CN111630142A - 自动变速器润滑油 - Google Patents
自动变速器润滑油 Download PDFInfo
- Publication number
- CN111630142A CN111630142A CN201880087168.7A CN201880087168A CN111630142A CN 111630142 A CN111630142 A CN 111630142A CN 201880087168 A CN201880087168 A CN 201880087168A CN 111630142 A CN111630142 A CN 111630142A
- Authority
- CN
- China
- Prior art keywords
- lubricating oil
- oil composition
- post
- succinimide
- 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
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 97
- 230000005540 biological transmission Effects 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 121
- 239000003921 oil Substances 0.000 claims abstract description 74
- 239000004760 aramid Substances 0.000 claims abstract description 8
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 3
- -1 phosphate amine salts Chemical class 0.000 claims description 98
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 88
- 229960002317 succinimide Drugs 0.000 claims description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 35
- 239000002270 dispersing agent Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 229910019142 PO4 Inorganic materials 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 20
- 230000001050 lubricating effect Effects 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 239000003599 detergent Substances 0.000 claims description 16
- 229920002367 Polyisobutene Polymers 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 description 70
- 239000002199 base oil Substances 0.000 description 54
- 239000000654 additive Substances 0.000 description 24
- 239000003607 modifier Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- 235000021317 phosphate Nutrition 0.000 description 20
- 125000003342 alkenyl group Chemical group 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 239000003112 inhibitor Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 230000000996 additive effect Effects 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 14
- 239000000314 lubricant Substances 0.000 description 14
- 229920000768 polyamine Polymers 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 229920013639 polyalphaolefin Polymers 0.000 description 12
- 229920001083 polybutene Polymers 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 229920001515 polyalkylene glycol Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229940014800 succinic anhydride Drugs 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 229920001281 polyalkylene Polymers 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 235000011044 succinic acid Nutrition 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000001993 wax Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000012445 acidic reagent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000994 depressogenic effect Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 239000003879 lubricant additive Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 229920000193 polymethacrylate Polymers 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
- 238000012545 processing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 150000004867 thiadiazoles Chemical class 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- 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
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 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
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
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- 229910052796 boron Inorganic materials 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical group C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
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- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 1
- OHRVKCZTBPSUIK-UHFFFAOYSA-N tridodecyl phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCC)OCCCCCCCCCCCC OHRVKCZTBPSUIK-UHFFFAOYSA-N 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
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- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- KENFVQBKAYNBKN-UHFFFAOYSA-N trihexadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCC KENFVQBKAYNBKN-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- FDGZUBKNYGBWHI-UHFFFAOYSA-N trioctadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC FDGZUBKNYGBWHI-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- VYEHCXHIPZIYIJ-UHFFFAOYSA-L zinc;dodecoxy-dodecylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCCCOP([O-])(=S)SCCCCCCCCCCCC.CCCCCCCCCCCCOP([O-])(=S)SCCCCCCCCCCCC VYEHCXHIPZIYIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
-
- 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
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
-
- 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/08—Ammonium or amine salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明总体上涉及用于自动变速器的润滑油组合物,并且尤其用于使用湿式离合器系统的汽车自动变速器和/或无级变速器的变速器油,特别是包含少量纤维素纤维和/或芳纶纤维的湿纸离合器。
Description
技术领域
本发明总体上涉及用于自动变速器的润滑油组合物,并且尤其是用于使用湿式离合器系统的汽车自动变速器和/或无级变速器的变速器油,特别是含有少量纤维素纤维和/或芳纶纤维的湿纸离合器。
发明背景
自动变速器润滑油,称为自动变速器油,通常用于辅助自动变速器的平稳运行,该自动变速器安装在汽车中并且包括变矩器、齿轮机构、湿式离合器和液压机构。
众所周知,润滑剂添加剂会影响湿式离合器和钢板的摩擦性能。添加剂作用是由于它们在离合器材料(例如,纤维素,芳纶(天然和合成)纤维,二氧化硅和钢板表面)上的物理和化学吸收而引起的。工业上一直在推动将用于汽车自动变速器的富纤维素湿式离合器纸转变为芳纶湿式离合器纸。纤维素和芳纶的比例对于湿式离合器的热稳定性和氧化稳定性很重要。高芳纶湿离合纸显示出出色的耐久性能。但是,芳纶纤维的成本高。
此外,监管方面的变化导致要求现代车辆改善燃油经济性并减少CO2排放,以防止全球变暖。除了改进发动机和传动系统的设计外,还需要润滑剂性能来解决此问题。在汽车自动变速器的情况下,需要最小化在启动时间内由变矩器引起的功率损失,并且已经引入了锁止离合器系统以提高燃油效率。锁止变矩器安装在变矩器系统中的锁止湿纸离合器中。由于它们可以在低速和较短时间进行液力偶合后接合湿式离合器,因此可以减少动力损失并提供出色的燃油经济性。
在润滑剂方面,为自动变速器配备合适的润滑剂并在变速器中锁止纸湿离合器也很重要。如果润滑剂提供的扭矩容量和抗抖动摩擦性能较差,则会发生因变速器中湿式离合器的锁止导致动力损失或不舒适的振动以及高噪音。因此,用于带锁止纸湿式离合器系统的自动变速器的润滑剂应提供良好的燃油经济性以及平稳的驾驶和操作条件。
发明人已经发现了一种润滑油组合物,该润滑油组合物具有优异的湿纸离合器摩擦特性,例如抗抖动性能,并且还可以保持优异的湿式离合器扭矩能力和湿离合器摩擦特性的持久性。
发明概要
根据本发明的一个实施方案,提供了一种润滑油组合物,所述润滑油组合物包含:
i)主要量的具有润滑粘度的油,
ii)至少一种或多种未后处理的琥珀酰亚胺分散剂,
iii)0.01-0.5重量%磷酸,
iv)向所述组合物中提供不超过350ppm金属的金属清净剂,v)至少一种或多种有机磷化合物,其中
所述未后处理的琥珀酰亚胺中的氮与磷酸中的磷之比为1-3。
根据本发明的另一个实施方案,提供了一种在配备有自动变速器或无级变速器的内燃机中改善抗抖动性能并减少摩擦的方法,所述方法包括用润滑油组合物润滑所述变速器,所述润滑油组合物包含:
i)主要量的具有润滑粘度的油,
ii)至少一种或多种未后处理的琥珀酰亚胺分散剂,
iii)0.01-0.5重量%磷酸,
iv)向组合物中提供不超过350ppm金属的金属清净剂,
v)至少一种或多种有机磷化合物,其中
所述未后处理的琥珀酰亚胺中的氮与磷酸中的磷之比为1-3。
发明详述
定义:
以下术语将在整个说明书中使用,并且除非另有说明,将具有以下含义。
术语基础油的“主要量”是指其中基础油的量占润滑油组合物的至少40重量%。在一些实施方案中,基础油的“主要量”是指基础油的量占润滑油组合物的大于50重量%、大于60重量%、大于70重量%、大于80重量%或大于90重量%。
在下面的描述中,本文公开的所有数字都是近似值,而不管是否使用词“约”或“近似”。它们可以变化1%、2%、5%,或者有时10%到20%。
术语“总碱值”或“TBN”是指油样品中的碱度水平,其指示组合物根据ASTM标准No.D2896或等效程序继续中和腐蚀性酸的能力。该测试测量电导率的变化,结果表示为mgKOH/g(中和1克产品所需的KOH毫克当量)。因此,高TBN反映了过碱性产品,因此,中和酸的碱储备更高。
术语“PIB”是指聚异丁烯。
润滑粘度的油
本文公开的润滑油组合物通常包含至少一种润滑粘度的油。本领域技术人员已知的任何基础油可以用作本文公开的润滑粘度的油。适用于制备润滑油组合物的一些基础油已在Mortier等,“润滑剂化学与技术(Chemistry and Technology of Lubricants),”第2版,伦敦,Springer,第1和2章(1996年);和A.Sequeria,Jr.,“润滑油基础油和石蜡加工(Lubricant Base Oil and Wax Processing),”纽约,Marcel Decker,第6章,(1994年);和D.V.Brock,润滑工程(Lubrication Engineering),第43卷,第184-5页(1987年),中描述,所有这些文献通过引用并入本文。通常,基于润滑油组合物的总重量,润滑油组合物中基础油的量可以为约70至约99.5重量%。在一些实施方案中,基于润滑油组合物的总重量,润滑油组合物中基础油的量为约75至约99重量%、约80至约98.5重量%,或约80至约98重量%。
在某些实施方案中,基础油是或者包含任何天然或合成的润滑基础油馏分。合成油的一些非限制性实例包括由至少一种α-烯烃(例如乙烯)的聚合制备的油,例如聚α-烯烃或PAO,或者使用一氧化碳和氢气的烃合成方法制备的油,例如费托工艺(Fisher Tropschprocess)。在某些实施方案中,基于基础油的总重量,基础油包含小于约10重量%的一种或多种重馏分。重馏分是指在100℃下粘度为至少约20cSt的润滑油馏分。在某些实施方案中,重馏分在100℃下的粘度为至少约25cSt或至少约30cSt。在进一步的实施方案中,基于基础油的总重量,基础油中一种或多种重馏分的量小于约10重量%、小于约5重量%、小于约2.5重量%、小于约1重量%或小于约0.1重量%。在另外的实施方案中,基础油不包含重馏分。
在某些实施方案中,润滑油组合物包含主要量的润滑粘度的基础油。在一些实施方案中,基础油在100℃下的运动粘度为约1.5厘斯(cSt)至约20cSt、约2厘斯(cSt)至约20cSt、或约2cSt至约16cSt。本文公开的基础油或润滑油组合物的运动粘度可以根据ASTMD 445测量,其通过引用并入本文。
在其它实施方案中,基础油是或者包含基础原料或基础原料的共混物。在另外的实施方案中,使用多种不同的方法制造基础油料,包括但不限于蒸馏、溶剂精制、加氢处理、低聚、酯化和再精炼。在一些实施方案中,基础油料包含再精炼油料。在另外的实施方案中,再精制原料应基本上不含通过制造、污染或先前使用引入的材料。
在一些实施方案中,基础油包含一种或多种第I-V类中的一种或多种基础油,如美国石油协会(API)出版物1509,第14版,1996年12月中所规定(即用于客车发动机油和柴油发动机油的API基础油互换准则),其通过引用并入本文。API准则将基础油料定义为可以使用多种不同方法制造的润滑剂组分。第I、II和III类基础油是矿物油,各自具有饱和烃含量、硫含量和粘度指数的具体范围。第IV类基础油料是聚α烯烃(PAO)。第V类基础油料包括不包括在第I、II、III或IV组中的所有其它基础油。
在一些实施方案中,基础油包含第I、II、III、IV、V类或其组合中的一种或多种基础油料。在其它实施方案中,基础油包含第II、III、IV类或其组合中的一种或多种基础油料。在另外的实施方案中,基础油包含第II、III、IV组或其组合中的一种或多种基础油,其中基础油在100℃下运动粘度为约1.5厘斯(cSt)至约20cSt、约2cSt至约20cSt、或约2cSt至约16cSt。在一些实施方案中,基础油为第II类基础油。
基础油可以选自润滑粘度的天然油、润滑粘度的合成油及其混合物。在一些实施方案中,基础油包括通过合成蜡和散蜡的异构化所获得的基料,以及通过原油的芳族和极性组分的氢化裂化(而非溶剂提取)所生产的氢化裂化物基料。在其他实施方案中,润滑粘度的基础油包括天然油品,例如动物油、植物油、矿物油(例如,链烷烃,环烷烃或混合链烷烃-环烷烃类型的液体石油和溶剂处理或经酸处理的矿物油)、衍生自煤或者页岩的油及其组合。动物油的一些非限定性例子包括骨油、羊毛脂、鱼油、猪油、海豚油、海豹油、鲨鱼油、牛脂油和鲸油。植物油的一些非限定性例子包括蓖麻油、橄榄油、花生油、菜籽油、玉米油、芝麻油、棉籽油、大豆油、向日葵油、红花油、大麻油、亚麻籽油、桐油、奥蒂树油、加州希蒙得木油和草地泡沫油。这样的油可以是部分或者完全氢化的。
在一些实施方案中,润滑粘度的合成油包括烃油和卤代烃油例如聚合的和互聚的烯烃、烷基苯、聚苯、烷基化二苯基醚、烷基化二苯基硫醚以及它们的衍生物,其类似物和同系物等。在其他实施方案中,合成油包括环氧烷聚合物、互聚物、共聚物和其衍生物,其中端羟基可以通过酯化、醚化等来改性。在另一实施方案中,合成油包括二羧酸与多种醇的酯。在某些实施方案中,合成油包括由C5-C12单羧酸与多元醇和多元醇醚制成的酯。在另一实施方案中,合成油包括三烷基磷酸酯油,例如三正丁基磷酸酯和三异丁基磷酸酯。
在一些实施方案中,润滑粘度的合成油包括硅基基础油(例如聚烷基-、聚芳基-、聚烷氧基-、聚芳氧基-硅氧烷油和硅酸酯/盐油)。在其他实施方案中,合成油包括含磷酸的液体酯、聚合四氢呋喃、聚α烯烃等。
还可以使用衍生自蜡的加氢异构化的基础油,其是单独使用或者与前述天然和/或合成基础油组合使用。这样的蜡异构化物油是通过天然或者合成蜡或者其混合物在加氢异构化催化剂上加氢异构化来生产的。
在另一实施方案中,基础油包含聚-α-烯烃(PAO)。通常,聚-α-烯烃可以衍生自具有约1.5-约30、约2-约20、或者约2-约16个碳原子的α-烯烃。合适的聚-α-烯烃的非限定性例子包括衍生自辛烯、癸烯,其混合物等的那些。这些聚-α-烯烃在100℃的粘度可以是约1.5-约15、约1.5-约12、或者约1.5-约8厘斯。在一些情况中,聚-α-烯烃可以与其他基础油例如矿物油一起使用。
在另一实施方案中,基础油包含聚亚烷基二醇或者聚亚烷基二醇衍生物,其中聚亚烷基二醇的端羟基可以通过酯化、醚化、乙酰化等来改性。合适的聚亚烷基二醇的非限定性例子包括聚乙二醇、聚丙二醇、聚异丙二醇及其组合。合适的聚亚烷基二醇衍生物的非限定性例子包括聚亚烷基二醇的醚(例如聚异丙二醇的甲基醚、聚乙二醇的二苯基醚、聚丙二醇的二乙基醚等)、聚亚烷基二醇的单-和聚羧酸酯及其组合。在一些情况中,聚亚烷基二醇或者聚亚烷基二醇衍生物可以与其他基础油例如聚-α-烯烃和矿物油一起使用。
在另一实施方案中,基础油包含二羧酸(例如苯二甲酸、琥珀酸、烷基琥珀酸、烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、亚油酸二聚体、丙二酸、烷基丙二酸、烯基丙二酸等)与多种醇(例如丁醇、己醇、十二烷醇、2-乙基己醇、乙二醇、二乙二醇单醚、丙二醇等)的任意酯。这些酯的非限定性例子包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、富马酸二正己酯、癸二酸二辛酯、壬二酸二异辛酯、壬二酸二异癸酯、苯二甲酸二辛酯、苯二甲酸二癸酯、癸二酸二(二十烷基)酯、亚油酸二聚体的2-乙基己基二酯等。
在另一实施方案中,基础油包含通过费-托方法所制备的烃。费-托方法由含有氢和一氧化碳的气体,使用费-托催化剂制备烃。这些烃可能需要进一步加工来用作基础油。例如烃可以使用本领域技术人员已知的方法脱蜡、加氢异构化、和/或氢化裂化。
在另一实施方案中,基础油包含未精制的油、精制的油、再精制的油或者其混合物。未精制的油是直接获自天然或者合成来源而没有进一步净化处理的那些。未精制的油的非限定性例子包括直接获自干馏作业的页岩油、直接获自初级蒸馏的石油、和直接获自酯化方法的酯油,并且没有进一步处理而使用。精制的油类似于未精制的油,除了前者已经通过一种或多种净化方法处理来改进一种或多种性能之外。许多这样的净化方法是本领域技术人员已知的,例如溶剂萃取、二级蒸馏、酸或者碱萃取、过滤、渗滤等。再精制的油是通过对精制的油使用类似于用于获得精制的油的那些方法来获得的。这样的再精制的油也称作再生或者再加工的油,并且经常通过涉及除去废添加剂和油裂解产物的方法来另外处理。
含氮无灰琥珀酰亚胺分散剂
一方面,润滑油组合物中存在一种或多种含氮的无灰琥珀酰亚胺分散剂。一方面,一种或多种含氮无灰琥珀酰亚胺分散剂是未后处理的分散剂。
含氮无灰分散剂的典型实例包括衍生自聚烯烃的烯基或烷基琥珀酰亚胺及其衍生物。琥珀酰亚胺可以通过被高分子量烯基或烷基取代的琥珀酸酐与每分子平均含有3至10个(优选4至7个)氮原子的多亚烷基多胺之间的反应而获得。一方面,高分子量烯基或烷基优选为数均分子量为约900至5000的聚烯烃,其中聚丁烯是特别有利的。一方面,高分子量烯基或烷基优选为数均分子量为900至4000、900至3500、900至3000、900至2500、900至2000、900至1500、900到1000、90到1000、1000的聚烯烃。
在一些方面,在通过聚丁烯和马来酸酐之间的反应获得聚丁烯基琥珀酸酐的步骤中利用了其中使用氯的氯化方法。然而,利用这种方法,尽管反应性良好,但是最终的琥珀酰亚胺产物中残留了大量的氯(例如约2000ppm)。另一方面,如果使用不涉及氯的热反应,则最终产品中残留的氯量可以保持在非常低的水平(例如40ppm以下)。而且,与常规的聚丁烯(主要具有β-烯烃结构的)相比,使用高反应性的聚丁烯(其中至少约50%具有甲基亚乙烯基结构)是有利的,即使通过热反应方法也可以提高反应性。如果反应性高,则分散剂中未反应的聚丁烯较少,因此可以获得具有高浓度的活性成分(琥珀酰亚胺)的分散剂。因此,优选通过首先使用高反应性聚丁烯通过热反应获得聚丁烯基琥珀酸酐,然后使该聚丁烯基琥珀酸酐与多胺反应来制造琥珀酰亚胺。琥珀酰亚胺可以通过与硼酸,醇,醛,酮,烷基酚,环状碳酸酯,有机酸等进一步反应而以所谓的改性琥珀酰亚胺的形式使用。通过与硼酸或硼化合物反应获得的含硼的烯基(或烷基)琥珀酰亚胺在热和氧化稳定性方面是特别有利的。琥珀酰亚胺根据每个分子的酰亚胺结构数而具有单、双和多型,但是作为用于本发明目的的琥珀酰亚胺,优选双型。
含氮无灰分散剂的其他实例包括衍生自乙烯-α-烯烃共聚物(例如分子量为1000至15,000的一种)的聚合琥珀酰亚胺分散剂,和链烯基苄胺基无灰分散剂。
特别优选的含氮无灰分散剂是衍生自烷基或链烯基琥珀酸或酸酐或亚烷基多胺的反应的单和双烷基或链烯基琥珀酰亚胺。这些化合物通常被认为具有式(I)
其中R1基本上是分子量为约450-3000的烃链,即,R1是烃链,优选烯基,其含有约30-约200个碳原子;Alk是2-10个,优选2-6个,碳原子的亚烷基链,R2,R3和R4选自C1-C4烷基或者烷氧基或者氢,优选氢,和x是整数0-10,优选0-3;
或式(II)
其中R5和R7都基本上是分子量为约450-3000的烃链,即,R5和R7是烃链,优选是烯链,其含有约30-约200个碳原子;Alk是2-10个,优选2-6个,碳原子的亚烷基链,R6选自C1-C4烷基或者烷氧基或者氢,优选氢,和y是整数0-10,优选0-3。在一种实施方案中,R1,R5和R7是聚异丁基。
在一种实施方案中,亚烷基或者亚烯基琥珀酸或者酸酐和亚烷基多胺的实际反应产物将包含包括单琥珀酰亚胺和双琥珀酰亚胺的化合物的混合物。所产生的单烯基琥珀酰亚胺和双烯基琥珀酰亚胺可以取决于多胺与琥珀酸基团的加料摩尔比和所用的具体多胺。多胺与琥珀酸基团的加料摩尔比约1:1可产生主要的单烯基琥珀酰亚胺。多胺与琥珀酸基团的加料摩尔比约1:2可产生主要的双烯基琥珀酰亚胺。琥珀酰亚胺分散剂的例子包括描述在例如美国专利No.3172892,4234435和6165235中的那些,其在此全部引入作为参考。
在一种实施方案中,所述取代基衍生自其的聚烯烃通常是2-约16个碳原子,通常2-6个碳原子,的可聚合烯烃单体的均聚物和互聚物。与琥珀酰化剂反应来形成羧酸分散剂组合物的胺可以是单胺或者多胺。
在一个优选的方面,烯基琥珀酰亚胺可以通过聚亚烷基琥珀酸酐与亚烷基多胺反应来制备。聚亚烷基琥珀酸酐是聚烯烃(优选聚异丁烯)与马来酸酐的反应产物。可以使用常规的聚异丁烯,或者高甲基亚乙烯基聚异丁烯来制备这样的聚亚烷基琥珀酸酐。在这种制备中可以使用热,氯化,自由基,酸催化或者任何其他方法。合适的聚亚烷基琥珀酸酐的例子是热PIBSA(聚异丁烯基琥珀酸酐),其描述在美国专利No.3361673中;氯化PIBSA,其描述在美国专利No.3172892中;热和氯化PIBSA的混合物,其描述在美国专利No.3912764中;高琥珀酸比PIBSA,其描述在美国专利No.4234435中;聚PIBSA,其描述在美国专利No.5112507和5175225中;高琥珀酸比聚PIBSA,其描述在美国专利No.5565528和5616668中;自由基PIBSA,其描述在美国专利No.5286799,5319030和5625004中;由高甲基亚乙烯基聚丁烯制造的PIBSA,其描述在美国专利No.4152499,5137978和5137980中;由高甲基亚乙烯基聚丁烯制造的高琥珀酸比PIBSA,其描述在欧洲专利申请公开No.EP355895中;三元共聚物PIBSA,其描述在美国专利No.5792729中;磺酸PIBSA,其描述在美国专利No.5777025和欧洲专利申请公开No.EP542380中;和净化的PIBSA,其描述在美国专利No.5523417和欧洲专利申请公开No.EP602863中。每个这些文献的公开内容在此以它们全部引入作为参考。聚亚烷基琥珀酸酐优选是聚异丁烯基琥珀酸酐。在一个优选的实施方案中,聚亚烷基琥珀酸酐是衍生自数均分子量为1200或更小的聚异丁烯的聚异丁烯基琥珀酸酐,优选数均分子量为400至1200、优选为500至1100、550至1100、600到1100、650到1100、700到1100、750到1100、800到1000、850到1000、900到1000以及950到1000。
用于制备琥珀酰亚胺的优选的多亚烷基胺是式(III):
其中z是整数0-10和Alk是2-10个,优选2-6个碳原子的亚烷基,R8,R9和R10选自C1-C4烷基或者烷氧基或者氢,优选氢,和z是整数0-10,优选0-3。
亚烷基胺主要包括亚甲基胺,亚乙基胺,亚丁基胺,亚丙基胺,亚戊基胺,亚己基胺,亚庚基胺,亚辛基胺,其他聚亚甲基胺以及这样的胺的环状和高级同系物,如哌嗪和氨基烷基取代的哌嗪。它们具体的示例是亚乙基二胺,三亚乙基四胺,亚丙基二胺,十甲基二胺,八亚甲基二胺,二(七亚甲基)三胺,三亚丙基四胺,四亚乙基五胺,三亚甲基二胺,五亚乙基六胺,二(三亚甲基)三胺,2-庚基-3-(2-氨基丙基)-咪唑啉,4-甲基咪唑啉,N,N-二甲基-1,3-丙二胺,1,3-双(2-氨基乙基)咪唑啉,1-(2-氨基丙基)-哌嗪,1,4-双(2-氨基乙基)哌嗪和2-甲基-1-(2-氨基丁基)哌嗪。例如获自两种或更多种上述亚烷基胺缩合的高级同系物同样是有用的。
亚乙基胺是特别有用的。它们更详细地描述在标题“Ethylene Amines”,Encyclopedia of Chemical Technology,Kirk-Othmer,第5卷第898-905页(IntersciencePublishers,纽约,1950)中。术语“亚乙基胺”以通用含义使用来表示一类多胺,其在最大程度上符合式(IV):
H2N(CH2CH2NH)αH
式IV
其中α是整数1-10。在一个实施方案中,α是整数3-5。因此,它包括例如亚乙基二胺,二亚乙基三胺,三亚乙基四胺,四亚乙基五胺,五亚乙基六胺等。
用于本发明的烯基琥珀酰亚胺组合物中的单个烯基琥珀酰亚胺可以通过常规方法来制备,其例如公开在美国专利No.2992708;3018250;3018291;3024237;3100673;3172892;3202678;3219666;3272746;3361673;3381022;3912764;4234435;4612132;4747965;5112507;5241003;5266186;5286799;5319030;5334321;5356552;5716912,其公开内容全部在此以它们全部引入用于全部目的之参考。
还包括在术语“烯基琥珀酰亚胺”中的是后处理的琥珀酰亚胺例如公开在Wollenberg等人的美国专利No.4612132;Wollenberg等人的美国专利No.4746446中的涉及硼酸酯/盐或者碳酸亚乙酯的后处理方法;等等以及其他后处理方法,其每个在此以其全部引入作为参考。优选碳酸酯/盐处理的烯基琥珀酰亚胺是聚丁烯琥珀酰亚胺,其衍生自分子量为450-3000,优选900-2500,更优选1300-2300和优选2000-2400,以及这些分子量的混合的聚丁烯。优选它是通过在反应性条件下,将聚丁烯琥珀酸衍生物,不饱和酸性试剂和烯烃的不饱和酸性试剂共聚物,和多胺的混合物反应来制备的,如美国专利No.5716912所教导的,其在此引入作为参考。
在一个实施方案中,分散剂体系占润滑油组合物重量的1至20重量%,优选1至15重量%,优选1–10重量%,优选1–8重量%,优选1-6重量%,优选1-5重量%,优选1-4.4重量%,优选1-4重量%,优选1-3重量%,优选1.5–4.0重量%,优选1.5–3.5重量%,优选1.5–3.0重量%,优选2.0–3.0重量%。
在另一个实施方案中,未后处理的分散剂是未后处理的琥珀酰亚胺分散剂。在其他实施方案中,未后处理的琥珀酰亚胺分散剂在润滑油组合物中以0.3至8重量%、0.3至5重量%、0.3至4.4重量%、0.5至4.4重量%、0.5至3.0重量%、0.6至2.0重量%存在。
用于本发明的链烯基琥珀酰亚胺组合物中的各个链烯基琥珀酰亚胺可通过常规方法制备,例如在美国专利Nos.2,992,708;3,018,250;3,018,291;3,024,237;3,100,673;3,172,892;3,202,678;3,219,666;3,272,746;3,361,673;3,381,022;3,912,764;4,234,435;4,612,132;4,747,965;5,112,507;5,241,003;5,266,186;5,286,799;5,319,030;5,334,321;5,356,552;5,716,912,中公开的,其公开内容出于所有目的通过引用整体并入本文。
后处理的琥珀酰亚胺也包括在术语“链烯基琥珀酰亚胺”中,例如在Wollenberg,等美国专利No.4,612,132;Wollenberg,等美国专利No.4,746,446;以及其他后处理方法中公开的涉及硼酸盐或碳酸亚乙酯的后处理方法,其全部通过引用整体并入本文。优选地,经碳酸酯处理的链烯基琥珀酰亚胺是衍生聚丁烯的聚丁烯琥珀酰亚胺,所述聚丁烯的分子量为450至3000,优选为600至2500,优选为700至2500,优选为800至2500,优选为900至2500,更优选900至2400,和优选900至2300以及这些分子量的混合物。优选地,其通过在反应条件下使聚丁烯琥珀酸衍生物,不饱和酸性试剂和烯烃的不饱和酸性试剂共聚物与多胺的混合物反应来制备,例如美国专利No.5,716,912中所教导的,其通过引用并入本文。
在一实施方案中,不对分散剂进行后处理。在另一个实施方案中,分散剂用硼化合物后处理。
一方面,硼的存在量是润滑油组合物的小于500,小于450,小于400,小于350,小于300,小于250,小于200,小于150,小于100wt.ppm。
磷酸/亚磷酸
在一个实施方案中,润滑油组合物中存在无机磷酸或亚磷酸。在另一个实施方案中,所述酸是磷酸。
在一个实施方案中,无机磷酸或亚磷酸在溶液中的含量为75-90重量%。
在一个实施方案中,无机磷酸或亚磷酸的存在量为润滑油组合物的0.01至1.0重量%。在其他实施方案中,无机磷酸或亚磷酸在润滑油组合物中的存在量为0.01至0.5重量%、0.01至0.1重量%、0.01至0.08重量%、0.01至0.07重量%、0.01至0.06重量%、0.02至0.06重量%、0.03至0.05重量%。
在一个实施方案中,润滑油组合物中未后处理的琥珀酰亚胺的氮与磷酸的磷之比为1.0至10.0。在其他实施方案中,本发明的润滑油组合物中的氮/磷比为1.0至8.0、1.0至6.0、1.0至5.0、1.0至4.0、1.0至3.5、1.0至3.0、1.0至2.5、1.5至1.5、1.5至2.0。
在一个实施方案中,润滑油组合物中的总磷含量为500ppm或更低。
金属清静剂
在一个实施方案中,润滑油组合物包含金属清洁剂化合物。合适的金属清净剂的非限制性实例包括硫化或未硫化的烷基或烯基酚盐、烷基或烯基芳族磺酸盐、硼酸化磺酸盐、多羟基烷基或烯基芳族化合物的硫化或未硫化的金属盐、烷基或烯基羟基芳族磺酸盐、硫化或未硫化的烷基或烯基环烷酸盐、烷酸的金属盐、烷基或烯基多酸的金属盐,以及其化学和物理混合物。合适的金属清净剂的其它非限制性实例包括金属磺酸盐、酚盐、水杨酸盐、膦酸盐、硫代膦酸盐以及其组合。该金属可以是适于制造磺酸盐、酚盐、水杨酸盐或膦酸盐清净剂的任何金属。合适的金属的非限制性实例包括碱土金属、碱性金属和过渡金属。在一些实施方案中,该金属是Ca、Mg、Ba、K、Na、Li等等。
一些合适的清净剂已经描述在Mortier等人,“Chemistry and Technology ofLubricants”,第2版,London,Springer,第3章,第75-85页(1996);和Leslie R.Rudnick,“Lubricant Additives:Chemistry and Applications”,NewYork,Marcel Dekker,第4章,第113-136页(2003)中,其内容均经此引用并入本文。
通常,基于润滑油组合物的总重量,金属清净剂的量为约0.001重量%至约5重量%、约0.01重量%至约3重量%、约0.01重量%至约2重量%、约0.01重量%至约1重量%、约0.02重量%至约0.5重量%、约0.02重量至约0.4重量%,或约0.03重量%至约0.3重量%。
在一个实施方案中,金属清净剂是具有420mg KOH/gm的TBN和16重量%的钙含量的磺酸钙清洁剂。
在另一个实施方案中,润滑油组合物中的钙以不超过350wt.ppm的量存在。在其他实施方案中,润滑油组合物中的钙以25至350、30至340、34至337wt.ppm的量存在。
摩擦改进剂
可以使用多种已知的摩擦改进剂作为本发明的润滑油组合物中所含的摩擦改进剂,但是优选低分子量的C6至C30烃取代的琥珀酰亚胺、脂肪酸酰胺或多元醇。摩擦改进剂可以单独使用或组合使用。在一些方面,摩擦改进剂在润滑油组合物中的存在量为0.01至5重量%。在其他方面,摩擦改进剂在润滑油组合物中的存在量为0.01至3.0、0.01至2.0重量%、0.01至1.5、0.01至1.0、0.01至1.0。
(FM1):琥珀酰亚胺摩擦改进剂:
在本发明的一方面,本发明的摩擦改进剂是双琥珀酰亚胺。
在本发明的一方面,本发明的双琥珀酰亚胺摩擦改进剂是由式(V)表示的链烯基取代的琥珀酰亚胺或其后处理的衍生物:
其中每个R1和R1′独立地是如下式(VI)表示的在β-位具有支化结构的烯基,R2是氢原子、具有1到12个碳原子的烷基、具有6到12个碳原子的芳基、具有7到13个碳原子的芳烷基或5-8元杂环基,x是1到6的整数,以及y是0到20的整数:
其中每个R3和R4是脂肪族烃基以及R3和R4的总碳原子数在3到45的范围内,条件是R3的碳原子数比R4的碳原子数多3个或者R3的碳原子数比R4的碳原子数少1个。
在另一方面,本发明在于包含下式(VII)的烯基取代琥珀酰亚胺或其后处理衍生物的摩擦改进剂:
其中每个R1和R1′独立地是在β-位具有支化结构的烯基,其衍生自具有3到24个碳原子的单一线型α-烯烃的二聚体,以及Q是具有1到20个碳原子以及至少在其每个末端包含氨基的亚烷基-多胺的残基。
由本发明提供的摩擦改进剂对于赋予润滑油组合物改进的摩擦性能是有效的,这由提高的摩擦系数和延长的摩擦系数稳定性证明。因此,本发明的包含该摩擦改进剂的润滑油组合物能使得自动传动装置相对长时间内不抖动。
本发明的摩擦改进剂可以是本身由上述式(V)或(VII)表示的链烯基取代的琥珀酰亚胺。另外,摩擦改进剂可以是后处理的链烯基取代的琥珀酰亚胺,其通过用已知的后处理剂例如硼酸、磷酸、羧酸或碳酸亚乙酯对链烯基取代的琥珀酰亚胺进行后处理而获得。
(FM2):乙氧基化胺
在本发明的一方面,本发明的摩擦改进剂是乙氧基化胺。
R-N(C2H4OH)2 (VIII)
在通式(VIII)中,R表示氢、烷基或链烯基。也可以使用具有不同烷基或链烯基的化合物的混合物。烷基或链烯基可以是直链或支链的,并且优选为8-22个碳原子。
(FM3):多元醇:
在本发明的一方面,本发明的多元醇是由下式(IX)表示的二醇化合物。
在通式(IX)中,R表示氢、烷基或链烯基。也可以使用具有不同烷基或链烯基的化合物的混合物。烷基或链烯基可以是直链或支链的,并且优选的数目为10-30个碳原子。
磷化合物
磷化合物可以是在润滑油组合物中作为抗磨剂采用的那些。磷化合物的实例包括磷酸、磷酸酯、亚磷酸、亚磷酸酯、硫代磷酸和硫代磷酸酯。还可以使用的是磷酸酯和亚磷酸酯的胺盐。
磷酸酯的实例包括三芳基磷酸酯、三烷基磷酸酯、三烷基芳基磷烷基(phosphalkyl)磷酸酯、三芳基烷基磷酸酯和三烯基磷酸酯。具体的实例包括三苯基磷酸酯、三甲苯基磷酸酯、苄基二苯基磷酸酯、乙基二苯基磷酸酯、三丁基磷酸酯、乙基二丁基磷酸酯、甲苯基二苯基磷酸酯、二甲苯基苯基磷酸酯、乙基苯基二苯基磷酸酯、二(乙基苯基)苯基磷酸酯、丙基苯基二苯基磷酸酯、二(丙基苯基)苯基磷酸酯、三乙基苯基磷酸酯、三丙基苯基磷酸酯、丁基苯基二苯基磷酸酯、二(丁基苯基)苯基磷酸酯、三丁基苯基磷酸酯、三己基磷酸酯、三(2-乙基己基)磷酸酯、三癸基磷酸酯、三月桂基磷酸酯、三肉豆蔻基磷酸酯、三棕榈基磷酸酯、三硬脂基磷酸酯和三油烯基磷酸酯。
酸式磷酸酯的实例包括2-乙基己基酸式磷酸酯、乙基酸式磷酸酯、丁基酸式磷酸酯、油烯基酸式磷酸酯、二十四烷基酸式磷酸酯、异癸基酸式磷酸酯、月桂基酸式磷酸酯、十三烷基酸式磷酸酯、硬脂基酸式磷酸酯和异硬脂基酸式磷酸酯。
亚磷酸酯的实例包括三乙基亚磷酸酯、三丁基亚磷酸酯、三苯基亚磷酸酯、三甲苯基亚磷酸酯、三(壬基苯基)亚磷酸酯、三(2-乙基己基)亚磷酸酯、三癸基亚磷酸酯、三月桂基亚磷酸酯、三异辛基亚磷酸酯、二苯基异癸基亚磷酸酯、三硬脂基亚磷酸酯、三油烯基亚磷酸酯、二丁基氢亚磷酸酯、二月桂基氢亚磷酸酯、二油烯基氢亚磷酸酯、二硬脂基氢亚磷酸酯和二苯基氢亚磷酸酯。在这些磷酸酯中,三甲苯基磷酸酯和三苯基磷酸酯是优选的。
与磷酸酯形成胺盐的胺的实例包括单取代的胺、二取代的胺和三取代的胺。单取代的胺的实例包括丁胺、戊胺、己胺、环己胺、辛胺、月桂胺、硬脂胺、油胺和苄胺。二取代胺的实例包括二丁胺、二戊胺、二己胺、二环己胺、二辛胺、二月桂胺、二硬脂胺、二油烯基胺、二苄基胺、硬脂基单乙醇胺、癸基单乙醇胺、己基单丙醇胺、苄基单乙醇胺、苯基单乙醇胺和甲苯基单丙醇胺。三取代胺的实例包括三丁胺、三戊胺、三己胺、三环己胺、三辛胺、三月桂胺、三硬脂胺、三油烯基胺、三苄基胺、二油烯基单乙醇胺、二月桂基单丙醇胺、二辛基单乙醇胺、二己基单丙醇胺、二丁基单丙醇胺、油烯基二乙醇胺、硬脂基二丙醇胺、月桂基二乙醇胺、辛基二乙醇胺、丁基二乙醇胺、苄基二乙醇胺、苯基二乙醇胺、甲苯基二丙醇胺、二甲苯基二乙醇胺、三乙醇胺和三丙醇胺。
硫代磷酸酯的例子包括烷基三硫代磷酸酯、芳基或烷基芳基硫代磷酸酯和二烷基二硫代磷酸锌。其中,月桂基三硫代亚磷酸酯、三苯基硫代磷酸酯和二月桂基二硫代磷酸锌是尤其优选的。
这些极压试剂可单独或以两种或多种的组合使用,且通常以基于传动流体组合物总量的0.01到10质量%的量使用,优选0.05到5质量,例如,从效果和成本之间平衡的角度而言。
在一个实施方案中,磷化合物是磷酸酯胺盐化合物、芳族氢磷酸酯化合物或其组合。
一方面,磷酸酯胺盐在润滑油组合物中以0.01至0.5、0.02至0.3、0.02至0.2、0.03至0.02、0.04至0.02、0.05至0.18、0.05至0.15重量%存在。
在另一方面,磷酸酯胺盐和芳族氢磷酸酯化合物的组合在润滑油组合物中以0.01至0.5、0.02至0.3、0.02至0.2、0.03至0.2、0.04至0.2、0.05至0.2、0.05至0.20重量%存在。
在一实施方案中,润滑油组合物中的总磷为500ppm以下。在一个实施方案中,润滑油组合物中的总磷为450、425、400ppm或更少。
在一个实施方案中,润滑油组合物中的总磷为450至50、450至100、450至150、400至50、400至100、400至150ppm。
在一个实施方案中,润滑油组合物包含硫基的极压剂。在另一个实施方案中,润滑油组合物不包含硫基的极压剂。
其他添加剂
任选的,润滑油组合物可以进一步包含至少一种添加剂或者改性剂(下文称作“添加剂”),其可赋予或者改进润滑油组合物的任何令人期望的性能。本领域技术人员已知的任何添加剂可以用于本文公开的润滑油组合物中。一些合适的添加剂已经描述在Mortier等人,“Chemistryand Technology of Lubricants,”第2版,伦敦,Springer,(1996);和Leslie R.Rudnick,“Lubricant Additives:Chemistry and Applications,”纽约,MarcelDekker(2003),其二者在此引入作为参考。在一些实施方案中,添加剂可以选自抗氧化剂,抗磨剂,清净剂,防锈剂,破乳剂,摩擦改进剂,多功能添加剂,粘度指数提高剂,倾点降低剂,泡沫抑制剂,金属钝化剂,分散剂,腐蚀抑制剂,润滑性改进剂,热稳定性改进剂,抗雾浊添加剂,结冰抑制剂,染料,标记剂,静电耗散剂,生物杀灭剂及其组合。通常,在使用时,每种添加剂在润滑油组合物中的浓度可以是约0.001wt%-约15wt%,约0.01wt%-约10wt%,或者约0.1wt%-约8wt%,基于润滑油组合物的总重量。此外,添加剂在润滑油组合物中的总量可以是约0.001wt%-约20wt%,约0.01wt%-约10wt%,或者约0.1wt%-约8wt%,基于润滑油组合物的总重量。
任选的,本文公开的润滑油组合物可以进一步包含抗氧化剂,其可减少或者防止基油的氧化。本领域技术人员已知的任何抗氧化剂可以用于润滑油组合物中。合适的抗氧化剂的非限定性例子包括基于胺的抗氧化剂(例如烷基二苯基胺,苯基-α-萘基胺,烷基或者芳烷基取代的苯基-α-萘基胺,烷基化的对亚苯基二胺,四甲基-二氨基二苯基胺等),酚抗氧化剂(例如2-叔丁基酚,4-甲基-2,6-二叔丁基酚,2,4,6-三叔丁基酚,2,6-二叔丁基对甲酚,2,6-二叔丁基酚,4,4′-亚甲基双-(2,6-二叔丁基酚),4,4′-硫代双(6-二叔丁基邻甲酚)等),基于硫的抗氧化剂(例如二月桂基-3,3′-硫代二丙酸酯,硫化酚抗氧化剂等),基于磷的抗氧化剂(例如亚磷酸酯/盐等),二硫代磷酸锌,油溶性铜化合物及其组合。抗氧化剂的量可以在以下范围内变化:约0.01wt%-约10wt%,约0.05wt%-约5wt%,或者约0.1wt%-约3wt%,基于润滑油组合物的总重量。一些合适的抗氧化剂已经描述在LeslieR.Rudnick,“Lubricant Additive:Chemistry and Applications,”纽约,MarcelDekker,第1章,第1-28页(2003)中,其在此引入作为参考。
本文公开的润滑油组合物可以任选地包含倾点下降剂,其可降低润滑油组合物的倾点。本领域技术人员已知的任何倾点下降剂可以用于润滑油组合物。合适的倾点下降剂的非限定性例子包括聚甲基丙烯酸酯/盐,烷基丙烯酸酯/盐聚合物,烷基甲基丙烯酸酯/盐聚合物,二(四链烷烃酚)苯二甲酸酯/盐(di(tetra-paraffin phenol)phthalate),四链烷烃酚的缩合物(condensates of tetra-paraffin phenol),氯化的链烷烃与萘的缩合物及其组合。在一些实施方案中,倾点下降剂包含乙烯-乙酸乙烯酯共聚物,氯化链烷烃和酚的缩合物,聚烷基苯乙烯等。倾点下降剂的量可以在以下范围内变化:约0.01wt%-约10wt%,约0.05wt%-约5wt%,或者约0.1wt%-约3wt%,基于润滑油组合物的总重量。一些合适的倾点下降剂已经描述在Mortier等人,“Chemistry and Technology of Lubricants,”第2版,伦敦,Springer,第6章第187-189页(1996);和Leslie R.Rudnick,“LubricantAdditives:Chemistry and Applications,”纽约,Marcel Dekker第11章第329-354页(2003),其都在此引入作为参考。
本文公开的润滑油组合物可以任选地包含泡沫抑制剂或者消泡剂,其可破坏油中的泡沫。本领域技术人员已知的任何泡沫抑制剂或者消泡剂可以用于润滑油组合物中。合适的消泡剂的非限定性例子包括有机硅油或者聚二甲基硅氧烷,氟有机硅,烷氧化的脂肪酸,聚醚(例如聚乙二醇),支化的聚乙烯基醚,烷基丙烯酸酯/盐聚合物,烷基甲基丙烯酸酯/盐聚合物,聚烷氧基胺及其组合。在一些实施方案中,消泡剂包含甘油单硬脂酸酯/盐,聚二醇棕榈酸酯/盐,三烷基单硫代磷酸酯/盐,磺化的蓖麻油酸的酯,苯甲酰丙酮,水杨酸甲酯,甘油单油酸酯/盐或者甘油二油酸酯/盐。消泡剂的量可以在以下范围内变化:约0.0001wt%-约1wt%,约0.0005wt%-约0.5wt%,或者约0.001wt%-约0.1wt%,基于润滑油组合物的总重量。一些合适的消泡剂已经描述在Mortier等人,“Chemistry andTechnology of Lubricants,”第2版,伦敦,Springer,第6章第190-193页(1996)中,其在此引入作为参考。
本文公开的润滑油组合物可以任选地包含腐蚀抑制剂,其可降低腐蚀。本领域技术人员已知的任何腐蚀抑制剂可以用于润滑油组合物中。合适的腐蚀抑制剂的非限定性例子包括十二烷基琥珀酸的半酯或者酰胺、磷酸酯、硫代磷酸酯、烷基咪唑啉、肌氨酸、苯并三唑、噻二唑及其组合。腐蚀抑制剂的量可以在以下范围内变化:约0.001重量%-约5重量%,约0.005重量%-约1重量%,或者约0.005重量%-约0.5重量%,基于润滑油组合物的总重量。一些合适的腐蚀抑制剂已经描述在Mortier等人,“Chemistry and Technology ofLubricants,”第2版,伦敦,Springer,第6章第193-196页(1996)中,其在此引入作为参考。
本文公开的润滑油组合物可任选地包含极压(EP)剂,该极压剂可防止滑动金属表面在极压条件下卡住。本领域普通技术人员已知的任何极压剂可用于该润滑油组合物。通常,该极压剂是能够与金属化学结合以形成表面膜的化合物,所述表面膜防止在相对金属表面中的微刺在高负荷下烧接。合适的极压剂的非限制性实例包括硫化的动物或植物脂肪或油、硫化的动物或植物脂肪酸酯、磷的三价或五价酸的完全或部分酯化的酯、硫化烯烃、二烃基多硫化物、硫化的狄尔斯阿德耳加成物、硫化的二环戊二烯、硫化或共硫化的脂肪酸酯与单不饱和烯烃的混合物、脂肪酸、脂肪酸酯和α-烯烃的共硫化共混物、官能取代的二烃基多硫化物、硫杂醛、硫杂酮、环硫化合物、含硫乙缩醛衍生物、萜烯和无环烯烃的共硫化共混物、以及多硫化物烯烃产物、磷酸酯或硫代磷酸酯的胺盐以及其组合。该极压剂的量可以为该润滑油组合物的总重量的大约0.01重量%至大约5重量%、大约0.05重量%至大约3重量%、或大约0.1重量%至大约1重量%不等。一些合适的极压剂已经描述在LeslieR.Rudnick,“Lubricant Additives:Chemistry and Applications”,NewYork,MarcelDekker,第8章,第223-258页(2003)中,其经此引用并入本文。
在一实施方案中,润滑油组合物不包含硫基极压剂。
本文公开的润滑油组合物可以任选地包含防锈剂,其可抑制铁金属表面的腐蚀。本领域技术人员已知的任何防锈剂可以用于润滑油组合物中中。合适的防锈剂的非限定性例子包括油溶性单羧酸(例如2-乙基己酸,月桂酸,豆蔻酸,棕榈酸,油酸,亚油酸,亚麻酸,山嵛酸,蜂蜡酸等),油溶性聚羧酸(例如由妥尔油脂肪酸,油酸,亚油酸等所生产的那些),烯基琥珀酸,其中烯基包含10或更多个碳原子(例如四丙烯基琥珀酸,十四碳烯基琥珀酸,十六碳烯基琥珀酸等);分子量为600-3000道尔顿的长链α,ω-二羧酸及其组合。防锈剂的量可以在以下范围内变化:约0.01重量%-约10重量%,约0.05重量%-约5重量%,或者约0.1重量%-约3重量%,基于润滑油组合物的总重量。
合适的防锈剂的其他非限定性例子包括非离子聚氧乙烯表面活性剂例如聚氧乙烯月桂基醚,聚氧乙烯高级醇醚,聚氧乙烯壬基苯基醚,聚氧乙烯辛基苯基醚,聚氧乙烯辛基硬脂基醚,聚氧乙烯油基醚,聚氧乙烯山梨糖醇单硬脂酸酯/盐,聚氧乙烯山梨糖醇单油酸酯/盐,和聚乙二醇单油酸酯/盐。合适的防锈剂的另外的非限定性例子包括硬脂酸和其他脂肪酸,二羧酸,金属皂,脂肪酸胺盐,重质磺酸的金属盐,多羟基醇的偏羧酸酯,和磷酸酯。
在一些实施方案中,润滑油组合物包含至少多功能添加剂。合适的多官能添加剂的一些非限定性例子包括二硫代氨基甲酸硫化氧钼,二硫代有机磷酸硫化氧钼,单甘油酸氧钼,二乙基化酰胺氧钼,胺-钼络合物化合物,和含硫钼络合物化合物。
在某些实施方案中,润滑油组合物包含至少粘度指数改进剂。合适的粘度指数改进剂的一些非限定性例子包括聚甲基丙烯酸酯/盐型聚合物,乙烯-丙烯共聚物,苯乙烯-异戊二烯共聚物,水合苯乙烯-异戊二烯共聚物,聚异丁烯,和分散剂型粘度指数改进剂。
在一些实施方案中,润滑油组合物包含至少金属钝化剂。合适的金属钝化剂的一些非限定性例子包括双亚水杨基亚丙基二胺,三唑衍生物,噻二唑衍生物和巯基苯并咪唑。
本文公开的添加剂可以处于添加剂浓缩物的形式,其具有大于一种的添加剂。添加剂浓缩物可以包含合适的稀释剂,例如合适粘度的烃油。这样的稀释剂可以选自天然油(例如矿物油),合成油及其组合。矿物油的一些非限定性例子包括链烷烃基油,环烷烃基油,沥青基油及其组合。合成基油的一些非限定性例子包括聚烯烃油(特别是氢化的α-烯烃低聚物),烷基化的芳族烃油,聚环氧烷,芳族醚,和羧酸酯(特别是二酯油)及其组合。在一些实施方案中,稀释剂是轻质烃油,其是天然或者合成。通常,稀释剂油在40℃的粘度可以是约13厘斯-约35厘斯。
通常,期望的是稀释剂容易增溶本发明的润滑油可溶性添加剂,并且提供一种油添加剂浓缩物,其易溶于润滑剂基油料或者燃料中。另外,期望的是稀释剂不向润滑剂基油料中引入任何不期望的特性,包括例如高挥发性,高粘度和杂质例如杂原子,且因此最终不引入最终的润滑剂或者燃料中。
本发明进一步提供一种油溶性添加剂浓缩物组合物,其包含惰性稀释剂和基于浓缩物总重量为2.0-90重量%,优选10-50重量%的本发明的油溶性添加剂组合物。
以下实施例说明了本发明的示例性实施方案,但并非打算将本发明限制到所述的具体实施方案。除非有相反指示,否则全部的份数和百分比是重量单位的。全部数值是近似的。当给定数值范围时,应当理解处于所述范围之外的实施方案可以仍然落入本发明的范围内。描述在每个实施例中的具体细节不应当解释为是本发明的必需特征。
实施例
分散剂1:衍生自MW 950 PIB的未后处理的双琥珀酰亚胺,N 2.0重量%。
分散剂2:衍生自MW 950 PIB的硼化双琥珀酰亚胺。
分散剂3:衍生自MW 1300 PIB的硼化双琥珀酰亚胺。
磷酸:85重量%H3PO4,P为27重量%。
清净剂:磺酸钙,TBN 420,钙16重量%。
摩擦改进剂1(FM1):双琥珀酰亚胺摩擦改进剂。
摩擦改进剂2(FM2):乙氧基化胺。
摩擦改进剂3(FM3):多元醇。
磷化合物1(P1):磷酸酯的胺盐。
磷化合物2(P2):芳族氢亚磷酸酯
基础油:第2类基础油。
抗氧化剂:酚类和胺类抗氧化剂的混合物。
腐蚀抑制剂:噻二唑或三唑。
密封膨胀剂:酯型密封膨胀剂。
VII:分散型聚甲基丙烯酸酯(PMA)
根据发明实施例1至4和比较例1至5制备润滑油组合物,并总结在表1中。
表1
N1:来自未后处理的琥珀酰亚胺的氮
P2:来自磷酸的磷
使用JASO M349-2012测试程序评价本发明实施例1至4和比较例1至5的湿式离合器抗抖动性能。结果在下表2中。
湿式离合器抗抖动性能测试JASO M349-2012
抗抖动性能的持久性通过低速摩擦设备根据描述在JASO M-349:2012中的“Roadvehicles-Test method for anti-shudder performance of automatic transmissionfluids”测定。该试验方法的细节描述如下。
○试验条件
■摩擦材料:纤维素盘/钢板
■油用量:大约150mL
○磨合条件
■接触压力:1MPa
■油温:80℃
■滑动速度:0.6m/s
■滑动时间:30分钟
○μ-V性能试验条件
■接触压力:1MPa
■油温:40,80,120℃
■滑动速度:在0m/s到1.5m/s之间连续增大和减小
○耐久性试验条件
■接触压力:1MPa
■油温:120℃
■滑动速度:0.9m/s
■时间:30分钟
■停止时间:1分钟
■性能测定时间:μ-V特性从0小时每24小时(或6小时如有必要,例如由于离合器故障)测试
■注意:抗抖动性能通过测定在在0.9m/s下的dμ/dV达到0的时间段而评价。测定的时间段越长,抗抖动性能越好。
表2.抗抖动性能结果
实施例1-4显示出比比较例1-5优异的改善的抗抖动性能,其中本发明实施例的dμ/dv即使在48小时后仍为正。
金属-金属摩擦和磨损试验(JASO M358-2005):
发明例1至4和比较例1的摩擦系数按照金属-金属摩擦系数通过“块在环上”测试仪根据描述在JASO M358:2005的“Standard test method for metal on metal frictioncharacteristics of belt CVT fluids”来测定。该试验方法的细节如下所述。
○试验条件
■环:Falex S-10试验环(SAE 4620钢)
■块:Falex H-60试验块(SAE 01钢)
○油的量
■大约110mL(测试油位在测试环的中心)
○磨合条件
■油温:110℃
■载荷:在890N下5min.和在1112N下25min.
■滑动速度:在0.5m/s下5min.在1.0m/s下25min.
○测试条件
■油温:110℃
■载荷:1112N
■滑动速度:在1.0,0.5,0.25,0.125,0.075,0.025m/s每个下5min.
■摩擦系数:在变化滑动速度前30sec.的摩擦系数
结果在下表3中。
表3.摩擦系数和磨损测试结果
注意:小于1.0mg的磨损量是小的。
数据显示,对于每种测试油,测试环和块的磨损损失都很小,但是不含有机磷化合物的测试油(比较例4)会同时损坏环和块表面。当不存在有机磷化合物时,承载能力性能不足,这会导致表面损坏,这对于齿轮润滑剂是不可接受的。
应该理解,可以对这里公开的实施例进行各种修改。因此,上面的描述不应被解释为限制,而仅仅是作为优选实施例的示例。例如,上述用于操作本发明的最佳模式而实现的功能仅用于说明目的。在不脱离本发明的范围和精神的情况下,本领域技术人员可以实施其他布置和方法。而且,本领域技术人员将在所附权利要求的范围和精神内设想其他修改。
Claims (19)
1.一种润滑油组合物,所述润滑油组合物包含:
a)主要量的具有润滑粘度的油,
b)至少一种或多种未后处理的琥珀酰亚胺分散剂,
c)0.01-0.5重量%磷酸,
d)向所述组合物中提供不超过350ppm金属的金属清净剂,
e)至少一种或多种有机磷化合物,其中
所述未后处理的琥珀酰亚胺中的氮与磷酸中的磷之比为1-3。
2.根据权利要求1所述的润滑油组合物,其中所述组合物是自动变速器或无级变速器组合物。
3.根据权利要求2所述的润滑油组合物,其中所述自动变速器或无级变速器装备有湿纸离合器。
4.根据权利要求3所述的润滑油组合物,其中所述湿式离合器包含纤维素纤维和/或芳纶纤维。
5.根据权利要求1所述的润滑油组合物,其中所述金属清净剂向所述润滑油组合物提供25至350重量ppm的钙。
6.根据权利要求1所述的润滑油组合物,其中所述一种或多种未后处理的琥珀酰亚胺分散剂的存在量为0.3-8重量%。
7.根据权利要求1所述的润滑油组合物,其中所述一种或多种未后处理的琥珀酰亚胺分散剂是双琥珀酰亚胺。
8.根据权利要求1所述的润滑油组合物,其中所述双琥珀酰亚胺衍生自950分子量的聚异丁烯(PIB)。
9.根据权利要求1所述的润滑油组合物,其中所述琥珀酰亚胺分散剂是衍生自900至1500分子量聚异丁烯(PIB)的硼化双琥珀酰亚胺。
10.根据权利要求1所述的润滑油组合物,其中所述有机磷化合物向所述润滑油组合物提供0.01至0.5重量%的磷。
11.根据权利要求1所述的润滑油组合物,其中所述一种或多种有机磷化合物选自磷酸酯胺盐和芳族氢亚磷酸酯。
12.根据权利要求1所述的润滑油组合物,其中所述润滑油组合物中的总磷为500ppm或以下。
13.一种在配备有自动变速器或无级变速器的内燃机中改善抗抖动性能并减少摩擦的方法,所述方法包括用润滑油组合物润滑所述变速器,所述润滑油组合物包含:
a)主要量的具有润滑粘度的油,
b)至少一种或多种未后处理的琥珀酰亚胺分散剂,
c)0.01-0.5重量%磷酸,
d)向所述组合物中提供不超过350ppm金属的金属清净剂,
e)至少一种或多种有机磷化合物,其中
所述未后处理的琥珀酰亚胺中的氮与磷酸中的磷之比为1-3。
14.根据权利要求13所述的方法,其中自动变速器或无级变速器配备有湿纸离合器。
15.根据权利要求13所述的方法,其中所述一种或多种未后处理的琥珀酰亚胺分散剂的存在量为0.3-8重量%。
16.根据权利要求13所述的方法,其中所述一种或多种未后处理的琥珀酰亚胺分散剂是双琥珀酰亚胺。
17.根据权利要求13所述的方法,其中所述有机磷化合物向所述润滑油组合物提供0.01至0.5重量%的磷。
18.根据权利要求13所述的方法,其中所述一种或多种有机磷化合物选自磷酸酯胺盐和芳族氢亚磷酸酯。
19.根据权利要求13所述的方法,其中所述润滑油组合物中的总磷为500ppm或以下。
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