethylhexyl) pyrophosphate] titanium tetra [mono (isodecylammonium) di (isodecyl) pyrophosphate] hafnium di [mono (cyclopentylarnmonium) di (p-cresyl) pyrophosphate] mono [di (p-cresyl) pyrophosphate] zirconium tetra [mono (butylammonium) mono (2-ethylhexyl) mono benzyl) pyrophosphate] amine adduct of ethylenediamine and ruthenium tetra [monoacid di (butyl) pyrophosphate] amine adduct of aniline and platinum tetra [monoacid di (decyl) pyrophosphate] amine adduct of beta-aminooctadecene and germanium tetra [monoacid di (decyl) pyrophosphate].
Particularly preferred amine adducts for use in hydrocarbon compositions are those represented by Formula 11 above, wherein M is a Group IV-B metal (e.g. titanium), each R, R, R" and R' is a branched-chain hydrocarbyl radical having from 6 to 22 carbon atoms, (e.g. 2-ethylhexyl), n is 0, n is 4, and A is an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group, which may be alkyl or alkenyl.
When used as gasoline additives, the compositions of the present invention, namely metal [hydrocarbyl pyrophosphates], metal [acid hydrocarbyl pyrophosphates] and amine salts of metal [acid hydrocarbyl pyrophosphate], are used in an amount between 10 and about 500 parts per million parts of gasoline by weight, preferably from 20 to about 250 p.p.m. and particularly from about 25 to 200 ppm. The gasoline composition can be either leaded or unleaded, although leaded gasoline is preferred. In accordance with the preferred embodiment of the invention a gasoline composition is provided which comprises a major portion of leaded hydrocarbon base fuel boiling in the gasoline range and containing between 10 and 500 ppm. of the amine salts represented by Formula II above, and particularly the salts obtained by reacting an amine containing from 6 to 22 carbon atoms arranged in an aliphatic hydrocarbyl group with a metal ('IV-B) [monoacid di (branched-chain C to C hydrocarbyl) pyrophosphate]. It will be understood that the terms gasoline, hydrocarbon base boiling in a gasoline range and similar terms refer to a petroleum fraction boiling in the gasoline range (e.g. between 50 F. and about 450 F). The term leaded gasoline refers to gasoline to which there has been added a small amount, such as between 0.1 and about 6.0 ml. per gallon of metallo organic anti-knock compound such as tetraethyl lead (TEL), tetramethyl lead (TML), tetraisopropyl lead, etc.
In addition to the additives of the present invention and optionally the lead anti-knock compounds, the gasoline compositions of this invention can also include, for instance, light hydrocarbon lubricating oils having viscosities at of between about 50 and about 200 Saybolt Universal seconds (SSU) and viscosity indexes of between about 30 and about 130. Such oils may be present in suitable amounts such as between about 0.1 and about 1.0% by weight of the gasoline composition.
When employed in lubricating compositions, such as lubricating oils, the additives provided by the present invention improve the boundary lubrication properties of the composition. Thus, lubricants containing the additives of this invention inhibit the stick-slip sliding tendencies that are often found in automatic transmission clutching surfaces.
In preparing lubricant compositions with the additives of this invention, it has been found that the amount of additive can vary over a wide range such as from 0.01% to about 3%, by weight, of the lubricant base material. The amine salts of the metal [acid hydrocarbyl pyrophosphates] are particularly desirable lubricating oil additives. In preparing lubricant compositions a wide variety of both mineral oil and synthetic base stock, including mixtures of the same, can be used. Suitable mineral oil base materials include 100 and 200 neutral oils, light and heavy intermediate mineral oils, bright stock as well as combinations of the foregoing. If a synthetic base material is used, it can be that of diesters, polyesters, silicones, silicates, fluorocarbons, phosphates and the like.
In addition to gasoline and lubricating oil compositions, the additives of the present invention may also be used in other hydrocarbon compositions. For example, they may be used in minor quantities of diesel fuel oil compositions to impart anti-rust activity, etc. to the composition.
The invention will now be further described with reference to the following specific and illustrative examples:
EXAMPLE 1 Titanium tetra [monoacid di (Z-ethylhexyl) pyrophosphate] is obtained by reacting phosphorous pentoxide, titanium tetrachloride and 2-ethyl-1-hexanol as shown below:
P=O o l 205 TiCh 4 0( 2H5)OH Ti HO O 41101 P=O R0 4 wherein R is Z-ethylhexyl.
To a suitable reaction vessel equipped with a mechanical stirrer, stoppered pressure equalizing additional funnel, thermometer, gas inlet tube, and a reflux condenser protected with a drying tube, there are added 400 ml. of anhydrous n-heptane and 61.0 g. (0.43 mole) of phosphorous pentoxide. With the stirrer operating at a rate to insure a uniform dispersion, 20.4 g. (0.11 mole) of titanium tetrachloride are added next. Finally, 112 g. (0.86 of 2 ethyl 1 hexanol, contained in the pressure equalizing addition funnel, is charged into the reaction vessel at a rate such that the temperature of the reactants does not rise above 36 C. When this step is completed, the solution is homogeneous. The reactants are then heated under reflux at 88 C. to 100 C, and when evolution of hydrogen chloride moderates, dry air is passed through the solution to displace the acid gas more rapidly and to accelerate the reaction. When evolution of hydrogen chloride ceases, as revealed by Congo red indicator, the n-heptane and any unreacted 2-ethyl-l-hexanol are removed by distillation in vacuo. The final temperature of the light yellow residual product in the reaction vessel is 125 C. at 6 mm. The product is very viscous and weighs 175 g. which is 96% of theory based on the metal halide. Upon analysis, the product is found to contain 2.98% titanium and 15.36% phosphorous, theory being 2.89% titanium and 14.99% phosphorous.
EXAMPLE 2 In the manner described in Example 1, a mixture of 0.4 mole (56.8 g.) of P and 0.1 mole (23.3 g.) of ZrCl in 500 ml. of anhydrous n-heptane is reacted with 0.84 mole (133 g.) of isodecyl alcohol to form zirconium tetra [monacid di (isodecyl) pyrophosphate], which is represented by the following formula:
wherein R is isodecyl.
EXAMPLE 3 P 0 in the amount of 28.4 g. (0.2 mole), and GeC1 in the amount of 21.4 g. (0.1 mole), are dispersed in 500 ml. of toluene. A blend, consisting of 33.2 g. (0.21 mole) of isodecanol and 43.3 g. (0.21 mole) of octylphenol, is added to the toluene dispersion in a manner described in Example 1. When liberation of hydrogen chloride is completed upon heating the reaction solution at 90 C-100" C,. the solvent is removed by distillation at reduced pressure. The hydrocarbyl garmanium pyrophosphate can be represented by the following formula:
OR R0 wherein two of the R groups are isodecyl and the two remaining R groups are octylphenol.
EXAMPLE 4 A mixture of 0.2 mole (56.8 g.) of P 0 and 0.1 mole (27.2 g.) of cadmium bromide is finely dispersed by vigorous stirring in 400 ml. of a reaction medium consisting of equal volumes of n-heptane and toluene. Then 0.42 mole (55 g) of iso-octanol is added in the manner described in Example 1. The reactants are heated under reflux at 98 C.-105 C. until liberation of by-product HBr is completed. The solvent is removed by distillation at lower pressure to obtain as the residue cadmium bis [monoacid di (iso-octyl) pyrophosphate] as shown below:
\P=O -o 1 Cd 0 P=o no 2 wherein R is iso-octyl.
EXAMPLE 5 To a mixture of 4 moles (568 g.) of P 0 and 1 mole (170 g.) of SiCl in 1500 ml. of dry n-heptane, there is added 8.4 moles (1683 g.) of tridecanol in the manner described in Example 1. Upon completion of the reaction, as evidenced by no further liberation of HCl at C., the n-heptane and any remaining tridecanol are removed by distillation at 120 C. and 2 mm. pressure. The remaining viscous product is silicon tetra [monoacid di (tridecyl) pyrophosphate].
EXAMPLE 6 EXAMPLE 7 The titanium tetra [monoacid di (2-ethylhexyl) pyrophosphate] product of Example 1 is mixed with various amines to obtain products having a pH of 7. The reactants are thoroughly mixed at room temperature while protected from carbon dioxide in a vessel blanketed with air. The amounts of amines employed to obtain adducts of pH 7 are given in the following tabulation.
Grams amine to make adduct of pH 7 with 10 grams of titanium tetra [monoacid di (Z-ethylhexyl) Amine: pyrophosphate] Cocamine (C 8.51 Soya amine (C 10.30 Oleylamine (C 11.20 N-oleyl-1,3-propylene diamine 7.94
The following example illustrates the use of each of the above-noted amine adducts as an additive in lubricants.
EXAMPLE 8 A measure of the boundary lubricating ability of each of the amine adducts of titanium tetra [monoacid di (2- ethylhexyl) pyrophosphate] of Example 7 in lubricating oil, and consequently their eifectiveness in reducing wear, is obtained by means of a special apparatus used to access the boundary properties of lubricants in the 50 F.-350 F. range. The measurement is reported as Normal Lubricity Indices, NLI, and values of 200 and above are considered very good.
One part by weight of the various amine adducts is blended with 99 parts by weight of a neutral oil having a viscosity of 100 SUS at 100 F. The NLI values are set forth in the following tabulation.
11 Friction modifier: Normal lubricity index None 100 Titanium tetra [cocoammonium di (2-ethylhexyl) pyrophosphate] 257 Titanium tetra [soya ammonium di (2-ethylhexyl) pyrophosphate] 315 Titanium tetra [oleylammonium di (2-ethy1- hexyl) pyrophosphate] 370 Amine adduct of N oleyl 1,3 propylene diamine and titanium tetra [monoacid di (2- ethylhexyl) pyrophosphate] 386 The following example illustrates the use of the amine adducts of Example 7 as additives in gasoline compositions.
EXAMPLE 9 Gasoline compositions are prepared by employing each of the previously-noted amine adducts of titanium tetra [monoacid di (Z-ethylhexyl) pyrophosphate] in an amount of 50 ppm. in a base gasoline having the following characteristics.
ASTM rust tests are run at 75 F. with each of the additive-containing gasoline compositions using distilled water. Each of the compositions passed the test.
While the invention has been described above with respect to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as expressed in the appended claims.
Therefore, I claim:
1. A fuel composition comprising a major proportion of a liquid hydrocarbon fuel and a minor proportion sufficient to improve performance characteristics of an adduct of an amine containing from 1 to about 30 carbon atoms with a compound having the formula:
/OR "R wherein M is a polyvalent metal; n is an integer of from 1 to 4; n is an integer of from 0 to 1; the sum of it plus 2n is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R and R" are hydrocarbyl groups having from 1 to about 30 carbon atoms.
2. A gasoline composition comprising a major proportion of gasoline and dissolved therein from about 10 to about 500 ppm. of an adduct of an amine containing from 1 to about 30 carbon atoms with a compound having the formula:
wherein M is a polyvalent metal; n is an integer of from 1 to 4; n is an integer of from 0 to 1; the sum of n plus 211 is equal to the valence of the metal and is an integer from 2 to 4; and R, R, R are hydrocarbyl groups having from 1 to about 30 carbon atoms.
3. A gasoline composition of claim 2 wherein M is selected from the group consisting of manganese, chromium, molybdenum, copper, gold and silicon and the metals of Groups II, IV and VIII of the Periodic Table.
4. A gasoline composition of claim 2 wherein R, R, R" and R are aliphatic hydrocarbyl groups.
5. A gasoline composition of claim 4 wherein R, R, R and R are branched chain aliphatic hydrocarbyl groups having from about 6 to about 22 carbon atoms, and said amine is an aliphatic amine containing from about 6 to about 22 carbon atoms.
6. A gasoline composition of claim 3 wherein M is a Group IV-B metal, n is 2 and n is 1, and said amine is an aliphatic amine containing from about 6 to about 22 carbon atoms.
References Cited UNITED STATES PATENTS 2,228,659 1/1941 Farrington et al. 252-325 2,301,370 11/1942 Cook et al. 2,345,156 3/1944 Roberts 252-325 XR 2,777,874 1/1957 Asseff et al. 260431 XR 2,857,334 10/1958 Thompson. 3,012,056 12/1961 Cyba. 3,063,820 11/1962 Chenicek 252325 XR 3,305,330 2/1967 McCoy et al. 3,334,978 8/1967 Revukas. 3,338,935 8/ 1967 Kerschner.
DANIEL E. WYMAN, Primary Examiner I. VAUGHN, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US459089A US3354189A (en) | 1965-05-26 | 1965-05-26 | Metal (hydrocarbyl and acid hydrocarbyl pyrophosphates) and amine adducts |
| US66898467A | 1967-08-17 | 1967-08-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3533762A true US3533762A (en) | 1970-10-13 |
Family
ID=27039244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US668984A Expired - Lifetime US3533762A (en) | 1965-05-26 | 1967-08-17 | Hydrocarbon fuels containing polyvalent metal hydrocarbyl pyrophosphate salts and amine adducts thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3533762A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3664954A (en) * | 1968-09-05 | 1972-05-23 | Sylvania Electric Prod | Group vi{14 b transition metal-amino-phosphorodithioates in lubricating oil |
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| US2228659A (en) * | 1938-11-21 | 1941-01-14 | Standard Oil Co | Compounded mineral oil |
| US2301370A (en) * | 1941-02-26 | 1942-11-10 | American Cyanamid Co | Stabilization of tetraethyl lead |
| US2345156A (en) * | 1941-01-15 | 1944-03-28 | Texas Co | Lubricating oil |
| US2777874A (en) * | 1952-11-03 | 1957-01-15 | Lubrizol Corp | Metal complexes and methods of making same |
| US2857334A (en) * | 1956-06-20 | 1958-10-21 | Universal Oil Prod Co | Corrosion inhibitors |
| US3012056A (en) * | 1960-08-11 | 1961-12-05 | Universal Oil Prod Co | Alkyl acid phosphate salt of the reaction product of epihalohydrin and amine |
| US3063820A (en) * | 1959-05-18 | 1962-11-13 | Universal Oil Prod Co | Stabilization of hydrocarbons |
| US3305330A (en) * | 1963-11-20 | 1967-02-21 | Texaco Inc | Amine-phosphorus-containing adducts and motor fuel containing same |
| US3334978A (en) * | 1964-12-18 | 1967-08-08 | Cities Service Oil Co | Hydrocarbon fuel composition |
| US3338935A (en) * | 1964-03-06 | 1967-08-29 | Cities Service Oil Co | Amine salts of metal organo orthophosphates |
-
1967
- 1967-08-17 US US668984A patent/US3533762A/en not_active Expired - Lifetime
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2228659A (en) * | 1938-11-21 | 1941-01-14 | Standard Oil Co | Compounded mineral oil |
| US2345156A (en) * | 1941-01-15 | 1944-03-28 | Texas Co | Lubricating oil |
| US2301370A (en) * | 1941-02-26 | 1942-11-10 | American Cyanamid Co | Stabilization of tetraethyl lead |
| US2777874A (en) * | 1952-11-03 | 1957-01-15 | Lubrizol Corp | Metal complexes and methods of making same |
| US2857334A (en) * | 1956-06-20 | 1958-10-21 | Universal Oil Prod Co | Corrosion inhibitors |
| US3063820A (en) * | 1959-05-18 | 1962-11-13 | Universal Oil Prod Co | Stabilization of hydrocarbons |
| US3012056A (en) * | 1960-08-11 | 1961-12-05 | Universal Oil Prod Co | Alkyl acid phosphate salt of the reaction product of epihalohydrin and amine |
| US3305330A (en) * | 1963-11-20 | 1967-02-21 | Texaco Inc | Amine-phosphorus-containing adducts and motor fuel containing same |
| US3338935A (en) * | 1964-03-06 | 1967-08-29 | Cities Service Oil Co | Amine salts of metal organo orthophosphates |
| US3334978A (en) * | 1964-12-18 | 1967-08-08 | Cities Service Oil Co | Hydrocarbon fuel composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3664954A (en) * | 1968-09-05 | 1972-05-23 | Sylvania Electric Prod | Group vi{14 b transition metal-amino-phosphorodithioates in lubricating oil |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: CITGO PETROLEUM CORPORATION, A CORP OF DE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CITIES SERVICE COMPANY;REEL/FRAME:004225/0709 Effective date: 19830830 |
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| AS | Assignment |
Owner name: CITIES SERVICE COMPANY A CORP. OF DE. Free format text: MERGER;ASSIGNOR:CITIES SERVICE OIL COMPANY;REEL/FRAME:004561/0817 Effective date: 19781220 |