EP0881277A2 - Friction modifier comprising metal sulfonate and lubricating oil composition containing the same - Google Patents
Friction modifier comprising metal sulfonate and lubricating oil composition containing the same Download PDFInfo
- Publication number
- EP0881277A2 EP0881277A2 EP98304251A EP98304251A EP0881277A2 EP 0881277 A2 EP0881277 A2 EP 0881277A2 EP 98304251 A EP98304251 A EP 98304251A EP 98304251 A EP98304251 A EP 98304251A EP 0881277 A2 EP0881277 A2 EP 0881277A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocarbon group
- group
- lubricating oil
- metal
- oil composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 81
- 239000002184 metal Substances 0.000 title claims abstract description 81
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 74
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000003607 modifier Substances 0.000 title claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 67
- 238000005259 measurement Methods 0.000 claims abstract description 27
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 22
- 239000003112 inhibitor Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000006078 metal deactivator Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 230000001603 reducing effect Effects 0.000 abstract description 11
- 150000003871 sulfonates Chemical class 0.000 abstract description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 42
- 239000002585 base Substances 0.000 description 37
- 229910052791 calcium Inorganic materials 0.000 description 31
- 239000011575 calcium Substances 0.000 description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 30
- 239000003921 oil Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001050 lubricating effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- -1 phosphite ester amine salts Chemical class 0.000 description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010730 cutting oil Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 0 *S(ONOS(*)(=O)=O)(=O)=O Chemical compound *S(ONOS(*)(=O)=O)(=O)=O 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910013724 M(OH)2 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 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 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010718 automatic transmission oil Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000003901 ceryl 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])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000000446 fuel Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 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 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 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
- 239000010705 motor oil Substances 0.000 description 1
- 125000001802 myricyl 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])C([H])([H])[H] 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 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 1
- 125000001196 nonadecyl 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])[H] 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 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
- 125000002460 pentacosyl 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])[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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 125000004079 stearyl 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])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 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 1
- COTPAMORPWZHKE-UHFFFAOYSA-H trizinc;thiophosphate;thiophosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=O.[O-]P([O-])([O-])=S COTPAMORPWZHKE-UHFFFAOYSA-H 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/32—Wires, ropes or cables lubricants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/34—Lubricating-sealants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/36—Release agents or mold release agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/38—Conveyors or chain belts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/40—Generators or electric motors in oil or gas winning field
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/42—Flashing oils or marking oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/44—Super vacuum or supercritical use
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/50—Medical uses
Definitions
- This invention relates to a friction modifier comprising a metal sulfonate and to a lubricating oil composition with the metal sulfonate added therein, and more specifically to a friction modifier comprising a metal sulfonate containing a specific chain hydrocarbon group and to a lubricating oil composition with the metal sulfonate added therein.
- an automatic transmission oil which had been obtained by adding magnesium sulfonate, which is used as a metallic detergent, for example, for the dispersion of sludge occurring in lubricating oils, the solubilization of a precursor and the neutralization of an acid, especially over-based magnesium sulfonate having a base number of 300 mg-KOH/g or greater in a base stock, in order to improve friction characteristics (see JP Kokai 62-84190).
- a lubricating oil making combined use of a metallic detergent, such as calcium sulfonate, barium sulfonate or magnesium sulfonate, with a molybdenum dialkyldithiocarbamate was also proposed (see JP Kokai 62-215697).
- a metallic detergent such as calcium sulfonate, barium sulfonate or magnesium sulfonate
- metal sulfonates when employed singly, are however still insufficient in friction reducing effects, so that they are merely friction modifier adjuvants for use in combination with friction modifiers such as phosphate esters and molybdenum dithiocarbamate. If a metal sulfonate having still higher friction reducing ability is identified, it is therefore believed it will find utility in a much wider range of fields and hence to have a significantly-increased industrial value. There is accordingly an outstanding intense desire for the development of such a metal sulfonate.
- the present invention has as objects thereof the provision of a novel metal sulfonate having friction reducing ability and also the provision of a lubricating oil composition with the metal sulfonate added.
- the present invention relates in a first aspect thereof to a friction modifier comprising a metal sulfonate composed of an organic sulfonic group, which contains a hydrocarbon group, and a metal, characterized in that said hydrocarbon group is a chain hydrocarbon group or an aromatic group with at least one chain hydrocarbon group bonded thereto, and said chain hydrocarbon group has an alkyl chain linearity of 20% or higher as determined by 13 C-NMR measurement.
- the present invention also relates in a second aspect thereof to a lubricating oil composition characterized in that said lubricating oil composition comprises:
- the metal sulfonate which is used as the friction modifier according to the present invention is composed of an organic sulfonic group, which contains a hydrocarbon group, and a metal, and is a compound which can be represented, for example, by the following formula (I): (RSO 3 ) x M
- R in the organic sulfonic group RSO 3 is a hydrocarbon group, which is a chain hydrocarbon group or an aromatic group with at least one chain hydrocarbon group bonded thereto.
- Illustrative of the chain hydrocarbon group can be alkyl groups, each of which has 12-40 carbon atoms on average per organic sulfonic group as measured by 13 C-NMR and calculated supposing that there is one carbon atom bonded to a sulfonic group. It is particularly preferred to contain at least one or more alkyl groups having 12-30 carbon atoms.
- alkyl group can include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, pentatriacontyl, and octatriacontyl.
- metal sulfonate according to the present invention one having an alkyl chain linearity of 20% or higher, especially of from 30% to 80% as determined by a 13 C-NMR measurement is preferred.
- alkyl chain linearity is based on a unique concept established by the present inventors as a result of repetition of numerous experiments, and means the ratio of the number of carbon atoms in a linear portion located 5 or more atoms apart from an end of the alkyl group or 4 or more atoms apart from a branched site of the alkyl group to the total number of carbon atoms in the alkyl group. Its value is dependent on the bonding site of an aromatic group and the site of branching of the alkyl group.
- alkyl chain linearity has been determined specifically by the following formula from a 13 C-NMR measurement.
- Alkyl chain linearity (%) Integral intensity over a chemical shift range of from 29 ppm to 31 ppm Sum of all integral intensity over a chemical shift range of from 5 ppm to 60 ppm x 100
- the 13 C-NMR measurement was conducted by converting the metal sulfonate into its corresponding sulfonic acid.
- the present inventors recognized the existence of a correlation between the alkyl chain linearity and the friction reducing effects of its metal sulfonate, and have ascertained that the metal sulfonate exhibits better friction reducing effects as the linearity becomes higher and also that a linearity lower than 20% cannot exhibit the effects fully although a linearity of 20% or higher, especially of from 30% to 80% shows particularly marked effects.
- the metal sulfonate contains two or more chain hydrocarbon groups per organic sulfonic group or is a mixture of two or more different compounds (metal sulfonates), the metal sulfonate exhibits friction reducing effects and is effective as a metal sulfonate according to the present invention provided that the alkyl chain linearity as determined by a 13 C-NMR measurement is 20% or higher.
- a metal sulfonate, the chain hydrocarbon groups of which are each an alkyl group having 12 or more carbon atoms and a linearity of 20% or higher is preferred from the viewpoint of making it possible to substantially increase friction reducing ability.
- the aromatic group bonded to the chain hydrocarbon groups can be either monocyclic or fused polycyclic. Those represented by the following structural formulas (a) to (g), respectively, are effective, with a phenyl group being particularly preferred.
- the metal component represented by M in the above-described metal sulfonate (formula (I)) (RSO 3 ) x M can be an alkali metal or an alkaline earth metal. Further, a metal of an atomic number in a range of from 12 to 56 is also suited. Specific examples can include sodium, potassium, lithium, calcium, magnesium and barium. In addition, aluminum, zinc, tin, chromium, copper, cobalt and the like are also effective. Of these, calcium, magnesium, barium and the like are particularly preferred.
- x is a value corresponding to the valence of the metal component M.
- Typical illustrative compounds of the metal sulfonate according to the present invention can be represented by the following formula (II):
- a and B may be the same or different and are each (i) an alkyl group or (ii) an aromatic group with at least one alkyl group bonded thereto, and the alkyl groups are those capable of providing 20% or higher as an average linearity of the whole alkyl groups as determined by a 13 C-NMR measurement.
- the aromatic group can be at least one aromatic group selected from the group consisting of the above-described structural formulas (a) to (g).
- M in the formula represents the above-described divalent metal, with an alkaline earth metal being preferred.
- R 1 to R 10 are alkyl groups and as already described, the average total carbon numbers of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 , said average total carbon numbers being equivalent to the numbers of carbon atoms per the corresponding organic sulfonic acids, may preferably be from 12 to 40, and R 1 to R 10 have alkyl chain linearities of 20% or higher as determined by 13 C-NMR measurement.
- each n represents the number of alkyl groups bonded to the associated aromatic group and may stand for an integer of 1 to 5, preferably of 1 to 3. In each formula, two n values can be the same or different.
- Ms in the formulas (III) to (VII) are preferably alkaline earth metals, although they can be other divalent metals described above.
- a process for the preparation of a metal sulfonate according to the present invention which contains one or more alkyl groups which are large in chain length and high in linearity. It is possible to adopt, for example, a process in which a sulfonic acid available by sulfonation of an alkyl-substituted aromatic hydrocarbon obtained from a petroleum fraction or of an alkyl-substituted aromatic hydrocarbon, which is an alkylation product of an aromatic hydrocarbon by an olefinic hydrocarbon, is neutralized with an alkali metal oxide, hydroxide, alkoxide or the like, followed by the adjustment of a quantity of a metal.
- a metal sulfonate according to the present invention which has a specific alkyl chain linearity, can be prepared by mixing various metal sulfonates of different alkyl chain linearities so that the overall alkyl chain linearity is controlled to fall within the above-descried particular range.
- the metal sulfonate can be a basic salt or over-based salt in addition to a neutral salt.
- Its salt type can be chosen as desired depending on its application.
- a basic salt can be one prepared by a conventional process, and can be prepared, for example, by dispersing M(OH) 2 or MCO 3 (wherein M represents an alkaline earth metal or the like) in a colloidal form in a sulfonate.
- M(OH) 2 or MCO 3 wherein M represents an alkaline earth metal or the like
- the present invention provides a friction modifier, especially a friction modifier for lubricating oils, which is composed of a particular metal sulfonate.
- This friction modifier is oil-soluble. It can be used by dissolving it in a hydrocarbon or another solvent and diluting the resultant concentrate as needed or as a component of an additive package in combination with other additives.
- the base stock can be any one of mineral base stocks, synthetic base stocks and vegetable base stocks, or can be a blended base stock of two or more of these base stocks.
- a mineral base stock it is possible to use, for example, a mineral oil obtained by the treatment of a lubricating oil fraction, which is in turn available by vacuum distillation of an atmosphere distillation residue of paraffin-base, neutral or naphthene-base crude oil, through a refining step such as solvent refining, hydrocracking, hydro-refining, catalytic dewaxing, solvent dewaxing or clay treatment; a mineral oil obtained by subjecting a vacuum distillation residue to solvent deasphalting and then treating the resulting deasphalted oil through the above-described refining step; a mineral oil obtained by isomerizing wax components; or a blended oil thereof.
- a refining step such as solvent refining, hydrocracking, hydro-refining, catalytic dewaxing, solvent dewaxing or clay treatment
- an aromatic extraction solvent such as phenol, furfural or N-methyl-pyrrolidone
- a solvent for the solvent dewaxing liquefied propane, MEK/toluene, MEK/MIBK, or the like
- hydro-refined oil is preferred from the standpoint of oxidation stability and the like, and one containing, for example, 2 wt% or less of aromatic hydrocarbons and 90 wt% or more of saturated hydrocarbons can be used.
- Examples of synthetic base stocks can include poly( ⁇ -olefin) oligomers of lubricating viscosity; polybutene; alkylbenzenes; polyol esters such as trimethylolpropane esters and pentaerythritol esters; polyoxyalkylene glycols; polyoxyalkylene glycol esters; polyoxyalkylene glycol ethers; dibasic acid esters; phosphate esters; and silicone oils.
- These base stocks can be used either singly or in combination.
- usable examples of vegetable base stocks can include rape seed oil, soybean oil, coconut oil, olive oil and sunflower oil.
- the lubricating base stock employed in the lubricating oil composition according to the present invention can be produced by suitably preparing a blended base stock so that the blended base stock has properties desired for the intended application of the lubricating oil composition.
- Concerning viscosity for example, it is preferred to control the kinematic viscosity at 100°C in a range of from 2 mm 2 /s to 30 mm 2 /s, especially from 3 mm 2 /s to 10 mm 2 /s for a lubricating oil for internal combustion engines, the kinematic viscosity at 100°C in a range of from 2 mm 2 /s to 30 mm 2 /s, especially from 3 mm 2 /s to 15 mm 2 /s for an automatic transmission fluid, and the kinematic viscosity at 40°C in a range of from 10 mm 2 /s to 1,000 mm 2 /s, especially from 20 mm 2 /s to 500 mm 2 /s.
- the metal sulfonate according to the present invention can exhibit sufficient friction reducing effects when added to the lubricating base stock in a proportion of from 0.01 to 10 wt%, preferably from 0.05 to 5 wt% based on the whole weight of the lubricating oil composition or in a proportion of from I ppm to 10,000 ppm, preferably from 50 ppm to 5,000 ppm in terms of the metal, although the proportion varies depending on the application field of the lubricating oil.
- viscosity index improvers ashless dispersants, oxidation inhibitors, extreme pressure agents, wear inhibitors, metal deactivators, pour-point depressants, rust inhibitors, other friction modifiers and other additives as needed.
- Illustrative usable examples of the viscosity index improvers can include polymethacrylates, polyisobutylenes, ethylene-propylene copolymers, and hydrogenated styrene-butadiene copolymers. These viscosity index improvers are used generally in a proportion of from 3 wt% to 35 wt%.
- Illustrative of the ashless dispersants can be polybutenylsuccinimides, polybutenylsuccinamides, benzylamines, and succinate esters. They can be used generally in a proportion of from 0.05 wt% to 7 wt%.
- Illustrative examples of the oxidation inhibitors can include amine-type oxidation inhibitors such as alkylated diphenylamines, phenyl- ⁇ -naphthylamine and alkylated phenyl- ⁇ -naphthylamines; phenolic oxidation inhibitors such as 2,6-di-t-butylphenol and 4,4'-methylene-bis(2,6-di-t-butyl-phenol); and zinc dithiophosphate. They can be used generally in a proportion of from 0.05 wt% to 5 wt%.
- extreme pressure agents can be dibenzyl sulfide and dibutyl disulfide. They can be used generally in a proportion of from 0.05 wt% to 3 wt%.
- metal deactivators can include benzotriazole, benzotriazole derivatives, and thiadiazole. They can be used generally in a proportion of from 0.01 wt% to 3 wt%.
- pour-point depressants can be ethylene-vinyl acetate copolymers, chlorinated paraffin-naphthalene condensation products, polymethacrylates, and polyalkylstyrenes. They can be used generally in a proportion of from 0.1 wt% to 10 wt%.
- wear inhibitors can be phosphate esters, zinc thiophosphate, and sulfur compounds. They can be used generally in a proportion of from 0.01 wt% to 5 wt%.
- a lubricating oil composition comprising as a base stock a hydro-refined oil, which contains 2 wt% or less of aromatic hydrocarbons and 90 wt% or more of saturated hydrocarbons, and a calcium sulfonate containing 1 to 2 C 14 - 24 alkyl groups per organic sulfonic group and having an alkyl chain linearity of 40% or higher as determined by a 13 C-NMR measurement, said calcium sulfonate having been added in a proportion of from 50 ppm to 5,000 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
- the metal sulfonate according to the present invention can be used as a friction modifier in hydraulic working oils, wet brake oils, sliding surface oils, plastic working oils, cutting oils and the like in addition to lubricating oils for internal combustion engines, automatic transmission fluids and gear oils.
- the metal sulfonate can be used without limitations in any other oils insofar as it can exhibit its friction reducing effects.
- alkyl chain linearities of the metal sulfonates employed in the following Examples and the performance evaluation of the lubricating oil compositions were measured or conducted by the following methods.
- a lubricating oil composition was formulated by adding the sulfonate to a solvent-refined mineral oil "100N" (kinematic viscosity at 100°C: 4.2 mm 2 /s) in a proportion of 140 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
- the friction coefficient of the resultant lubricating oil composition was measured by the above-described method. It was found to be 0.09.
- a lubricating oil composition was formulated in exactly the same manner as in Example 1 except that the proportion of Calcium Sulfonate 1 was increased from 140 ppm to 560 ppm in terms of calcium.
- the resultant lubricating oil composition was subjected to a performance evaluation. Its friction coefficient was found to be 0.08, thereby indicating an improvement in friction characteristics.
- Calcium Sulfonate 2 of the following characteristics:
- a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 1,200 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
- the resultant lubricating oil composition was subjected to the above-described performance evaluation. Its friction coefficient was found to be 0.10.
- a lubricating oil composition was formulated in exactly the same manner as in Example 3 except that the proportion of Calcium Sulfonate 2 was increased from 1,200 ppm to 2,400 ppm in terms of calcium.
- the resultant lubricating oil composition was subjected to a performance evaluation. Its friction coefficient was found to be 0.08.
- Calcium Sulfonate 3 of the following characteristics:
- a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 2,400 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
- the resultant lubricating oil composition was subjected to the above-described performance evaluation. Its friction coefficient was found to be 0.09.
- a lubricating oil composition was formulated in exactly the same manner as in Example 5 except that the proportion of Calcium Sulfonate 3 was increased from 2,400 ppm to 4,800 ppm in terms of calcium.
- the resultant lubricating oil composition was subjected to a performance evaluation. Its friction coefficient was found to be 0.08.
- Calcium Sulfonate 4 of the following characteristics:
- a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 2,400 ppm in terms of calcium based on the whole weight of the lubricating oil composition. As a result of a performance evaluation, its friction coefficient was found to be 0.13.
- Calcium Sulfonate 5 of the following characteristics:
- a lubricating oil composition was formulated by adding the sulfonate to the same lubricating base stock as that employed in Example 1 in a proportion of 2,400 ppm in terms of calcium based on the whole weight of the lubricating oil composition.
- the friction coefficient of the resultant lubricating oil composition was found to be 0.14.
- a lubricating oil composition was formulated in exactly the same manner as in Comparative Example 2 except that the proportion of Calcium Sulfonate 5 was increased from 2,400 ppm to 4,800 ppm in terms of calcium. Its friction coefficient was found to be 0.13. The calcium sulfonate, the alkyl chain linearity of which is low, was also found to be unable to bring about any substantial advantageous effects on friction characteristics despite the increase in its proportion.
- the solvent-refined mineral oil "100N” (kinematic viscosity at 100°C: 4.2 mm 2 /s), which was employed as a lubricating base stock in Example 1, was subjected by itself to a performance evaluation. Its friction coefficient was found to be 0.14.
- a metal sulfonate having an alkyl chain linearity of 20% or higher is useful as a friction modifier for lubricating oils, and can improve the friction characteristics of lubricating oil compositions.
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Abstract
Novel metal sulfonates having friction reducing ability and also
various lubricating oil compositions containing the metal sulfonates are
disclosed. The metal sulfonates which provide a friction modifier comprise a
metal sulfonate composed of an organic sulfonic group, which contains a
hydrocarbon group, and a metal. The hydrocarbon group of the organic sulfonic
group is a chain hydrocarbon group or an aromatic group with at least one chain
hydrocarbon group bonded thereto. The chain hydrocarbon group has an alkyl
chain linearity of 20% or higher as determined by a carbon nuclear magnetic
resonance measurement (13C-NMR measurement). Lubricating oil compositions
added with the metal sulfonate are also provided.
Description
This invention relates to a friction modifier comprising a metal
sulfonate and to a lubricating oil composition with the metal sulfonate added
therein, and more specifically to a friction modifier comprising a metal sulfonate
containing a specific chain hydrocarbon group and to a lubricating oil composition
with the metal sulfonate added therein.
From the need for resource and energy saving measures in all the
industrial fields in view of environmental conservation, reductions in friction
and wear through improvements in lubricating oils have also been investigated in
the field of lubricating oils from a variety of viewpoints in recent years with a
view to lowering fuel consumption rates. As a result, it has already become indispensable
to incorporate additives in base stocks for lubricating oils so that the
base stocks can be provided with desired friction characteristics. Accordingly, a
number of friction modifiers have been proposed to date, resulting in the use of
fatty acids and their metal salts, esters, amines and the like - all of which are of
the oiliness improver type - and phosphate esters, phosphite esters, zinc dithiophosphate
and the like - all of which are of the extreme pressure agent type - in
wet brake oils, automatic transmission fluids, sliding surface oils, plastic working
oils and the like and also in the use of phosphate esters, phosphite esters,
acidic phosphite ester amine salts, molybdenum dithiophosphate, molybdenum
dithiocarbamate and the like - all of which are of the extreme pressure agent type
- in engine oils, gear oils, cutting oils and the like.
Meanwhile, an automatic transmission oil was disclosed, which
had been obtained by adding magnesium sulfonate, which is used as a metallic
detergent, for example, for the dispersion of sludge occurring in lubricating oils,
the solubilization of a precursor and the neutralization of an acid, especially
over-based magnesium sulfonate having a base number of 300 mg-KOH/g or
greater in a base stock, in order to improve friction characteristics (see JP Kokai
62-84190). Further, a lubricating oil making combined use of a metallic
detergent, such as calcium sulfonate, barium sulfonate or magnesium sulfonate,
with a molybdenum dialkyldithiocarbamate was also proposed (see JP Kokai
62-215697).
These metal sulfonates, when employed singly, are however still
insufficient in friction reducing effects, so that they are merely friction modifier
adjuvants for use in combination with friction modifiers such as phosphate esters
and molybdenum dithiocarbamate. If a metal sulfonate having still higher
friction reducing ability is identified, it is therefore believed it will find utility in
a much wider range of fields and hence to have a significantly-increased
industrial value. There is accordingly an outstanding intense desire for the
development of such a metal sulfonate.
In view of the circumstances of development of friction modifiers
as described above, the present invention has as objects thereof the provision of
a novel metal sulfonate having friction reducing ability and also the provision of
a lubricating oil composition with the metal sulfonate added.
It has been discovered that a metal sulfonate having an alkyl group,
which has a specific linear portion determinable by carbon nuclear magnetic
resonance measurement (13C-NMR measurement) (hereinafter referred to as
13C-NMR measurement, as needed), has excellent friction reducing ability.
Having been interested in its effectiveness as a friction modifier, it has also been
found that its addition to a base stock for lubricating oil makes it possible to
furnish a lubricating oil composition having improved friction characteristics and
utility in a variety of technical fields. Based on these findings, the present
invention has now been completed.
The present invention relates in a first aspect thereof to a friction
modifier comprising a metal sulfonate composed of an organic sulfonic group,
which contains a hydrocarbon group, and a metal, characterized in that said
hydrocarbon group is a chain hydrocarbon group or an aromatic group with at
least one chain hydrocarbon group bonded thereto, and said chain hydrocarbon
group has an alkyl chain linearity of 20% or higher as determined by 13C-NMR
measurement.
The present invention also relates in a second aspect thereof to a
lubricating oil composition characterized in that said lubricating oil composition
comprises:
The present invention will hereinafter be described in detail.
The metal sulfonate which is used as the friction modifier according
to the present invention is composed of an organic sulfonic group, which
contains a hydrocarbon group, and a metal, and is a compound which can be
represented, for example, by the following formula (I):
(RSO3)xM
It may consist of one type of the compound or may be a mixture of two or more
compounds having different hydrocarbon groups. In the formula (I), R in the
organic sulfonic group RSO3 is a hydrocarbon group, which is a chain hydrocarbon
group or an aromatic group with at least one chain hydrocarbon group
bonded thereto. Illustrative of the chain hydrocarbon group can be alkyl groups,
each of which has 12-40 carbon atoms on average per organic sulfonic group as
measured by 13C-NMR and calculated supposing that there is one carbon atom
bonded to a sulfonic group. It is particularly preferred to contain at least one or
more alkyl groups having 12-30 carbon atoms. Specific examples of the alkyl
group can include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, octadecyl, nonadecyl, eicosyl, tetracosyl, pentacosyl, hexacosyl,
heptacosyl, octacosyl, nonacosyl, triacontyl, pentatriacontyl, and octatriacontyl.
As the metal sulfonate according to the present invention, one
having an alkyl chain linearity of 20% or higher, especially of from 30% to 80%
as determined by a 13C-NMR measurement is preferred.
Here, the term "alkyl chain linearity" is based on a unique concept
established by the present inventors as a result of repetition of numerous experiments,
and means the ratio of the number of carbon atoms in a linear portion
located 5 or more atoms apart from an end of the alkyl group or 4 or more atoms
apart from a branched site of the alkyl group to the total number of carbon atoms
in the alkyl group. Its value is dependent on the bonding site of an aromatic
group and the site of branching of the alkyl group.
In the present invention, the alkyl chain linearity has been determined
specifically by the following formula from a 13C-NMR measurement.
Alkyl chain linearity (%) = Integral intensity over a chemical shift range of from 29 ppm to 31 ppmSum of all integral intensity over a chemical shift range of from 5 ppm to 60 ppm x 100
Incidentally, the 13C-NMR measurement was conducted by
converting the metal sulfonate into its corresponding sulfonic acid.
The present inventors recognized the existence of a correlation
between the alkyl chain linearity and the friction reducing effects of its metal
sulfonate, and have ascertained that the metal sulfonate exhibits better friction
reducing effects as the linearity becomes higher and also that a linearity lower
than 20% cannot exhibit the effects fully although a linearity of 20% or higher,
especially of from 30% to 80% shows particularly marked effects.
Even when the metal sulfonate contains two or more chain hydrocarbon
groups per organic sulfonic group or is a mixture of two or more different
compounds (metal sulfonates), the metal sulfonate exhibits friction reducing
effects and is effective as a metal sulfonate according to the present invention
provided that the alkyl chain linearity as determined by a 13C-NMR measurement
is 20% or higher. In particular, a metal sulfonate, the chain hydrocarbon
groups of which are each an alkyl group having 12 or more carbon atoms and a
linearity of 20% or higher, is preferred from the viewpoint of making it possible
to substantially increase friction reducing ability. The aromatic group bonded to
the chain hydrocarbon groups can be either monocyclic or fused polycyclic.
Those represented by the following structural formulas (a) to (g), respectively,
are effective, with a phenyl group being particularly preferred.
The metal component represented by M in the above-described
metal sulfonate (formula (I)) (RSO3)xM can be an alkali metal or an alkaline
earth metal. Further, a metal of an atomic number in a range of from 12 to 56 is
also suited. Specific examples can include sodium, potassium, lithium, calcium,
magnesium and barium. In addition, aluminum, zinc, tin, chromium, copper,
cobalt and the like are also effective. Of these, calcium, magnesium, barium and
the like are particularly preferred.
In the above formula (I), x is a value corresponding to the valence
of the metal component M.
Typical illustrative compounds of the metal sulfonate according to
the present invention can be represented by the following formula (II):
In the above formula (II), A and B may be the same or different
and are each (i) an alkyl group or (ii) an aromatic group with at least one alkyl
group bonded thereto, and the alkyl groups are those capable of providing 20%
or higher as an average linearity of the whole alkyl groups as determined by a
13C-NMR measurement. Further, the aromatic group can be at least one
aromatic group selected from the group consisting of the above-described
structural formulas (a) to (g). In addition, M in the formula represents the above-described
divalent metal, with an alkaline earth metal being preferred.
Accordingly, more specific illustrative examples of the metal
sulfonate according to the present invention can be represented by the following
formulas (III) to (VII):
In the above formulas (III) to (VII), R1 to R10 are alkyl groups and
as already described, the average total carbon numbers of R1, R2, R3, R4, R5, R6,
R7, R8, R9 and R10, said average total carbon numbers being equivalent to the
numbers of carbon atoms per the corresponding organic sulfonic acids, may
preferably be from 12 to 40, and R1 to R10 have alkyl chain linearities of 20% or
higher as determined by 13C-NMR measurement.
In each of the above formulas (III) to (VII), each n represents the
number of alkyl groups bonded to the associated aromatic group and may stand
for an integer of 1 to 5, preferably of 1 to 3. In each formula, two n values can
be the same or different.
Further, Ms in the formulas (III) to (VII) are preferably alkaline
earth metals, although they can be other divalent metals described above.
No particular limitation is imposed on a process for the preparation
of a metal sulfonate according to the present invention, which contains one or
more alkyl groups which are large in chain length and high in linearity. It is
possible to adopt, for example, a process in which a sulfonic acid available by
sulfonation of an alkyl-substituted aromatic hydrocarbon obtained from a
petroleum fraction or of an alkyl-substituted aromatic hydrocarbon, which is an
alkylation product of an aromatic hydrocarbon by an olefinic hydrocarbon, is
neutralized with an alkali metal oxide, hydroxide, alkoxide or the like, followed
by the adjustment of a quantity of a metal.
Further, a metal sulfonate according to the present invention,
which has a specific alkyl chain linearity, can be prepared by mixing various
metal sulfonates of different alkyl chain linearities so that the overall alkyl chain
linearity is controlled to fall within the above-descried particular range.
In the present invention, the metal sulfonate can be a basic salt or
over-based salt in addition to a neutral salt. Its salt type can be chosen as desired
depending on its application. A basic salt can be one prepared by a conventional
process, and can be prepared, for example, by dispersing M(OH)2 or MCO3
(wherein M represents an alkaline earth metal or the like) in a colloidal form in a
sulfonate. A conventionally-adopted preparation process can be relied upon.
As has been described above, the present invention provides a
friction modifier, especially a friction modifier for lubricating oils, which is
composed of a particular metal sulfonate. This friction modifier is oil-soluble. It
can be used by dissolving it in a hydrocarbon or another solvent and diluting the
resultant concentrate as needed or as a component of an additive package in
combination with other additives.
A description will next be made about the lubricating oil composition
according to the present invention.
No particular limitation is imposed on the base stock employed in
the lubricating oil composition according to the present invention. The base
stock can be any one of mineral base stocks, synthetic base stocks and vegetable
base stocks, or can be a blended base stock of two or more of these base stocks.
As a mineral base stock, it is possible to use, for example, a
mineral oil obtained by the treatment of a lubricating oil fraction, which is in
turn available by vacuum distillation of an atmosphere distillation residue of
paraffin-base, neutral or naphthene-base crude oil, through a refining step such
as solvent refining, hydrocracking, hydro-refining, catalytic dewaxing, solvent
dewaxing or clay treatment; a mineral oil obtained by subjecting a vacuum
distillation residue to solvent deasphalting and then treating the resulting
deasphalted oil through the above-described refining step; a mineral oil obtained
by isomerizing wax components; or a blended oil thereof. In the above solvent
refining, an aromatic extraction solvent such as phenol, furfural or N-methyl-pyrrolidone
can be used, whereas as a solvent for the solvent dewaxing, liquefied
propane, MEK/toluene, MEK/MIBK, or the like can be used. Among the above-described
mineral base stocks, hydro-refined oil is preferred from the standpoint
of oxidation stability and the like, and one containing, for example, 2 wt% or
less of aromatic hydrocarbons and 90 wt% or more of saturated hydrocarbons
can be used.
Examples of synthetic base stocks, on the other hand, can include
poly(α-olefin) oligomers of lubricating viscosity; polybutene; alkylbenzenes;
polyol esters such as trimethylolpropane esters and pentaerythritol esters; polyoxyalkylene
glycols; polyoxyalkylene glycol esters; polyoxyalkylene glycol
ethers; dibasic acid esters; phosphate esters; and silicone oils. These base stocks
can be used either singly or in combination. Further, usable examples of
vegetable base stocks can include rape seed oil, soybean oil, coconut oil, olive
oil and sunflower oil.
The lubricating base stock employed in the lubricating oil
composition according to the present invention can be produced by suitably
preparing a blended base stock so that the blended base stock has properties
desired for the intended application of the lubricating oil composition.
Concerning viscosity, for example, it is preferred to control the kinematic
viscosity at 100°C in a range of from 2 mm2/s to 30 mm2/s, especially from
3 mm2/s to 10 mm2/s for a lubricating oil for internal combustion engines, the
kinematic viscosity at 100°C in a range of from 2 mm2/s to 30 mm2/s, especially
from 3 mm2/s to 15 mm2/s for an automatic transmission fluid, and the kinematic
viscosity at 40°C in a range of from 10 mm2/s to 1,000 mm2/s, especially from
20 mm2/s to 500 mm2/s.
The metal sulfonate according to the present invention can exhibit
sufficient friction reducing effects when added to the lubricating base stock in a
proportion of from 0.01 to 10 wt%, preferably from 0.05 to 5 wt% based on the
whole weight of the lubricating oil composition or in a proportion of from I ppm
to 10,000 ppm, preferably from 50 ppm to 5,000 ppm in terms of the metal,
although the proportion varies depending on the application field of the lubricating
oil.
To the lubricating oil composition according to the present
invention, it is possible to add selected ones of viscosity index improvers, ashless
dispersants, oxidation inhibitors, extreme pressure agents, wear inhibitors, metal
deactivators, pour-point depressants, rust inhibitors, other friction modifiers and
other additives as needed.
Illustrative usable examples of the viscosity index improvers can
include polymethacrylates, polyisobutylenes, ethylene-propylene copolymers,
and hydrogenated styrene-butadiene copolymers. These viscosity index
improvers are used generally in a proportion of from 3 wt% to 35 wt%.
Illustrative of the ashless dispersants can be polybutenylsuccinimides,
polybutenylsuccinamides, benzylamines, and succinate esters.
They can be used generally in a proportion of from 0.05 wt% to 7 wt%.
Illustrative examples of the oxidation inhibitors can include amine-type
oxidation inhibitors such as alkylated diphenylamines, phenyl-α-naphthylamine
and alkylated phenyl-α-naphthylamines; phenolic oxidation inhibitors
such as 2,6-di-t-butylphenol and 4,4'-methylene-bis(2,6-di-t-butyl-phenol); and
zinc dithiophosphate. They can be used generally in a proportion of from
0.05 wt% to 5 wt%.
Illustrative of the extreme pressure agents can be dibenzyl sulfide
and dibutyl disulfide. They can be used generally in a proportion of from
0.05 wt% to 3 wt%.
Illustrative examples of the metal deactivators can include benzotriazole,
benzotriazole derivatives, and thiadiazole. They can be used generally
in a proportion of from 0.01 wt% to 3 wt%.
Illustrative of the pour-point depressants can be ethylene-vinyl
acetate copolymers, chlorinated paraffin-naphthalene condensation products,
polymethacrylates, and polyalkylstyrenes. They can be used generally in a
proportion of from 0.1 wt% to 10 wt%.
Illustrative of the wear inhibitors can be phosphate esters, zinc
thiophosphate, and sulfur compounds. They can be used generally in a
proportion of from 0.01 wt% to 5 wt%.
As preferred embodiments of the present invention, it is possible to
provide:
As a more preferable embodiment of the lubricating oil composition
according to the present invention, there is provided a lubricating oil
composition comprising as a base stock a hydro-refined oil, which contains
2 wt% or less of aromatic hydrocarbons and 90 wt% or more of saturated
hydrocarbons, and a calcium sulfonate containing 1 to 2 C14-24 alkyl groups per
organic sulfonic group and having an alkyl chain linearity of 40% or higher as
determined by a 13C-NMR measurement, said calcium sulfonate having been
added in a proportion of from 50 ppm to 5,000 ppm in terms of calcium based on
the whole weight of the lubricating oil composition.
As has been described above, the metal sulfonate according to the
present invention can be used as a friction modifier in hydraulic working oils,
wet brake oils, sliding surface oils, plastic working oils, cutting oils and the like
in addition to lubricating oils for internal combustion engines, automatic transmission
fluids and gear oils. Without being limited to them, the metal sulfonate
can be used without limitations in any other oils insofar as it can exhibit its
friction reducing effects.
The present invention will next be described specifically by
Examples and Comparative Examples. It is however to be noted that the
Examples and the like are to primarily demonstrate the unique effects of the
alkyl group or groups in the metal sulfonate according to the present invention
and that the present invention shall not be limited by these Examples and the
like.
The alkyl chain linearities of the metal sulfonates employed in the
following Examples and the performance evaluation of the lubricating oil
compositions were measured or conducted by the following methods.
Each metal sulfonate was converted into its corresponding sulfonic acid,
and under the following measuring conditions, its 13C-NMR spectrum was
measured. Further, its alkyl chain linearity was calculated in accordance
with the below-described formula.
Alkyl chain linearity (%) =
Integral intensity over the chemical shift range
of from 29 ppm to 31 ppm Sum of all integral intensity over the chemical shift range of from 5 ppm to 60 ppm x 100
| Measuring conditions | |
| Used instrument | EX400 (manufactured by JEOL Ltd.) |
| Observed nucleus | 13C |
| Observing frequency | 100.50 MHz |
| Measuring mode | Inverse gated 1H decoupling |
| Internal standard | TMS (= 0 ppm) |
| Relaxation reagent | Cr(acac)3 |
| Solvent | CDCl3 |
| Quantity of sample | 300 mg |
| Temperature | 30°C |
Concerning lubricating oil compositions with corresponding metal
sulfonates added in predetermined proportions, their friction coefficients
were measured under the following conditions by using "LFW-1" as a
testing machine.
| Friction materials | steel/steel |
| Load | 200 lb. |
| Oil temperature | 80°C |
| Revolution speed | 600 rpm |
| Measuring period | 30 minutes |
Provided was Calcium Sulfonate I of the following characteristics:
- Average number of alky I carbons per organic sulfonic group 31
- Alkyl chain linearity 47.2%
- Calcium content 2.8 wt%
- Total base number 25 mg-KOH/g
A lubricating oil composition was formulated by adding the
sulfonate to a solvent-refined mineral oil "100N" (kinematic viscosity at 100°C:
4.2 mm2/s) in a proportion of 140 ppm in terms of calcium based on the whole
weight of the lubricating oil composition. The friction coefficient of the
resultant lubricating oil composition was measured by the above-described
method. It was found to be 0.09.
A lubricating oil composition was formulated in exactly the same
manner as in Example 1 except that the proportion of Calcium Sulfonate 1 was
increased from 140 ppm to 560 ppm in terms of calcium. The resultant lubricating
oil composition was subjected to a performance evaluation. Its friction
coefficient was found to be 0.08, thereby indicating an improvement in friction
characteristics.
Provided was Calcium Sulfonate 2 of the following characteristics:
- Average number of alkyl carbons per organic sulfonic group 35
- Alkyl chain linearity 39.9%
- Calcium content 12 wt%
- Total base number 300 mg-KOH/g
A lubricating oil composition was formulated by adding the
sulfonate to the same lubricating base stock as that employed in Example 1 in a
proportion of 1,200 ppm in terms of calcium based on the whole weight of the
lubricating oil composition. The resultant lubricating oil composition was
subjected to the above-described performance evaluation. Its friction coefficient
was found to be 0.10.
A lubricating oil composition was formulated in exactly the same
manner as in Example 3 except that the proportion of Calcium Sulfonate 2 was
increased from 1,200 ppm to 2,400 ppm in terms of calcium. The resultant
lubricating oil composition was subjected to a performance evaluation. Its
friction coefficient was found to be 0.08.
Provided was Calcium Sulfonate 3 of the following characteristics:
- Average number of alky 1 carbons per organic sulfonic group 26
- Alkyl chain linearity 31.0%
- Calcium content 11.8 wt%
- Total base number 295 mg-KOH/g
A lubricating oil composition was formulated by adding the
sulfonate to the same lubricating base stock as that employed in Example 1 in a
proportion of 2,400 ppm in terms of calcium based on the whole weight of the
lubricating oil composition. The resultant lubricating oil composition was
subjected to the above-described performance evaluation. Its friction coefficient
was found to be 0.09.
A lubricating oil composition was formulated in exactly the same
manner as in Example 5 except that the proportion of Calcium Sulfonate 3 was
increased from 2,400 ppm to 4,800 ppm in terms of calcium. The resultant
lubricating oil composition was subjected to a performance evaluation. Its
friction coefficient was found to be 0.08.
Provided was Calcium Sulfonate 4 of the following characteristics:
- Average number of alkyl carbons per organic sulfonic group 33
- Alkyl chain linearity 17.2%
- Calcium content 12 wt%
- Total base number 300 mg-KOH/g
A lubricating oil composition was formulated by adding the
sulfonate to the same lubricating base stock as that employed in Example 1 in a
proportion of 2,400 ppm in terms of calcium based on the whole weight of the
lubricating oil composition. As a result of a performance evaluation, its friction
coefficient was found to be 0.13.
Provided was Calcium Sulfonate 5 of the following characteristics:
- Average number of alkyl carbons per organic sulfonic group 31
- Alkyl chain linearity 12.6%
- Calcium content 11.7 wt%
- Total base number 295 mg-KOH/g
A lubricating oil composition was formulated by adding the
sulfonate to the same lubricating base stock as that employed in Example 1 in a
proportion of 2,400 ppm in terms of calcium based on the whole weight of the
lubricating oil composition. The friction coefficient of the resultant lubricating
oil composition was found to be 0.14.
A lubricating oil composition was formulated in exactly the same
manner as in Comparative Example 2 except that the proportion of Calcium
Sulfonate 5 was increased from 2,400 ppm to 4,800 ppm in terms of calcium. Its
friction coefficient was found to be 0.13. The calcium sulfonate, the alkyl chain
linearity of which is low, was also found to be unable to bring about any substantial
advantageous effects on friction characteristics despite the increase in its
proportion.
The solvent-refined mineral oil "100N" (kinematic viscosity at
100°C: 4.2 mm2/s), which was employed as a lubricating base stock in Example
1, was subjected by itself to a performance evaluation. Its friction coefficient
was found to be 0.14.
The measurement results of the friction coefficients in the above
Examples and Comparative Examples and the calcium sulfonates employed
therein are summarized in Table 1 and Table 2, respectively. From these results,
it is appreciated that an alkyl chain linearity of 20% or higher in a metal
sulfonate provides a low friction coefficient even if the metal sulfonate is added
in a small proportion (Examples 1 and 2) whereas a lower alkyl chain linearity
cannot provide a low friction coefficient even if the proportion of the metal
sulfonate is increased (Comparative Example 3). From a comparison between
Comparative Example 2 and Comparative Example 4, it is indicated that use of a
metal sulfonate having a linearity lower than 20% results in a lubrication oil
composition the friction coefficient of which is the same as that of the base stock
alone. It has therefore been elucidated that the alkyl chain linearity is a primary
element governing friction characteristics.
From this it is readily seen that a metal sulfonate having an alkyl
chain linearity of 20% or higher is useful as a friction modifier for lubricating
oils, and can improve the friction characteristics of lubricating oil compositions.
Claims (9)
- A friction modifier comprising a metal sulfonate composed of an organic sulfonic group, which contains a hydrocarbon group, and a metal, characterized in that said hydrocarbon group is a chain hydrocarbon group or an aromatic group with at least one chain hydrocarbon group bonded thereto, and said chain hydrocarbon group has an alkyl chain linearity of 20% or higher as determined by a carbon nuclear magnetic resonance measurement (13C-NMR measurement).
- The friction modifier comprising a metal sulfonate as defined in claim 1, wherein said chain hydrocarbon group is an alkyl group.
- The friction modifier of claim 2 wherein the chain hydrocarbon group is one or more alkyl group each of which has 12-40 carbon atoms on average per organic sulfonic group as measured by 13C-NMR measurement.
- The friction modifier of claim 1, 2 or 3 wherein the chain hydrocarbon group has an alkyl chain linearity of 30% to 80% as determined by 13C-NMR measurement.
- A lubricating oil composition characterized in that said lubricating oil composition comprises:a base stock; anda metal sulfonate composed of an organic sulfonic group, which contains a hydrocarbon group, and a metal, said hydrocarbon group being a chain hydrocarbon group or an aromatic group with at least one chain hydrocarbon group bonded thereto, said chain hydrocarbon group being an alkyl group, said chain hydrocarbon group having an alkyl chain linearity of 20% or higher as determined by a carbon nuclear magnetic resonance measurement (13C-NMR measurement), and said metal sulfonate having been added in a proportion of from 1 ppm to 10,000 ppm in terms of the metal thereof based on a whole weight of said lubricating oil composition.
- The lubricating oil composition of claim 5 wherein the chain hydrocarbon group is an alkyl group.
- The lubricating oil composition of claim 6 wherein the chain hydrocarbon group is one or more alkyl group each of which has 12-40 carbon atoms on average per organic sulfonic group as measured by 13C-NMR measurement.
- The lubricating oil composition of claim 5, 6 or 7 wherein the chain hydrocarbon group has an alkyl chain linearity of 30% to 80% as determined by 13C-NMR measurement.
- The lubricating oil composition of claim 5, 6 or 7 further containing at least one additive selected from the group consisting of viscosity index improvers, ashless dispersants, oxidation inhibitors, extreme pressure agents, metal deactivators, pour point depressants, and wear inhibitors.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP157921/97 | 1997-05-31 | ||
| JP15792197 | 1997-05-31 | ||
| JP15792197 | 1997-05-31 | ||
| JP104021/98 | 1998-03-31 | ||
| JP10104021A JPH1143687A (en) | 1997-05-31 | 1998-03-31 | Friction reducer comprising metal sulfonate and lubricating oil composition containing the same |
| JP10402198 | 1998-03-31 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0881277A2 true EP0881277A2 (en) | 1998-12-02 |
| EP0881277A3 EP0881277A3 (en) | 1999-09-08 |
| EP0881277B1 EP0881277B1 (en) | 2005-08-17 |
| EP0881277B8 EP0881277B8 (en) | 2005-10-19 |
Family
ID=26444578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98304251A Expired - Lifetime EP0881277B8 (en) | 1997-05-31 | 1998-05-29 | Use of metal sulfonates as friction modifiers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0881277B8 (en) |
| JP (1) | JPH1143687A (en) |
| CA (1) | CA2235701C (en) |
| DE (1) | DE69831189T2 (en) |
| SG (1) | SG77644A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999055808A1 (en) * | 1998-04-27 | 1999-11-04 | Infineum Holdings B.V. | Lubricating oil compositions |
| EP1384769A1 (en) * | 2002-07-26 | 2004-01-28 | Chevron Oronite Company LLC | Method of improving the frictional properties of functional fluids |
| EP1930401A1 (en) * | 2006-11-21 | 2008-06-11 | Chevron Oronite Company LLC | Functional fluids comprising alkyl toluene sulfonates |
| US7407919B2 (en) | 2001-11-05 | 2008-08-05 | The Lubrizol Corporation | Sulfonate detergent system for improved fuel economy |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4673465B2 (en) * | 2000-05-17 | 2011-04-20 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
| JP5027426B2 (en) * | 2006-02-17 | 2012-09-19 | 昭和シェル石油株式会社 | Lubricant composition |
| JP5211126B2 (en) * | 2010-09-30 | 2013-06-12 | 東燃ゼネラル石油株式会社 | Lubricating oil composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3910994A (en) * | 1972-07-26 | 1975-10-07 | Universal Oil Prod Co | Alkylaromatic sulfonate detergent process |
| US4225446A (en) * | 1978-04-03 | 1980-09-30 | Calumet Industries, Inc. | Process for preparing highly basic magnesium sulfonates |
| GB2182948A (en) * | 1985-10-07 | 1987-05-28 | Nippon Oil Co Ltd | Automatic transmission fluid composition |
| EP0312313A1 (en) * | 1987-10-12 | 1989-04-19 | Exxon Chemical Patents Inc. | Overbased metal sulphonate composition |
-
1998
- 1998-03-31 JP JP10104021A patent/JPH1143687A/en active Pending
- 1998-05-25 CA CA002235701A patent/CA2235701C/en not_active Expired - Fee Related
- 1998-05-29 DE DE69831189T patent/DE69831189T2/en not_active Expired - Fee Related
- 1998-05-29 EP EP98304251A patent/EP0881277B8/en not_active Expired - Lifetime
- 1998-05-29 SG SG1998001723A patent/SG77644A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3910994A (en) * | 1972-07-26 | 1975-10-07 | Universal Oil Prod Co | Alkylaromatic sulfonate detergent process |
| US4225446A (en) * | 1978-04-03 | 1980-09-30 | Calumet Industries, Inc. | Process for preparing highly basic magnesium sulfonates |
| GB2182948A (en) * | 1985-10-07 | 1987-05-28 | Nippon Oil Co Ltd | Automatic transmission fluid composition |
| EP0312313A1 (en) * | 1987-10-12 | 1989-04-19 | Exxon Chemical Patents Inc. | Overbased metal sulphonate composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999055808A1 (en) * | 1998-04-27 | 1999-11-04 | Infineum Holdings B.V. | Lubricating oil compositions |
| US7407919B2 (en) | 2001-11-05 | 2008-08-05 | The Lubrizol Corporation | Sulfonate detergent system for improved fuel economy |
| EP1384769A1 (en) * | 2002-07-26 | 2004-01-28 | Chevron Oronite Company LLC | Method of improving the frictional properties of functional fluids |
| EP1930401A1 (en) * | 2006-11-21 | 2008-06-11 | Chevron Oronite Company LLC | Functional fluids comprising alkyl toluene sulfonates |
| US9550957B2 (en) | 2006-11-21 | 2017-01-24 | Chevron Oronite Company Llc | Functional fluids comprising alkyl toluene sulfonates |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0881277B1 (en) | 2005-08-17 |
| DE69831189D1 (en) | 2005-09-22 |
| EP0881277A3 (en) | 1999-09-08 |
| EP0881277B8 (en) | 2005-10-19 |
| CA2235701A1 (en) | 1998-11-30 |
| JPH1143687A (en) | 1999-02-16 |
| DE69831189T2 (en) | 2006-06-08 |
| CA2235701C (en) | 2007-05-22 |
| SG77644A1 (en) | 2001-01-16 |
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