CN1215153C - 柱塞发动机的润滑 - Google Patents
柱塞发动机的润滑 Download PDFInfo
- Publication number
- CN1215153C CN1215153C CNB011408049A CN01140804A CN1215153C CN 1215153 C CN1215153 C CN 1215153C CN B011408049 A CNB011408049 A CN B011408049A CN 01140804 A CN01140804 A CN 01140804A CN 1215153 C CN1215153 C CN 1215153C
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- CN
- China
- Prior art keywords
- lubricant
- mass
- oil
- sulfurized
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- -1 amine phosphate Chemical class 0.000 claims abstract description 72
- 239000000314 lubricant Substances 0.000 claims abstract description 67
- 239000000654 additive Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 239000003599 detergent Substances 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 230000001050 lubricating effect Effects 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 229920000098 polyolefin Polymers 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 23
- 150000001412 amines Chemical class 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical group O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims description 4
- 239000010763 heavy fuel oil Substances 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 2
- 238000010248 power generation Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000000203 mixture Substances 0.000 description 23
- 150000002989 phenols Chemical class 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 22
- 239000004094 surface-active agent Substances 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 230000002378 acidificating effect Effects 0.000 description 18
- 239000000523 sample Substances 0.000 description 18
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 description 14
- 239000000543 intermediate Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 150000005691 triesters Chemical class 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 150000002736 metal compounds Chemical class 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 10
- 150000003460 sulfonic acids Chemical class 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 6
- 150000002924 oxiranes Chemical class 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000002199 base oil Substances 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 229960004889 salicylic acid Drugs 0.000 description 5
- 150000003870 salicylic acids Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000007866 anti-wear additive Substances 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 4
- 229960001860 salicylate Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 125000005608 naphthenic acid group Chemical group 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Chemical group 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- RPOTYPSPQZVIJY-UHFFFAOYSA-N 1-aminopentan-3-ol Chemical compound CCC(O)CCN RPOTYPSPQZVIJY-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- 239000010689 synthetic lubricating oil Substances 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-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
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- NGONMGMXBMGUGD-UHFFFAOYSA-N 1-[di(nonyl)amino]propan-2-ol Chemical compound CCCCCCCCCN(CC(C)O)CCCCCCCCC NGONMGMXBMGUGD-UHFFFAOYSA-N 0.000 description 1
- NPOYJZOTOXKWCU-UHFFFAOYSA-N 1-amino-2h-naphthalen-1-ol Chemical compound C1=CC=C2C(N)(O)CC=CC2=C1 NPOYJZOTOXKWCU-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 description 1
- QAWJAMQTRGCJMH-UHFFFAOYSA-N 2-(4-methylphenyl)oxirane Chemical compound C1=CC(C)=CC=C1C1OC1 QAWJAMQTRGCJMH-UHFFFAOYSA-N 0.000 description 1
- UVYBWDBLVDZIOX-UHFFFAOYSA-N 2-(octylamino)ethanol Chemical compound CCCCCCCCNCCO UVYBWDBLVDZIOX-UHFFFAOYSA-N 0.000 description 1
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 description 1
- SNAUWGUVQBOHMZ-UHFFFAOYSA-N 2-methyl-3-pentyloxirane Chemical compound CCCCCC1OC1C SNAUWGUVQBOHMZ-UHFFFAOYSA-N 0.000 description 1
- WYAPIOHQETXJHU-UHFFFAOYSA-N 2-n-butan-2-ylbenzene-1,2-diamine Chemical compound CCC(C)NC1=CC=CC=C1N WYAPIOHQETXJHU-UHFFFAOYSA-N 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
一种适用于柱塞柴油发动机的润滑剂，其特征是该发动机具有200kW或更大的动力输出。柱塞柴油发动机可用于船舶、发电或铁路牵引应用中。润滑剂包含润滑粘度的基本原料、高碱性金属洗涤剂、优选具有至少0.85%硫酸盐灰分的灰分含量、和无灰分或无金属辅助添加剂，上述辅助添加剂至少包含下列之一：油溶性硫化烷基酚，磷硫化烃或硫化烃，油、脂肪或聚烯烃的硫化物，或磷酸胺。
Description
本发明涉及一种适用于柱塞柴油(压燃)发动机的润滑剂。柱塞柴油发动机被用于船舶、发电和铁路牵引应用中。
柱塞柴油发动机已被用在水上船只中，即用于所谓的船舶应用，包含辅助的发电和用于陆基应用，例如发电。与例如使用船舶柴油汽缸润滑剂的需要独立汽缸润滑的慢速十字头发动机相比，可以将柱塞柴油发动机归属为中速发动机。
在柱塞柴油发动机润滑中存在的问题是润滑剂承受着高温。例如用于柱塞柴油发动机的润滑油组合物或润滑剂(通常称作柱塞发动机油或TPEO)在抑制活塞顶下沉积物的形成方面不具有最佳的性能。
本发明通过使用能够使油抑制高温负面影响的特定添加剂，提供了一种解决上述问题的方案。
这样，在第一方面，本发明是一种在四冲程柱塞柴油发动机中使用的润滑剂，该润滑剂包含，或通过混合下列物质制得：
(A)润滑粘度的基本原料，占较多的量。
(B)至少一种高碱性金属洗涤剂，优选具有至少0.85％硫酸盐灰分的灰分含量(根据ASTM D874测定)，占较少的量；和
(C)至少一种辅助的无灰分或无金属添加剂成分，占较少的量，且与(B)不同，可从下面选择：
(C1)油溶性硫化烷基酚、磷硫化(phosphorosulfurized)烃或硫化烃、和油、脂肪或聚烯烃的硫化物，和/或
(C2)磷酸胺
本发明的第二方面是一种润滑在船舶、发电或铁路牵引中使用的四冲程柱塞柴油发动机的方法，其中上述发动机具有200或更大，例如400或更大，优选550或更大，更优选在600到100000kW范围内的动力输出，该方法包含给上述发动机供应上述定义的润滑剂。
本发明的第三方面是一种在船舶、发电或铁路牵引中使用的四冲程柱塞柴油发动机运行时，提高流体动力薄膜起始温度的方法，其中上述发动机具有200或更大，例如400或更大，优选550或更大，更优选在600到100000kW范围内的动力输出，该方法包含用上述定义的润滑剂润滑上述发动机的步骤。
本发明的第四方面是如上面定义的添加剂(B)和(C)在润滑剂中的用途，为的是在船舶、发电或铁路牵引中使用的四冲程柴油发动机中使用该润滑剂时，使沥青质成分悬浮在该润滑剂中，其中上述发动机具有200或更大，例如400或更大，优选550或更大，更优选在600到100000kW范围内的动力输出。
本发明的第四方面涉及一个在TPEO的使用中出现的通常被称作“黑漆”的问题，其中它们可以受到使用过的燃料(当存在剩余燃料时)中的沥青成分的污染，从而导致使用中的清洁问题。这样，本发明的润滑剂将进一步包含含有剩余燃料的燃料油，占较少的量。
酚盐基洗涤剂对TPEO的高温性能有益；然而，它们的使用限制了水杨酸盐基洗涤剂的量，上述水杨酸盐基洗涤剂对于解决上述“黑漆”和其它问题是必要的，可以使用它。本发明，通过不使用酚盐来提供良好的高温性能，能够使更多的水杨酸盐用作洗涤剂，因此能够满足高温性能和“黑漆”控制需要。因此在本发明中，润滑剂可以基本上不含有酚盐基洗涤剂和/或包含水杨酸盐作为唯一类型的洗涤剂。
在本说明书中，下列词和表达应具有下述意思：
“较多量”—超过润滑剂的50质量％；
“较少量”—小于润滑剂的50质量％，两者就所述添加剂而言和就润滑剂中含有的所有添加剂的总质量％而言，被称作该添加剂或多种添加剂中的有效成份；
“有效成份(a.i.)”指的是非稀释剂的添加原料。
“包含或含有，或同源词”—特指具有所述特点、步骤、整体或部分的出现，但不排除一种或更多种其它特点、步骤、整体、部分或它们的组合的存在或加入；
“TBN”—按ASTM D 2896测定的总碱值；
“油溶性的或油可分散的”—不必指在油中有任意比的溶解性、溶解度、可混性或悬浮(suppression)能力。然而，它们确实意味着在使用油的情况下具有足够的溶解性或稳定的可分散性。而且，如果需要，可加入其它添加剂使特定添加剂以更高的量加入；应该了解，不同的润滑剂成分，不仅是基本的成分，还有最佳的和通常的成分，均可以在配制、存储或使用条件下发生反应，本发明也提供作为任何此类反应的结果而可得到的或得到的产物。
本发明的特点在下面将给予更详细的论述：
柱塞柴油发动机
柱塞柴油发动机可以是例如适合在船舶、发电或铁路牵引应用中使用的四冲程柱塞柴油发动机。该发动机优选具有200或更大，例如400或更大，优选550或更大，更优选在600到100000kW范围内的动力输出。进一步，该发动机可以具有例如范围为200到2000，优选400到1000rpm的发动机速度，且每个汽缸50到10000，优选100到7000的制动马力(BHP)。
润滑剂
润滑剂可以具有例如范围为25到100，例如从25或30到60、到55、优选40，例如60到100的TBN。优选地，润滑剂的粘度指数至少为90，更优选至少为95，并且至多为140，例如120，优选110。优选粘度指数范围是95到115。
润滑剂可以在例如100℃时具有至少9，优选至少13，更优选14到24范围内，例如14到22mm2s-1的运动粘度(通过ASTM D 445测定)。
(A)润滑粘度的基本原料
基本原料是一种润滑粘度的油(有时称作基油)，它可以是适用于柱塞发动机润滑的任何油。该润滑油可以是动物油、蔬菜油或矿物油。合适的润滑油是石油衍生得到的润滑油，例如环烷基油、石蜡基油或混合基油。此外，该润滑油可以是合成润滑油。适用的合成润滑油包含合成酯润滑油，该油包含二酯，例如二辛基己二酸酯、二辛基癸二酸酯和三癸基己二酸酯，或聚合烃润滑油，例如液体聚异丁烯和聚-α-烯烃。通常使用矿物油。该润滑油通常含有大于60％，典型地大于70％(基于润滑剂的质量)，和典型地在100℃时具有2到40，例如3到15mm2s-1的动态粘度，和80到100，例如90到95的粘度指数。
另一类润滑油是加氢裂化油，在氢气存在下，在高温和中压下，精炼过程进一步使中间的和重的馏份裂解，加氢裂化油典型地在100℃时具有2到40，例如3到15mm2s-1的动态粘度，和典型地从100到110，例如105到108的粘度指数。
这里使用的术语“光亮油”指进行了溶剂抽提，从真空残油中脱除了沥青产物的基油，通常在100℃时具有28到36mm2s-1的动态粘度和典型地以低于30，优选低于20，更优选低于15，最优选低于10，例如低于5质量％(基于润滑剂的质量)的比例使用。
(B)高碱性金属洗涤剂
适用于本发明润滑剂的高碱性金属化合物包括碱金属和碱土金属添加剂，例如选自酚、磺酸、羧酸、水杨酸和环烷酸的表面活性剂的高碱性油溶性或油可分散性钙、镁、钠或钡盐，其中高碱性由非油溶性金属盐(由表面活性剂的油溶性盐来稳定)，例如碳酸盐、碱式碳酸盐、乙酸盐、甲酸盐、氢氧化物或草酸盐来提供。油溶性表面活性剂盐的金属可以与非油溶性盐的金属相同或不同，无论是油溶性或非油溶性盐的金属均优选金属钙。
优选地，一种或每一种高碱性金属化合物的TBN至少为100，例如至少为250且高达500。
用于高碱性金属化合物表面活性剂体系的表面活性剂优选含有至少一个烃基，例如作为芳环上的取代基。这里使用的术语“烃基”指的是主要由氢和碳原子组成，借助于碳原子与分子的剩余部分相连的基团，但不排除含有不足以改变基团的基本烃特征的比例的其它原子或基团的存在。有利地，根据本发明使用的表面活性剂中的烃基是脂族基团，优选烷基或亚烷基，特别是烷基，它们可以是直链或支链的。在上述表面活性剂中的碳原子总数应至少足以提供所需的油溶性。
本发明中使用的酚可以是非硫化的或，优选硫化的。进一步，这里使用的术语“酚”包含含有一个羟基的酚(例如，烷基儿茶酚)或稠合芳环的酚(例如，烷基萘酚)和通过化学反应改性的酚，例如，亚烷基桥连酚和曼尼希碱-缩合酚；和水杨苷型酚(在碱性条件下，由酚和醛反应制得)。
优选的酚可从下式衍生出：
其中，R表示烃基，y表示1到4。当y大于1时，烃基可以相同或不相同。
酚经常以硫化的形式使用。硫化烃基酚典型地可以用下式表示：
其中，x一般从1到4。在一些情况下，可以用Sx来桥连多于两个以上的酚分子。
在上面的式子中，用R表示的烃基优先为烷基，该烷基有利地含有5到100，优选5到40，特别9到12个碳原子，在所有R基团中平均碳原子数至少为9，以保证在油中具有足够的溶解度。优选烷基是壬基(三聚丙烯)。
在下面的讨论中，出于方便，将把烃基取代酚称为烷基酚。
在制备硫化酚或酚盐时使用的硫化剂可以是在烷基酚单体基团之间引入-(S)x-桥连基的任何化合物或元素，其中x一般从1到大约4。这样，反应可以用元素硫或它的卤化物，例如二氯化硫或，更优选，一氯化硫来实施。如果使用元素硫，通过在50到250，优选至少100℃时加热烷基酚化合物影响硫化反应。元素硫的使用典型地将生成如上所述的桥连基-(S)x-的混合物。如果使用卤化硫，通过在-10到120，优选至少60℃时处理烷基酚影响硫化反应。该反应可在合适的稀释剂的存在下来进行。上述稀释剂有利地包含基本上惰性的有机稀释剂，例如矿物油和烷烃。在任何情况下，该反应将持续足以影响基本反应的一段时间。通常优选每当量硫化剂使用0.1到5摩尔烷基酚原料。
当元素硫被用作硫化剂时，需要使用碱性催化剂，例如氢氧化钠或有机胺，优选杂环胺(例如吗啉)。
硫化过程的细节为本领域的熟练人员所熟知。
不管用哪种方式来制备它们，在制备高碱性金属化合物时，有用的硫化烷基酚通常包含稀释剂和未反应的烷基酚，并且通常含有2到20，优选4到14，最优选6到12质量％的硫(基于硫化烷基酚的质量)。
如上面指出的那样，这里使用的术语“酚”包括通过用，例如醛进行化学反应来改性过的酚，和曼尼希碱-缩合酚。
可以对酚进行改性的醛包括，例如，甲醛、丙醛和丁醛。优选的醛是甲醛。适合使用的醛改性酚如US-A-5 256 967所述。
曼尼希碱-缩合酚通过酚、醛和胺的反应来制备。合适的曼尼希碱-缩合酚的例子在GB-A-2 121 432中有描述。
通常，酚可以含有除上述那些取代基以外的取代基，只要这类取代基不会明显地损害酚的表面活性剂性能。这类取代基的例子是甲氧基和卤原子。
根据本发明使用的水杨酸可以是非硫化的或硫化的，并且可以进行化学改性和/或含有附带的取代基，例如上面讨论的用于酚的取代基。类似于上述的那些过程也可用来硫化烃基取代的水杨酸，并且为本领域的熟练人员所熟知。水杨酸典型地通过科尔伯-施密特过程对酚盐进行羧化来制备，在此情况下，一般得到(通常在稀释剂中)混有非羧化酚的水杨酸。
可以衍生出根据本发明的高碱性洗涤剂的油溶性水杨酸的优选取代基是在上述讨论的酚中用R表示的取代基。在烷基取代水杨酸中，烷基优先含有5到100，优选9到30，特别14到20个碳原子。
根据本发明使用的磺酸典型地可以通过烃基取代的，特别烷基取代的芳烃，例如从通过蒸馏和/或萃取得到的石油馏份得到的那些的磺化反应或通过芳烃的烷基化反应来制得。例子包括通过烷基化苯、甲苯、二甲苯、萘、联苯或它们的卤素衍生物，例如，氯苯、氯甲苯或氯萘得到的那些。芳烃的烷基化可以在催化剂的存在下用含有3到多于100个碳原子的烷基化试剂，例如，卤化石蜡，可以通过石蜡的脱氢得到的烯烃，和聚烯烃，例如乙烯、丙烯、和/或丁烯的聚合物来进行。烷基芳基磺酸通常含有7到100或更多的碳原子。它们优选每个烷基取代芳香部分含有16到80，或12到40个碳原子，这取决于制备它们的原料。
当中和这些烷基芳基磺酸来制备磺酸盐时，在反应混合物中也可以包含烃溶剂和/或稀释油，还可包含助催化剂和粘度控制剂。
可以根据本发明使用的另一种类型的磺酸包含烷基酚磺酸。这类磺酸可以被硫化。无论硫化或未硫化的磺酸与那些磺酸相比被认为具有类似的表面活化性能，而与那些酚相比不具有类似的表面活化性能。
根据本发明适用的磺酸也包含烷基磺酸，例如链烯基磺酸。在这类化合物中，烷基适合含有9到100，有利地12到80，特别16到60个碳原子。
根据本发明可以使用的羧酸包含一元和二元羧酸，优选的一元羧酸是含有1到30，特别是8到24个碳原子的那些。(本说明书中提及了羧酸中的碳原子数，该数字包含羧基中的碳原子)。一元羧酸的例子是异辛酸、硬脂酸、油酸、棕榈酸和山萮酸。如果需要，异辛酸可以ExxonChemicals以商标名“Cekanoic”市售的C8酸异构体混合物的形式来使用。其它适合的酸是在α碳原子上三取代的那些和用2个以上的碳原子分隔羧基的二羧酸。进一步，含有多于35，例如36到100个碳原子的二羧酸也适用。不饱和羧酸可以被硫化。尽管水杨酸含有羧基，但为了本发明的目的，它们被认为是表面活性剂的分隔基团，没有被认为是羧酸表面活性剂。(尽管它们含有羟基，它们也不被认为是酚表面活性剂。)
根据本发明可以使用的其它表面活性剂的例子包括下列化合物和它们的衍生物：环烷酸，特别是含有一个或更多烷基的环烷酸、二烷基磷酸、二烷基硫代磷酸和二烷基二硫代磷酸、高分子量(优选乙氧基化)醇、二硫代氨基甲酸、硫代膦，和分散剂。这些类型的表面活性剂为本领域的熟练人员所熟知。烃基取代羧基亚烷基键连酚，或亚烷基二羧酸的二烃基酯，羟基和附加的羧酸基团取代的亚烷基，或亚烷基键连聚芳香分子，芳香部分含有至少一种烃基取代酚和至少一种羧基酚的表面活性剂在本发明中也适用；EP-A-708 171中描述了这类表面活性剂。
在本发明中有用的洗涤剂的其它例子是用羧酸，例如硬脂酸改性过的任意硫化的碱土金属烃基酚盐，如EP-A-271 262(LZ-Adibis)中所述；和EP-A-750 659(Chevron)中所述的酚盐。
高碱性金属化合物在本发明中也适用，优选为高碱性钙洗涤剂，所述高碱性金属化合物至少含有两个表面活性剂基团，例如酚、磺酸、羧酸、水杨酸和环烷酸，它可以通过混杂原料的制备来获得，其中在高碱性化过程中混合使用了两种或更多种不同的表面活性剂基团。
混杂原料的例子是表面活性剂酚和磺酸的高碱性钙盐；表面活性剂酚和羧酸的高碱性钙盐；表面活性剂酚，磺酸和水杨酸的高碱性钙盐；和表面活性剂酚和水杨酸的高碱性钙盐。
用“表面活性剂的高碱性钙盐”意味着高碱性洗涤剂中，非油溶性金属盐的金属阳离子基本上是钙阳离子。小数量的其它阳离子可以含在非油溶性金属盐中，但在非油溶性金属盐中，典型地至少80，更典型地至少90，例如至少95摩尔％的阳离子是钙离子。除钙以外的阳离子可以，例如从在表面活性剂盐(其中，阳离子是除钙以外的金属)的高碱性洗涤剂的制造时获得。优选地，表面活性剂的金属盐也是钙盐。
优选地，高碱性金属洗涤剂的TBN至少为330，例如至少为350，更优选至少为400，最优选在400到600之间，例如高达500。
在至少含有两种高碱性金属化合物的例子中，可以使用任何合适的质量百分比，优选任何一种高碱性金属化合物与任何其它金属高碱性化合物的质量比在5∶95到95∶5之间；例如从90∶10到10∶90；更优选从20∶80到80∶20；特别从70∶30到30∶70；优先从60∶40到40∶60。
混杂原料的具体例子包括，例如WO-A97/46643；WO-A97/46644；WO-A97/46645；WO-A97/46646；和WO-A97/46647中描述的那些。
典型地，每单位质量的润滑剂中，润滑剂中高碱性金属化合物的量至少为0.5，特别在0.5到20之间，例如从3到12或2到7质量％(基于活性成份)。
本发明的高碱性金属化合物可以被硼酸盐化，并且典型供硼化合物，例如金属硼酸盐，被认为形成了高碱性部分。本发明中在使用硼酸盐化的高碱性金属化合物的例子中，硼酸盐化的分散剂和/或油溶性或油可分散的硼化合物的使用可以是，或可以不是必要的，只要包含高碱性金属化合物的润滑剂组合物具有如这里定义的粘度指数和TBN。为了避免产生疑问，在本发明中，不排除非硼酸盐化的分散剂与硼酸盐化的高碱性金属化合物混合在一起。
高碱性金属化合物优选具有至少0.85％，更优选至少1.0％和再优选至少1.2％的硫酸盐灰分含量(按ASTM D874测定)。
(C)辅助添加剂组分
如上所述，这类组分是“无灰分的”，这意味着它是非金属有机原料，当燃烧时，与含金属和由此形成的灰分的化合物相比，其基本上不形成灰分。
辅助添加剂组分(C1)可以从下面选择：油溶性硫化烷基酚，磷硫化或硫化烃，和油、脂肪或聚烯烃的硫化物，优选在其中，分子结构中带有两个或更多个硫原子的硫基团连接在一起。其例子包含硫化鲸蜡油、硫化蒎烯油、硫化大豆油、硫化聚烯烃、硫化酯、二烷基二硫化物、二烷基多硫化物、二苄基二硫化物、二叔丁基二硫化物、聚烯烃多硫化物和噻二唑型化合物，例如双烷基多硫化物噻二唑。这类化合物基于本发明的组分(C1)。
根据本发明的组分(C2)是磷酸胺，优选包含酸性含磷中间体和胺的中和或部分中和产物。上述酸性中间体优选通过硫代磷酸的羟基取代的三酯与从磷酸、氧化磷、和卤化磷中选择的无机磷试剂反应形成。这样，磷酸胺可以，例如是二硫代磷酸胺。
硫代磷酸的羟基取代三酯原则上包含具有下列结构式的那些：
其中，R选自基本烃基团和羟基取代的基本烃基团，至少R基团中的一个是羟基取代的基本烃基团，X选自硫和氧，X基团中的至少一个是S。上述基本烃基团包含芳族、脂族、和脂环基团，例如芳基、烷基、芳烷基、烷芳基和环烷基基团。这类基团可以含有极性取代基，例如氯、溴、碘、烷氧基、芳氧基、硝基、酮基，或醛基。在大多数例子中，基团中不能含有多于一种的这类极性基团。
基本烃基团的具体例子是甲基、乙基、异丙基、仲丁基、异丁基、正戊基、十二烷基、聚异丁烯基团(分子量为1500)、环己基、环戊基、2-庚基-环己基、苯基、萘基、联苯基、对庚基苯基、2，6-二(叔丁基)苯基、苄基、苯基乙基、3，5-十二烷基苯基、氯苯基、α-甲氧基-β-萘基、对硝基苯基、对苯氧基苯基、2-溴甲基、3-氯环己基，和聚丙烯(分子量为300)取代苯基基团。
羟基取代基本烃基团原则上包含上面指出的含有羟基的基本烃基团。含有少于8个碳原子的那些是优选的，这是因为制备这种羟基取代三酯很方便。这类基团的例子是羟甲基、羟乙基、2-羟丙基、3-羟丙基、2-羟基环己基、2-羟基环戊基、2-羟基-1-辛基、1-羟基-3辛基、1-羟基-2-辛基、2-羟基-3-苯基环己基、1-羟基-2-苯基乙基、2-羟基-1-苯基乙基、2-羟基-1-对甲苯基乙基，和2-羟基-3-丁基基团。其它羟基取代基本烃基团的例子是2，5-二羟苯基、α-羟基-β-萘基、3-羟基-4-十二烷基、3-羟基-6-十八烷基，和对(对羟苯基)苯基基团。
羟基取代三酯的优选类别包含具有下列结构式的那些
其中，R”是上面所示的基本烃基团，R′是二价基本烃基团，例如从上述基本烃基团衍生来的亚烷基或亚芳基基团。制备这类酯的一种方便的方法涉及二硫代磷酸与环氧化物或乙二醇的反应。该反应在本领域为人所知。下列式子表示该反应。
其中
是环氧化物，HO-R’-OH是乙二醇。
出于经济的原因，在上述过程中，优选使用含有少于大约8个碳原子的脂族环氧化物和氧化苯乙烯。特别有用的环氧化物的例子是氧化乙烯、氧化丙烯、氧化苯乙烯、氧化α-甲基苯乙烯、氧化对甲基苯乙烯、氧化环己烯、氧化环戊烯、氧化十二碳烯、氧化十八碳烯、氧化2，3-丁烯、氧化1，2-丁烯、氧化1，2-辛烯、氧化3，4-戊烯，和4-苯基-1，2-氧化环己烯。乙二醇包含脂族和芳族二羟基化合物。后者的例子是氢醌、儿茶酚、间苯二酚和1，2-二羟基萘。脂族乙二醇特别有用，例如乙二醇、1，3-丙二醇、1，4-丁二醇、1，10-癸二醇、二甘醇、三甘醇和五甘醇。
另一种制备羟基取代三酯的方便方法包含将二硫代磷酸加入不饱和醇，例如烯丙醇、肉桂醇、或如US-A-2,528,723中描述的油醇中。还有另外一种方法涉及金属硫代磷酸盐与US RE-A-20,411中所述的卤代醇反应。
能够衍生出羟基取代的三酯的二硫代磷酸同样为人们所熟知。它们通过五硫化二磷与醇或酚进行反应来制备。该反应中，每摩尔五硫化二磷需要使用4摩尔醇或酚，反应温度在大约50℃到200℃。这样，O，O’-二正己基二硫代磷酸的制备涉及100℃时，持续2小时的五硫化二磷与4摩尔正己基醇的反应。释放出硫化氢，剩余物是定义过的酸。用蒸汽来处理相应的二硫代磷酸可以影响一硫代磷酸的制备。三硫代磷酸和四硫代磷酸可以通过五硫化二磷与硫醇或硫醇和酚的混合物的反应来得到。
五硫化二磷与酚或醇的混合物(例如，异丁醇和正己醇以2∶1的重量比)反应将生成带有两个有机基团不同的二硫代磷酸。这类酸在这里同样有用。
在与硫代磷酸的羟基取代三酯反应时，有用的无机磷试剂优选为五氧化二磷。其它氧化磷，例如三氧化二磷和四氧化二磷同样是有用的。含磷的酸和卤化磷也有用。它们的例子是磷酸、焦磷酸、偏磷酸、次磷酸(hypophosphoric acid)、亚磷酸、焦亚磷酸、偏亚磷酸、次亚磷酸(hypophosphorous acid)，三氯化磷、三溴化磷、五氯化磷、四氯一溴化磷、三氯氧化磷、三碘化磷。
硫代磷酸的羟基取代三酯与无机磷试剂反应将生成酸性产物。该酸性产物的化学结构取决于对所用无机磷试剂性质的大量的测定。在大多数情况下，产物是不为人所知的精确组成的复杂混合物。然而，已知反应涉及三酯的羟基基团与无机磷试剂的反应。在这一方面，可将该反应比作醇或酚与无机磷试剂的反应。这样，认为羟基取代的三酯与五氧化二磷之间的反应原则上将生成酸性磷酸酯，即磷酸的单酯或二酯，其中酯基团是硫代磷酸三酯反应物脱除羟基基团后得到的剩余物。产物中也可含有膦酸和次膦酸，其中存在一个或两个直接的碳磷键连。
据信羟基取代的三酯与三卤氧化磷或磷酸反应得到的酸性产物得到了酸性磷酸酯，膦酸，和/或次膦酸的类似混合物。另一方面，据信羟基取代的三酯与三氯化磷或亚磷酸的反应原则上生成酸性有机亚磷酸盐。还有其它产物可以通过使用前述的其它无机含磷试剂来得到。在任何情况下，产物是酸性的，这对于制备本发明中有用的中和产物的中间体来说是有用的。
通常，每摩尔无机磷试剂需2摩尔到5摩尔的三酯。三酯的优选比例是每摩尔磷试剂大约3-4摩尔。两种反应物中任意一种的量超过上述范围将导致上述反应物的使用量过量，通常不是优选的。
可简单地通过在大约高于室温的温度下，优选高于50℃下混合两种反应物来影响羟基取代的三酯与无机磷试剂反应生成酸性中间体的反应。可以用更高的温度，例如100℃或150℃，但通常没有必要。
用来中和酸性中间体的有用的胺可以是脂族胺、芳族胺、脂环胺、杂环胺或碳环胺。具有4到30个脂族碳原子的胺是优选的，至少含有8个碳原子，并具有式R”-NH2的脂族伯胺特别有用，其中R”是，例如脂族基团，例如叔辛基、叔十二烷基、叔十四烷基、叔十八烷基、十六烷基、山萮基(behenyl)、硬脂基、二十烷基、二十二烷基、二十四烷基、三十六烷基和六十五烷基。其它脂族胺的例子包括环己胺、正己胺、十二烷胺、二(十二烷基)胺、三(十二烷基)胺、N-甲基-辛胺、丁胺、山萮胺、硬脂胺、油胺、肉豆寇基胺和N-十二烷基1，3-丙二胺、苯胺、邻甲苯胺、联苯胺、苯二胺、N，N’-二(仲丁基)苯二胺、β-萘胺、α-萘胺、吗啉、哌嗪、盖烷二胺、环戊胺、乙二胺、六亚甲基四胺、八亚甲基二胺和N，N’-二丁基苯二胺。羟基取代的胺，例如乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺、对氨基苯酚、4-氨基萘酚-1、8-氨基萘酚-1、β-氨基茜素、2-氨基-2-乙基-1，3-丙二醇、4-氨基-4’-羟基二苯醚、2-氨基-间苯二酚等也有用。
关于可以使用的不同的羟基取代的胺，以羟基取代的脂族胺为优先选择，特别是大部分与下式相同的那些。
其中，R”的定义如前；A是低级亚烷基基团，例如亚甲基、1，2-亚乙基、1，2-亚丙基、1，3-亚丙基、1，2-亚丁基、1，4-亚丁基、1，3-戊基、1，5亚戊基等；x是1-10，包括1和10；Q是氢，(AO)xH或R”。在许多例子中使用这类羟基取代的脂族胺获得了改进的防锈性能。这类优选羟基取代脂族胺的例子包含N-4-羟丁基十二烷胺、N-2-羟乙基-正辛胺、N-2-羟丙基二壬胺、N，N-二(3-羟丙基)叔十二烷胺、N-羟基三(乙氧基)乙基叔十八烷胺、N-2-羟乙基叔十二烷胺、N-羟基六(丙氧基丙基)叔十八烷胺，N-5-羟戊基二(正癸基)胺等。制备这类羟基取代的脂族胺的方便和经济的方法涉及脂族伯胺或仲胺与至少大约等摩尔的环氧化物，优选在例如甲醇钠、氨基钠、钠金属等合适的催化剂存在下的已知反应。
在上式中，R”，x和A的定义如前。以式叔-R-NHAOH表示的N-一羟烷基取代一叔烷基胺作为特别的优先选择，其中叔-R是含有11到24个碳原子的叔烷基基团。为代替使用单一的式叔-R-NHAOH表示的化合物，通过使用例如环氧化物，如环氧乙烷、1，2-环氧丙烷或环氧丁烷与叔烷基伯胺，例如C11-C14叔烷基伯胺、C13-C22叔烷基伯胺等的商用混合物反应制得的这类化合物的混合物是方便和令人满意的。
用胺来中和酸性中间体的反应在大多数情况下都放热，可简单地通过在常温，优选从0℃到200℃下混合反应物来进行。反应的中和产物的化学组成很大程度上取决于温度。这样，在相对低的温度下，例如小于80℃下，产物主要包含胺与酸反应生成的盐。在高于100℃时，产物可能含有酰胺、脒、或它们的混合物。然而，酸性中间体与叔胺的反应仅生成盐。
反应中酸性中间体和使用的胺的相对比例优选为保证将相当大的部分的酸性中间体中和掉的比例。反应中使用的胺的最低量主要由生成产物的使用情况来决定。在大多数情况下，应使用足量的胺以中和中间体的酸度的至少50％。作为烃油中的添加剂使用时，希望得到大部分是中性产物的产物，例如可通过中和中间体酸度的至少90％来制得。这样，所用的胺的量取决于例如按ASTMD-664或D-974规定步骤测定的产品所需的酸度和中间体的酸度，其范围可在很宽的范围内变动。
特别优选的磷酸胺是当所述酸性中间体是通过P2O5与羟丙基O，O-二(4-甲基-2-戊基)二硫代磷酸酯反应时获得的。这种酸性中间体然后可用C12到C14叔脂族伯胺来中和或部分中和。这种胺的样品可在市场上买到，其商标名为Primene 81R。
优选组分(C1)是油溶性硫化烷基酚，优选组分(C2)是二硫代磷酸胺。
可以含于润滑剂中的组分(C1)的量例如至少为0.1，优选至少为0.3、0.5、1.5或2，且优选高达20、15、10、8、5质量％；且可以含于润滑剂中的组分(C2)的量例如至少为0.1到例如10，优选在0.4到5之间，或更优选0.6到2质量％。
共添加剂
润滑剂可以包含抗磨添加剂作为共添加剂，也可含有其它共添加剂，例如，抗氧化剂、防沫剂和/或防锈剂。具体的共添加剂的更多的细节如下。
氧化抑制剂，或抗氧化剂，减少使用中矿物油的变质倾向，这种变质的证据是，例如，在金属表面清漆状的沉积物的生成和残渣的生成，以及粘度的增加。适用的氧化抑制剂包括硫化烷基酚和它们的碱金属或碱土金属盐；二苯胺；苯基萘胺；和磷硫化烃或硫化烃。
在润滑剂中使用的其它氧化抑制剂或抗氧剂包含油溶性铜化合物。可将铜混在其中来作为任何适用的油溶性铜化合物。使用油溶性意思是在基本原料或添加剂配方中，在通常的混合条件下，化合物是油溶性的。铜可以是，例如二烃基硫代或二硫代磷酸铜的形式。此外，铜可以以合成或天然羧酸(例如，C8到C18脂肪酸、不饱和酸、或支链羧酸)的铜盐的形式加入。油溶性二硫代氨基甲酸酮、磺酸酮、酚铜和乙酰丙酮铜也是有用的。特别有用的铜化合物的例子是从烯基琥珀酸或酸酐衍生获得的碱性、中型或酸性铜Cu I和/或Cu II盐。
附加洗涤剂和金属抗腐蚀添加剂包含金属盐，其可以是高碱性的和TBN小于300的磺酸、烷基酚、硫化烷基酚、烷基水杨酸、硫代膦酸、环烷酸，和其它油溶性一和二羧酸。洗涤剂/抗腐蚀添加剂的代表例子和它们的制备方法在EP-A-208 560中给出。当为水杨酸金属盐时，金属盐的TBN可以小于200。
抗磨添加剂，如同它们的名字所指的那样，可降低金属件的磨损。二烃基二硫代磷酸锌(ZDDP)被广泛用作抗磨添加剂。特别优选的ZDDP是式Zn[SP(S)(OR1)(OR2)]2代表的那些，其中R1和R2表示烃基，例如含有1到18，优选2到12个碳原子的烷基。
倾点下降剂，也被认作是润滑油的流动改进剂，降低了液体流动或能流出的最低温度。这类添加剂广为人所知。通过加入聚硅氧烷型防泡沫剂，例如硅油或聚二甲基硅氧烷可以对泡沫进行控制。
比例
用于TPEO(柱塞发动机油)的除了本发明的添加剂C的添加剂的典型比例如下：
| 添加剂 | 质量％a.i.*(宽的) | 质量％a.i.*(优选的) |
| 洗涤剂分散剂抗磨添加剂抗氧化剂抗腐蚀添加剂倾点下降剂矿物油或合成基油 | 0.5-150.5-50.1-1.50.1-30.03-0.150.03-0.15平衡 | 2-71-30.3-1.30.5-1.50.05-0.10.05-0.1平衡 |
*基于成品油的质量％的有效成分。
也可以包含稳定剂和/或抗腐蚀添加剂。
当使用一组添加剂时，尽管不是必需的，需要准备含有一个或多个添加剂配方或包含添加剂的浓缩物，其中可以将几种添加剂同时加入基本原料中形成润滑剂。使用溶剂和在轻微的加热条件下混合(不是必需的)可便于将添加剂配方溶解进入基本原料中。当将添加剂配方与预定数量的基本原料混合时，在成品润滑剂中，添加剂配方典型地含有能够提供所需的浓度，和/或可以实现预期的功能的添加剂的量。这样，根据本发明的组分(B)和组分(C)可与少量的基本原料或其它相容的溶剂和其它所需的添加剂混合在一起形成添加剂配方，其中含有的有效成分的量(基于添加剂配方的量)是2.5到90且优选5到75且最优选8到60质量％，剩余部分是基本原料。
成品润滑剂典型地可以含有大约5到40质量％的添加剂配方，包括稀释剂，剩余部分是基本原料。
实施例
本发明将通过下列实施例来进行说明，但不限于此，将参考附图1，2和3。
作为下面将讨论的HFRR测试的结果，每幅图(1到3)代表以曲线图的形式表示的轨迹，其中x轴表示温度，单位为℃，y轴表示摩擦系数。
组分
实施例中使用的组分如下：
高碱性金属洗涤剂
B1：TBN为281的高碱性水杨酸钙
B2：TBN为168的高碱性水杨酸钙
B3：TBN为350的高碱性水杨酸钙
辅助添加剂组分
C1：硫化烷基酚添加剂，其特征为：大约70％的有效成份(a.i.)和6.4质量％的硫含量。
C2：二硫代磷酸胺齿轮油添加剂，其特征为：75％的有效成份(a.i.)和7.2％的磷含量，8.7％的硫含量，和1.2％的氮含量(所有都是质量％)。
稳定剂
D1：聚异丁烯取代的马来酸酐得到的聚异丁烯琥珀酸酐。
抗氧化剂
E1：烷基化的二苯胺
基本原料
A1：也含有光亮油的石蜡矿物油
A2：1组基油
如果需要，也可使用其它组分，例如抗腐蚀添加剂。
润滑剂和测试
TPEO的第一个样品通过混合基本原料A1，洗涤剂B1和稳定剂D1来制备。这是一个参比样品，被称作样品Z。TPEO的第二个和第三个样品通过按样品Z中的比例混合基本原料A1，洗涤剂B1和稳定剂D1，且在第二个样品中还混合化合物C1(3质量％，基于润滑剂的质量)且第三个样品中还混合化合物C2(0.8质量％，基于润滑剂的质量)来制得。第二和第三个实施例是包含于本发明中的实施例，分别被称作样品1和2。
在60℃时，将组分与基本原料混合1小时完成混合。
每一个样品用高频往复设备(HFRR)来测试，在80到350℃之间，将摩擦系数作为温度的函数来进行测定。这一测试用来检查在高温情况下，油保持润滑的能力。它涉及用测试油润滑静止样品，同时涉及在外加载荷条件下，用测试油来润滑移动样品。在15分钟内，温度从80稳定升到350℃。移动样品具有20HZ的频率和400g的外加载荷。每5秒种记录一次数据。
结果
样品Z：结果如图1所示，从中可以看到摩擦系数从75℃时的约0.16降到200℃时的约0.1，再降低(降幅变缓)到大约280℃时的约0.08。超过280℃，摩擦系数急剧上升到约0.25或更高，高达350℃时保持在0.25或大约保持在0.25。
样品1：结果如图2所示，从中可以看出75℃到190℃时，摩擦系数保持在0.15或大约保持在0.15，到200℃时降到约0.1。200到325℃之间时，摩擦系数保持在略高于，或约0.1处。325到350℃之间时，摩擦系数增加，但不超过0.15。
样品2：结果如图3所示，从中可以看出摩擦系数从75℃时的0.16平稳地降到300℃时的约0.06。325到350℃之间时，摩擦系数增加，但均不大于0.1。
上述测试结果清楚地说明了作为润滑剂的样品1和样品2的效率。这样，在高于270℃的温度下，上述润滑剂没有使机械磨损明显地增加，如摩擦系数所示。
其它测试
本发明包含的另外TPEO样品(称作样品X和Y)可按上面所述的方法来制备，并使其的TBN为33。每个样品用HFRR按上述方法来测试，在320℃时也用Komatsu Hot Tube(Komatsu热管)来测试，后一种测试方法在本领域中为人所知和承认。样品组成和测试结果总结在下表中。
| 样品组成： X 3 Y 4 | ||||
| B2B3E1C1A2 | 2.008.5789.43 | 2.008.570.7588.68 | 2.008.570.7588.68 | 2.008.570.750.7587.93 |
| HFRR结果最小摩擦系数所处温度(℃)摩擦系数的增加(％) | 0.051280194 | 0.05630771 | 0.060247218 | 0.05629554 |
| Komatsu热管结果目测等级沉积物重量(mg) | 014.4 | 35.6 | 047.9 | 1.57.7 |
因此可以看出，样品3和4(本发明的)在高温时的结果比样品X和Y的要好。
Claims (15)
1.一种用于柱塞柴油发动机的润滑剂，该润滑剂包含，或通过混合下列物质制得，前提是各物质质量％之和为100％：
(A)至少50％润滑粘度的基本原料；
(B)0.5～20质量％至少一种高碱性金属洗涤剂；
(C)至少一种辅助的无灰分或无金属添加剂成分，且与(B)不同，从下面选择：
(C1)0.1～20质量％油溶性硫化烷基酚，磷硫化烃或硫化烃，和油、脂肪或聚烯烃的硫化物，和/或
(C2)0.1～10质量％磷酸胺
其中该润滑剂的总碱值为25到100。
2.根据权利要求1的润滑剂，其中高碱性金属洗涤剂具有至少0.85％硫酸盐灰分的灰分含量。
3.根据权利要求1的润滑剂，其中润滑剂的总碱值为25-60。
4.根据权利要求1的润滑剂，其中润滑剂的总碱值为25-55。
5.根据权利要求3的润滑剂，其中润滑剂的总碱值为30-60。
6.根据权利要求4的润滑剂，其中润滑剂的总碱值为30-55。
7.根据权利要求1的润滑剂，其中高碱性金属洗涤剂中的金属是钙。
8.根据权利要求1的润滑剂，其中高碱性金属洗涤剂是水杨酸钙。
9.根据权利要求1的润滑剂，其中硫化烷基酚是烷基酚硫化物。
10.根据权利要求1的润滑剂，其中润滑剂中(C1)的含量为0.3质量％至20质量％。
11.根据权利要求1的润滑剂，其中(C2)以二硫代磷酸胺的形式。
12.根据权利要求1的润滑剂，其中润滑剂中(C2)的含量在0.4质量％到5质量％范围内。
13.根据权利要求1的润滑剂，其中润滑剂中(C2)的含量在0.6质量％到2质量％范围内。
14.根据权利要求1的润滑剂，其中润滑剂进一步包含具有剩余燃料含量的燃料油。
15.根据任意前述权利要求的润滑剂，其中润滑剂无酚盐洗涤剂。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00203292 | 2000-09-22 | ||
| EP00203292.8 | 2000-09-22 |
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| CN1215153C true CN1215153C (zh) | 2005-08-17 |
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| US (1) | US6521571B1 (zh) |
| JP (1) | JP2002105480A (zh) |
| CN (1) | CN1215153C (zh) |
| AT (1) | ATE320476T1 (zh) |
| CA (1) | CA2357592A1 (zh) |
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| EP1522572B1 (en) * | 2003-10-09 | 2016-11-16 | Infineum International Limited | Lubricant composition |
| US20050119140A1 (en) * | 2003-10-30 | 2005-06-02 | Laurent Chambard | Method of reducing deposit formation in a centrifuge system in a trunk piston diesel engine |
| EP1528099A1 (en) * | 2003-10-30 | 2005-05-04 | Infineum International Limited | A method of reducing deposit formation in a centrifuge system in a trunk piston diesel engine |
| US20060025314A1 (en) * | 2004-07-28 | 2006-02-02 | Afton Chemical Corporation | Power transmission fluids with enhanced extreme pressure and antiwear characteristics |
| FR2879621B1 (fr) * | 2004-12-16 | 2007-04-06 | Total France Sa | Huile pour moteur marin 4-temps |
| US20090305924A1 (en) * | 2006-08-07 | 2009-12-10 | Alexandra Mayhew | Method of Lubricating an Internal Combustion Engine |
| US9175237B2 (en) * | 2007-12-12 | 2015-11-03 | Chevron Oronite Technology B.V. | Trunk piston engine lubricating oil compositions |
| US20090203559A1 (en) * | 2008-02-08 | 2009-08-13 | Bera Tushar Kanti | Engine Lubrication |
| US9175236B2 (en) * | 2008-05-08 | 2015-11-03 | Chevron Oronite Technology B.V. | Lubricating oil composition and method for use with low sulfur marine residual fuel |
| SG175117A1 (en) * | 2009-04-07 | 2011-11-28 | Infineum Int Ltd | Marine engine lubrication |
| US9127229B2 (en) * | 2009-07-24 | 2015-09-08 | Cherron Oronite Technology B.V. | Trunk piston engine lubricating oil compositions |
| CN108774561B (zh) * | 2011-12-27 | 2022-07-01 | 雪佛龙奥伦耐有限责任公司 | 后处理过的烷基取代的羟基芳族组合物的硫化盐 |
| ES2612336T3 (es) * | 2012-03-29 | 2017-05-16 | Infineum International Limited | Lubrificación de motor marino |
| US9206373B2 (en) | 2012-08-17 | 2015-12-08 | Afton Chemical Corporation | Calcium neutral and overbased mannich and anhydride adducts as detergents for engine oil lubricants |
| US9102896B2 (en) * | 2012-12-17 | 2015-08-11 | Chevron Japan Ltd. | Fuel economical lubricating oil composition for internal combustion engines |
| US9200230B2 (en) | 2013-03-01 | 2015-12-01 | VORA Inc. | Lubricating compositions and methods of use thereof |
| ES2646051T3 (es) * | 2013-09-24 | 2017-12-11 | Infineum International Limited | Lubricación de motores marinos |
| US9506007B2 (en) * | 2014-11-14 | 2016-11-29 | Chevron Oronite Technology B.V. | Low sulfur marine distillate fuel trunk piston engine oil composition |
| EP3259337B1 (en) * | 2015-02-18 | 2019-04-24 | Chevron Oronite Technology B.V. | Low sulfur marine distillate fuel trunk piston engine oil composition |
| EP3378924B1 (en) * | 2017-03-24 | 2020-01-29 | Infineum International Limited | Marine engine lubrication |
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| GB2033923B (en) * | 1978-10-13 | 1982-12-22 | Exxon Research Engineering Co | Diesel lubricating oil compositions |
| US4849118A (en) | 1987-09-30 | 1989-07-18 | Amoco Corporation | Chlorine-free silver protective lubricant composition (III) |
| GB8826961D0 (en) | 1988-11-18 | 1988-12-21 | Castrol Ltd | Lubricant compositions |
| GB9319648D0 (en) | 1993-09-23 | 1993-11-10 | Bp Chemicals Additives | Lubricating oil compositions |
| US5370805A (en) | 1993-11-18 | 1994-12-06 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Chlorine-free diesel engine lubricating composition |
| US5415792A (en) * | 1993-12-23 | 1995-05-16 | Chevron Chemical Company | Overbased alkylated alkyl salicylates |
| GB9400417D0 (en) * | 1994-01-11 | 1994-03-09 | Bp Chemicals Additives | Lubricating oil composition |
| US6310011B1 (en) * | 1994-10-17 | 2001-10-30 | The Lubrizol Corporation | Overbased metal salts useful as additives for fuels and lubricants |
| EP0725129B1 (en) | 1995-02-01 | 2001-12-12 | The Lubrizol Corporation | Low ash lubricant compositions |
| GB9503993D0 (en) | 1995-02-28 | 1995-04-19 | Bp Chem Int Ltd | Lubricating oil compositions |
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| GB9800436D0 (en) | 1998-01-09 | 1998-03-04 | Exxon Chemical Patents Inc | Marine lubricant compositions |
| US6277794B1 (en) * | 1998-12-28 | 2001-08-21 | Infineum Usa L.P. | Lubricant compositions |
| GB9908771D0 (en) * | 1999-04-17 | 1999-06-09 | Infineum Uk Ltd | Lubricity oil composition |
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| DE60117913D1 (de) | 2006-05-11 |
| JP2002105480A (ja) | 2002-04-10 |
| ATE320476T1 (de) | 2006-04-15 |
| CA2357592A1 (en) | 2002-03-22 |
| SG103317A1 (en) | 2004-04-29 |
| US6521571B1 (en) | 2003-02-18 |
| CN1346875A (zh) | 2002-05-01 |
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