WO2015140822A1 - Halogen free ionic liquids as lubricant or lubricant additives and a process for the preparation thereof - Google Patents
Halogen free ionic liquids as lubricant or lubricant additives and a process for the preparation thereof Download PDFInfo
- Publication number
- WO2015140822A1 WO2015140822A1 PCT/IN2015/050022 IN2015050022W WO2015140822A1 WO 2015140822 A1 WO2015140822 A1 WO 2015140822A1 IN 2015050022 W IN2015050022 W IN 2015050022W WO 2015140822 A1 WO2015140822 A1 WO 2015140822A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lubricant
- ionic liquids
- group
- alkyl
- oils
- Prior art date
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 130
- 239000000314 lubricant Substances 0.000 title claims abstract description 58
- 239000003879 lubricant additive Substances 0.000 title claims abstract description 41
- 229910052736 halogen Inorganic materials 0.000 title claims description 13
- 150000002367 halogens Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 11
- 230000008569 process Effects 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 45
- 239000000194 fatty acid Substances 0.000 claims abstract description 45
- 229930195729 fatty acid Natural products 0.000 claims abstract description 45
- -1 fatty acid anions Chemical class 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 239000002199 base oil Substances 0.000 claims abstract description 14
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 12
- 230000007797 corrosion Effects 0.000 claims abstract description 9
- 238000005260 corrosion Methods 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 31
- 239000010687 lubricating oil Substances 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 30
- 235000019198 oils Nutrition 0.000 claims description 30
- 229920005862 polyol Polymers 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 15
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 15
- 229940049964 oleate Drugs 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 13
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000007866 anti-wear additive Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000005069 Extreme pressure additive Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000006078 metal deactivator Substances 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 239000010702 perfluoropolyether Substances 0.000 claims description 3
- 239000010695 polyglycol Chemical class 0.000 claims description 3
- 229920000151 polyglycol Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- YFSQYUBYYKHCQV-UHFFFAOYSA-O 3-hexyl-2-methyl-1h-imidazol-3-ium Chemical compound CCCCCCN1C=C[NH+]=C1C YFSQYUBYYKHCQV-UHFFFAOYSA-O 0.000 claims description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940049918 linoleate Drugs 0.000 claims description 2
- ZCMHUGNELHZQDN-UHFFFAOYSA-N methyl-dioctyl-pentylazanium Chemical compound CCCCCCCC[N+](C)(CCCCC)CCCCCCCC ZCMHUGNELHZQDN-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- XXVRKIMVRXELHH-UHFFFAOYSA-M decanoate;tetrabutylazanium Chemical compound CCCCCCCCCC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC XXVRKIMVRXELHH-UHFFFAOYSA-M 0.000 claims 1
- RFIZPFHJZNYWCI-UHFFFAOYSA-M dodecanoate;tetrabutylazanium Chemical compound CCCCCCCCCCCC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC RFIZPFHJZNYWCI-UHFFFAOYSA-M 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 10
- 231100001261 hazardous Toxicity 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 238000005461 lubrication Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 230000001050 lubricating effect Effects 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 239000010409 thin film Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000007655 standard test method Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 241000199911 Peridinium Species 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 238000004813 Moessbauer spectroscopy Methods 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- QTIMEBJTEBWHOB-PMDAXIHYSA-N [3-[(z)-octadec-9-enoyl]oxy-2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COC(=O)CCCCCCC\C=C/CCCCCCCC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC QTIMEBJTEBWHOB-PMDAXIHYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- POXCLHSSNCIBMO-UHFFFAOYSA-N cyclohexyl-hexyl-dimethylazanium Chemical compound CCCCCC[N+](C)(C)C1CCCCC1 POXCLHSSNCIBMO-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002149 estolides Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Classifications
-
- 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
-
- 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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/1213—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms used as base material
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/1253—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as base material
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/077—Ionic Liquids
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
Definitions
- the present invention relates to halogen free ionic liquids based lubricant or lubricant additives and a process for the preparation thereof.
- the present invention provides lubricant or lubricant additives composed of halogen-, phosphorus, and sulphur-free ionic liquids containing fatty acid anions. More particularly, the invention relates to the reduction of friction and wears using these ionic liquids as lubricants or lubricant additives mixed with mineral, synthetic, native lube oils.
- the good lubricant should be able to (a) keep surfaces of working parts separate under all loads, temperatures and speed, thus reducing the friction and wear, (b) enhance the energy efficiency of the system, (c) dissipate the heat from the contact surfaces and (d) increase the life of sliding machine tools by- protecting their contact surfaces.
- Ionic liquids are poorly coordinated salts, composed of bulk organic cations and organic / inorganic anions, which exist in liquid phase at below 100 °C.
- ionic liquids have attracted significant attention for diversified range of applications owing to combination of their unique and tunable physico-chemical characteristics such as low vapor pressure, good thermal stability, non-flammability, excellent conductivity, high viscosity, favorable miscibility for organic and inorganic compounds etc.
- These features make ionic liquids as potential candidates for lubricant applications to reduce both friction and wear.
- High conductivity of ionic liquids dissipate the heat from contact surfaces, which reduced the material loss from contact surfaces.
- Most of ionic liquids are non-flammable, hence they are more safer in transport and storage perspective compared to the conventional lube oils. Many ionic liquids are non-volatile hence make a significant positive environmental impact.
- a lubrication oil composition comprises a major amount of a base oil and a minor amount of an additive which is a non-halide, non-aromatic ionic liquids with a general formula of C A . where cation C being a quaternary phosphonium or ammonium ion, and the anion A-. comprising at least one oxygen atom and having an ionic head group attached to at least one alkyl or alicyclic hydrocarbyl group.
- the ionic liquid may be used as anti-wear and a friction modifier in the lubricating oil composition.
- the lubricating oil composition may be used in an ignition engine.
- the addressed ionic liquids contains phosphorus and sulphur elements as main constituents, which are not only hazardous and toxic to environment, but also corrodes the engineering surfaces of metals.
- an invention relates to the use of ionic liquids for improving the lubricating effect of synthetic, mineral and native oils, in particular to an improved lubricating composition that is protected from thermal and oxidative attack.
- the ionic liquids addressed in this invention carries halogen, phosphorus and sulphur elements as main constituents which are not only hazardous and toxic to environment, but also corrodes the engineering surfaces of metals.
- the main object of the present invention is to provide halogen-free ionic liquids based lubricant or lubricant additives and a process for the preparation thereof.
- Another object of the present invention is to provide lubricants or lubricant additives composed of halogen-, phosphorus- and sulphur-free ionic liquids containing fatty acids anions, which exhibit superior friction-reducing, anti-wear propeities.
- Another object of the present invention is to provide halogen-, phosphorus- and sulphur-free ionic liquids as lubricant or lubricant additive, which minimize hazardous and corrosion effect to the environment and engineering surfaces.
- Still another object of the present invention is to provide ionic liquids that exhibits a better combination of friction, wear and heat transfer properties as compared with corresponding lubricant or lubricant additives.
- the present invention provides a lubricant or lubricant additive(s) composition
- a lubricant or lubricant additive(s) composition comprising an ionic liquid(s), wherein anions in the ionic liquid(s) are fatty acids of the general formula RCOO-, wherein R is selected from C4 to C30 straight chain alkyl, branched alkyl, straight or branched alkenyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl; alkyl or alkenyl group(s) containing heteroatom selected from -OH, -CN, -C-0-C-; and cations in the ionic liquids are selected from the group consisting of:
- Rl to R12 is similar or different from one another, selected from the group consisting of hydrogen, -OH, C I to C I 8 alkyl group(s) including straight chain or branched structures.
- the ionic liquids are substantially or completely free of halogen, phosphorous, and/or sulphur.
- ionic liquid are selected from Tetrabutyiammonium oleate (TBA-OL), 1-Hexyl— metliylimidazolium oleate (HMIM-OL) and Tetrabutyiammonium linoleate (TBA-LN), Tetrabutyiammonium caprylate, Tetrabutyiammonium caprate, Tetrabutyiammonium laurate, Tetrabutyiammonium myrisate, Hexyldimethylcyclohexyl ammonium oleate and Dioctylmethylpentylammonium oleate.
- the composition further comprising one or more additives selected from dispersants, corrosion inhibitors, detergents, antioxidants, anti-wear and extreme pressure additives, viscosity improvers, fiction improvers, oiliness improver, metal deactivator, demulsiiiers, pour point depressants, foam inhibitors, seal-swelling agents, antimicrobial.
- the lubricant or lubricant additive composition is having high friction reducing and anti-wearing properties.
- a lubricating oil comprising the lubricant additive composition and a base lubricating oil.
- the concentration of ionic liquid (s) as lubricant additive(s) in the base lubricant oil(s) is in the range of 0.5 to 10 wt %.
- the base lubricant oil(s) is selected from synthetic, minerals and native base stock (s) or base oil (s).
- the synthetic oils is selected from the group consisting of polymerized and interpolymerized olefins: polyalphaolefm (PAO) derived from olefins, dioi or triol or polyo!
- PAO polyalphaolefm
- mineral base oil (s) is selected from Group 1 (solvent refined mineral oils), Group II (hydrocracked mineral oils), Group III (severely hydrocracked oils, also referred to as synthetic or semi-synthetic oils), Group V (esters, napthenes, and others); native oil(s) as lube base stock (s) is selected from animal and vegetable oils, which are predominantly composed of triglycerides with minor components of mono- and diglycerides.
- step (b) extracting the organic layer as obtained in step (a) using dichloromethane followed by washing with water then removing dichloromethane under reduced pressure subsequently drying under reduced pressure to get lubricant or lubricant additive composed of ionic liquid.
- ionic liquids are salts of one or mixtures of fatty acids anions.
- the suitable cations for the present invention may be imidazolium, ammonium, peridinium, pyrolidinium, pyrrolidinium and the like.
- the contact surfaces are independently composed of metal, ceramic or alloys and more: including the thin film (s) of metallic or ceramic materials on the contact surfaces.
- Figure 1 represents a bar graph of the friction coefficient for three representative fatty acid ionic liquids and two conventional lube oils.
- Figure 2 represents a bar graph of the wear scar diameter (WSD) for three representative fatty acid ionic liquids and two conventional lube oils.
- Figure 3 represents a composite bar graph of (a) wear scar diameter and (b) friction coefficient of tetrabutylammonium oleate with function of their concentration (wt %) blended with polyol ester lube base.
- Ionic liquids are composed of ions (cations and anions) that are liquids at below 100 °C. Ionic liquids exhibit unique physico-chemical characteristics such as higher thermo-oxidative stability, negligible volatility, broad liquid range, non-flammability and excellent heat conductivity, which meet the requirements of high performance lubricants.
- the flexible molecular structure with diversified range of cations and anions makes ionic liquids as versatile lubricants or lubricant additives for different engineering surfaces.
- the inherent polarity of ionic liquids found to provide strong adsorption to the matting surfaces and forms thin film of low shearing strength, consequently, reduction in friction and wear.
- the present invention provides halogen-, phosphorus- and sulphur-free ionic liquids composed of diversified cations and fatty acid anions as lube oils for anti-wear and anti -friction performance.
- the lube oil can be comprised of a base oil and an ionic liquid or mixed of two or more ionic liquids formed of a cation and an anion and having an ion concentration of 0.5 wt % or more.
- fatty acids in the form of ionic liquids as anions with various types of cations have been developed as anti-wear and friction-reducing agent. Owing to inherent polar nature of these fatty acids anions, they prone to interact with metallic surfaces and forms thin film of low shear strength, which reduces both friction and wear more efficiently compared to that of free fatty acids and fatty acids esters.
- a preferred group of lube oil or lube base stock to which the ionic liquids can be added, use in the present invention may be consist of one or more base stock (s) or base oil (s) selected from synthetic, minerals and native base stock (s) or base oil (s). Natural and synthetic oils (or mixture thereof) can be used unrefined, refined or re-refined.
- the synthetic oils may be selected from polymerized and interpolymerized olefins including commonly used polyalphaolefin (PAO) derived from olefins.
- PAO polyalphaolefin
- the synthetic oil may be selected from a diol or triol or polyol esters or polypheny! ether or alkylated di- or triphenyl ether, alkylated naphthalenes, alkylated benzene, polyglycols, polyalkylglycols, silicon oils, perfluoropolyethers and so on.
- Mineral and synthetic lube base oil (s) or lube base stock (s) may be selected from Group I (solvent refined mineral oils).
- Group II hydrocracked mineral oils
- Group III severely hydrocracked oils, also referred to as synthetic or semi-synthetic oils
- Group V esters, napthenes, and others.
- oils Animal and vegetable oils (native oils) are predominantly composed of triglycerides with minor components of mono- and digh ccrides and other substances. These oils either as it is or in refined or chemically derived form by known methods such as trans-esterifi cations, hydrogenations, estolide formation and so on, may be selected to which ionic liquids can be added.
- the use of native oils based on renewable raw materials is important owing to their advantages with regard to biodegradability and reducing or preventing C0 2 emission.
- ionic liquid(s) added lubricants or ionic liquids as lubricants may contain one or more chemicals to provide other desired chemical and physical properties to the lubricating system.
- chemical additives includes dispersants, corrosion inhibitors, detergents, antioxidants, anti-wear and extreme pressure additives, viscosity improvers, friction improvers, oiliness improver, metal deactivator, demulsifiers, pour point depressants, foam inhibitors, seal-swelling agents, antimicrobial additives etc.
- aforementioned chemical additives are used in the ionic liquid(s) added lubricant in required quantity, to improve the performance characteristics and properties of the base oil(s) or base stock(s).
- halogen-, phosphorus- and sulphur-free ionic liquids are salts of one or mixtures of fatty acids anions.
- the general chemical structure of fatty acid (carboxylate) anion for the resent invention may be represented as formula I:
- R may be C 4 to C 30 straight chain alkyl, branched alkyl, alkenyl (one or more double bonds) includes with or without branched structure, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl and so on.
- the alkyl or alkenyl group(s) may contain heteroatom comprise groups such as -OH. - N.-C-O- - and so on.
- R 1 to R 12 may be the similar or different from one another, represents a group consisting of hydrogen, -OH, C ( to C i8 alkyl group(s) includes straight chain or branched structure, C 2 to C !2 alkenyl group(s) includes straight chain or branched structure wherein the alkyl or alkenyl group(s) may contain heteroatom, C- to C 12 arylalkyl group(s), C7 to C 12 alkylaryl group(s).
- the halogen-, phosphorus- and sulphur-free ionic liquids addressed in the present invention not only significantly reduces both friction coefficient and wear between two or more contact surfaces but also minimize the hazardous and corrosive effects.
- the addressed halogen-, phosphorus- and sulphur-free ionic liquids in the present invention meets all these objectives and has an emergent scope for their practical utilization in lubrication applications.
- TBA-OL ionic liquid may be represented by general formula III.
- TBA-OL was prepared by mixing sodium salt of oleic acid (0.05 mol) in an aqueous solution of tetrabutylammonium bromide (0.05 mol ) at 45 °C for 4 hours under continuous stirring. This led to the formation of an organic layer in the reaction product, which was extracted using dichloromethane. This was followed by washing of organic content composed of TBA-OL ionic liquid with pure water until no more bromide ions were detected in the water. Finally, dichloromethane was removed under reduced pressure and the extracted product was dried in a vacuum oven at 80°C under reduced pressure for 48 hours. The synthesized ionic liquid was characterized by ⁇ MR and FTl R spectroscopy. The characterization detail is as follow
- HM I M-OL ionic liquid may be represented by general formula IV.
- H I -OL was prepared by mixing an cqui molar quantity of sodium salt of oleic acid (0.05 mol) and l-hexyl-3- methyiimidazoiium bromide (0.05 mol) at 45 °C for 4 hours under continuous stirring.
- the prepared HMIM-OL ionic liquid was extracted using dichloromethane and washed with pure water for couple of times to remove the inorganic slat, until no more of bromide ions were detected in the water.
- Hexyl-3-methylimidzolium bromide an ionic liquid precursor was prepared by using an equimolar amount of 1-bromohexane (0.1 mol) and N-methylimidazole (0.1 mol) in a round bottom flask. The reaction mixture was heated at 75 °C for 36 hours under a nitrogen atmosphere with continuous
- TBA-L ionic liquid may be represented by general formula V.
- TBA-LN was prepared by mixing sodium salt of linoleic acid (0.05 mol) in an aqueous solution of tetrabutylammonium bromide (0.05 mo! ) at 45 °C for 4 hours under continuous stirring. This led to the formation of an organic layer in the reaction product, which was extracted using dichloromethane. This was followed by washing of organic content composed of TBA-LN ionic liquid with pure water until no more bromide ions were detected in the water. Finally, dichloromethane was removed under reduced pressure and the extracted product was dried in a vacuum oven at 80°C under reduced pressure for 48 hours.
- the synthesized ionic liquid was characterized by ⁇ NMR and FTIR spectroscopy. The characterization detail is as follows:
- Lubricating properties in terms of friction coefficient and wear scar diameter (hereon it will be known as WSD) for the fatty acid ionic liquids as lubricants were evaluated on a four-ball test machine as per the ASTM D4172 standard test method.
- two conventional lube oils (fully formulated 10W40 lube oil and pentaeiythritol tetraoleate, polyol ester) were also evaluated under similar test conditions.
- a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes.
- the thin film of ionic liquids on metal surfaces avoid the direct contact between steel balls, consequently significant reduction in material loss ( SD) as shown in Figure 2. It is noted that all these ionic liquids performed better than 10W40 oil and polyol ester lube base stock.
- variable concentrations (wt %) of fatty acid ionic liquid are mixed with the conventional polyol ester (pentaerythritol tetraoleate) lube base and then evaluated their friction coefficient and WSD on a four-ball test machine as per the ASTM D4172 standard test method.
- TBA-OL was selected as representative fatty acid ionic liquid for this study.
- the friction coefficient and WSD for polyol ester lube oil are found to be about 0.08 and 556 ⁇ . respective! ⁇ '. Both friction coefficient and WSD decreases significantly with increasing concentration of tetrabutylammonium oleate.
- the 2 wt% of tetrabutylammonium oleate in polyol ester lube base shows 56% and 22% reduction in friction coefficient and WSD, respectively, compared to that of polyol ester lube base.
- Lubricant with high viscosity can bear high contact pressure between moving surfaces, however, it's high internal friction provides larger resistance to the movement of the lubricating parts.
- a lubricant with low viscosity offers low resistance to shear but the lubricant can be squeezed out of the lubricating surfaces, that may lead to high friction and more energy loss.
- viscosities and viscosity index of 1.5 wt% fatty acids ionic liquids blended with polyol ester lube base stock are evaluated and shown in Table 1. There is no significant change in both kinematic viscosities at 40 and 100 °C, and viscosity index of polyol ester on blending of fatty acid ionic liquids. High viscosity index reveals that all blends of various fatty acid ionic liquids can be even used at high temperature and are suitable for lubrication applications.
- Table 1 Kinematic viscosity and viscosity index of polyol ester having 1.5 % various fatty acids ionic liquids.
- Lubrication properties in terms of friction coefficient and WSD for 1.5 wt% fatty acid ionic liquids as lubricants additive blended with polyol ester lube base were evaluated on a four-ball test machine as per the ASTM D4172 standard test metliod.
- conventional polyol ester lube base was also evaluated under similar test conditions.
- a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm ) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes.
- the four balls were fully flooded with a test lube sample, which was used for the friction and WSD evaluation.
- the friction force was measured during the tri bo-test and WSD on the lubricated steel balls was examined by the microscopic measurements.
- the friction coefficient and SD for representative fatty acid ionic liquids and polyol lube base are compared in Table 2. All fatty acid ionic liquids as additives having wide structural variations shows better lubricating properties by reducing both friction coefficient (upto 54%) and WSD (upto 30%) compared to that of for polyol ester lube base. This is attributed to the formation of tribo thin film on contact surfaces, which provides low resistance to shear and avoid the direct contact between the metallic surfaces, resulting in significant reduction in both friction coefficient and WSD.
- Table 2 WSD and friction coefficient of representative fatty acids ionic liquids blended ( 1.5 wt%) with polyol ester.
- All fatty acid ionic liquids as additives shows very good lubricating properties by reducing both friction coefficient (17 - 29%) and wear scar diameter (upto 37%) compared to that for 10W40 lube oil.
- the fully formulated 10W T 40 lube oil contains all required additives including friction improver and anti-wear additives, but still 1 wt% dose of these fatty acids ionic liquids in such fully formulated oil, shows significantly improved tribo-characteristics. This is attributed to the formation of tribo thin film of low shearing strength on the contact surfaces.
- the present invention on halogen-, phosphorus- and sulphur-free ionic liquids as lubricants or lubricant additives composed of fatty acids anions exhibit superior anti-wear and antifriction properties compared to the conventional lubricants.
- the main advantages of the present invention are: o provide lubricants or lubricant additives composed of halogen-, phosphorus- and sulphur- free ionic liquids containing fatty acids anions, which exhibit superior friction-reducing and anti-wear properties.
- o provide halogen-, phosphorus- and sulphur-free ionic liquids as lubricant or lubricant additive, which minimize hazardous and corrosion effect to the environment and engineering surfaces, respectively.
- o provide halogen-, phosphorus- and sulphur-free ionic liquids that exhibits a better combination of friction, wear and heat transfer properties as compared with corresponding lubricant or lubricant additives.
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Abstract
A lubricant or lubricant additive composed of halogen-, phosphorus- and sulphur-free ionic liquids containing fatty acid anions exhibit superior friction-reducing and anti-wear properties. Preferably, the lubricant composition comprises a base oil and an ionic liquid or mixed of two or more ionic liquids having concentration of 0.5 wt% or more. These halogen-, phosphorus- and sulphur-free ionic liquids as lubricant or lubricant additive have minimal hazardous and corrosion effect to the environment and engineering surfaces, respectively. General chemical formula of fatty acid anion is represented as RCOO¯; whereas R may be C4 to C30 straight chain alkyl, branched alkyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl, alkenyl (single or more double bonds) includes with or without branched structure and may contain heteroatom.
Description
HALOGEN FREE IONIC LIQUIDS AS LUBRICANT OR LUBRICANT ADDITIVES AND A PROCESS FOR THE PREPARATION THEREOF
FIELD OF THE INVENTION
The present invention relates to halogen free ionic liquids based lubricant or lubricant additives and a process for the preparation thereof. Particularly, the present invention provides lubricant or lubricant additives composed of halogen-, phosphorus, and sulphur-free ionic liquids containing fatty acid anions. More particularly, the invention relates to the reduction of friction and wears using these ionic liquids as lubricants or lubricant additives mixed with mineral, synthetic, native lube oils.
BACKGROUND AND PRIOR ART OF THE INVENTION
Need to conserve energy and the environment has catalyzed an interest to develop a new generation green lubricants or lubricant additives, which can improve the efficiency of engineering system, where two or more surfaces are in contact and moving relative to each other. The energy and material loss in such engineering system (pistons, pumps, clutches, bearing, turbines, cutting tools, MEMS and so on) can be reduced by using the appropriate lubricant and / or lubricant additives. The good lubricant should be able to (a) keep surfaces of working parts separate under all loads, temperatures and speed, thus reducing the friction and wear, (b) enhance the energy efficiency of the system, (c) dissipate the heat from the contact surfaces and (d) increase the life of sliding machine tools by- protecting their contact surfaces.
Ionic liquids are poorly coordinated salts, composed of bulk organic cations and organic / inorganic anions, which exist in liquid phase at below 100 °C. Over the last few years, ionic liquids have attracted significant attention for diversified range of applications owing to combination of their unique and tunable physico-chemical characteristics such as low vapor pressure, good thermal stability, non-flammability, excellent conductivity, high viscosity, favorable miscibility for organic and inorganic compounds etc. These features make ionic liquids as potential candidates for lubricant applications to reduce both friction and wear. High conductivity of ionic liquids dissipate the heat from contact surfaces, which reduced the material loss from contact surfaces. Most of ionic liquids are non-flammable, hence they are more safer in transport and storage perspective compared to the conventional lube oils. Many ionic liquids are non-volatile hence make a significant positive environmental impact.
Reference may be made to (C. Ye, W. Liu, Y. Chen and L. Yu, "Room-temperature ionic liquids: a novel versatile lubricants" Chem. Commun. 2001, 2244-5) wherein the potential of ionic liquids as versatile lubricants was illustrated. They have found that alkylimidazolium tetraflurophosphate as lubricant reduced the both friction and wear for the contact surfaces of steel, aluminium, copper, silicon dioxide, silicon nitride, aluminium oxide and ceramics. Since then, the interest in ionic liquids
as novel lubricants is steadily increasing. The drawbacks are the use of halogenated ionic liquids, which not only corrodes the tribo-surfaces but also pollute the environment.
A large number of studies have been made to explore lubrication capabilities of various ionic liquids having molecular structure flexibility with a diversified range of cations such as imidazolium, pyridinium, ammonium, phosphonium, sulfonium etc., and anions such as tetrafluoroborate, hexafluorophosphate, bis(trifluoromethanesulfonyl) amide, sulphonate etc. It was noted that the inherent polarity of ionic liquids facilitates their strong adsorption to the interacting (contact ) surfaces, consequently reductions in friction and wear owing to thin film formation. Reference may be made to (M. Uerdingen, C. Treber, M. Balser, G. Schmitt and C. Werner, "Corrosion behavior of ionic liquids" Green ( hem. 2005, 7, 321-25, B. S. Phillips, G. John, and J. S. Zabinski, " Surface chemistry of fluorine containing ionic liquids on steel substrates at elevated temperature using Mossbauer spectroscopy" Tribo. Lett. 2007, 26, 85-91 , F. Zhou, Y. Liang and W. Liu, "Ionic liquids lubricants: designed chemistry for engineering applications" Chem. Soc. Rev. 2009, 38, 2590-9 and L. Pisarova, C. Gabler, N. Dorr, E. Pittenauer and G. Allmaier, "Thermo-oxidative stability and corrosion properties of ammonium based ionic liquids" Tribo. Intl. 2012, 46, 75-83.), wherein the most of ionic liquids studied for lubricant applications, usually contains halogen either in simple or complex form (tetrafluroboarte, hexaflurophosphate, Trifluoromethanesulfonate, bis(trifluoromethansulfonyl)amide), which are sensitive to moisture, particularly hydrophilic ionic liquids are more sensitive. Eventually, the interactions of these ionic liquids with metallic surfaces under tribological conditions (high temperature and pressure) cause corrosion, which damages the contact surfaces in the mechanical system. Addition to that halogenated ionic liquids releases toxic and corrosive hydrogen halides to the surrounding environment. Therefore, the use of these ionic liquids as lubricant additives with various lube base stocks is a great challenge owing to their hazardous, toxic and corrosive nature to the environment and engineering surfaces.
Reference may be made to US Patent 2007/0027038 A l wherein the ionic liquids as base oils or as components are mixed with synthetic base oils in concentration of 1 mol/dm3 or more, exhibits low vapor pressure, is non-flammable, exhibits excellent heat resistance, has tribological characteristics equivalent to those of conventional hydrocarbon-based lube oils, and can be used for long time under very severe conditions such as high temperature and vacuum. The drawbacks are (a) no significant improvement in tribological properties and (b) use of halogenated ionic liquids, which pollute the environment by halogen exposure.
Reference may be made to US Patent No. 7754664 B2, that ionic liquids as lubricants or lubricant additives composed of ammonium cations and | F ;( ( CF;K S(0) |:. anion are effective for lubrication of many surfaces including aluminum and ceramic surfaces. Herein, all claimed ionic liquids exhibit halogen (fluorine) content, which not only corrodes the contact surfaces of metals but also pollute the environment by halogen exposure.
Reference may be made to US Patent No. 2010/0093577 A l, a lubrication oil composition comprises a major amount of a base oil and a minor amount of an additive which is a non-halide, non-aromatic ionic liquids with a general formula of C A . where cation C being a quaternary phosphonium or ammonium ion, and the anion A-. comprising at least one oxygen atom and having an ionic head group attached to at least one alkyl or alicyclic hydrocarbyl group. The ionic liquid may be used as anti-wear and a friction modifier in the lubricating oil composition. The lubricating oil composition may be used in an ignition engine. The addressed ionic liquids contains phosphorus and sulphur elements as main constituents, which are not only hazardous and toxic to environment, but also corrodes the engineering surfaces of metals.
Reference may be made to US Patent No. 2010/0187481 Al, an invention relates to the use of ionic liquids for improving the lubricating effect of synthetic, mineral and native oils, in particular to an improved lubricating composition that is protected from thermal and oxidative attack. The ionic liquids addressed in this invention carries halogen, phosphorus and sulphur elements as main constituents which are not only hazardous and toxic to environment, but also corrodes the engineering surfaces of metals.
Reference may be made to US Patent No. 8268760 B2 that anti-wear and anti-friction properties of a 5W30 lubricating oils can be improved by use of ionic liquids as additives in the range of 0.01 to 5 wt% based on the total weight of the lubricating oils. The cation in '760 B2 are imidazolium, peridinium, pyrrolidinium, phosphonium and ammonium, while anion are tetrafluroboarte, hexafluorophosphate, bis(trifluoromethylsulfonyl) imides and the like. Theses ionic liquids exhibit no significant reduction in both friction and wear by adding to 5W30 oil as lubricant additives and possesses halogen contents, which not only corrodes the contact surfaces made of metals but also pollute the environment.
Reference may be made to US Patent No. 2012/0202724 Al , a method in which an improved composition containing ionic liquids is used to enable operation of chains, steel ball, wheel bearing, roller bearing, sliding bearing and electric motors by reducing the evaporation loss and the lackification tendency of the lubricant against thermal and oxidative attack. The drawback is that ionic liquids have not been explored for friction and wear reduction. Additionally, the addressed ionic liquids were based on halogen content, which not only corrodes the contact surfaces made of metals but also pollute the environment by halogen exposure.
However, so far no attempt was made on development of halogen-, phosphorus- and sulphur-free ionic liquids composed of fatty acids anions as lubricant or lubricant additives to improve the lubricating properties by reducing friction coefficient and wear between two or more contact surfaces and to minimize the hazardous and corrosive effects to the environment and engineering surfaces, which are emergent call of the hours owing to strict government regulations and policies on environment and energy efficient processes development.
OBJECT OF THE INVENTION
The main object of the present invention is to provide halogen-free ionic liquids based lubricant or lubricant additives and a process for the preparation thereof.
Another object of the present invention is to provide lubricants or lubricant additives composed of halogen-, phosphorus- and sulphur-free ionic liquids containing fatty acids anions, which exhibit superior friction-reducing, anti-wear propeities.
Another object of the present invention is to provide halogen-, phosphorus- and sulphur-free ionic liquids as lubricant or lubricant additive, which minimize hazardous and corrosion effect to the environment and engineering surfaces.
Still another object of the present invention is to provide ionic liquids that exhibits a better combination of friction, wear and heat transfer properties as compared with corresponding lubricant or lubricant additives.
SUMMARY OF THE IN VENTION
Accordingly, the present invention provides a lubricant or lubricant additive(s) composition comprising an ionic liquid(s), wherein anions in the ionic liquid(s) are fatty acids of the general formula RCOO-, wherein R is selected from C4 to C30 straight chain alkyl, branched alkyl, straight or branched alkenyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl; alkyl or alkenyl group(s) containing heteroatom selected from -OH, -CN, -C-0-C-; and cations in the ionic liquids are selected from the group consisting of:
wherein Rl to R12 is similar or different from one another, selected from the group consisting of hydrogen, -OH, C I to C I 8 alkyl group(s) including straight chain or branched structures. C2 to C 12 alkenyl group(s) including straight chain or branched structures, wherein the alkyl or alkenyl group(s) optionally contain heteroatom, C7 to 1 2 aryia!kyl group(s), C7 to C I 2 alkylaryi group(s).
In an embodiment of the present invention the ionic liquids are substantially or completely free of halogen, phosphorous, and/or sulphur.
In one embodiment of the present invention ionic liquid are selected from Tetrabutyiammonium oleate (TBA-OL), 1-Hexyl— metliylimidazolium oleate (HMIM-OL) and Tetrabutyiammonium linoleate (TBA-LN), Tetrabutyiammonium caprylate, Tetrabutyiammonium caprate, Tetrabutyiammonium laurate, Tetrabutyiammonium myrisate, Hexyldimethylcyclohexyl ammonium oleate and Dioctylmethylpentylammonium oleate.
In another embodiment of the present invention the composition further comprising one or more additives selected from dispersants, corrosion inhibitors, detergents, antioxidants, anti-wear and extreme pressure additives, viscosity improvers, fiction improvers, oiliness improver, metal deactivator, demulsiiiers, pour point depressants, foam inhibitors, seal-swelling agents, antimicrobial.
Still in another embodiment of the present invention the lubricant or lubricant additive composition is having high friction reducing and anti-wearing properties. Still in another embodiment of the present invention a lubricating oil comprising the lubricant additive composition and a base lubricating oil.
Still in another embodiment of the present invention the concentration of ionic liquid (s) as lubricant additive(s) in the base lubricant oil(s) is in the range of 0.5 to 10 wt %.
Still in another embodiment of the present invention the base lubricant oil(s) is selected from synthetic, minerals and native base stock (s) or base oil (s).
Still in another embodiment of the present invention the synthetic oils is selected from the group consisting of polymerized and interpolymerized olefins: polyalphaolefm (PAO) derived from olefins, dioi or triol or polyo! esters or poh phenyl ether or alkylated di- or tri henyl ether, alkylated naphthalenes, alkylated benzene, polyglycols, polyalkylglycols, silicon oils, perfluoropolyethers; mineral base oil (s) is selected from Group 1 (solvent refined mineral oils), Group II (hydrocracked mineral oils), Group III (severely hydrocracked oils, also referred to as synthetic or semi-synthetic oils), Group V (esters, napthenes, and others); native oil(s) as lube base stock (s) is selected from animal and vegetable oils, which are predominantly composed of triglycerides with minor components of mono- and diglycerides.
Still in another embodiment of the present invention a process for the preparation of lubricant or lubricant additive composition comprising ionic liquid(s), wherein the said process comprises the steps of:
a) mixing sodium salt of fatty acid in an aqueous solution of tetraalkylammonium halide or di-/ tri-alklyimidazolium tot rati u o robo rate in 1 : 1 molar ratio with stirring at a temperature ranging between 20-100 C for a period of time ranging between 4 to 48 hours to get organic layer in reaction mixture; and
b) extracting the organic layer as obtained in step (a) using dichloromethane followed by washing with water then removing dichloromethane under reduced pressure subsequently drying under reduced pressure to get lubricant or lubricant additive composed of ionic liquid.
Still in one embodiment of the present invention, ionic liquids are salts of one or mixtures of fatty acids anions. The suitable cations for the present invention may be imidazolium, ammonium, peridinium, pyrolidinium, pyrrolidinium and the like.
In yet another embodiment of the present invention the contact surfaces are independently composed of metal, ceramic or alloys and more: including the thin film (s) of metallic or ceramic materials on the contact surfaces. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 represents a bar graph of the friction coefficient for three representative fatty acid ionic liquids and two conventional lube oils.
Figure 2 represents a bar graph of the wear scar diameter (WSD) for three representative fatty acid ionic liquids and two conventional lube oils.
Figure 3 represents a composite bar graph of (a) wear scar diameter and (b) friction coefficient of tetrabutylammonium oleate with function of their concentration (wt %) blended with polyol ester lube base.
DETAILED DESCRIPTION OF THE INVENTION
Ionic liquids are composed of ions (cations and anions) that are liquids at below 100 °C. Ionic liquids exhibit unique physico-chemical characteristics such as higher thermo-oxidative stability, negligible volatility, broad liquid range, non-flammability and excellent heat conductivity, which meet the requirements of high performance lubricants. The flexible molecular structure with diversified range of cations and anions makes ionic liquids as versatile lubricants or lubricant additives for different engineering surfaces. The inherent polarity of ionic liquids found to provide strong adsorption to the matting surfaces and forms thin film of low shearing strength, consequently, reduction in friction and wear.
The present invention provides halogen-, phosphorus- and sulphur-free ionic liquids composed of diversified cations and fatty acid anions as lube oils for anti-wear and anti -friction performance. The lube oil can be comprised of a base oil and an ionic liquid or mixed of two or more ionic liquids formed of a cation and an anion and having an ion concentration of 0.5 wt % or more.
In this invention, fatty acids in the form of ionic liquids as anions with various types of cations have been developed as anti-wear and friction-reducing agent. Owing to inherent polar nature of these fatty acids anions, they prone to interact with metallic surfaces and forms thin film of low shear strength, which reduces both friction and wear more efficiently compared to that of free fatty acids and fatty acids esters.
A preferred group of lube oil or lube base stock to which the ionic liquids can be added, use in the present invention may be consist of one or more base stock (s) or base oil (s) selected from synthetic, minerals and native base stock (s) or base oil (s). Natural and synthetic oils (or mixture thereof) can be used unrefined, refined or re-refined.
The synthetic oils may be selected from polymerized and interpolymerized olefins including commonly used polyalphaolefin (PAO) derived from olefins. In addition, the synthetic oil may be
selected from a diol or triol or polyol esters or polypheny! ether or alkylated di- or triphenyl ether, alkylated naphthalenes, alkylated benzene, polyglycols, polyalkylglycols, silicon oils, perfluoropolyethers and so on.
Mineral and synthetic lube base oil (s) or lube base stock (s) may be selected from Group I (solvent refined mineral oils). Group II (hydrocracked mineral oils), Group III (severely hydrocracked oils, also referred to as synthetic or semi-synthetic oils), Group V (esters, napthenes, and others).
Animal and vegetable oils (native oils) are predominantly composed of triglycerides with minor components of mono- and digh ccrides and other substances. These oils either as it is or in refined or chemically derived form by known methods such as trans-esterifi cations, hydrogenations, estolide formation and so on, may be selected to which ionic liquids can be added. The use of native oils based on renewable raw materials is important owing to their advantages with regard to biodegradability and reducing or preventing C02 emission.
In the present invention, ionic liquid(s) added lubricants or ionic liquids as lubricants may contain one or more chemicals to provide other desired chemical and physical properties to the lubricating system. Such chemical additives includes dispersants, corrosion inhibitors, detergents, antioxidants, anti-wear and extreme pressure additives, viscosity improvers, friction improvers, oiliness improver, metal deactivator, demulsifiers, pour point depressants, foam inhibitors, seal-swelling agents, antimicrobial additives etc. In the present invention, aforementioned chemical additives are used in the ionic liquid(s) added lubricant in required quantity, to improve the performance characteristics and properties of the base oil(s) or base stock(s).
In the present invention, halogen-, phosphorus- and sulphur-free ionic liquids are salts of one or mixtures of fatty acids anions. The general chemical structure of fatty acid (carboxylate) anion for the resent invention may be represented as formula I:
The structure of suitable cations for the present invention may be represented as general formula II.
Herein, R1 to R12 may be the similar or different from one another, represents a group consisting of hydrogen, -OH, C( to Ci8 alkyl group(s) includes straight chain or branched structure, C2 to C!2 alkenyl group(s) includes straight chain or branched structure wherein the alkyl or alkenyl group(s) may contain heteroatom, C- to C12 arylalkyl group(s), C7 to C12 alkylaryl group(s).
The halogen-, phosphorus- and sulphur-free ionic liquids addressed in the present invention, not only significantly reduces both friction coefficient and wear between two or more contact surfaces but also minimize the hazardous and corrosive effects. Increasing strict regulations and government policies on (a) use of environment friendly lubricants and / or lubricant additives, and (b) improve the fuel efficiency in engineering systems, particularly in automotive industries, have propelled an interest to develop environment-friendly and energy efficient lubricants and lubricant additive. The addressed halogen-, phosphorus- and sulphur-free ionic liquids in the present invention meets all these objectives and has an emergent scope for their practical utilization in lubrication applications.
EXAMPLES
The following examples serve to provide the best modes of practice for the present invention, and should not be constructed as limiting the scope of the invention:
Example 1
Preparation of Halogen-. Phosphorus- and Sulphur-Free Ionic Liquids Containing Fatty Acid Anions (a) Tetrabutylammonium oleate (TBA-OL)
TBA-OL ionic liquid may be represented by general formula III. TBA-OL was prepared by mixing sodium salt of oleic acid (0.05 mol) in an aqueous solution of tetrabutylammonium bromide (0.05 mol ) at 45 °C for 4 hours under continuous stirring. This led to the formation of an organic layer in the reaction product, which was extracted using dichloromethane. This was followed by washing of organic content composed of TBA-OL ionic liquid with pure water until no more bromide ions were detected in the water. Finally, dichloromethane was removed under reduced pressure and the extracted product was dried in a vacuum oven at 80°C under reduced pressure for 48 hours. The synthesized ionic liquid was characterized by Ή MR and FTl R spectroscopy. The characterization detail is as follow
¾ NMR (ppm): 0.88-1.1 (t, 15Hg>k CH3), 1.2-1.4 (m, 12HCJ CH2), 1.45- 1.7 (m, 24Hd>! CH2), 1.9-2.1 (m, 4He CH2), 2.3-2.4 (m, 2Hb CH2), 2.45-2.55 (m, 2Ha CH2), 2.85-3.0 (t, 8H„ N-CH2), 5.3-5.4 (m, 2Hf CH=CH).
FTIR (cm 1): 3010, 2929, 2855, 1764, 1631, 1460, 1375, 1280, 1237, 1105, 993, 721.
(b) 1 -Hexyl— methylimidazolium oleate (HMIM-OL)
HM I M-OL ionic liquid may be represented by general formula IV. H I -OL was prepared by mixing an cqui molar quantity of sodium salt of oleic acid (0.05 mol) and l-hexyl-3- methyiimidazoiium bromide (0.05 mol) at 45 °C for 4 hours under continuous stirring. The prepared HMIM-OL ionic liquid was extracted using dichloromethane and washed with pure water for couple of times to remove the inorganic slat, until no more of bromide ions were detected in the water.
Finally, dichloromethane was removed under reduced pressure and the extracted HMIM-OL ionic liquid was dried in a vacuum oven at 80°C under reduced pressure for 48 hours. Prior to this, I-
Hexyl-3-methylimidzolium bromide, an ionic liquid precursor was prepared by using an equimolar amount of 1-bromohexane (0.1 mol) and N-methylimidazole (0.1 mol) in a round bottom flask. The reaction mixture was heated at 75 °C for 36 hours under a nitrogen atmosphere with continuous
Stirling. The prepared I -liexvl -3 -meth y I i m idazol i urn bromide was purified by washing with ethyl acetate and then used for the synthesis of HMIM-OL ionic liquid. The synthesized ionic liquid was characterized by Ή NMR and FTIR spectroscopy. The characterization detail is as follows:
¾ NMR (ppm ): 0.86-0.88 (m, 6H&, CH3), 1.26-1.29 (m, 22H( kj CH2), 1.54-1.55 (m, 4HC CH2), 1.81- 1.82 (m, 2Hm CH2), 2.0-2.1 (m, 4He CH2), 2.13-2.15 (m, 2Hb CH2), 2.75-2.8 (t, 2Ha, CH2COO), 3.94-3.96 (s, 3Hh, N-CH3), 4.19-4.22 (t, 2Hn, N-CH2), 5.31-5.34 (q, 2Hf CH=CH), 7.49 & 7.34 (s, 2Hp,0 CH), 9.6 (s, lHq CH).
FTIR (cm 1 ): 3149, 3080, 3006, 2956, 2926, 2852, 1718, 1635, 1569, 1465, 1377, 1277, 1242, 1 168, 991, 831, 721.
TBA-L ionic liquid may be represented by general formula V. TBA-LN was prepared by mixing sodium salt of linoleic acid (0.05 mol) in an aqueous solution of tetrabutylammonium bromide (0.05 mo! ) at 45 °C for 4 hours under continuous stirring. This led to the formation of an organic layer in the reaction product, which was extracted using dichloromethane. This was followed by washing of organic content composed of TBA-LN ionic liquid with pure water until no more bromide ions were detected in the water. Finally, dichloromethane was removed under reduced pressure and the extracted product was dried in a vacuum oven at 80°C under reduced pressure for 48 hours. The synthesized ionic liquid was characterized by Ή NMR and FTIR spectroscopy. The characterization detail is as follows:
¾ NMR (ppm): 0.86-0.89 (m, 1 H„, ( ! !·.). 0.98-1 .01 (m, 14Hd>k CH2), 1.26-1.3 (m, 2HC CH2), 1.41 - 1.48 (q, 2Hj CH2), 1.61-1.67 (m, 4He CH2), 1.95-2.1 (m, 2Hb CH2), 2.3-2.37 (m, 2Ha CH2COO), 2.65- 2.7 (m, 2Ho CH2), 3.32-3.35 (m, 8H„ N-CH2), 5.3-5.4 (m, 4Hf, CH=CH).
FTIR (cm"1): 3008, 2960, 2929, 2859, 1727, 1463, 1383, 1178, 1 108, 1031 , 737.
Example 2
Friction-reducing and Anti-Wear Properties of Fatty Acids Ionic liquids as Lubricants
Lubricating properties in terms of friction coefficient and wear scar diameter (hereon it will be known as WSD) for the fatty acid ionic liquids as lubricants were evaluated on a four-ball test machine as per
the ASTM D4172 standard test method. For comparison purpose, two conventional lube oils (fully formulated 10W40 lube oil and pentaeiythritol tetraoleate, polyol ester) were also evaluated under similar test conditions. In a typical experiment, a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes. During the experiments, the four balls were fully flooded with a test lube sample, which was used for the friction and WSD evaluation. The friction force was measured during the tribo-test and WSD on the lubricated steel balls was examined by the microscopic measurements. The friction coefficient and WSD for three representative fatty acid ionic liquids and two conventional lubricants are compared in Figure 1 and 2. All ionic liquids show very good lubricity with significant reduction in both friction coefficient and WSD compared to that of fully formulated 10W40 lube oil and polyol ester lube base stock. Under tribo-stress, carboxylic anions prepare a thin film of low shearing strength, resulting in large reduction in friction as shown in Figure 1. The thin film of ionic liquids on metal surfaces avoid the direct contact between steel balls, consequently significant reduction in material loss ( SD) as shown in Figure 2. It is noted that all these ionic liquids performed better than 10W40 oil and polyol ester lube base stock.
Example 3
Effect of Fatty Acid Ionic Liquid Concentration as Lubricant Additive on their Lubrication Properties In order to improve the lubrication properties, variable concentrations (wt %) of fatty acid ionic liquid are mixed with the conventional polyol ester (pentaerythritol tetraoleate) lube base and then evaluated their friction coefficient and WSD on a four-ball test machine as per the ASTM D4172 standard test method. TBA-OL was selected as representative fatty acid ionic liquid for this study. In a typical experiment, a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm ) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes. During the experiments, the four balls were fully flooded with a test lube sample. The friction force was measured during the tribo-test and WSD on the lubricated steel balls was examined by microscopic measurements. Figure 3 shows the changes in friction coefficient and W SD for different dose (0 to 2 wt %) of tetrabutylammonium oleate in the polyol ester lube base. The friction coefficient and WSD for polyol ester lube oil are found to be about 0.08 and 556 μιη. respective!}'. Both friction coefficient and WSD decreases significantly with increasing concentration of tetrabutylammonium oleate. The 2 wt% of tetrabutylammonium oleate in polyol ester lube base shows 56% and 22% reduction in friction coefficient and WSD, respectively, compared to that of polyol ester lube base. These results illustrate the ability of fatty' acid ionic liquid as an additive to improve the friction-reduction and anti-wear properties of convention lube base oil s.
Example 4
Friction-reducing and Anti-wear Performance of Representative Fatty Acid Ionic Liquids as Lubricant Additives in Polyol Ester Lube Base
In another set of experiment, eleven representative fatty acid ionic liquids as lubricant additives have been selected for lubrication performance. These fatty acid ionic liquids exhibit structural variations in anions (chain length and degree of unsaturation) and counter cations (ammonium, imidazolium). The structural changes in fatty acid anions influence the physico-chemical properties of ionic liquids. Viscosity is an important physical property of lubricant, which changes with temperature and plays crucial role to monitor lubrication and oil conditioning. Lubricant with high viscosity can bear high contact pressure between moving surfaces, however, it's high internal friction provides larger resistance to the movement of the lubricating parts. In contrast, a lubricant with low viscosity offers low resistance to shear but the lubricant can be squeezed out of the lubricating surfaces, that may lead to high friction and more energy loss. In the present invention, viscosities and viscosity index of 1.5 wt% fatty acids ionic liquids blended with polyol ester lube base stock are evaluated and shown in Table 1. There is no significant change in both kinematic viscosities at 40 and 100 °C, and viscosity index of polyol ester on blending of fatty acid ionic liquids. High viscosity index reveals that all blends of various fatty acid ionic liquids can be even used at high temperature and are suitable for lubrication applications.
Table 1: Kinematic viscosity and viscosity index of polyol ester having 1.5 % various fatty acids ionic liquids.
Lubrication properties in terms of friction coefficient and WSD for 1.5 wt% fatty acid ionic liquids as lubricants additive blended with polyol ester lube base were evaluated on a four-ball test machine as per the ASTM D4172 standard test metliod. For comparison purpose, conventional polyol ester lube
base was also evaluated under similar test conditions. In a typical experiment, a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm ) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes. During the experiments, the four balls were fully flooded with a test lube sample, which was used for the friction and WSD evaluation. The friction force was measured during the tri bo-test and WSD on the lubricated steel balls was examined by the microscopic measurements. The friction coefficient and SD for representative fatty acid ionic liquids and polyol lube base are compared in Table 2. All fatty acid ionic liquids as additives having wide structural variations shows better lubricating properties by reducing both friction coefficient (upto 54%) and WSD (upto 30%) compared to that of for polyol ester lube base. This is attributed to the formation of tribo thin film on contact surfaces, which provides low resistance to shear and avoid the direct contact between the metallic surfaces, resulting in significant reduction in both friction coefficient and WSD.
Table 2: WSD and friction coefficient of representative fatty acids ionic liquids blended ( 1.5 wt%) with polyol ester.
Example 5
Friction-reducing and Anti-wear Performance of Representative Fatty Acids Ionic Liquids as Lubricant Additives in 10W40 Lube
In another set of experiment, seven representative fatty acids ionic liquids as lubricant additives were blended with I0W40 lube oil and then evaluated for lubricity performance . Herein, the 10W40 lube oil is fully formulated commercial oil and contains all required additives in order to provide good lubrication performance. Lubricating propeities in terms of friction coefficient and WSD for 1.0 wt%
variable fatty aeid ionic liquids as lubricants additive blended with 10Wr40 lube oil were evaluated on a four-ball test machine as per the ASTM D4172 standard test method. For comparison purpose, 10W40 lube oil was also evaluated under similar test conditions. In a typical experiment, a 12.7 mm steel ball under the 392 N load is rotated (rotating speed: 1200 rpm) against three stationary steel balls clamped in the holder at temperature of 75 °C for a test duration of 60 minutes. During the experiments, the four balls were fully flooded with a test lube sample, which was used for the friction and WSD evaluation. The friction force was measured during the tribo-test and SD on the lubricated steel balls was examined by microscopic measurements. The friction coefficient and WSD for representative fatty acid ionic liquids as additives and 10W40 lube oil are compared in Table 3. All fatty acid ionic liquids as additives shows very good lubricating properties by reducing both friction coefficient (17 - 29%) and wear scar diameter (upto 37%) compared to that for 10W40 lube oil. Though the fully formulated 10WT40 lube oil contains all required additives including friction improver and anti-wear additives, but still 1 wt% dose of these fatty acids ionic liquids in such fully formulated oil, shows significantly improved tribo-characteristics. This is attributed to the formation of tribo thin film of low shearing strength on the contact surfaces.
Table 3: WSD and friction coefficient of representative fatty acids ionic liquids blended (1 wt%) with
10W40 lube oil
I conclusion, the present invention on halogen-, phosphorus- and sulphur-free ionic liquids as lubricants or lubricant additives composed of fatty acids anions exhibit superior anti-wear and antifriction properties compared to the conventional lubricants.
THE ADVANTAGES OF THE PRESENT INVENTION
The main advantages of the present invention are:
o provide lubricants or lubricant additives composed of halogen-, phosphorus- and sulphur- free ionic liquids containing fatty acids anions, which exhibit superior friction-reducing and anti-wear properties.
o provide halogen-, phosphorus- and sulphur-free ionic liquids as lubricant or lubricant additive, which minimize hazardous and corrosion effect to the environment and engineering surfaces, respectively.
o provide halogen-, phosphorus- and sulphur-free ionic liquids that exhibits a better combination of friction, wear and heat transfer properties as compared with corresponding lubricant or lubricant additives.
Claims
1. A lubricant or lubricant additive(s) composition comprising an ionic liquid(s), wherein anions in the ionic liquid(s) are fatty acids of the general formula RCOO . wherein R is selected from C4 to C3o straight chain alkyl, branched alkyl, straight or branched alkenyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl; alkyl or alkenyl group(s) containing heteroatom selected from - -CN, -C-0-C-; and cations in the ionic liquids are selected from the group consisting of:
wherein R1 to R12 is similar or different from one another, selected from the group consisting of hydrogen, -OH, C i to Cis alkyl group(s) including straight chain or branched structures, C2 to C12 alkenyl group(s) including straight chain or branched structures, wherein the alkyl or alkenyl group(s) optionally contain heteroatom, C- to Cn arylalkyl group(s), C- to C12 alkylaryl group(s).
2. The composition as claimed in claim 1, wherein the ionic liquids are substantially or completely free of halogen, phosphorous, and/or sulphur.
3. The composition as claimed in claim 1, wherein ionic liquid are selected from Tetrabutylammonium oleate (TBA-OL), 1-Hexyl— methylimidazolium oleate (HMIM-OL) and Tetrabutylammonium linoleate (TBA-LN ). Tetrabutylammonium caprylatc. Tetrabutylammonium caprate, Tetrabutylammonium laurate, Tetrabutylammonium myrisate,
Hexyldimethylcyclohexyiammonium oleate and Dioctylmethylpentylammonium oleate.
4. The composition as claimed in claim 1, further comprising one or more additives selected from dispersants, corrosion inhibitors, detergents, antioxidants, anti-wear and extreme pressure additives, viscosity improvers, fiction improvers, oiliness improver, metal deactivator, demuisifiers, pour point depressants, foam inhibitors, seal-swelling agents, antimicrobial.
5. The lubricant or lubricant additive composition as claimed in claim 1 is having high friction reducing and anti-wearing properties.
6. A lubricating oil comprising the lubricant additive composition as claimed in any of the preceding claims and a base lubricating oil.
7. The lubricating oil as claimed in claim 6, wherein the concentration of ionic liquid (s) as lubricant additive(s) in the base lubricant oil(s) is in the range of 0.5 to 10 wt %.
8. The lubricating oil as claimed in claim 6 or 7, wherein the base lubricant oil(s) is selected from synthetic, minerals and native base stock (s) or base oil (s).
9. The lubricating oil as claimed in claim 8, wherein the synthetic oils is selected from the group consisting of polymerized and interpoh nierizcd olefins: polyalphaoiefin (PAO) derived from olefins, diol or triol or polyol esters or polyphenyl ether or alkylated di- or tri phenyl ether, alkylated naphthalenes, alkylated benzene, polyglycols, polyalkylglycols, silicon oils, perfluoropolyethers; mineral base oil (s) is selected from Group I (solvent refined mineral oils), Group 11 (hvdrocracked mineral oils). Group III (severely hydrocracked oils, also referred to as synthetic or semi-synthetic oils), Group V (esters, napthenes, and others); native oil(s) as lube base stock (s) is selected from animal and vegetable oils, which are predominantly composed of triglycerides with minor components of mono- and diglycerides.
10. A process for the preparation of lubricant or lubricant additive composition comprising ionic liquid(s) as claimed in claim 1, wherein the said process comprises the steps of:
a) mixing sodium salt of fatty acid in an aqueous solution of tetraalkylammonium halide or di-/ tri-alklyimidazolium tetrafluoroborate in 1 : 1 molar ratio with stirring at a temperature ranging between 20- 100 C for a period of time ranging between 4 to 48 hours to get organic layer in reaction mixture; and
b) extracting the organic layer as obtained in step (a) using dichloromethane followed by- washing with water then removing dichloromethane under reduced pressure
subsequently drying under reduced pressure to get lubricant or lubricant additive composed of ionic liquid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15722777.8A EP3119859A1 (en) | 2014-03-18 | 2015-03-17 | Halogen free ionic liquids as lubricant or lubricant additives and a process for the preparation thereof |
| US15/126,963 US20170096614A1 (en) | 2014-03-18 | 2015-03-17 | Halogen free ionic liquids as lubricant or lubricant additives and a process for the preparation thereof |
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| IN790DE2014 | 2014-03-18 | ||
| IN0790/DEL/2014 | 2014-03-18 |
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