CN101108994A - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
- Publication number
- CN101108994A CN101108994A CNA2007101360860A CN200710136086A CN101108994A CN 101108994 A CN101108994 A CN 101108994A CN A2007101360860 A CNA2007101360860 A CN A2007101360860A CN 200710136086 A CN200710136086 A CN 200710136086A CN 101108994 A CN101108994 A CN 101108994A
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- CN
- China
- Prior art keywords
- acid
- composition
- lubricating oil
- oil
- oil composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 claims abstract description 60
- -1 alkaline earth metal sulfonate Chemical class 0.000 claims abstract description 35
- 239000010687 lubricating oil Substances 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000003599 detergent Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 239000006185 dispersion Substances 0.000 claims description 36
- 239000000314 lubricant Substances 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 230000003028 elevating effect Effects 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000005461 lubrication Methods 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 28
- 239000002270 dispersing agent Substances 0.000 abstract description 5
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 description 25
- 150000001412 amines Chemical group 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- 239000002199 base oil Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 229920002367 Polyisobutene Polymers 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000003949 imides Chemical class 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000000269 nucleophilic effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 238000005885 boration reaction Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001414 amino alcohols Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010688 mineral lubricating oil Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000008442 polyphenolic compounds Polymers 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-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
- 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
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical class CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- CUIFMTWQFFCFCH-UHFFFAOYSA-N 2-ethylhexylbenzene Chemical compound CCCCC(CC)CC1=CC=CC=C1 CUIFMTWQFFCFCH-UHFFFAOYSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- 239000005749 Copper compound Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- C10M2205/022—Ethene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- C10M2205/024—Propene
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- C10M2205/026—Butene
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- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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- C10M2215/28—Amides; Imides
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Abstract
内燃机润滑油组合物具有不超过0.09质量％的P含量；不超过0.3质量％的S含量；和不超过1质量％的硫酸化灰分含量。其含有下列添加剂：聚烯基取代的单羧酸或二羧酸、酐或酯的至少一种无灰含氮衍生物，所述聚烯基取代的单羧酸或二羧酸、酐或酯由聚烯烃仅通过热“烯”反应制成，作为润滑油组合物中唯一的无灰含氮分散剂，并提供0.03至0.07质量％的氮；至少一种高碱性碱土金属磺酸盐，作为唯一的高碱性金属清净剂；和至少一种粘度改进剂。
Description
技术领域
本发明涉及内燃机曲轴箱润滑油组合物(或润滑剂)，更尤其涉及适用于乘用车(passenger car)活塞式发动机、尤其是汽油机(火花点火)和柴油机(压缩点火)润滑的组合物；还涉及添加剂在这类组合物中的应用。
背景技术
曲轴箱润滑剂是用于下述内燃机中的一般润滑的油--在该内燃机中，油底壳通常位于发动机曲轴下方且循环油回到其中。为数种目的在曲轴箱润滑剂中掺入添加剂是公知的。
为了提高废气处理催化剂的耐久性，需要和/或要求降低曲轴箱润滑剂中的磷含量。但是，磷含量的降低会导致发动机磨损增加。
WO 2005/012468 A1(‘468)描述了使用分散剂的组合，以提供重型柴油机用的现代低磷低硫润滑剂中所需的密封适应性、腐蚀保护和耐磨性能的适当平衡。在‘468中，分散剂组合物的例子包括胺、醇或氨基醇与烃基取代琥珀酸酐组分的产物，其中后一组分包含：(a)10至95重量％的通过使聚异丁烯与马来酸酐在氯存在下反应而制成的组分；和(b)5至90重量％的通过使聚异丁烯与马来酸酐在基本不存在氯的情况下反应而制成的组分。
‘468的公开中的问题在于，尽管其论述了磨损并描述了HFRR磨损密封试验和高温Cameron Plint试验，但其本身不涉及凸轮和升降杆磨损。凸轮+升降杆磨损是sequence IIIG试验的参数之一，该试验是在高温条件下进行的API类目SM，ILSAC类目GF-4试验，并模拟相对较高环境温度条件下的高速运行。此外，‘468没有论述或描述活塞沉积物。‘468的进一步问题在于其要求使用一定量的氯，而氯由于环境原因而通常被视为不合意的。
发明概要
本发明通过使用下述无灰含氮分散剂解决了上述问题，该分散剂基本无氯，源自通过热“烯”反应制成的官能化聚烯烃，并在润滑剂中表现出优异的凸轮和升降杆磨损、活塞沉积和/或粘度性能。
第一方面，本发明提供了内燃机曲轴箱润滑油组合物，其具有以磷原子表示的不超过0.09、例如0.05至0.08质量％的磷含量；以硫原子表示的不超过0.3、例如不超过0.2质量％的硫含量；和不超过1、例如0.5至0.8质量％的硫酸化灰分含量，该组合物含有各次要量的下列添加剂组分，或通过将各次要量的下列添加剂组分混合而制成：
A.聚烯基取代的单羧酸或二羧酸、酐或酯的至少一种油溶性或油分散性含氮衍生物，所述聚烯基取代的单羧酸或二羧酸、酐或酯由聚烯烃仅通过热“烯”反应制成，是润滑油组合物中唯一的无灰含氮分散剂，并在润滑油组合物中提供0.03至0.07质量％的氮；
B.至少一种油溶性或油分散性高碱性的碱土金属磺酸盐，其是润滑油组合物中唯一的高碱性金属清净剂体系；和
C.至少一种粘度改进剂。
第二方面，本发明提供了润滑乘用车内燃机曲轴箱的方法，包括向曲轴箱供应根据本发明第一方面的润滑油组合物。
第三方面，本发明提供了本发明第一方面中定义的分散剂组合物的用途，用于通过根据本发明第一方面的润滑油组合物改进乘用车内燃机曲轴箱润滑中的凸轮和升降杆磨损、活塞沉积物和/或润滑剂粘度，所述改进是与使用包括下述相应分散剂组合物的相应润滑组合物比较而言的--在该相应分散剂组合物中，聚烯基取代的单羧酸或二羧酸、酐或酯由聚烯烃通过氯化反应制成。
在本说明书中，如果使用下列词语或措辞，其具有如下含义：
“活性成分”或“(a.i.)”是指不是稀释剂或溶剂的添加剂材料；
“包含”或任何同源词指明所述特征、步骤或整数或组分的存在，但不排除一种或多种其它特征、步骤、整数、组分或其组别的存在和加入；措辞“由...构成”或“基本由...构成”或同源词可以包括在“包含”或同源词中，其中“基本由...构成”允许包含不会实质性影响应用该词的组合物的特征的物质；
“主要量”是指超过组合物的50质量％；
“次要量”是指低于组合物的50质量％；
“TBN”是指通过ASTM D2896测得的总碱值。
此外，在本说明书中：
“磷含量”通过ASTM D5185测量；
“硫酸化灰分含量”通过ASTM D874测量；
“硫含量”通过ASTM D2622测量；
“KV100”是指通过ASTM D445测得的在100℃的运动粘度。
此外，要理解的是，所用的各种基本的、优化的和常规的组分可以在配制、储存或使用条件下反应，且本发明还提供了可以或已经由任何这类反应获得的产物。
此外，要理解的是，本文所述的任何上限和下限量、范围和比率限度可以独立地组合。
发明详述
现在如下更详细地描述本发明的特征，如果适当，其涉及本发明的每一和所有方面。
润滑油组合物
其含有主要比例的具有润滑粘度的油(有时称为基油或基本油料)，作为该组合物的主要液体成分，添加剂和可能的其它油掺入该组合物中。该润滑油组合物含有在其中提供0.03至0.07质量％氮的分散剂，由此将该组合物分类为用于汽油机的乘用车机油(PCMO)或用于轻型柴油机的乘用车柴油(PCDO)。
基油可以选自天然(植物、动物或矿物)和合成润滑油和它们的混合物。其在粘度上可以从轻馏分矿物油到重润滑油，例如，气体发动机润滑油、矿物润滑油、机动车油和重型柴油。通常，油粘度在100℃为2至30、尤其是5至20mm2s-1。
天然油包括动物和植物油(例如蓖麻油和猪油)、液体石蜡油和加氢精制的、溶剂处理过的链烷、环烷和混合链烷-环烷型矿物润滑油。源自煤或页岩的具有润滑粘度的油也是可用的基油。
合成润滑油包括烃油，例如聚合的和共聚的烯烃(例如，聚丁烯、聚丙烯、丙烯-异丁烯共聚物、氯化的聚丁烯、聚(1-己烯)、聚(1-辛烯)、聚(1-癸烯))；烷基苯(例如十二烷基苯、十四烷基苯、二壬基苯、二(2-乙基己基)苯)；聚酚(例如，联苯、三联苯、烷基化的聚酚)；和烷基化的二苯醚和烷基化的二苯硫及其衍生物、类似物和同系物。
合成润滑油的另一合适类型包括二羧酸(例如，苯二甲酸、琥珀酸、烷基琥珀酸和烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、反丁烯二酸、己二酸、亚油酸二聚物、丙二酸、烷基丙二酸、烯基丙二酸)与各种醇(例如，丁醇、己醇、十二烷基醇、2-乙基己基醇、乙二醇、二甘醇单醚、丙二醇)的酯。这些酯的具体例子包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、反丁烯二酸酸二正己酯、癸二酸二辛酯、壬二酸二异辛酯、壬二酸二异癸酯、邻苯二甲酸二辛酯、邻苯二甲酸二癸酯、癸二酸二(廿烷基)酯、亚油酸二聚物的2-乙基己基二酯、和通过使1摩尔癸二酸与2摩尔四甘醇和2摩尔2-乙基己酸反应形成的复合酯。
可用作合成油的酯还包括由C5至C12单羧酸和多元醇、和多元醇醚(例如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇和三季戊四醇)制成的那些。
在本发明的组合物中可以使用未精制、精制和再精制的油。未精制油是未经进一步提纯处理直接获自天然或合成来源的那些。例如，直接获自干馏操作的页岩油、直接获自蒸馏的石油和直接获自酯化法且不经进一步处理即使用的酯油是未精制油。精制油与未精制油类似，不同的是它们在一个或多个提纯步骤中进一步处理以改进一种或多种性能。许多这种提纯技术是本领域技术人员已知的，例如蒸馏、溶剂萃取、酸或碱萃取、过滤和渗滤。再精制油是通过对已付诸使用的精制油施加与用于获得精制油类似的方法而获得的。这类再精制油也被称作再生油或再加工油，并通常通过用于废添加剂和油裂解产品的技术额外加工。
基油的其它例子是天然气液化(“GTL”)基油，即基油可以是源自使用费托催化剂由含氢和一氧化碳的合成气制成的费托法合成烃的油。这些烃通常需要进一步加工才可用作基油。例如，它们可以，通过本领域已知的方法，加氢异构；加氢裂化和加氢异构；脱蜡；或加氢异构和脱蜡。
基油可以根据API EOLCS 1509定义归入I至V类。优选为II类基本油料，即含有大于或等于90％饱和物和少于或等于0.03％硫、并具有大于或等于80且小于120的粘度指数。
具有润滑粘度的油是以主要量、与次要量的添加剂(A)、(B)和(C)和如果必要，一种或多种如下所述的辅助添加剂结合提供的，从而构成润滑油组合物。可以通过将添加剂直接加入油中、或通过将其以其浓缩物形式加入以使添加剂分散或溶解来实现这种制备。添加剂可以在添加其它添加剂之前、同时或之后通过本领域技术人员已知的任何方法供应到油中。因此，各种组分可以通过以所需浓度在基本油料或基油掺合物中分散或溶解来直接添加到基本油料或基油掺合物中。这种掺合可以在环境温度或升高的温度下进行。
优选地，将除粘度改进剂和倾点下降剂(如果包含的话)外的所有添加剂掺入浓缩物或组合添加剂，然后将该浓缩物或组合添加剂掺入基本油料以制造最终润滑剂。浓缩物通常配制成含有适当量的添加剂，以在浓缩物与预定量的基础润滑剂结合时在最终制剂中提供所需浓度，
浓缩物优选根据US 4,938,880中所述的方法制造。
最终曲轴箱润滑油组合物可以使用2至20、优选4至18、最优选5至17质量％的浓缩物或组合添加剂，其余部分为基本油料。
本文所用的术语“油溶性”或“油分散性”或同源术语不一定是指化合物或添加剂全部可溶、可分解、混溶或能够悬浮或悬浮在油中。它们是指，例如，化合物或添加剂在油中可溶或可稳定分散至足以在使用该油的环境中发挥其预期作用的程度。此外，如果需要，其它添加剂的额外掺入也可能允许特定添加剂以较高含量掺入。
分散剂(A)
无灰含氮分散剂的特征在于它们是由仅通过热“烯”反应(一种已知的反应)而官能化的聚烯烃制成的。这类聚烯烃是主要含有末端亚乙烯基(例如至少65、例如70、更优选至少85％)的混合物。例如，可以提到被称作高反应性聚异丁烯(HR-PIB)的聚烯烃，其可以以商品名GlissopalTM(出自BASF)和UltravisTM(出自BP-Amoco)购得。US-A-4152499描述了这类聚合物的制备。
相反，通过所谓氯化法(即，与本发明无关)而官能化的聚异丁烯只有次要百分比的聚合物链(小于20％)带有末端亚乙烯基。
聚烯烃通过在如下条件下利用热“烯”反应使聚合物反应而例如被生成羧酸的残基(优选酸或酐)官能化：该条件使得官能残基或试剂，即酸、酐或酯残基，主要在碳-碳不饱和(也称作烯键式或烯烃式不饱和)位点添加到聚合物链上。
可用于将聚烯烃官能化的优选的单不饱和反应物包括单羧酸和二羧酸材料，即酸、酐或酸酯材料，包括(i)单不饱和C4至C10二羧酸，其中(a)羧基是邻位的(即位于相邻碳原子上)，和(b)所述相邻碳原子的至少一个、优选两个是所述单不饱和的一部分；(ii)(i)的衍生物，例如(i)的酐或C1至C5醇衍生的单酯或二酯；(iii)单不饱和C3至C10单羧酸，其中碳-碳双键与羧基共轭，即具有-C＝C-CO-的结构；和(iv)(iii)的衍生物，例如C1至C5醇衍生的(iii)的单酯或二酯。也可以使用单不饱和羧酸材料(i)-(iv)的混合物。在与聚烯烃反应时，单不饱和羧酸反应物的单不饱和性变为饱和。因此，例如，马来酸酐变成聚烯烃取代的琥珀酸酐，丙烯酸变成聚烯烃取代的丙酸。这类单不饱和羧酸反应物的例子是富马酸、衣康酸、马来酸、马来酸酐、丙烯酸、甲基丙烯酸、巴豆酸、肉桂酸和前述物质的低碳烷基(例如C1至C4烷基)酸酯，例如马来酸甲酯、富马酸乙酯和富马酸甲酯。
为了提供所需官能度，以聚烯烃的摩尔量为基础，单不饱和羧酸反应物(优选马来酸酐)通常以等摩尔量至100、优选5至50重量％过量的量使用。如果需要，可以通过例如汽提(通常在真空下)从最终分散剂产物中去除未反应的过量单不饱和羧酸反应物。
然后用亲核反应物，例如胺、氨基醇、醇或其混合物，将官能化的油溶性聚烯烃衍生，以形成含有该分散剂的相应衍生物。可用于将官能化的聚合物衍生的胺化合物包含至少一种胺，并可包含一种或多种其它胺或其它反应性或极性基团。这些胺可以是烃基胺或可以主要是烃基胺，其中烃基包括其它基团，例如羟基、烷氧基、酰胺基团、腈和咪唑啉基团。特别可用的胺化合物包括单胺和多胺，例如每分子含有2至60个、例如2至40个(例如3至20个)总碳原子和1至12个、例如3至12个、优选3至9个、最优选6至7个氮原子的聚烯烃和聚氧化烯多胺。可以有利地使用胺化合物的混合物。优选的胺是脂族饱和胺，包括，例如，1，2-二氨基乙烷；1，3-二氨基丙烷；1，4-二氨基丁烷；1，6-二氨基己烷；多亚乙基胺，例如二亚乙基三胺、三亚乙基四胺、四亚己基五胺；和多亚丙基胺，例如1，2-丙二胺、和二-(1，2-亚丙基)三胺。被称作PAM的这类多胺混合物是可购得的。特别优选的多胺混合物是通过从PAM产物中蒸馏出轻馏分而得的混合物。所得混合物，被称作“重”PAM或HPAM，也是可购得的。例如在美国专利4,938,881、4,927,551、5,230,714、5,241,003、5,565,128、5,756,431、5,792,730和5,854,186中描述了PAM和/或HPAM的性质和特征。
其它可用的胺化合物包括：脂环族二胺，例如1，4-二(氨基甲基)环己烷，和杂环氮化合物，例如咪唑啉。另一可用的胺类型是如美国专利4,857,217、4,956,107、4,963,275和5,229,022中所公开的聚酰氨基和相关的酰氨基-胺。同样可用的是如美国专利4,102,798、4,113,639、4,116,876和UK 989,409中所述的三(羟甲基)氨基甲烷(TAM)。也可以使用树形聚合物、星形胺、和梳形结构胺。类似地，可以使用美国专利5,053,152中所述的缩合胺。使用例如美国专利4,234,435和5,229,022以及EP-A-208,560中所述的传统技术使官能化聚合物与胺化合物反应。
本发明中所得和所用的分散剂是含氮的无灰(无金属)分散剂。官能团能够与待分散的粒子发生联系。衍生化提供的含氮基团是连接到聚合物骨架上(通常通过桥连基连接)的极性基团。合适的无灰分散剂可以例如，选自长链烃取代的单羧酸和多羧酸或其酐的油溶性盐、酯、氨基酯、酰胺、酰亚胺和噁唑啉；长链烃的硫代羧酸酯衍生物；和含有直接连接到其上的多胺残基的长链脂族烃。
本发明的分散剂优选包含至少一种源自聚烯基取代的单羧酸或二羧酸、酐或酯的分散剂，该分散剂具有数均分子量为至少900的聚烯基残基，每有一个聚烯基残基则有大于1.3至1.7、优选大于1.3至1.6、最优选大于1.3至1.5个官能团(生成单羧酸或二羧酸的残基)(中等官能度分散剂)。官能度(F)可以根据下式测定：
F＝(SAP×Mn)/((112,200×A.I.)-(SAP×98)) (1)
其中SAP是皂化值(即，根据ASTM D94测定的，在1克含琥珀酸的反应产物中，酸基团完全中和所消耗的KOH的毫克数)；Mn是原料烯烃聚合物的数均分子量；A.I.是含琥珀酸的反应产物的活性成分百分比(其余部分是未反应的烯烃聚合物、琥珀酸酐和稀释剂)。
通常，各生成单羧酸或二羧酸的残基将与亲核基团(胺、醇、酰胺或酯极性残基)反应，且聚烯基取代的羧酸酰化剂中官能团的数将决定最终分散剂中亲核基团的数。
本发明分散剂的聚烯基残基可以具有至少900、合适地至少1500、优选1800至3000、例如2000至2800、更优选大约2100至2500、最优选大约2200至大约2400的数均分子量。分散剂的分子量通常以聚烯基残基的分子量表示；这是因为分散剂的确切分子量范围取决于许多参数，包括用于将分散剂衍化的聚合物的类型、官能团的数和所用亲核基团的类型。聚合物分子量，具体而言是
，可以通过多种已知技术测定。一种方便的方法是凝胶渗透色谱法(GPC)，该方法另外还提供分子量分布信息(参见W.W.Yau，J.J.Kirkland和D.D.Bly，“Modern Size ExclusionLiquid Chromatography”，John Wiley and Sons，New York，1979)。测定分子量、特别是较低分子量聚合物的分子量的另一有用方法是蒸气压渗透法(参见，例如ASTM D3592)。
本发明分散剂中的聚烯基残基优选具有窄的分子量分布(MWD)，也称作多分散性，这是由重均分子量(Mw)与数均分子量(Mn)的比率确定的。Mw/Mn小于2.2、优选小于2.0的聚合物是最合意的。合适的聚合物具有大约1.5至2.1、优选大约1.6至大约1.8的多分散性。
形成本发明分散剂所用的合适的聚烯烃包括均聚物、共聚体或较低分子量烃。这样的聚合物的一种类型包括乙烯和/或至少一种式H2C＝CHR1的C3至C28α-烯烃的聚合物，其中R1是含有1至26个碳原子的直链或支链烷基，且其中该聚合物含有碳-碳不饱和性，和高度的末端亚乙烯基不饱和性。优选地，这类聚合物包含乙烯与至少一种上式的α-烯烃的共聚物，其中R1是含有1至18个碳原子的烷基，更优选是含有1至8个碳原子的烷基，再更优选含有1至2个碳原子。
聚合物的另一有用类型是通过例如异丁烯和苯乙烯之类单体的阳离子聚合制成的聚合物。该类型中的常见聚合物包括通过丁烯含量为35至75重量％、异丁烯含量为30至60重量％的C4精制厂物流经由热“烯”反应的聚合而获得的聚异丁烯。用于制造聚正丁烯的单体的优选来源是石油进料流，例如残液II。在例如美国专利4,952,739之类的文献中公开了这些进料。优选实施方案采用由纯异丁烯流或残液I流制成的聚异丁烯制备如上所述具有末端亚乙烯基烯烃的反应性异丁烯聚合物。
可用的聚异丁烯聚合物通常基于1500至3000的聚合物链。
本发明的分散剂优选为非聚合的(例如，单或双琥珀酰亚胺)。
本发明的分散剂可以通过传统方式(通常如美国专利3,087,936、3,254,025和5,430,105中所教导的那样)硼酸化。通过以足以提供每摩尔酰基化氮组合物0.1至20原子比例的硼的量，用硼化合物，例如氧化硼、卤化硼、硼酸、和硼酸的酯处理含酰基氮的分散剂，容易实现分散剂的硼酸化。
在产物中表现为脱水硼酸聚合物(主要是(HBO2)3)的硼被认为例如以胺盐、例如二酰亚胺的偏硼酸盐形式连接到分散剂酰亚胺和二酰亚胺上。硼酸化可以如下进行：在酰基氮化合物中添加足量的硼化合物(通常以浆液形式)，优选硼酸，并在搅拌下在135℃至190℃、例如140℃至170℃加热1至5小时，然后氮汽提。或者，通过在二羧酸材料和胺的热反应混合物中添加硼酸，同时去除水，可以进行硼处理。也可以使用本领域已知的其它后反应方法。
通常，润滑油组合物可以含有0.1至20、例如1至8、优选2至6质量％分散剂。
清净剂(B)
本发明要求存在一种或多种高碱性碱土金属清净剂，例如，它们具有150至450的TBN，由至少一种碱土金属磺酸盐构成。这些清净剂可以以能够提供其正常的伴随功能的量存在，只要油的硫酸化灰分含量保持不超过1重量％、例如0.8重量％或更低即可，且通常以0.5至3重量％的量使用。碱土金属可以是钙或镁，优选为钙。
磺酸盐可以由通常通过烷基取代的芳烃(例如由石油的分馏或通过芳烃的烷基化获得的那些)的磺化获得的磺酸制成。烷芳基磺酸盐通常每个烷基取代的芳族残基含有9至80或更高、优选16至60个碳原子。
粘度改进剂(C)
它们用于使润滑油具有高温和低温可操作性。所用VM可以具有这种唯一功能，或可以是多功能的。
同时充当分散剂的多功能粘度改进剂也是已知的。
合适的粘度改进剂是聚异丁烯、乙烯与丙烯和高级α-烯烃的共聚物、聚甲基丙烯酸酯/盐、聚烷基甲基丙烯酸酯、甲基丙烯酸酯/盐共聚物、不饱和二羧酸与乙烯基化合物的共聚物、苯乙烯与丙烯酸酯的共聚物、苯乙烯/异戊二烯、苯乙烯/丁二烯、和异戊二烯/丁二烯的部分氢化的共聚物、以及丁二烯和异戊二烯和异戊二烯/二乙烯基苯的部分氢化的均聚物。
它们可以构成润滑油组合物的0.01至10、例如0.25至3质量％。
其它添加剂
在本发明的润滑油组合物中还可以存在如下的其它添加剂。
抗磨剂可以包含二烃基二硫代磷酸金属盐，其中金属可以是碱金属或碱土金属或铝、铅、锡、钼、锰、镍、铜或优选锌。
二烃基二硫代磷酸金属盐可以根据已知技术制备：首先，通常通过一种或多种醇或酚与P2S5的反应，形成二烃基二硫代磷酸(DDPA)，然后用金属化合物中和已形成的DDPA。例如，可以通过使伯醇和仲醇的混合物反应来制造二硫代磷酸。或者，可以制备多种二硫代磷酸，其中一种二硫代磷酸上的烃基在性质上完全是仲烃基，其它二硫代磷酸上的烃基在性质上完全是伯烃基。为了制造金属盐，可以使用任何碱性或中性金属化合物，但最通常使用氧化物、氢氧化物和碳酸盐。商业添加剂通常由于在中和反应中使用过量碱性金属化合物而含有过量金属。
优选的二烃基二硫代磷酸锌(ZDDP)是二烃基二硫代磷酸的油溶性盐，并可以表示为下式：
其中R和R’可以是相同或不同的、含有1至18个、优选2至12个碳原子、并包括例如烷基、烯基、芳基、芳烷基、烷芳基和脂环族基团之类的基团的烃基。特别优选作为R和R’基团的是含有2至8个碳原子的烷基。因此，所述基团可以，例如，是乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、正己基、异己基、正辛基、癸基、十二烷基、十八烷基、2-乙基己基、苯基、丁基苯基、环己基、甲基环戊基、丙烯基、丁烯基。为了获得油溶性，二硫代磷酸中碳原子(即R和R’)的总数通常为大约5个或更多。因此，二烃基二硫代磷酸锌可以包括二烷基二硫代磷酸锌。
为了将通过ZDDP引入润滑油组合物中的磷的量限制为不超过0.09质量％，基于润滑油组合物的总质量，ZDDP应该优选以不超过1.1至1.3质量％的量添加到润滑油组合物中。
氧化抑制剂或抗氧化剂降低了基本油料在使用中劣化的趋势，这种劣化可以通过金属表面上的氧化产物(例如淤泥和清漆状沉积物)和粘度升高表现出来。这种氧化抑制剂包括受阻酚、芳族胺、含有优选C5至C12烷基侧链的烷基酚硫酯的碱土金属盐、壬基酚硫化钙、无灰油溶性酚盐、和硫化酚盐、磷硫化或硫化烃、磷酯、金属硫代氨基甲酸盐和如U.S.4,867,890中所述的油溶性铜化合物。
摩擦改性剂，可以使用包括降低摩擦系数并因此改进燃料经济性的边界润滑添加剂的摩擦改性剂。例子包括基于酯的有机摩擦改性剂，例如多元醇的部分脂肪酸酯，例如单油酸甘油酯；和基于胺的有机摩擦改性剂。其它例子是沉积二硫化钼的添加剂，例如有机钼化合物，其中钼是例如二核或三核形式。
防锈剂，可以使用选自由非离子聚氧化烯多元醇及其酯、聚氧化烯酚、和阴离子烷基磺酸组成的组的防锈剂。
可以使用少量反乳化组分。在EP 330,522中描述了优选的反乳化组分。其通过使环氧烷与由双-环氧化物与多元醇反应获得的加合物反应而得。反乳化剂应该以不超过0.1质量％活性成分的量使用。0.001至0.05质量％的活性成分处理率是方便的。
倾点下降剂，或称作润滑油流动改进剂，降低了流体流动或可以倾倒的最小温度。这类添加剂是公知的。改进流体的低温流动性的典型添加剂是C8至C18二烷基富马酸酯/乙酸乙烯酯共聚物、聚烷基甲基丙烯酸酯等。
许多化合物可以提供泡沫控制，包括聚硅氧烷型防沫剂，例如硅油或聚二甲基硅氧烷。
发动机
本发明适用于乘用车内燃机，例如火花点火和轻型压缩点火的二冲程或四冲程往复式发动机。
实施例
现在在下列实施例中具体描述本发明，这些实施例不是为了限制权利要求的范围。
通过本领域已知的方法掺合两种全配方的5W30润滑油组合物(或润滑剂)，润滑剂1和润滑剂A。两种润滑剂的不同之处在于：
润滑剂1，本发明的润滑剂，含有由聚异丁烯基-琥珀酰亚胺构成的无灰分散剂，其中聚异丁烯基残基源自通过热“烯”反应制成的聚异丁烯琥珀酸酐；和
润滑剂A，参比润滑剂，含有与润滑剂1所含无灰分散剂相对应的无灰分散剂，不同的是聚异丁烯基残基源自通过氯化法制成的聚异丁烯琥珀酸酐。
各润滑剂通过将下列成分混合来制造：
3.2质量％的分散剂；
1.6质量％的高TBN磺酸钙清净剂；
10质量％的烯烃共聚物粘度改进剂；
和II类基本油料，包括相应量的本领域已知的辅助添加剂，例如一种或多种抗磨剂、抗氧化剂、摩擦改性剂和防沫剂。
此外，各润滑剂具有下列分析：
0.77质量％硫酸化灰分
0.08质量％磷
0.2质量％硫
根据Sequence IIIG试验测试两种润滑剂各自的凸轮和升降杆磨损。该试验采用1996通用汽车3800cc Series II、水冷型4循环V-6汽油机作为试验装置。Sequence III G试验发动机是顶阀设计(OHV)的，并使用单凸轮轴通过以滑动-从动轮(silding-follower)方式设置的阀门挺杆和液压阀挺杆操作进气阀和排气阀。使用无铅汽油，发动机运行10分钟初始油匀化程序，然后进行15分钟缓慢提速，直至到达速度和载荷条件。然后使发动机在125bhp、3600rpm和150℃油温下运行100小时，以20小时为间隔中断进行油位检查。
在试验最后，测量凸轮凸角和升降杆的磨损。结果如下，表示为以微米为单位的平均凸轮+升降杆磨损，其中该试验的合格限为最大60微米。
润滑剂1：28.8
润滑剂A：87.2
结果表明，使用润滑剂1中的分散剂在公认发动机试验中产生比使用润滑剂A中的分散剂更好的磨损性能，其程度为润滑剂1通过该试验，而润滑剂A没有通过。
根据sequence 111G程序对润滑剂进行进一步试验，以测量粘度升高和活塞清洁度。
所得结果如下：
| 润滑剂 | ％粘度升高 | 加权平均的活塞沉积物指标 |
| 1 | 43.7 | 4.1 |
| A | 144 | 2.26 |
| 合格限 | ＝或＜150 | ＝或＞3.5 |
结果表明，尽管两者都在试验限度内，但润滑剂1与润滑剂A相比产生了更低的、即更好的粘度升高；润滑剂1与润滑剂A相比产生更好的活塞沉积物性能，其程度为润滑剂1通过该试验，而润滑剂A没有通过。
Claims (6)
1.内燃机曲轴箱润滑油组合物，其具有以磷原子表示的不超过0.09、例如0.05至0.08质量％的磷含量；以硫原子表示的不超过0.3质量％的硫含量；和不超过1、例如0.5至0.8质量％的硫酸化灰分含量，该组合物含有各次要量的下列添加剂组分，或通过将各次要量的下列添加剂组分混合而制成：
A.聚烯基取代的单羧酸或二羧酸、酐或酯的至少一种油溶性或油分散性含氮衍生物，所述聚烯基取代的单羧酸或二羧酸或酯由聚烯烃仅通过热“烯”反应制成，是润滑油组合物中唯一的无灰含氮分散剂，并在润滑油组合物中提供0.03至0.07质量％的氮；
B.至少一种油溶性或油分散性的高碱性碱土金属磺酸盐，其是润滑油组合物中唯一的高碱性金属清净剂体系；和
C.至少一种粘度改进剂。
2.如权利要求1所述的组合物，其中分散剂(A)中的聚烯基是聚异丁烯基。
3.如权利要求1或权利要求2所述的组合物，其中所述清净剂体系中的碱土金属是钙。
4.如权利要求1至3任一项所述的组合物，其中所述粘度改进剂是烯烃共聚物。
5.润滑乘用车内燃机曲轴箱的方法，包括向曲轴箱供应根据权利要求1至4任一项的润滑油组合物。
6.如权利要求1或权利要求2中定义的分散剂的用途，用于通过如权利要求1至4任一项的润滑油组合物改进乘用车内燃机曲轴箱润滑中的凸轮和升降杆磨损、活塞沉积物和/或润滑剂粘度，所述改进是与使用包括下述相应分散剂组合物的相应润滑组合物比较而言的一一其中聚烯基取代的单羧酸或二羧酸、酐或酯是由聚烯烃通过氯化反应制成的。
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2007
- 2007-07-10 US US11/775,247 patent/US9012382B2/en active Active
- 2007-07-17 CN CN200710136086.0A patent/CN101108994B/zh active Active
- 2007-07-17 SG SG200705272-3A patent/SG139671A1/en unknown
- 2007-07-18 CA CA2594029A patent/CA2594029C/en active Active
- 2007-07-19 JP JP2007187899A patent/JP5374842B2/ja active Active
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2013
- 2013-06-25 JP JP2013132838A patent/JP2013177642A/ja active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103354832A (zh) * | 2010-12-10 | 2013-10-16 | 卢布里佐尔公司 | 含有粘度指数改进剂的润滑剂组合物 |
| CN103354832B (zh) * | 2010-12-10 | 2015-11-25 | 路博润公司 | 含有粘度指数改进剂的润滑剂组合物 |
| CN103476910A (zh) * | 2011-02-17 | 2013-12-25 | 卢布里佐尔公司 | 具有良好tbn保持力的润滑剂 |
| CN103476910B (zh) * | 2011-02-17 | 2017-08-08 | 路博润公司 | 具有良好tbn保持力的润滑剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2594029C (en) | 2013-12-17 |
| US9012382B2 (en) | 2015-04-21 |
| US20080020950A1 (en) | 2008-01-24 |
| SG139671A1 (en) | 2008-02-29 |
| JP5374842B2 (ja) | 2013-12-25 |
| JP2008024937A (ja) | 2008-02-07 |
| JP2013177642A (ja) | 2013-09-09 |
| CN101108994B (zh) | 2014-04-30 |
| CA2594029A1 (en) | 2008-01-19 |
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