US20150232782A1 - Lubricant compositions - Google Patents
Lubricant compositions Download PDFInfo
- Publication number
- US20150232782A1 US20150232782A1 US14/421,473 US201314421473A US2015232782A1 US 20150232782 A1 US20150232782 A1 US 20150232782A1 US 201314421473 A US201314421473 A US 201314421473A US 2015232782 A1 US2015232782 A1 US 2015232782A1
- Authority
- US
- United States
- Prior art keywords
- lubricant composition
- lubricant
- composition according
- viscosity
- oil
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 137
- 239000000314 lubricant Substances 0.000 title claims abstract description 108
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 30
- 229920002545 silicone oil Polymers 0.000 claims abstract description 18
- -1 tackifiers Substances 0.000 claims description 87
- 229920013639 polyalphaolefin Polymers 0.000 claims description 62
- 239000012530 fluid Substances 0.000 claims description 36
- 239000002480 mineral oil Substances 0.000 claims description 34
- 239000003921 oil Substances 0.000 claims description 31
- 235000010446 mineral oil Nutrition 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000000654 additive Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 230000001050 lubricating effect Effects 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000002199 base oil Substances 0.000 claims description 11
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000004519 grease Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 239000005069 Extreme pressure additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 235000006708 antioxidants Nutrition 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229940123457 Free radical scavenger Drugs 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 3
- 239000007866 anti-wear additive Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 239000004599 antimicrobial Substances 0.000 claims description 2
- 239000007865 axle lubricant Substances 0.000 claims description 2
- 239000012208 gear oil Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims 1
- 239000002585 base Substances 0.000 description 27
- 235000019198 oils Nutrition 0.000 description 27
- 238000012360 testing method Methods 0.000 description 25
- 101150085511 PEDS1 gene Proteins 0.000 description 24
- 102100037592 Plasmanylethanolamine desaturase Human genes 0.000 description 24
- 229920003199 poly(diethylsiloxane) Polymers 0.000 description 24
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 22
- 239000004205 dimethyl polysiloxane Substances 0.000 description 21
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 14
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 238000005461 lubrication Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 231100000241 scar Toxicity 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 6
- 0 [1*][Si]([2*])([3*])O[Si]([4*])(C)O[Si]([5*])([5*])O[Si](C)(C)O[Si]([1*])([2*])[3*] Chemical compound [1*][Si]([2*])([3*])O[Si]([4*])(C)O[Si]([5*])([5*])O[Si](C)(C)O[Si]([1*])([2*])[3*] 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012612 commercial material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical group N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004966 cyanoalkyl group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000003106 haloaryl group Chemical group 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 125000001190 organyl group Chemical group 0.000 description 2
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 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 2
- 150000003900 succinic acid esters Chemical class 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 150000003568 thioethers Chemical group 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RDAGYWUMBWNXIC-UHFFFAOYSA-N 1,2-bis(2-ethylhexyl)benzene Chemical compound CCCCC(CC)CC1=CC=CC=C1CC(CC)CCCC RDAGYWUMBWNXIC-UHFFFAOYSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Definitions
- lubricant compositions comprising a non silicone lubricant base stock and a silicone oil.
- Lubricant oils and compositions are used to reduce friction and wear between moving elements or surfaces.
- the main component of lubricant oils and compositions is commonly referred to as a base stock.
- Base stocks are classified by the American Petroleum Institute in five Groups, namely Groups I, II, III, IV and V.
- Lubricant base stocks include natural lubricating oils, synthetic lubricating oils, and mixtures thereof.
- Groups I to III include base stocks derived from petroleum based oils, while Groups IV and V include synthetic base stocks including silicones.
- Viscosity Index is an empirical, unit less number which indicates the rate of change in the viscosity of an oil in a given temperature range, usually between 40° C. and 100° C.
- the Viscosity Index is defined as the gradient of kinematic viscosities of a material, between 40° C. and 100° C. When the Viscosity Index is low (below 100) the fluid exhibits a relatively large change of viscosity with temperature. When the Viscosity Index is high (above 150), the fluid exhibits relatively less change of viscosity with temperature. In a variety of applications, a high or very high Viscosity Index is preferred.
- the chemical composition of the base stocks from Group I, Group II and Group III can vary substantially, for example regarding the proportions of aromatics, paraffinics, and naphthenics.
- the degree of refining and the source materials used to produce the lubricant base stocks generally determine this composition.
- Lubricant base stock oils from Group I, Group II and Group III include paraffinic mineral oils and naphthenic mineral oils.
- Mineral oils of viscosities ranging of from 4.0 to 8.0 mPa.s, at 100° C., (ASTM D445-12) have a Viscosity Index ranging of from 80 to 120, or 140 for high performance grades (ASTM D2270-10e1).
- Group IV base stocks are composed of polyalphaolefins (PAO) which are hydrogenated oligomers obtained from the oligomerization of alphaolefin monomers.
- PEO polyalphaolefins
- alphaolefin monomers may have from about 4 to about 30 or from about 4 to about 20 or from about 6 to about 12 carbon atoms, such as hexene, octene or decene.
- the oligomers may be dimers, trimers, tetramers, pentamers, hexamers of the alphaolefin monomer.
- Group V base stocks include base stocks not included in Groups I-IV such as polyinternal olefins (PIO); polyalkylene glycols (PAG); alkylated aromatics such as alkylated benzenes, e.g. dodecylbenzene, tetradecylbenzene, di-nonylbenzene, and di-(2-ethylhexyl)benzene; polyphenyls e.g. biphenyls, terphenyl and alkylated polyphenyls; synthetic esters such as esters of dicarboxylic acids e.g.
- esters of carboxylic acids e.g. neopentyl glycol, trimethylolethane, trimethylpropane, pentaerythritol, dipentaerythritol and tripentaerythritol; phosphate esters, e.g. tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid; silicones; and further polyisobutylene (PIB) and halogenated hydrocarbons.
- PIB polyisobutylene
- lubricant base stocks include those of vegetal and animal origin, such as rapeseed oil, castor oil and lard oil.
- Silicones (Group V) may be used in lubricant compositions in both critical (metal-to-metal) applications and non critical (plastic-to-plastic) applications mainly due to their good low and high temperature behavior. They show chemical resistance, lubricity, thermal stability and oxidative stability.
- silicones with the exception of halogenated silicones, are generally both inferior to organic base oil as described above and are typically more costly than organic base stocks.
- GB 1224885 claims a composition
- a composition comprising a mineral oil and 0.1 to 15 per cent by weight thereof of an oil-miscible diorganopolysiloxane as a viscosity index improver in which a major proportion of the organo groups are methyl groups and the remainder of the organo groups are substituted or unsubstituted alkyl, alkaryl or aralkyl groups having at least 6 and not more than 30 carbon atoms in amount sufficient to render it miscible with mineral oil.
- EP0177825 discloses lubricating compositions based on organopolysiloxane miscible with mineral oil, which have a pour point (measured according to DIN 51583) below ⁇ 15° C.
- U.S. Pat. No. 3,634,246 discloses lubricant compositions containing a major amount of triaryl phosphate and a minor amount of a silicone polymer containing at least 40 mole percent phenylsiloxane units.
- a silicone polymer containing at least 40 mole percent phenylsiloxane units.
- Exemplary is a blend of 60 volume percent tricresylphosphate and 40 volume percent of a 50-50 copolymer of dimethylsiloxane units and phenylmethylsiloxane units.
- U.S. Pat. No. 4,190,546 discloses a traction fluid comprising from 50 to 90% wt of a naphthenic hydrocarbon or mixture of naphthenic hydrocarbons, from 8 to 40% wt of a silicone fluid and from 2 to 10% wt of a co-solvent which ensures complete miscibility between the naphthenic hydrocarbon and silicone fluid, the percentages being by weight of the three components.
- the silicone fluid improves the low temperature properties of the fluid without substantial damage to the good traction properties of the naphthenic hydrocarbons.
- Preferred co-solvents are aromatic hydrocarbons or aromatic ethers.
- EP0283922 discloses a homogeneous blend of a dimethylsiloxane/alkylmethylsiloxane copolymer with a hydrogenated polyalphaolefin based on oligomers of decene-1.
- the blend serves as a base fluid which has a viscosity-temperature profile and flash point suitable for use in a ⁇ 54° C. to 135° C. fire-resistant hydraulic fluid having particular utility in military aircraft hydraulic systems.
- U.S. Pat. No. 4,449,415 discloses traction fluids containing certain siloxane components and, optionally, certain cycloaliphatic hydrocarbon components. These traction fluids possess high traction coefficients and good low temperature viscosity properties which make these fluids ideally suited for use in traction drive systems subjected to wide operating temperature conditions.
- U.S. Pat. No. 7,553,429 discloses simple dimethylsilicone fluids of the proper viscosity/molecular weight distribution to modify the low temperature properties of cycloaliphatic hydrocarbon fluids. Addition of the dimethylsilicone fluid to cycloaliphatic fluids improves their low temperature performance without degrading the requisite elastohydrodynamic shear strength properties. Low viscosity dimethylsilicone lubricating fluids combined with cycloaliphatic hydrocarbon fluids are suitable for use in infinitely variable transmissions and other traction-drive transmission providing good low temperature flow properties and high elastohydrodynamic shear strength.
- RU2194741 discloses lubricating oil intended for stable functioning of parts and mechanisms comprising steel-steel friction couples based on liquid polyethylsiloxanes (65-85%) with molecular weight 500-100 and viscosity 40-50 mm 2 /s and containing 14.25-33.25% poly-alpha-olefins with average degree of oligomerization 7-8 and molecular weight 900-1200 and 0.75-1.75% dioctyl sebacate, for lowered freezing temperature and improved lubrication property.
- VI Improvers Viscosity Index Improvers
- VI Improvers are currently typically high molecular weight organic polymers but their use does not always increase the Viscosity Index to the desired values for the purpose concerned and due to their high molecular weight said VI Improvers often lack shear stability.
- VI improvers are selected because they generally swell with increasing temperature which tends to counteract the decreasing viscosity of a base fluid as said temperature increases.
- VI Improvers are subject to shearing forces when present in lubricating situations and their stability as a result of these shearing forces (Shear Stability) may reduce their effectiveness. Excessive permanent shear effectively reduces lubricating temperature range of a lubricant and as such it is advantageous for lubricants to contain shear stable VI improvers in order to maintain or maximize the functional temperature range in which the fluid will lubricate.
- shear stability of lubricant compositions are usually measured with the KRL shear stability test according to DIN 51350-6 where a reduction in viscosity after the test of less than 10% is considered shear stable and values above 10% are considered shear unstable.
- a lubricant composition comprising
- lubricant composition as hydraulic fluid, transmission fluid, gear fluid and/or compressor fluid.
- the non silicone base stock oil (Component (A)) is an oil that is mainly based on hydrocarbons and potentially nitrogen-, oxygen- and sulfur-containing hydrocarbon derivatives, from any of API Groups I to V discussed above and mixtures thereof, excluding silicone lubricant oils.
- Component (A) may for example be:
- Component (A) may additionally or alternatively consist of mixtures of the above.
- Component (A) consists of mineral oil based lubricant base stock oils (i), polyalphaolefins (PAO) (ii) and polyinternal olefins (PIO) (iii) or mixtures thereof.
- Component (A) has a viscosity in the range of from 1 to 10000 mPa.s at 40° C., alternatively 2 to 1000 mPa.s at 40° C. ASTM D445-12).
- Component (A (alone or in combination with component (B)) may be formulated into a grease after addition of a thickener to one of the non-silicone base stock oils described in API Groups I to V discussed above and mixtures thereof.
- Component (A) is present in the lubricant composition of from 50wt % to 99.5 wt %, alternatively 60wt % to 99wt %, alternatively 60wt % to 95wt %, alternatively 80wt % to 95wt %, alternatively 90wt % to 95wt % based on the total weight of (A)+(B), which is 100wt %.
- the silicone oil (Component (B)) is to be understood as mainly based on silicon-oxygen atom bonds forming the backbone of the polymer.
- Silicone oils include, but are not limited to, silicone fluids, liquid silicone resins, silicone waxes.
- silicone and siloxane may be used interchangeably to designate silicone oils such as trialkylsilyl terminated polydialkylsiloxane, trialkylsilyl terminated polyalkylalkylsiloxane and trialkylsilyl terminated polyalkylarylsiloxanes.
- Siloxanes generally conform to a polymeric backbone consisting of units of the formula R m SiO 4-m/2 in which m is zero, 1, 2 or 3 and where m has an average value of from 1.98 to 2.5 per molecule and has a degree of polymerisation ⁇ 2.
- R may be the same or different and denotes, hydrogen or an organic group.
- R may be selected from hydrocarbon groups having from 1 to 45 carbon atoms, such as alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, octyl, nonyl, tetradecyl, octadecyl); cycloalkyl groups (cyclohexyl, cycloheptyl); alkenyl groups (vinyl, hexenyl); aryl groups (phenyl, diphenyl, naphthyl); alkaryl groups (tolyl, xylyl, ethylphenyl); aralkyl groups (benzyl, phenylethyl).
- alkyl groups methyl, ethyl, propyl, isopropyl, butyl, octyl, nonyl, tetradecyl, octadecyl
- cycloalkyl groups cyclohexyl,
- R when R is an organic group R may be those hydrocarbon groups wherein one or more hydrogen atoms has been replaced with another substituent, also referred to as organyl groups.
- substituents include, but are not limited to, halogen atom containing groups such as haloalkyl groups (chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl) and haloaryl groups (monochlorophenyl, dibromophenyl, tetrachlorophenyl, monofluorophenyl); oxygen atoms; oxygen atom containing groups such as carboxyl, carbinol, ester, ether, acrylic groups and polyoxyalkylene groups (polyoxyethylene, polyoxypropylene, polyoxybutylene); nitrogen atoms; nitrogen atom containing groups such as nitrile, amino, amido, cyano, cyanoalkyl and urethane groups; sulphur atoms; sulph
- Component B may be a cyclic, linear or branched silicone polymer.
- Cyclic siloxanes have the general formula (R 2 SiO) x where R is as described above, and x is 3 to 20 and the total number of carbon atoms in the R groups is between 20 and 1000.
- cyclic siloxanes examples include hexamethylcyclotrisiloxane (solid at 25° C.), octamethylcyclotetrasiloxane, tetraphenyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, tetramethyltetraoctylcyclotetrasiloxane, pentamethylpentaoctylcyclopentasiloxane, pentamethylpentadodecylcyclopentasiloxane.
- Linear siloxanes conform to the general formula R(SiR 2 O) r SiR 3 , where R is as described above and r is 1 to 5000 or higher.
- Linear siloxanes include polydimethylsiloxane when R is methyl and polydiethylsiloxane when R is ethyl.
- Such compounds may have a wide variety of terminal groups which typically include, for the sake of example methyl, ethyl phenyl groups.
- Polydimethylsiloxane and polydiethylsiloxane may have viscosities ranging of from 0.5 to 600 000 mPa.s at 25° C.
- the polydiethylsiloxane may be branched or contain other siloxanes units to depress the crystallization.
- component (B) may have the following formula:
- each R 1 , each R 2 and each R 3 is individually selected from hydrocarbon groups having from 1 to 45 carbon atoms
- each R 5 is individually selected from a hydrocarbon group containing from 1 to 18 carbon atoms e.g. linear or branched alkyl groups, phenyl groups and/or alkylaryl groups
- each R 4 group is a hydrocarbon groups having from 2 to 45 carbon atoms, n is zero or an integer, v is zero or an integer and t is zero or an integer and wherein n+v+t>1; and that when v is >zero, n is zero and t is zero and that when t>zero, v is zero and n is zero or an integer.
- each R 1 , each R 2 , each R 3 and each R 4 may independently be alkyl groups having at least 2 alkyl groups, (ethyl, propyl, isopropyl, butyl, octyl, nonyl, tetradecyl, octadecyl); cycloalkyl groups (cyclohexyl, cycloheptyl); alkenyl groups (vinyl, hexenyl); aryl groups (phenyl, diphenyl, naphthyl); alkaryl groups (tolyl, xylyl, ethylphenyl); aralkyl groups (benzyl, phenylethyl).
- alkyl groups having at least 2 alkyl groups, (ethyl, propyl, isopropyl, butyl, octyl, nonyl, tetradecyl, octadecyl); cycloalky
- Further organic groups include those hydrocarbon groups with at least 2 carbon atoms wherein one or more hydrogen atoms has been replaced with another substituent, also referred to as organyl groups.
- substituents include, but are not limited to, halogen atoms (chlorine, fluorine, bromine, iodine); halogen atom containing groups such as haloalkyl groups (chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl) and haloaryl groups (monochlorophenyl, dibromophenyl, tetrachlorophenyl, monofluorophenyl); oxygen atoms; oxygen atom containing groups such as carboxyl, carbinol, ester, ether, acrylic groups and polyoxyalkylene groups (polyoxyethylene, polyoxypropylene, polyoxybutylene); nitrogen atoms; nitrogen atom containing groups such as nitrile, amino, amido, cyan
- each R 1 , each R 2 , and each R 3 may be independently selected from alkyl groups, of 1 to 45, alternatively of 1 to 30 and further alternatively 1 to 16 carbon atoms or phenyl groups containing 6 to 16 carbon atoms and each R 4 is independently an alkyl group having from 2 to 16 carbon atoms.
- R 5 groups may be ethyl groups in which case the formula given above may be re-written as follows:
- polyalkylalkylsiloxane polymers such as polymethyloctylsiloxane, polymethylphenylsiloxane
- Branched siloxanes which may be utilized as component (B) include, for the sake of example, silicone resins.
- the silicone oil (B) may, for example, be selected from polydiethylsiloxane, polydimethylsiloxane, polydimethylmethylalkylsiloxane, polymethylalkylsiloxane.
- R 1 , R 2 and R 3 are independently selected from alkyl of 1 to 45, alternatively of 1 to 30 and further alternatively 1 to 16 of carbon atoms, v is an integer greater than zero, for the sake of example v may be from 3 to 10000, alternatively from 5 to 1000.
- R 1 , R 2 and R 3 are independently selected from alkyl groups of 1 to 45, alternatively of 1 to 30 and further alternatively 1 to 16 carbon atoms or phenyl groups containing 6 to 16 carbon atoms and each R 4 is independently an alkyl group having from 2 to 16 carbon atoms, n is zero or an integer, and t is an integer. Hence, when n is zero, the polymer may be a random or block copolymer as previously discussed.
- the silicone oil (B) can be a blend of multiple silicone oils described above.
- the silicone oil (B) is present in an amount of from 0.5 wt % to 50 wt %, alternatively 1 wt % to 40 wt %, alternatively 5 wt % to 40 wt %, alternatively 5 wt % to 20 wt %, alternatively 5% to 10 wt % based on the total weight of (A)+(B), which is 100 wt %.
- Lubricant additives may be used to impart or improve certain properties to the lubricating composition.
- Such additives include friction modifiers, anti-wear additives, extreme pressure additives, seal swelling agents, rust and corrosion inhibitors, thickeners, Viscosity Index improvers “other than (B)”, pour point depressants, anti-oxidants, free-radical scavengers, hydroperoxide decomposers, metal passivators, surface active agents such as detergents, emulsifiers, demulsifiers, defoamants, compatibilizers, dispersants, and mixtures thereof.
- Further additives include deposit control additives, film forming additives, tackifiers, antimicrobials, additives for biodegradable lubricants, haze inhibitors, chromophores, and limited slip additives.
- friction modifiers include long-chain fatty acids and their derivatives, molybdenum compounds, aliphatic amines or ethoxylated aliphatic amines, ether amines, alkoxylated ether amines, acylated amines, tertiary amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters, polyol esters, aliphatic carboxylic ester-amides, imidazolines, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates.
- anti-wear additives and extreme pressure additives include organosulfur and organo-phosphorus compounds, such as organic polysulfides among which alkylpolysulfides; phosphates among which trihydrocarbyl phosphate, dibutyl hydrogen phosphate, amine salt of sulfurized dibutyl hydrogen phosphate, dithiophosphates; dithiocarbamates dihydrocarbyl phosphate; sulfurized olefins, such as sulfurized isobutylene, and sulfurized fatty acid esters.
- organosulfur and organo-phosphorus compounds such as organic polysulfides among which alkylpolysulfides; phosphates among which trihydrocarbyl phosphate, dibutyl hydrogen phosphate, amine salt of sulfurized dibutyl hydrogen phosphate, dithiophosphates; dithiocarbamates dihydrocarbyl phosphate; sulfurized olefins, such as sulfurized isobutylene, and sulfurized
- seal swell agents examples include esters, adipates, sebacates, azeealates, phthalates, sulfones such as 3-alkoxytetraalkylene sulfone, substituted sulfolanes, aliphatic alcohols of 8 to 13 carbon atoms such as tridecyl alcohol, alkylbenzenes, aromatics, naphthalene depleted aromatic compounds, mineral oils.
- rust and corrosion inhibitors include monocarboxylic acids such as octanoic acid, decanoic acid and dodecanoic acid; polycarboxylic acids such as dimer and trimer acids from tall oil fatty acids, oleic acid, linoleic acid; thiazoles; triazoles such as benzotriazole, decyltriazole, 2-mercapto benzothiazole; thiadiazoles such as 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole; metal dithiophosphates; ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines; ethoxylated phenols; ethoxylated alcohols; imidazolines; aminosuccinic acids.
- monocarboxylic acids such as octanoic acid, decanoic
- thickeners examples include metallic soaps such as lithium soaps, silica, expanded graphite, polyurea, clays such as hectorite or bentonite.
- the lubricant composition when thickened, may become a grease composition.
- Viscosity Index improvers “other than (B)” include polymethacrylates, olefin copolymers, polyisoalkylene such as polyisobutylene, styrene-diene copolymers, and styrene-ester copolymers such as styrenemaleic ester.
- pour point depressants examples include wax-alkylated naphthalenes and phenols, polymethacrylates, styrene-ester copolymers.
- anti-oxidants include phenolic antioxidants such as 2,6-di-tert-butylphenol, tertiary butylated phenols such as 2,6-di-tert-butyl-4-methylphenol, 4,4′-methylenebis(2,6-di-tert-butylphenol),2,2′-methylenebis(4-methyl6-tert-butylphenol), 4,4′-thiobis(2-methyl-6-tert-butylphenol); mixed methylene-bridged polyalkyl phenols; aromatic amine antioxidants; sulfurized phenolic antioxidants; organic phosphites; amine derivatives such as p-, p′-dioctyldiphenylamine, N,N′-di-sec-butylphenylenediamine, 4-isopropylaminodiphenylamine, phenyl-.alpha.-naphthyl amine, phenyl-.alpha.-naphthyl
- free-radical scavengers examples include zinc dialkyl dithiophosphates, hindered phenols, and alkylated arylamines.
- hydroperoxide decomposers examples include organo-sulfur compounds and organo-phosphorus compounds.
- metal passivators examples include poly-functional (polydentate) compounds, such as ethylenediaminetetraacetic acid (EDTA) and salicylaldoxime.
- poly-functional (polydentate) compounds such as ethylenediaminetetraacetic acid (EDTA) and salicylaldoxime.
- Examples of surface active agents such as detergents, dispersants, emulsifiers, demulsifiers include alkali metal or alkaline earth metal salts of organic acids such as magnesium sulfonate, zinc sulfonate, magnesium phenate, zinc phenate, lithium sulfonate, lithium carboxylate, lithium salicylate, lithium phenate, sulfurized lithium phenate, magnesium sulfonate, magnesium carboxylate, magnesium salicylate, magnesium phenate, sulfurized magnesium phenate, potassium sulfonate, potassium carboxylate, potassium salicylate, potassium phenate, sulfurized potassium phenate; common acids such as alkylbenzenesulfonic acids, alkylphenols, fatty carboxylic acids, polyamine, polyhydric alcoholderived polyisobutylene derivatives.
- organic acids such as magnesium sulfonate, zinc sulfonate, magnesium phenate, zinc phenate, lithium sulfonate, lithium carboxylate, lithium salicy
- defoamants include polysiloxanes, polyacrylates and styrene ester polymers.
- compatibilizers include aromatic hydrocarbons such as 1-methyl-naphthalene, aromatic ethers such as diphenyl ether or anisole (methyl phenyl ether), long chain alcohols such as nonyl phenol, octanol and decanol.
- dispersants include alkenylsuccinimide such as polyisobutylene succinimide, N-substituted polyisobutenyl succinimides such as polyisobutenyl succinimide-polyethylenepolyamine, succinates, succinate esters, alkyl methacrylate-vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylaminoethyl methacrylate copolymers, alkylmethacrylate-polyethylene glycol methacrylate copolymers, polystearamides, high molecular weight amines, phosphoric acid derivatives such as bis-hydroxypropyl phosphorate.
- alkenylsuccinimide such as polyisobutylene succinimide
- N-substituted polyisobutenyl succinimides such as polyisobutenyl succinimide-polyethylenepolyamine
- succinates succinate esters
- Some additives may possess multiple properties and provide for a multiplicity of affects.
- graphite and molybdenum disulfide may both be used as friction modifiers and extreme pressure additives or functionalized soaps may be used to thicken but also provide extreme pressure and antiwear performances to greases. This approach is well known by the person skilled in the art and need not be further elaborated herein.
- An additive may be used alone or in combination with other additives.
- the sole or multiple additive(s) may be used at a level of from 0 to 10 wt %, alternatively 0.1 to 5 wt %, based on the total weight of the lubricant composition.
- Thickeners to produce greases may be used at a level of from 5 to 25% wt based on the total weight of the lubricant grease composition.
- the lubricant composition is produced by mixing the lubricant base oil and the silicone oil and the optional additives, by conventional mixing means, optionally with heating.
- the lubricant composition may be homogeneous, or non homogeneous. Homogeneity of the composition is considered at 25° C., after mixing, and the optional heating, is (are) disrupted.
- a homogeneous composition is meant herein as a composition where the lubricant base oil and the silicone oil are compatible or miscible and form a monophasic system.
- a homogeneous composition may be hazy, clear or opaque.
- the intimate blend of the 2 oils is uniform and posses the same properties throughout. The compatibility of mixtures may be assessed using ASTM D7155-11: Standard Practice for Evaluating Compatibility of Mixtures of Turbine Lubricating Oils.
- a non homogeneous composition is meant herein as a composition where the lubricant base oil and the silicone oil form a biphasic system upon rest.
- a non homogeneous composition will be characterized by a varying composition of the blend throughout the container.
- a non homogeneous system may be rendered homogenous by shaking, heating or addition of a compatibilizer, or a combination thereof. These non homogenous compositions will return to non homogeneous state upon disruption of the shaking or heating.
- a compatibilizer is used, the duration of improved homogeneity will depend on the effectiveness of the compatibilizer—temporarily or over a longer period of time.
- Compatibilizers may be surfactants or co-solvents. Homogeneity may be obtained through emulsification, dispersion or any other means known by the person skilled in the art. Emulsification techniques are known by the person skilled in the art and will not be further exemplified herein.
- homogeneous compositions include polydiethylsiloxane with polyalphaolefin, polydiethylsiloxane with mineral oil, polymethyloctylsiloxane with polyalphaolefin.
- non homogenous compositions include polytrifluoropropylmethylsiloxane with mineral oil, polydiethylsiloxane with polyol ester, polymethyloctylsiloxane with polyalkylene glycol, polymethyloctylsiloxane with polyol esters.
- compositions as hereinbefore described are shear stable in accordance with DIN 51350-6 (the KRL Tapered Roller Bearing Test in accord with DIN 51350-6) where a reduction in viscosity after the test of less than 10% is considered shear stable and values above 10% are considered shear unstable. It has been found that lubricant compositions as hereinbefore described result in much smaller rises in viscosity subsequent to testing according to DIN 51350-6 than that of conventional VI improvers,
- Lubricating compositions may be used in a variety of applications where friction occurs between rubbing surfaces.
- the surfaces may be plastic or metal.
- Types of friction include sliding, rolling, static, kinetic, stick-slip, solid (dry), boundary, mixed, wear, erosion, elasto-hydrodynamic frictions.
- the present invention includes a method to lubricate metal-metal surfaces comprising:
- the present lubricant composition may be used in any system that includes machine elements that contain gears of any kind and roller bearings.
- Examples of such systems include electricity generating systems, industrial manufacturing equipments such as paper, steel and cement mills hydraulic systems, automotive drive trains, aircraft propulsion systems, etc.
- crankcases 2-stroke engines, 4-stroke engines, diesel engines, internal combustion engines, gears for manual or differential transmissions, industrial lubricants, hydraulic, compressor, turbine, metal working, metal forming, lubrication grease, solid.
- Further systems also include traction and torque systems.
- the lubricant composition may alternatively be used as an automatic transmission fluid, a manual transmission fluid, an axle lubricant, a transaxle lubricant, an industrial gear lubricant, a circulating lubricant, a gear oil for wind turbines, an open gear lubricant, an enclosed gear lubricant, an hydraulic fluid, a compressor fluid, or a grease.
- Operating temperatures for the use of the lubricant composition meaning the temperatures at which the lubricant composition may be used for prolonged time (also called service temperatures), range of from ⁇ 55° C. to +200° C. Short term peak temperature may be higher.
- Viscosity Index is measured/calculated using ASTM D 2270-10E: Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100° C.
- the density may be measured using glass pycnometer according to DIN 51757 (Procedure V2). Ideal mixing is assumed for blends of materials, meaning that the density of the blend can be calculated from the respective values of the ingredients. The values of dynamic viscosities were subsequently used to calculate kinematic viscosities using the material densities tabulated below. The calculated kinematic viscosities were then used to calculate Viscosity Index as per formula:
- Viscosity Index [((antilog N ) ⁇ 1)/0.00715+100]
- Y N H/U
- H kinematic viscosity at 40° C. of a 100 Viscosity Index oil with the same viscosity at 100° C. as the unknown
- U kinematic viscosity at 40° C. of the oil whose viscosity index is to be calculated.
- the Load Carrying Capability (LCC) properties of the lubricant compositions being assessed were determined in accordance with ASTM D 5706-05 ‘Standard test method for determining extreme pressure properties of lubricating greases using a high-frequency, linear-oscillation (SRV) test machine’.
- the SRV test machine may be used to determine load carrying and wear properties and coefficient of friction of lubricating greases at selected temperatures and loads specified for use in applications where high-speed vibrational or start-stop motions are present for extended periods of time under initial high Hertzian point contact pressures.
- This method has found application in qualifying lubricating greases used in constant velocity joints of front-wheel-drive automobiles and for lubricating greases used in roller bearings. This method may also be used for determining a fluid lubricant's ability to protect against wear and its coefficient of friction under similar test conditions.
- a lubricating fluid was evaluated instead of lubrication greases; a steel cylinder was used instead of a steel ball; frequency was 10 Hz instead of 50 Hz.
- the measurements were carried out at 40° C. using 1 mm stroke. The load was increased in increments of 50N every two minutes up to a maximum load of 2000N.
- Wearing properties or lubrication performance may be evaluated by standard test method DIN 51350-3 ‘Testing of lubricants in the Shell four-ball tester’.
- the Shell Four Ball Tester (FBT) is a testing device used to determine welding and metal loads as well as different friction and wear characteristics of lubricants.
- the standard test consists of a rotating ball of a ball bearing being pressed onto three similar but immobile balls while applying a load of 100N, 400N and 800N for 1 hour test duration. Wear is determined by optically measuring the formed calotte (the worn depression area).
- This testing device is especially common in the lubricant industry where it is used for routine product development and quality control testing.
- the friction torque can be recorded continuously.
- Shear stability of lubricant compositions was measured according to DIN 51350-6 using a tapered roller bearing to shear the lubricant composition for 4 hours (method A) and report the relative drop of viscosity after the test in percentage,
- v 0 is the kinematic viscosity (mm 2 /s at 100° C.) before and v 1 after the test.
- the lubricant composition of the present invention is characterized by a Viscosity Index ⁇ 180, alternatively ⁇ 200, alternatively ⁇ 250.
- the lubricant composition of the present invention is characterized by a load carrying capability according to the procedure described above.
- the lubricant composition of the present invention is characterized by a relative viscosity drop according to the procedure described above.
- R v 10%, alternatively R v ⁇ 7.5%, alternatively R v ⁇ 6%.
- R v (v 0 ⁇ v 1 )/v 0 *100, where v 0 is the kinematic viscosity (mm 2 /s at 100° C.) before and v 1 after the test when measured according to DIN 51350-6 (method A).
- PDMS polydimethylsiloxanes having a typical viscosity of 50 cst at 25° C., determined using a glass capillary viscosimeter
- Viscosity Index Type PiB Polyisobutylene Viscosity Improver: commercial material Hitec® 7389, from Afton Chemical Corporation, with a typical viscosity of 176 mm 2 /s at 100° C. (Producers datasheet)
- the density of the materials was measured using a glass pycnometer according to DIN 51757 (Procedure V2).
- Blending The blends were prepared by adding a total of 50 g of materials to a glass bottle and shaking them until a homogenous mixture was obtained.
- PDES PAO LCC (wt %)
- B (wt %)
- A (N) 0 100 450 5 95 2000 10 90 2000 40 60 2000 60 40 1500 80 20 750 90 10 1200 100 0 250
- Example 1a shows that mixtures according to the invention containing PDES have an LCC much higher than the pure oils in the range of between 0.5 and 50% wt of component (B), namely the PDES. The effect can be already seen with a 5% wt % addition level of PDES into the PAO.
- Example 1b shows that mixtures according to the invention containing PDES (i.e. component B) have much higher Viscosity Index values (at least 10% greater) than 100% PAO (*: Viscosity Index 143 from suppliers datasheet).
- PDES Mineral Oil LCC (Wt %) (B) (Wt %) (A) (N) 0 100 1000 5 95 1400 10 90 2000 20 80 1800 40 60 1050 60 40 1100 80 20 450 95 5 450 100 0 250
- Example 2 a shows that compositions as hereinbefore described containing PDES and mineral oil have an LCC much higher than 100% mineral oil. The effect can be seen at 5% addition level of PDES into the mineral oil.
- PDES Mineral Oil Four ball wear scar (Wt %) (B) (Wt %) (A) at 400N load (mm) 0 100 1.727 5 95 0.730 10 90 1.122 20 80 1.538 40 60 1.160 60 40 0.941 80 20 2.112 90 10 3.564 95 5 nm 100 0 Nm
- Example 2b shows that that compositions as hereinbefore described containing PDES and mineral oil have a lower wear scar in the four ball test than the pure mineral oil (nm stands for non measurable, load is too high to run the test).
- PMOS 1 PAO LCC (Wt %)
- B (Wt %)
- A (N) 0 100 450 10 90 2000 40 60 1800 90 10 1200 100 0 1300
- Example 3a shows that compositions as hereinbefore described containing PMOS1 have an LCC much higher than the 100% PAO. The effect can clearly be identified with a 10% addition level of PMOS1 into the PAO.
- Example 3b shows that that compositions as hereinbefore described containing PMOS1 and PAO have a lower wear scar in the four ball test at high loads (800N) than the pure PAO (nm stands for non measurable, load is too high to run the test).
- Example 3c shows that mixtures according to the invention containing PMOS1 have Viscosity Index much higher (at least 10% greater) than for 100% PAO (*: Viscosity Index 143 as provided by the supplier).
- Example 4a shows that mixtures according to the invention containing PMOS2 have an LCC much higher than value for 100% PAO, i.e. component (A) alone. The effect is clearly evident at 10% addition level of PMOS1 into the PAO.
- Example 4b shows that mixtures according to the invention containing PMOS2 have much higher VI values (greater than 10% higher) than 100% PAO.
- the Viscosity Index value for PAO provided by the supplier is 143 as previously indicated by *.
- PDMS PAO LCC (Wt %)
- B (Wt %)
- A (N) 0 100 450 5 95 2000 10 90 2000 20 80 1800 40 60 1850 60 40 1750 80 20 650 90 10 400 95 5 350 100 0 300
- Example 5a shows that mixtures according to the invention containing PDMS have an LCC much higher than 100% PAO. The effect can be clearly identified at 5% addition level of PDMS.
- Example 5b shows that mixtures according to the invention containing PDMS have much higher Viscosity Index values (much greater than 10%) than the 100% value for PAO.
- the Viscosity Index value for PAO provided by the supplier is 143 as previously indicated by *.
- PDMS Mineral Oil LCC (Wt %)
- B (Wt %)
- A (N) 0 100 1000 5 95 2000 10 90 2000 20 80 1550 40 60 1150 60 40 1400 80 20 850 90 10 500 100 0 300
- Example 6a shows that mixtures according to the invention containing PDMS have an LCC much higher than 100% mineral oil. The effect can be already seen at 5% addition level of PDMS in the mineral oil.
- Example 6b shows that that compositions as hereinbefore described containing PDMS and mineral oil have a lower wear scar in the four ball test than the pure mineral oil (nm stands for non measurable, load is too high to run the test).
- Example 7 shows that mixtures according to the invention containing PDMS have LCC of above 1000N
- Example 8 shows that mixtures according to the invention containing PMOS2 have an LCC of above 1000N.
- Example 9 shows that mixtures according to the invention containing PDES have a load carrying (LCC) above 400N.
- Example 10 shows that mixtures according to the invention containing PDES have an LCC higher than 650N.
- PAO Blends with organic VI Improvers were prepared using the commercial Hitec® 5704 and Hitec® 7389
- Viscosity example VI improver (mPa ⁇ s) (mPa ⁇ s) Index 1 5% Hitec ® 5704 40.4 7.1 168 2 10% Hitec ® 5704 60.1 9.6 167 3 20% Hitec ® 5704 113.8 18.2 199 4 5% % Hitec ® 7389 30.7 6.1 186 5 10% Hitec ® 7389 37.6 7.1 184 6 20% % Hitec ® 57.4 10.4 196 7389
- Comparative examples 1-6 indicate that the commercial viscosity improvers are less efficient than the disclosed siloxanes disclosed in Examples 1-10. Furthermore, the comparative viscosity improvers do not allow achieving viscosity indices above 200 when used with polyalphaolefin (density of the pure PAO was used to calculate the Viscosity Index values of the blends).
- PAO blends with organic VI improver Hitec® 5704 and with PMOS 1 were tested for shear stability
- Viscosity at Viscosity at Relative 100° C. (mPa ⁇ 100° C. (mPa ⁇ drop of s) before s) after 4h viscos- VI improver KRL test KRL test ity (%) Compar- 20% Hitec ® 18.2 10.0 45.0 itive 5704 example 3
- Example 3 20% PMOS 1 12.6 11.9 5.6
- Example 3 shows a composition according to the invention that is shear stable, while Comparative example 3 is shear instable.
- compositions according to the invention at 10% siloxanes content in PAO have a “low temperature”-viscosity significantly lower than commercial VI improvers at the same addition level (Comparative 7a and b).
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Abstract
A lubricant composition comprises: (A) a non-silicone base stock oil; and (B) a silicone oil. The Viscosity Index of the lubricant composition, as measured in accordance with ASTM D 2270-10e1, is greater than that of the non-silicone lubricant base stock oil (A) by at least 10% and is shear stable according to DIN 51350-6.
Description
- This application claims priority to and all the advantages of U.S. Provisional Patent Application No. 61/628,871, filed on Aug. 14, 2013, the content of which is incorporated herein by reference.
- Disclosed herein are lubricant compositions comprising a non silicone lubricant base stock and a silicone oil.
- Lubricant oils and compositions are used to reduce friction and wear between moving elements or surfaces. The main component of lubricant oils and compositions is commonly referred to as a base stock. Base stocks are classified by the American Petroleum Institute in five Groups, namely Groups I, II, III, IV and V. Lubricant base stocks include natural lubricating oils, synthetic lubricating oils, and mixtures thereof. Groups I to III include base stocks derived from petroleum based oils, while Groups IV and V include synthetic base stocks including silicones.
- The viscosity of a lubricant changes with temperature. As temperature rises viscosity decreases and vice versa. Viscosity Index (VI) is an empirical, unit less number which indicates the rate of change in the viscosity of an oil in a given temperature range, usually between 40° C. and 100° C. The Viscosity Index is defined as the gradient of kinematic viscosities of a material, between 40° C. and 100° C. When the Viscosity Index is low (below 100) the fluid exhibits a relatively large change of viscosity with temperature. When the Viscosity Index is high (above 150), the fluid exhibits relatively less change of viscosity with temperature. In a variety of applications, a high or very high Viscosity Index is preferred.
- The chemical composition of the base stocks from Group I, Group II and Group III can vary substantially, for example regarding the proportions of aromatics, paraffinics, and naphthenics. The degree of refining and the source materials used to produce the lubricant base stocks generally determine this composition. Lubricant base stock oils from Group I, Group II and Group III include paraffinic mineral oils and naphthenic mineral oils. Mineral oils of viscosities ranging of from 4.0 to 8.0 mPa.s, at 100° C., (ASTM D445-12) have a Viscosity Index ranging of from 80 to 120, or 140 for high performance grades (ASTM D2270-10e1).
- The materials of Groups I, II and III are divided into groups based on sulphur content and Viscosity Index as follows:
- Group I base stock oils generally have a Viscosity Index of between about 80 to 120 and contain greater than about 0.03% by weight of sulfur and/or less than about 90% by weight of saturated organic components (hereafter referred to as “saturates”.
- Group II base stock oils generally have a Viscosity Index of between about 80 to 120, and contain less than or equal to about 0.03% by weight of sulfur and greater than or equal to about 90% by weight of saturates.
- Group III oils generally have a Viscosity Index greater than about 120 and contain sulphur in an amount less than or equal to about 0.03% weight and greater than about 90% weight of saturates.
- Group IV base stocks are composed of polyalphaolefins (PAO) which are hydrogenated oligomers obtained from the oligomerization of alphaolefin monomers. These alphaolefin monomers may have from about 4 to about 30 or from about 4 to about 20 or from about 6 to about 12 carbon atoms, such as hexene, octene or decene. The oligomers may be dimers, trimers, tetramers, pentamers, hexamers of the alphaolefin monomer.
- Group V base stocks include base stocks not included in Groups I-IV such as polyinternal olefins (PIO); polyalkylene glycols (PAG); alkylated aromatics such as alkylated benzenes, e.g. dodecylbenzene, tetradecylbenzene, di-nonylbenzene, and di-(2-ethylhexyl)benzene; polyphenyls e.g. biphenyls, terphenyl and alkylated polyphenyls; synthetic esters such as esters of dicarboxylic acids e.g. dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate and dieicosyl sebacate, esters of carboxylic acids, polyol esters, e.g. neopentyl glycol, trimethylolethane, trimethylpropane, pentaerythritol, dipentaerythritol and tripentaerythritol; phosphate esters, e.g. tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid; silicones; and further polyisobutylene (PIB) and halogenated hydrocarbons.
- Other lubricant base stocks include those of vegetal and animal origin, such as rapeseed oil, castor oil and lard oil.
- Silicones (Group V) may be used in lubricant compositions in both critical (metal-to-metal) applications and non critical (plastic-to-plastic) applications mainly due to their good low and high temperature behavior. They show chemical resistance, lubricity, thermal stability and oxidative stability.
- However in respect of lubrication under high loads, silicones, with the exception of halogenated silicones, are generally both inferior to organic base oil as described above and are typically more costly than organic base stocks.
- GB 1224885 claims a composition comprising a mineral oil and 0.1 to 15 per cent by weight thereof of an oil-miscible diorganopolysiloxane as a viscosity index improver in which a major proportion of the organo groups are methyl groups and the remainder of the organo groups are substituted or unsubstituted alkyl, alkaryl or aralkyl groups having at least 6 and not more than 30 carbon atoms in amount sufficient to render it miscible with mineral oil.
- EP0177825 discloses lubricating compositions based on organopolysiloxane miscible with mineral oil, which have a pour point (measured according to DIN 51583) below −15° C.
- U.S. Pat. No. 3,634,246 discloses lubricant compositions containing a major amount of triaryl phosphate and a minor amount of a silicone polymer containing at least 40 mole percent phenylsiloxane units. Exemplary is a blend of 60 volume percent tricresylphosphate and 40 volume percent of a 50-50 copolymer of dimethylsiloxane units and phenylmethylsiloxane units.
- U.S. Pat. No. 4,190,546 discloses a traction fluid comprising from 50 to 90% wt of a naphthenic hydrocarbon or mixture of naphthenic hydrocarbons, from 8 to 40% wt of a silicone fluid and from 2 to 10% wt of a co-solvent which ensures complete miscibility between the naphthenic hydrocarbon and silicone fluid, the percentages being by weight of the three components. The silicone fluid improves the low temperature properties of the fluid without substantial damage to the good traction properties of the naphthenic hydrocarbons. Preferred co-solvents are aromatic hydrocarbons or aromatic ethers.
- EP0283922 discloses a homogeneous blend of a dimethylsiloxane/alkylmethylsiloxane copolymer with a hydrogenated polyalphaolefin based on oligomers of decene-1. The blend serves as a base fluid which has a viscosity-temperature profile and flash point suitable for use in a −54° C. to 135° C. fire-resistant hydraulic fluid having particular utility in military aircraft hydraulic systems.
- U.S. Pat. No. 4,449,415 discloses traction fluids containing certain siloxane components and, optionally, certain cycloaliphatic hydrocarbon components. These traction fluids possess high traction coefficients and good low temperature viscosity properties which make these fluids ideally suited for use in traction drive systems subjected to wide operating temperature conditions.
- U.S. Pat. No. 7,553,429 discloses simple dimethylsilicone fluids of the proper viscosity/molecular weight distribution to modify the low temperature properties of cycloaliphatic hydrocarbon fluids. Addition of the dimethylsilicone fluid to cycloaliphatic fluids improves their low temperature performance without degrading the requisite elastohydrodynamic shear strength properties. Low viscosity dimethylsilicone lubricating fluids combined with cycloaliphatic hydrocarbon fluids are suitable for use in infinitely variable transmissions and other traction-drive transmission providing good low temperature flow properties and high elastohydrodynamic shear strength.
- RU2194741 discloses lubricating oil intended for stable functioning of parts and mechanisms comprising steel-steel friction couples based on liquid polyethylsiloxanes (65-85%) with molecular weight 500-100 and viscosity 40-50 mm2/s and containing 14.25-33.25% poly-alpha-olefins with average degree of oligomerization 7-8 and molecular weight 900-1200 and 0.75-1.75% dioctyl sebacate, for lowered freezing temperature and improved lubrication property.
- There is a need for lubricant compositions with a Viscosity Index (VI) of above 150, alternatively above 200, and good metal-to-metal lubrication, at acceptable cost. Currently Viscosity Index values of lubricant compositions are increased through the addition of additives typically referred to as viscosity index Improvers (VI Improvers). VI Improvers are currently typically high molecular weight organic polymers but their use does not always increase the Viscosity Index to the desired values for the purpose concerned and due to their high molecular weight said VI Improvers often lack shear stability. VI improvers are selected because they generally swell with increasing temperature which tends to counteract the decreasing viscosity of a base fluid as said temperature increases. This results in a lubricant that maintains sufficient oil thickness for lubrication at high temperatures. Conversely the VI improvers tend to shrink as temperatures decrease. In such situations the properties of the base oil dominate the viscosity of the fluid. However, VI Improvers are subject to shearing forces when present in lubricating situations and their stability as a result of these shearing forces (Shear Stability) may reduce their effectiveness. Excessive permanent shear effectively reduces lubricating temperature range of a lubricant and as such it is advantageous for lubricants to contain shear stable VI improvers in order to maintain or maximize the functional temperature range in which the fluid will lubricate.
- The shear stability of lubricant compositions are usually measured with the KRL shear stability test according to DIN 51350-6 where a reduction in viscosity after the test of less than 10% is considered shear stable and values above 10% are considered shear unstable.
- There is also a need for lubricant compositions having high levels of Viscosity Index improvement combined with good lubrication.
- There is provided herein a lubricant composition comprising
- (A) a non silicone base stock oil, and
- (B) 0.5 to 50% by weight, based on the total weight of (A)+(B) of a silicone oil, characterized in that the Viscosity Index of the lubricant composition, as measured in accordance with ASTM D 2270-10e1, is greater than that of the non silicone lubricant base oil (A) by at least 10% and in that the lubricant composition is shear stable when measured according to DIN 51350-6 (Method (A).
- There is also provided herein a lubricant composition comprising
- (A) a non silicone base stock oil, and
- (B) 0.5 to 50% by weight, based on the total weight of (A)+(B) of a silicone oil, characterized in that the Viscosity Index of the lubricant composition, as measured in accordance with ASTM D 2270-10e1, is greater than that of the non silicone lubricant base oil (A) by at least 10% and in that the Load Carrying Capacity (LCC) according to ASTM D 5706-05 is greater than those of the non silicone lubricant base oil (A) by at least 40%.
- Also disclosed is a method to lubricate metal-to-metal surfaces using the aforementioned lubricant compositions.
- Further disclosed is the use of the lubricant composition as hydraulic fluid, transmission fluid, gear fluid and/or compressor fluid.
- The non silicone base stock oil (Component (A)) is an oil that is mainly based on hydrocarbons and potentially nitrogen-, oxygen- and sulfur-containing hydrocarbon derivatives, from any of API Groups I to V discussed above and mixtures thereof, excluding silicone lubricant oils.
- Component (A) may for example be:
- i mineral oil based lubricant base stock oils having a wide variety of aromatics, paraffinics, and naphthenics, said mineral oils having viscosities ranging of from 4.0 to 8.0 mPa.s, at 100° C., (ASTM D445-12) have a Viscosity Index ranging of from 80 to 120, or 140 for high performance grades (ASTM D2270-10e1);
- ii polyalphaolefins (PAO), which are hydrogenated oligomers obtained from the oligomerization of alphaolefin monomers. These alphaolefin monomers may have from about 4 to about 30 or from about 4 to about 20 or from about 6 to about 12 carbon atoms, such as hexene, octene or decene. The oligomers may be dimers, trimers, tetramers, pentamers or hexamers of the alphaolefin monomer. When the PAO is based on alphaolefin monomers of 6 to 16 carbon atoms, its viscosity may range from 1.7 to 100 mPa.s, at 100° C. (ASTM D445-12), and its viscosity index (VI) may range of from 120 to 150 (ASTM D2270-10e1). Typically, the PAO may have a viscosity of from about 2 to about 15, or from about 3 to about 12, or from about 4 to about 8 mPa.s, at 100° C. (ASTM D445-12). Examples of PAOs include poly-alpha-olefins 4 mPa.s, at 100° C., poly-alpha-olefins 6 mPa.s, at 100° C., and mixtures thereof;
- iii polyinternal olefins (PIO), hydrogenated (saturated) olefin oligomers usually manufactured from linear or cyclic internal olefins, obtained from cracked paraffinic base stock oils. The internal olefin may have from about 10 to 30 or from 10 to 20 or from 12 to 16 carbon atoms, such as the mixtures C13-14, C15-17 or C14-19. After oligomerization, dimers and trimers may be obtained. Typically, the PIO may have a viscosity of from about 2 to about 15, or from about 3 to about 12, or from about 4 to about 8 mPa.s, at 100° C. (ASTM D445-12); Polyinternal olefins have a Viscosity Index 10 to 20 units lower than polyalphaolefins of equivalent viscosity (test method ASTM D2270-10e1); and
- iv polyalkylene glycols, (PAG), include homopolymers, block and random copolymers of ethylene oxide, propylene oxide or butylene oxide. Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, polymers of butylene oxide , copolymers of ethylene oxide and propylene oxide (diols or monobutyl ethers), polymers of propylene oxide (dimethyl ethers).
- Component (A) may additionally or alternatively consist of mixtures of the above. In one alternative Component (A) consists of mineral oil based lubricant base stock oils (i), polyalphaolefins (PAO) (ii) and polyinternal olefins (PIO) (iii) or mixtures thereof.
- Component (A) has a viscosity in the range of from 1 to 10000 mPa.s at 40° C., alternatively 2 to 1000 mPa.s at 40° C. ASTM D445-12).
- Alternatively Component (A (alone or in combination with component (B)) may be formulated into a grease after addition of a thickener to one of the non-silicone base stock oils described in API Groups I to V discussed above and mixtures thereof.
- The processes to obtain the lubricant base stocks are known by the skilled in the art and will therefore not be described here any further.
- Component (A) is present in the lubricant composition of from 50wt % to 99.5 wt %, alternatively 60wt % to 99wt %, alternatively 60wt % to 95wt %, alternatively 80wt % to 95wt %, alternatively 90wt % to 95wt % based on the total weight of (A)+(B), which is 100wt %.
- The silicone oil (Component (B)) is to be understood as mainly based on silicon-oxygen atom bonds forming the backbone of the polymer. Silicone oils include, but are not limited to, silicone fluids, liquid silicone resins, silicone waxes. The terms silicone and siloxane may be used interchangeably to designate silicone oils such as trialkylsilyl terminated polydialkylsiloxane, trialkylsilyl terminated polyalkylalkylsiloxane and trialkylsilyl terminated polyalkylarylsiloxanes.
- Siloxanes generally conform to a polymeric backbone consisting of units of the formula RmSiO4-m/2 in which m is zero, 1, 2 or 3 and where m has an average value of from 1.98 to 2.5 per molecule and has a degree of polymerisation ≧2. Each R may be the same or different and denotes, hydrogen or an organic group.
- When R is an organic group R may be selected from hydrocarbon groups having from 1 to 45 carbon atoms, such as alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, octyl, nonyl, tetradecyl, octadecyl); cycloalkyl groups (cyclohexyl, cycloheptyl); alkenyl groups (vinyl, hexenyl); aryl groups (phenyl, diphenyl, naphthyl); alkaryl groups (tolyl, xylyl, ethylphenyl); aralkyl groups (benzyl, phenylethyl).
- Alternatively when R is an organic group R may be those hydrocarbon groups wherein one or more hydrogen atoms has been replaced with another substituent, also referred to as organyl groups. Examples of such substituents include, but are not limited to, halogen atom containing groups such as haloalkyl groups (chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl) and haloaryl groups (monochlorophenyl, dibromophenyl, tetrachlorophenyl, monofluorophenyl); oxygen atoms; oxygen atom containing groups such as carboxyl, carbinol, ester, ether, acrylic groups and polyoxyalkylene groups (polyoxyethylene, polyoxypropylene, polyoxybutylene); nitrogen atoms; nitrogen atom containing groups such as nitrile, amino, amido, cyano, cyanoalkyl and urethane groups; sulphur atoms; sulphur atom containing groups such as sulphide, sulphone, sulphate, sulphonate and mercapto groups; phosphorus atoms; phosphorus atom containing groups such as phosphate, phosphate and phosphonate groups.
- Component B may be a cyclic, linear or branched silicone polymer.
- Cyclic siloxanes have the general formula (R2SiO)x where R is as described above, and x is 3 to 20 and the total number of carbon atoms in the R groups is between 20 and 1000.
- Examples of cyclic siloxanes include hexamethylcyclotrisiloxane (solid at 25° C.), octamethylcyclotetrasiloxane, tetraphenyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, tetramethyltetraoctylcyclotetrasiloxane, pentamethylpentaoctylcyclopentasiloxane, pentamethylpentadodecylcyclopentasiloxane.
- Linear siloxanes conform to the general formula R(SiR2O)rSiR3, where R is as described above and r is 1 to 5000 or higher. Linear siloxanes include polydimethylsiloxane when R is methyl and polydiethylsiloxane when R is ethyl. Such compounds may have a wide variety of terminal groups which typically include, for the sake of example methyl, ethyl phenyl groups. Polydimethylsiloxane and polydiethylsiloxane may have viscosities ranging of from 0.5 to 600 000 mPa.s at 25° C. (using a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1). The polydiethylsiloxane may be branched or contain other siloxanes units to depress the crystallization.
- In one alternative component (B) may have the following formula:
- in which Me is a methyl group and each R1, each R2 and each R3 is individually selected from hydrocarbon groups having from 1 to 45 carbon atoms, each R5 is individually selected from a hydrocarbon group containing from 1 to 18 carbon atoms e.g. linear or branched alkyl groups, phenyl groups and/or alkylaryl groups; and each R4 group is a hydrocarbon groups having from 2 to 45 carbon atoms, n is zero or an integer, v is zero or an integer and t is zero or an integer and wherein n+v+t>1; and that when v is >zero, n is zero and t is zero and that when t>zero, v is zero and n is zero or an integer.
- The organic group of each R1, each R2, each R3 and each R4 may independently be alkyl groups having at least 2 alkyl groups, (ethyl, propyl, isopropyl, butyl, octyl, nonyl, tetradecyl, octadecyl); cycloalkyl groups (cyclohexyl, cycloheptyl); alkenyl groups (vinyl, hexenyl); aryl groups (phenyl, diphenyl, naphthyl); alkaryl groups (tolyl, xylyl, ethylphenyl); aralkyl groups (benzyl, phenylethyl).
- Further organic groups include those hydrocarbon groups with at least 2 carbon atoms wherein one or more hydrogen atoms has been replaced with another substituent, also referred to as organyl groups. Examples of such substituents include, but are not limited to, halogen atoms (chlorine, fluorine, bromine, iodine); halogen atom containing groups such as haloalkyl groups (chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl) and haloaryl groups (monochlorophenyl, dibromophenyl, tetrachlorophenyl, monofluorophenyl); oxygen atoms; oxygen atom containing groups such as carboxyl, carbinol, ester, ether, acrylic groups and polyoxyalkylene groups (polyoxyethylene, polyoxypropylene, polyoxybutylene); nitrogen atoms; nitrogen atom containing groups such as nitrile, amino, amido, cyano, cyanoalkyl and urethane groups; sulphur atoms; sulphur atom containing groups such as sulphide, sulphone, sulphate, sulphonate and mercapto groups; phosphorus atoms; phosphorus atom containing groups such as phosphate, phosphate and phosphonate groups. In one alternative, each R1, each R2, and each R3 may be independently selected from alkyl groups, of 1 to 45, alternatively of 1 to 30 and further alternatively 1 to 16 carbon atoms or phenyl groups containing 6 to 16 carbon atoms and each R4 is independently an alkyl group having from 2 to 16 carbon atoms.
- In one alternative all R5 groups may be ethyl groups in which case the formula given above may be re-written as follows:
- With Et standing for an ethyl group.
- Examples of linear siloxanes include polyalkylalkylsiloxane polymers such as polymethyloctylsiloxane, polymethylphenylsiloxane; polyalkylarylsiloxanes; having a viscosity at 40° C. of from 2 to 10.000 mPa.s, alternatively of from 10 to 1.000 mPa.s (using a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1).
- Branched siloxanes which may be utilized as component (B) include, for the sake of example, silicone resins. Silicone resins generally contain two or more of the following groups (R1 3SiO1/2)a (R2 2SiO2/2))b (R3SiO3/2)c and (SiO4/2)d with R1, R2 and R3 independently represent an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group, an alkoxy group (preferably methoxy or ethoxy) or an amino group, 0.05≦a≦0.5; 0≦b≦0.3; c≧0; 0.05≦d≦0.6, and a+b+c+d=1 (with a, b, c and d being mole fractions), having a viscosity at 40° C. of from 2 to 10.000 mPa.s (using a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1), alternatively of from 20 to 1.000 mPa.s.
- The silicone oil (B) may, for example, be selected from polydiethylsiloxane, polydimethylsiloxane, polydimethylmethylalkylsiloxane, polymethylalkylsiloxane.
- In an alternative embodiment there is provided a lubricant composition as hereinbefore described comprising
- (A) a non silicone base stock oil as described above and,
- (B) 0.5 to 50% by weight, based on the total weight of (A)+(B) of a silicone oil of the structure,
- wherein R1, R2 and R3 are independently selected from alkyl of 1 to 45, alternatively of 1 to 30 and further alternatively 1 to 16 of carbon atoms, v is an integer greater than zero, for the sake of example v may be from 3 to 10000, alternatively from 5 to 1000.
- In a still further alternative embodiment there is provided a lubricant composition as hereinbefore described comprising
- (A) a non silicone base stock oil as described above and,
- (B) 0.5 to 50% by weight, based on the total weight of (A)+(B) of a silicone oil of the structure,
- wherein R1, R2 and R3 are independently selected from alkyl groups of 1 to 45, alternatively of 1 to 30 and further alternatively 1 to 16 carbon atoms or phenyl groups containing 6 to 16 carbon atoms and each R4 is independently an alkyl group having from 2 to 16 carbon atoms, n is zero or an integer, and t is an integer. Hence, when n is zero, the polymer may be a random or block copolymer as previously discussed.
- The silicone oil (B) may have a viscosity at 40° C. of from 0.5 to 100.000 mPa.s, alternatively of from 1 to 10.000 mPa.s, alternatively 20 to 1.000 mPa.s. (using a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1).
- The silicone oil (B) can be a blend of multiple silicone oils described above.
- The silicone oil (B) is present in an amount of from 0.5 wt % to 50 wt %, alternatively 1 wt % to 40 wt %, alternatively 5 wt % to 40 wt %, alternatively 5 wt % to 20 wt %, alternatively 5% to 10 wt % based on the total weight of (A)+(B), which is 100 wt %.
- Lubricant additives may be used to impart or improve certain properties to the lubricating composition. Such additives include friction modifiers, anti-wear additives, extreme pressure additives, seal swelling agents, rust and corrosion inhibitors, thickeners, Viscosity Index improvers “other than (B)”, pour point depressants, anti-oxidants, free-radical scavengers, hydroperoxide decomposers, metal passivators, surface active agents such as detergents, emulsifiers, demulsifiers, defoamants, compatibilizers, dispersants, and mixtures thereof.
- Further additives include deposit control additives, film forming additives, tackifiers, antimicrobials, additives for biodegradable lubricants, haze inhibitors, chromophores, and limited slip additives.
- Examples of friction modifiers include long-chain fatty acids and their derivatives, molybdenum compounds, aliphatic amines or ethoxylated aliphatic amines, ether amines, alkoxylated ether amines, acylated amines, tertiary amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters, polyol esters, aliphatic carboxylic ester-amides, imidazolines, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates.
- Examples of anti-wear additives and extreme pressure additives include organosulfur and organo-phosphorus compounds, such as organic polysulfides among which alkylpolysulfides; phosphates among which trihydrocarbyl phosphate, dibutyl hydrogen phosphate, amine salt of sulfurized dibutyl hydrogen phosphate, dithiophosphates; dithiocarbamates dihydrocarbyl phosphate; sulfurized olefins, such as sulfurized isobutylene, and sulfurized fatty acid esters.
- Examples of seal swell agents include esters, adipates, sebacates, azeealates, phthalates, sulfones such as 3-alkoxytetraalkylene sulfone, substituted sulfolanes, aliphatic alcohols of 8 to 13 carbon atoms such as tridecyl alcohol, alkylbenzenes, aromatics, naphthalene depleted aromatic compounds, mineral oils.
- Examples of rust and corrosion inhibitors include monocarboxylic acids such as octanoic acid, decanoic acid and dodecanoic acid; polycarboxylic acids such as dimer and trimer acids from tall oil fatty acids, oleic acid, linoleic acid; thiazoles; triazoles such as benzotriazole, decyltriazole, 2-mercapto benzothiazole; thiadiazoles such as 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole; metal dithiophosphates; ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines; ethoxylated phenols; ethoxylated alcohols; imidazolines; aminosuccinic acids.
- Examples of thickeners include metallic soaps such as lithium soaps, silica, expanded graphite, polyurea, clays such as hectorite or bentonite.
- In some instances, when thickened, the lubricant composition may become a grease composition.
- Examples of Viscosity Index improvers “other than (B)” include polymethacrylates, olefin copolymers, polyisoalkylene such as polyisobutylene, styrene-diene copolymers, and styrene-ester copolymers such as styrenemaleic ester.
- Examples of pour point depressants include wax-alkylated naphthalenes and phenols, polymethacrylates, styrene-ester copolymers.
- Examples of anti-oxidants include phenolic antioxidants such as 2,6-di-tert-butylphenol, tertiary butylated phenols such as 2,6-di-tert-butyl-4-methylphenol, 4,4′-methylenebis(2,6-di-tert-butylphenol),2,2′-methylenebis(4-methyl6-tert-butylphenol), 4,4′-thiobis(2-methyl-6-tert-butylphenol); mixed methylene-bridged polyalkyl phenols; aromatic amine antioxidants; sulfurized phenolic antioxidants; organic phosphites; amine derivatives such as p-, p′-dioctyldiphenylamine, N,N′-di-sec-butylphenylenediamine, 4-isopropylaminodiphenylamine, phenyl-.alpha.-naphthyl amine, phenyl-.alpha.-naphthyl amine, ring-alkylated diphenylamines; bisphenols; cinnamic acid derivatives.
- Examples of free-radical scavengers include zinc dialkyl dithiophosphates, hindered phenols, and alkylated arylamines.
- Examples of hydroperoxide decomposers include organo-sulfur compounds and organo-phosphorus compounds.
- Examples of metal passivators include poly-functional (polydentate) compounds, such as ethylenediaminetetraacetic acid (EDTA) and salicylaldoxime.
- Examples of surface active agents such as detergents, dispersants, emulsifiers, demulsifiers include alkali metal or alkaline earth metal salts of organic acids such as magnesium sulfonate, zinc sulfonate, magnesium phenate, zinc phenate, lithium sulfonate, lithium carboxylate, lithium salicylate, lithium phenate, sulfurized lithium phenate, magnesium sulfonate, magnesium carboxylate, magnesium salicylate, magnesium phenate, sulfurized magnesium phenate, potassium sulfonate, potassium carboxylate, potassium salicylate, potassium phenate, sulfurized potassium phenate; common acids such as alkylbenzenesulfonic acids, alkylphenols, fatty carboxylic acids, polyamine, polyhydric alcoholderived polyisobutylene derivatives.
- Examples of defoamants include polysiloxanes, polyacrylates and styrene ester polymers.
- Examples of compatibilizers include aromatic hydrocarbons such as 1-methyl-naphthalene, aromatic ethers such as diphenyl ether or anisole (methyl phenyl ether), long chain alcohols such as nonyl phenol, octanol and decanol.
- Examples of dispersants include alkenylsuccinimide such as polyisobutylene succinimide, N-substituted polyisobutenyl succinimides such as polyisobutenyl succinimide-polyethylenepolyamine, succinates, succinate esters, alkyl methacrylate-vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylaminoethyl methacrylate copolymers, alkylmethacrylate-polyethylene glycol methacrylate copolymers, polystearamides, high molecular weight amines, phosphoric acid derivatives such as bis-hydroxypropyl phosphorate.
- Some additives may possess multiple properties and provide for a multiplicity of affects. For example, graphite and molybdenum disulfide may both be used as friction modifiers and extreme pressure additives or functionalized soaps may be used to thicken but also provide extreme pressure and antiwear performances to greases. This approach is well known by the person skilled in the art and need not be further elaborated herein.
- An additive may be used alone or in combination with other additives.
- When present in the lubricant composition of the invention, the sole or multiple additive(s) may be used at a level of from 0 to 10 wt %, alternatively 0.1 to 5 wt %, based on the total weight of the lubricant composition. Thickeners to produce greases may be used at a level of from 5 to 25% wt based on the total weight of the lubricant grease composition.
- The lubricant composition is produced by mixing the lubricant base oil and the silicone oil and the optional additives, by conventional mixing means, optionally with heating.
- The lubricant composition may be homogeneous, or non homogeneous. Homogeneity of the composition is considered at 25° C., after mixing, and the optional heating, is (are) disrupted.
- A homogeneous composition is meant herein as a composition where the lubricant base oil and the silicone oil are compatible or miscible and form a monophasic system. A homogeneous composition may be hazy, clear or opaque. The intimate blend of the 2 oils is uniform and posses the same properties throughout. The compatibility of mixtures may be assessed using ASTM D7155-11: Standard Practice for Evaluating Compatibility of Mixtures of Turbine Lubricating Oils.
- A non homogeneous composition is meant herein as a composition where the lubricant base oil and the silicone oil form a biphasic system upon rest. A non homogeneous composition will be characterized by a varying composition of the blend throughout the container.
- A non homogeneous system may be rendered homogenous by shaking, heating or addition of a compatibilizer, or a combination thereof. These non homogenous compositions will return to non homogeneous state upon disruption of the shaking or heating. When a compatibilizer is used, the duration of improved homogeneity will depend on the effectiveness of the compatibilizer—temporarily or over a longer period of time.
- Compatibilizers may be surfactants or co-solvents. Homogeneity may be obtained through emulsification, dispersion or any other means known by the person skilled in the art. Emulsification techniques are known by the person skilled in the art and will not be further exemplified herein.
- Examples of homogeneous compositions include polydiethylsiloxane with polyalphaolefin, polydiethylsiloxane with mineral oil, polymethyloctylsiloxane with polyalphaolefin.
- Examples of non homogenous compositions include polytrifluoropropylmethylsiloxane with mineral oil, polydiethylsiloxane with polyol ester, polymethyloctylsiloxane with polyalkylene glycol, polymethyloctylsiloxane with polyol esters.
- Compositions as hereinbefore described are shear stable in accordance with DIN 51350-6 (the KRL Tapered Roller Bearing Test in accord with DIN 51350-6) where a reduction in viscosity after the test of less than 10% is considered shear stable and values above 10% are considered shear unstable. It has been found that lubricant compositions as hereinbefore described result in much smaller rises in viscosity subsequent to testing according to DIN 51350-6 than that of conventional VI improvers,
- Lubricating compositions may be used in a variety of applications where friction occurs between rubbing surfaces. The surfaces may be plastic or metal.
- Types of friction include sliding, rolling, static, kinetic, stick-slip, solid (dry), boundary, mixed, wear, erosion, elasto-hydrodynamic frictions.
- The present invention includes a method to lubricate metal-metal surfaces comprising:
- i. obtaining a lubricant composition comprising the composition as hereinbefore described and;
- ii. lubricating the metal-metal surface with said lubricant composition.
- The present lubricant composition may be used in any system that includes machine elements that contain gears of any kind and roller bearings. Examples of such systems include electricity generating systems, industrial manufacturing equipments such as paper, steel and cement mills hydraulic systems, automotive drive trains, aircraft propulsion systems, etc.
- Further systems include crankcases, 2-stroke engines, 4-stroke engines, diesel engines, internal combustion engines, gears for manual or differential transmissions, industrial lubricants, hydraulic, compressor, turbine, metal working, metal forming, lubrication grease, solid.
- Further systems also include traction and torque systems.
- The lubricant composition may alternatively be used as an automatic transmission fluid, a manual transmission fluid, an axle lubricant, a transaxle lubricant, an industrial gear lubricant, a circulating lubricant, a gear oil for wind turbines, an open gear lubricant, an enclosed gear lubricant, an hydraulic fluid, a compressor fluid, or a grease.
- Operating temperatures for the use of the lubricant composition, meaning the temperatures at which the lubricant composition may be used for prolonged time (also called service temperatures), range of from −55° C. to +200° C. Short term peak temperature may be higher.
- Viscosity Index is measured/calculated using ASTM D 2270-10E: Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100° C.
-
- The dynamic viscosity is determined by a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1 and at the two different required temperatures: 40° C. and 100° C.
- The density may be measured using glass pycnometer according to DIN 51757 (Procedure V2). Ideal mixing is assumed for blends of materials, meaning that the density of the blend can be calculated from the respective values of the ingredients. The values of dynamic viscosities were subsequently used to calculate kinematic viscosities using the material densities tabulated below. The calculated kinematic viscosities were then used to calculate Viscosity Index as per formula:
-
Viscosity Index=[((antilog N)−1)/0.00715+100] - where YN=H/U,
Y=kinematic viscosity at 100° C. of the oil whose viscosity index is to be calculated,
H=kinematic viscosity at 40° C. of a 100 Viscosity Index oil with the same viscosity at 100° C. as the unknown,
U=kinematic viscosity at 40° C. of the oil whose viscosity index is to be calculated. - The Load Carrying Capability (LCC) properties of the lubricant compositions being assessed were determined in accordance with ASTM D 5706-05 ‘Standard test method for determining extreme pressure properties of lubricating greases using a high-frequency, linear-oscillation (SRV) test machine’. The SRV test machine may be used to determine load carrying and wear properties and coefficient of friction of lubricating greases at selected temperatures and loads specified for use in applications where high-speed vibrational or start-stop motions are present for extended periods of time under initial high Hertzian point contact pressures. This method has found application in qualifying lubricating greases used in constant velocity joints of front-wheel-drive automobiles and for lubricating greases used in roller bearings. This method may also be used for determining a fluid lubricant's ability to protect against wear and its coefficient of friction under similar test conditions.
- In the following examples a lubricating fluid was evaluated instead of lubrication greases; a steel cylinder was used instead of a steel ball; frequency was 10 Hz instead of 50 Hz. The measurements were carried out at 40° C. using 1 mm stroke. The load was increased in increments of 50N every two minutes up to a maximum load of 2000N.
- Wearing properties or lubrication performance may be evaluated by standard test method DIN 51350-3 ‘Testing of lubricants in the Shell four-ball tester’. The Shell Four Ball Tester (FBT) is a testing device used to determine welding and metal loads as well as different friction and wear characteristics of lubricants. The standard test consists of a rotating ball of a ball bearing being pressed onto three similar but immobile balls while applying a load of 100N, 400N and 800N for 1 hour test duration. Wear is determined by optically measuring the formed calotte (the worn depression area).
- This testing device is especially common in the lubricant industry where it is used for routine product development and quality control testing. The friction torque can be recorded continuously.
- The testing was done according to DIN 51350-3 and the wear scar is reported as the average of the three steel balls in mm.
- Shear stability of lubricant compositions was measured according to DIN 51350-6 using a tapered roller bearing to shear the lubricant composition for 4 hours (method A) and report the relative drop of viscosity after the test in percentage,
-
R v=(v 0 −v 1)/v 0*100, - where v0 is the kinematic viscosity (mm2/s at 100° C.) before and v1 after the test.
- The lubricant composition of the present invention is characterized by a Viscosity Index≧180, alternatively ≧200, alternatively ≧250.
- The lubricant composition of the present invention is characterized by a load carrying capability according to the procedure described above. LCC≧800N, SRV-load ≧1000N, alternatively ≧1200N, alternatively ≧1500N (ASTM D 5706-05).
- The lubricant composition of the present invention is characterized by a relative viscosity drop according to the procedure described above. In the case of the compositions as hereinbefore described, Rv<10%, alternatively Rv<7.5%, alternatively Rv<6%. Where Rv=(v0−v1)/v0*100, where v0 is the kinematic viscosity (mm2/s at 100° C.) before and v1 after the test when measured according to DIN 51350-6 (method A).
- All percentages in the following examples are in wt. % unless otherwise indicated.
- PDMS: polydimethylsiloxanes having a typical viscosity of 50 cst at 25° C., determined using a glass capillary viscosimeter
- PDES: polydiethylsiloxane obtained from GNIIChTEOS, having a viscosity of 344 mPa.s at 20° C. determined using a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1;
- PAO: polyalphaolefin (PAO SpectraSyn™ 6 from ExxonMobil Chemicals) having a typical viscosity of 30.3 mm2/s at 40° C. (Producers datasheet dated 27 Feb. 2012)
- Mineral oil: Nynas® NS-100 (severely hydrotreated base oil obtained from Nynas AB) having a typical viscosity of 96 mm2/s at 40° C. (Producers datasheet, dated 3 Mar. 2008)
- PMOS 1: polymethyloctylsiloxane, prepared by reacting a trimethylsilyl terminated methylhydrogen siloxanes (having a viscosity of approx 30 mPa.s at 20° C.) with an excess of 1-octene using a Pt catalyst at 120° C. The reaction was monitored by IR spectroscopy until the SiH stretch peak (at about 2180 cm−1) had disappeared. The excess of 1-octene was then removed by vacuum distillation and a clear oil having a viscosity of 1130 mPa.s at 20° C. was obtained (using a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1
- PMOS 2: polymethyloctylsiloxane, prepared by reacting a trimethylsilyl terminated methylhydrogen siloxanes (having a viscosity of approx 6 mPa.s at 20° C.) with an excess of 1-octene using a Pt catalyst at 120° C. The reaction was monitored by IR spectroscopy until the SiH peak had disappeared. The excess of 1-octene was then removed by vacuum distillation and a clear oil having a viscosity of 170 mPas at 20° C. was obtained (using a cone/disk viscometer (Physica® MCR 301) at constant shear rate of D=8.7 s−1)
- Polyol Ester: polyol ester based on dipentaerithrytol and C5/C8/C10 acids: commercial material Hatcol® 2926, from Hatco, with a typical viscosity of 53 mm2/s (ASTM D-445) at 40° C. (Producers datasheet, dated (Aug. 4, 2006)
- Polyglycol: polyalkylene glycol B01/40 from Clariant, with a typical viscosity of 58 mm2/s at 40° C. (Producers datasheet)
- Viscosity Index Type PiB: Polyisobutylene Viscosity Improver: commercial material Hitec® 7389, from Afton Chemical Corporation, with a typical viscosity of 176 mm2/s at 100° C. (Producers datasheet)
- Viscosity Index Type OCP: Olefin Copolymer Viscosity Improver: commercial material Hitec® 5704, from Afton Chemical Corp., with a typical viscosity of 1100 mm2/s at 100° C.
- The density of the materials was measured using a glass pycnometer according to DIN 51757 (Procedure V2). The following parameters for the densities ρ in g/ml (for a given temperature ρ=a−(b×Temperature (° C.)) were obtained using linear regression which were then used to calculate the densities at 40 and 100° C.
-
A b PAO 0.8343 0.0006 PDES 1.0149 0.0007 PMOS 1 0.9216 0.0006 PMOS 2 0.9161 0.0007
The values for PDMS are calculated using an equation from the Polymer Data Handbook (1999 Oxford University Press) to be 0.957 g/ml at 40° C. and 0.905 g/ml at 100° C. - For the blends ideal mixing was assumed meaning that the density of the blend can be calculated from the respective values of the ingredients.
- Blending: The blends were prepared by adding a total of 50 g of materials to a glass bottle and shaking them until a homogenous mixture was obtained.
- The viscosity, viscosity index, the wear properties i.e. Load Carrying Capability (LCC) and the relative viscosity drop were measured for different compositions. The results are shown in the following tables; values for the individual components are given as a reference. (Note the symbols (A) and (B) in the Tables below indicate the respective ingredients as identified in e.g. claim 1).
-
-
PDES PAO LCC (wt %) (B) (wt %) (A) (N) 0 100 450 5 95 2000 10 90 2000 40 60 2000 60 40 1500 80 20 750 90 10 1200 100 0 250 - Example 1a shows that mixtures according to the invention containing PDES have an LCC much higher than the pure oils in the range of between 0.5 and 50% wt of component (B), namely the PDES. The effect can be already seen with a 5% wt % addition level of PDES into the PAO.
-
-
Viscosity at Viscosity at PDES PAO 40° C. 100° C. Viscosity (Wt %) (B) (Wt %) (A) (mPa · s) (mPa · s) Index 0 100 — — 143* 20 80 30.91 6.62 207 40 60 38.27 8.3 222 60 40 50.76 12.5 271 80 20 82.34 19.33 267 90 10 118.93 28.08 285 - Example 1b shows that mixtures according to the invention containing PDES (i.e. component B) have much higher Viscosity Index values (at least 10% greater) than 100% PAO (*: Viscosity Index 143 from suppliers datasheet).
-
-
PDES Mineral Oil LCC (Wt %) (B) (Wt %) (A) (N) 0 100 1000 5 95 1400 10 90 2000 20 80 1800 40 60 1050 60 40 1100 80 20 450 95 5 450 100 0 250 - Example 2 a shows that compositions as hereinbefore described containing PDES and mineral oil have an LCC much higher than 100% mineral oil. The effect can be seen at 5% addition level of PDES into the mineral oil.
-
-
PDES Mineral Oil Four ball wear scar (Wt %) (B) (Wt %) (A) at 400N load (mm) 0 100 1.727 5 95 0.730 10 90 1.122 20 80 1.538 40 60 1.160 60 40 0.941 80 20 2.112 90 10 3.564 95 5 nm 100 0 Nm - Example 2b shows that that compositions as hereinbefore described containing PDES and mineral oil have a lower wear scar in the four ball test than the pure mineral oil (nm stands for non measurable, load is too high to run the test).
-
-
PMOS 1 PAO LCC (Wt %) (B) (Wt %) (A) (N) 0 100 450 10 90 2000 40 60 1800 90 10 1200 100 0 1300 - Example 3a shows that compositions as hereinbefore described containing PMOS1 have an LCC much higher than the 100% PAO. The effect can clearly be identified with a 10% addition level of PMOS1 into the PAO.
-
-
PMOS PAO Four ball wear scar (Wt %) (B) (Wt %) (A) at 800N load (mm) 0 100 Nm 20 80 3.346 60 40 1.475 80 20 1.432 - Example 3b shows that that compositions as hereinbefore described containing PMOS1 and PAO have a lower wear scar in the four ball test at high loads (800N) than the pure PAO (nm stands for non measurable, load is too high to run the test).
-
-
Viscosity at Viscosity at PMOS 1 PAO 40° C. 100° C. Viscosity (Wt %) (B) (Wt %) (A) (mPa · s) (mPa · s) Index 0 100 — — 143* 10 90 38.15 8.02 216 20 80 55.62 11.77 234 40 60 106.1 22.44 259 60 40 183.6 39.02 278 80 20 310.0 69.92 310 90 10 402.0 95.95 332 95 5 458.0 111.0 341 100 0 497.3 131.0 364 - Example 3c shows that mixtures according to the invention containing PMOS1 have Viscosity Index much higher (at least 10% greater) than for 100% PAO (*: Viscosity Index 143 as provided by the supplier).
-
-
PMOS 2 PAO LCC (Wt %) (B) (Wt %) (A) (N) 0 100 450 10 90 1750 40 60 2000 90 10 1550 100 0 1450 - Example 4a shows that mixtures according to the invention containing PMOS2 have an LCC much higher than value for 100% PAO, i.e. component (A) alone. The effect is clearly evident at 10% addition level of PMOS1 into the PAO.
-
-
Viscosity at Viscosity at PMOS 2 PAO 40° C. 100° C. (Wt %) (B) (Wt %) (A) (mPa · s) (mPa · s) VI 0 100 143* 5 95 27.8 6.09 211 20 80 33.59 7.24 218 40 60 42.55 9.81 248 60 40 52.45 12.49 265 80 20 66.25 16.59 287 90 10 75.51 19.59 301 95 5 76.46 20.18 306 100 0 82.77 22.34 314 - The Example 4b shows that mixtures according to the invention containing PMOS2 have much higher VI values (greater than 10% higher) than 100% PAO. The Viscosity Index value for PAO provided by the supplier is 143 as previously indicated by *.
-
-
PDMS PAO LCC (Wt %) (B) (Wt %) (A) (N) 0 100 450 5 95 2000 10 90 2000 20 80 1800 40 60 1850 60 40 1750 80 20 650 90 10 400 95 5 350 100 0 300 - The Example 5a shows that mixtures according to the invention containing PDMS have an LCC much higher than 100% PAO. The effect can be clearly identified at 5% addition level of PDMS.
-
-
Viscosity at Viscosity at PDMS PAO 40° C. 100° C. Viscosity (Wt %) (B) (Wt %) (A) (mPa · s) (mPa · s) Index 0 100 143* 5 95 27.8 5.7 188 10 90 29.1 7.6 276 20 80 39.6 8.8 234 40 60 39.7 9.5 257 60 40 38.4 9.5 266 80 20 36.7 12.3 369 90 10 35.0 11.7 368 95 5 36.1 14.5 435 100 0 35.0 16.7 502 - Example 5b shows that mixtures according to the invention containing PDMS have much higher Viscosity Index values (much greater than 10%) than the 100% value for PAO. The Viscosity Index value for PAO provided by the supplier is 143 as previously indicated by *.
-
-
PDMS Mineral Oil LCC (Wt %) (B) (Wt %) (A) (N) 0 100 1000 5 95 2000 10 90 2000 20 80 1550 40 60 1150 60 40 1400 80 20 850 90 10 500 100 0 300 - Example 6a shows that mixtures according to the invention containing PDMS have an LCC much higher than 100% mineral oil. The effect can be already seen at 5% addition level of PDMS in the mineral oil.
-
-
PDMS Mineral Oil Four ball wear scar (Wt %) (B) (Wt %) (A) at 400N load (mm) 0 100 1.727 5 95 1.147 10 90 0.926 40 60 0.989 60 40 1.125 80 20 Nm 100 0 Nm - Example 6b shows that that compositions as hereinbefore described containing PDMS and mineral oil have a lower wear scar in the four ball test than the pure mineral oil (nm stands for non measurable, load is too high to run the test).
-
-
PMOS 1 Polyol ester LCC (Wt %) (B) (Wt %) (A) (N) 10 90 1250 50 50 2000 100 0 1300 - Example 7 shows that mixtures according to the invention containing PDMS have LCC of above 1000N
-
-
PMOS 2 Polyester LCC (Wt %) (B) (Wt %) (A) (N) 10 90 1500 50 50 1350 90 10 1400 100 0 1450 - Example 8 shows that mixtures according to the invention containing PMOS2 have an LCC of above 1000N.
-
-
PDES Polyester LCC (wt %) (B) (wt %) (A) (N) 10 90 1500 50 50 1500 90 10 450 100 0 250 - Example 9 shows that mixtures according to the invention containing PDES have a load carrying (LCC) above 400N.
-
-
PDES Hatcol 2926 LCC (wt %) (B) (Wt %) (A) (N) 10 90 2000 50 50 1900 90 10 700 100 0 250 - Example 10 shows that mixtures according to the invention containing PDES have an LCC higher than 650N.
- PAO Blends with organic VI Improvers were prepared using the commercial Hitec® 5704 and Hitec® 7389
-
Compar- Viscosity at Viscosity at ative 40° C. 100° C. Viscosity example VI improver (mPa · s) (mPa · s) Index 1 5% Hitec ® 5704 40.4 7.1 168 2 10% Hitec ® 5704 60.1 9.6 167 3 20% Hitec ® 5704 113.8 18.2 199 4 5% % Hitec ® 7389 30.7 6.1 186 5 10% Hitec ® 7389 37.6 7.1 184 6 20% % Hitec ® 57.4 10.4 196 7389 - Comparative examples 1-6 indicate that the commercial viscosity improvers are less efficient than the disclosed siloxanes disclosed in Examples 1-10. Furthermore, the comparative viscosity improvers do not allow achieving viscosity indices above 200 when used with polyalphaolefin (density of the pure PAO was used to calculate the Viscosity Index values of the blends).
- PAO blends with organic VI improver Hitec® 5704 and with PMOS 1 were tested for shear stability
-
Viscosity at Viscosity at Relative 100° C. (mPa · 100° C. (mPa · drop of s) before s) after 4h viscos- VI improver KRL test KRL test ity (%) Compar- 20% Hitec ® 18.2 10.0 45.0 itive 5704 example 3 Example 3 20% PMOS 1 12.6 11.9 5.6
Example 3 shows a composition according to the invention that is shear stable, while Comparative example 3 is shear instable. -
-
Viscosity at VI improver in −35° C. PAO (mPa · s) Comparative example 7a 10% Hitec ® 5704 9520 Comparative example 7b 10% Hitec ® 7389 6175 Example 11a 10% PMOS1 4520 Example 11b 10% PMOS2 3331 Example 11c 10% PDES 2790 - The examples 3, 4, 1 show that compositions according to the invention at 10% siloxanes content in PAO have a “low temperature”-viscosity significantly lower than commercial VI improvers at the same addition level (Comparative 7a and b).
Claims (20)
1. A lubricant composition comprising:
(A) a non-silicone base stock oil; and
(B) 0.5 to 50% by weight, based on the total weight of (A)+(B) of a silicone oil; wherein the Viscosity Index of the lubricant composition, as measured in accordance with ASTM D 2270-10e1, is greater than that of the non-silicone lubricant base stock oil (A) by at least 10% and the lubricant composition is shear stable when measured according to DIN 51350-6 (Method (A).
2. The lubricant composition according to claim 1 , where (A) is selected from any non-silicone lubricant base oil of Group I to V, as per the API classification of lubricant base oils, or mixtures or greases thereof.
3. The lubricant composition according to claim 1 , where (A) is selected from mineral oil, polyalphaolefins, polyinternal olefins, polyalkylene glycols, or mixtures or greases thereof.
4. The lubricant composition according to claim 1 , where (B) is of the structure
wherein R1, R2 and R3 are independently selected from alkyl groups having from 1 to 45 carbon atoms or phenyl groups containing 6 to 16 carbon atoms, each R4 is independently an alkyl group having from 2 to 16 carbon atoms, Me is a methyl group, Et is an ethyl group, n is zero or an integer, v is zero or an integer and t is zero or an integer, with the proviso that n+v+t>1; and that when v is >zero, n is zero and t is zero and that when t>zero, v is zero and n is zero or an integer.
5. The lubricant composition according to claim 1 , where (A) is present in an amount of from 60 wt % to 99 wt %, based on the total weight of (A)+(B).
6. The lubricant composition according to claim 1 , where (B) is present in an amount of from 40 wt % to 5 wt %, based on the total weight of (A)+(B).
7. The lubricant composition according to claim 1 , further comprising an additive (C), where (C) is selected from the group consisting of friction modifiers, anti-wear additives, extreme pressure additives, seal swelling agents, rust and corrosion inhibitors, thickeners, Viscosity Index improvers “other than (B)”, pour point depressants, anti-oxidants, free-radical scavengers, hydroperoxide decomposers, metal passivators, surface active agents, detergents, emulsifiers, demulsifiers, defoamants, compatibilizers, dispersants, deposit control additives, film forming additives, tackifiers, antimicrobials, additives for biodegradable lubricants, haze inhibitors, chromophores, limited slip additives, or mixtures thereof.
8. The lubricant composition according to claim 7 , wherein (C) is present in an amount up to 10 wt %, based on the total weight of the lubricant composition.
10. The lubricant composition according to claim 1 , where (B) is of the structure
wherein R1, R2 and R3 are independently selected from alkyl groups having from 1 to 12 carbon atoms, Me is a methyl group, R4 is an alkyl group having from 2 to 12 carbon atoms, n is zero or an integer, and t is an integer ≧0.
11. The lubricant composition according to claim 9 , where (A) is selected from mineral oil, polyalphaolefins, polyinternal olefins, polyalkylene glycols, or mixtures or greases thereof.
12. The lubricant composition according to according to claim 9 , further comprising an additive (C), where (C) is present in an amount up to 10 wt %, based on the total weight of the lubricant composition.
13. The lubricant composition according to claim 1 , where (B) is a silicone resin.
14. The lubricant composition according to claim 1 , where (B) is an amino or mercapto siloxane.
15. The lubricant composition according to claim 1 , where (A) consists of mineral oil based lubricant base stock oils, polyalphaolefins (PAO), polyinternal olefins (PIO), or mixtures thereof.
16. The lubricant composition according to claim 1 , where the Load Carrying Capacity (LCC) according to ASTM D 5706-05 is greater than those of the non-silicone lubricant base stock oil (A) alone by at least 40%.
17. An emulsion comprising a lubricant composition according to claim 1 .
18. A method to lubricate a metal-metal surface comprising:
obtaining a lubricant composition according to claim 1 ; and
lubricating the metal-metal surface with the lubricant composition.
19. A lubricant composition according to claim 1 and further defined as an automatic transmission fluid, a manual transmission fluid, an axle lubricant, a transaxle lubricant, an industrial gear lubricant, a circulating lubricant, an open gear lubricant, an enclosed gear lubricant, an hydraulic fluid, a compressor fluid, a gear oil for wind turbines, or a grease.
20. The lubricant composition according to claim 10 , where (A) is selected from mineral oil, polyalphaolefins, polyinternal olefins, polyalkylene glycols, or mixtures or greases thereof.
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- 2013-08-14 EP EP13751071.5A patent/EP2885383A1/en not_active Withdrawn
- 2013-08-14 US US14/421,473 patent/US20150232782A1/en not_active Abandoned
- 2013-08-14 JP JP2015527577A patent/JP2015525827A/en active Pending
- 2013-08-14 WO PCT/US2013/054966 patent/WO2014028632A1/en not_active Ceased
- 2013-08-14 CN CN201380043406.1A patent/CN104583379A/en active Pending
- 2013-08-14 BR BR112015003038A patent/BR112015003038A2/en not_active IP Right Cessation
- 2013-08-14 KR KR20157006053A patent/KR20150042246A/en not_active Withdrawn
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| US20060135379A1 (en) * | 2004-12-21 | 2006-06-22 | Chevron Oronite Company Llc | Anti-wear additive composition and lubricating oil composition containing the same |
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| US20150307808A1 (en) * | 2012-11-28 | 2015-10-29 | Dow Corning Corporation | Siloxane Traction Fluids with Ring-Shaped Branch Structures and Method of Using |
| US20150315514A1 (en) * | 2012-11-28 | 2015-11-05 | Dow Corning Corporation | A method of reducing friction and wear between surfaces under a high load condition |
| US9896640B2 (en) * | 2012-11-28 | 2018-02-20 | Dow Corning Corporation | Method of reducing friction and wear between surfaces under a high load condition |
| EP3318620A1 (en) * | 2016-11-02 | 2018-05-09 | Evonik Oil Additives GmbH | Use of a lubricant for improving the low temperature viscosity of lubricant compositions |
| US20180237718A1 (en) * | 2017-02-22 | 2018-08-23 | Infineum International Limited | Relating to lubricating compositions |
| CN108456583A (en) * | 2017-02-22 | 2018-08-28 | 英菲诺姆国际有限公司 | Improvement in lubricating composition and improvement related with lubricating composition |
| US12031101B2 (en) * | 2017-02-22 | 2024-07-09 | Infineum International Limited | Relating to lubricating compositions |
| US11655430B2 (en) * | 2017-10-17 | 2023-05-23 | Industry-University Cooperation Foundation Hanyang University | Coating composition for producing article |
| US20220154095A1 (en) * | 2017-10-17 | 2022-05-19 | Industry-University Cooperation Foundation Hanyang University | Coating composition for producing article |
| US11441093B2 (en) * | 2018-04-13 | 2022-09-13 | Moresco Corporation | Lubricating oil composition and lubricating agent using same |
| CN112088205A (en) * | 2018-04-13 | 2020-12-15 | 株式会社Moresco | Lubricating oil composition and lubricant using same |
| US11274263B2 (en) * | 2018-07-24 | 2022-03-15 | Klüber Lubrication München Se & Co. Kg | Hybrid grease with low friction coefficients and high wearing protection |
| CN111770979A (en) * | 2018-07-24 | 2020-10-13 | 慕尼黑克吕伯尔润滑器股份两合公司 | Mixed grease with low friction coefficient and high wear resistance |
| US20240084853A1 (en) * | 2019-10-10 | 2024-03-14 | Ntn Corporation | Axle bearing, grease composition and rolling ball bearing |
| US12085128B2 (en) * | 2019-10-10 | 2024-09-10 | Ntn Corporation | Axle bearing, grease composition and rolling ball bearing |
| US20230037110A1 (en) * | 2019-12-04 | 2023-02-02 | POSTECH Research and Business Development Foundation | Oleogel based on fatty acid amide-containing polymer and preparation method therefor |
| US11945916B2 (en) * | 2019-12-04 | 2024-04-02 | POSTECH Research and Business Development Foundation | Oleogel based on fatty acid amide-containing polymer and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104583379A (en) | 2015-04-29 |
| BR112015003038A2 (en) | 2017-07-04 |
| WO2014028632A1 (en) | 2014-02-20 |
| EP2885383A1 (en) | 2015-06-24 |
| JP2015525827A (en) | 2015-09-07 |
| KR20150042246A (en) | 2015-04-20 |
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