CN101821368A - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
- Publication number
- CN101821368A CN101821368A CN200880112470A CN200880112470A CN101821368A CN 101821368 A CN101821368 A CN 101821368A CN 200880112470 A CN200880112470 A CN 200880112470A CN 200880112470 A CN200880112470 A CN 200880112470A CN 101821368 A CN101821368 A CN 101821368A
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- CN
- China
- Prior art keywords
- lubricating oil
- acid
- carbonatoms
- amine
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 61
- -1 alkali metal borate Chemical class 0.000 claims abstract description 177
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 65
- 239000003921 oil Substances 0.000 claims description 63
- 239000003963 antioxidant agent Substances 0.000 claims description 31
- 230000003078 antioxidant effect Effects 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000003925 fat Substances 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 58
- 125000000217 alkyl group Chemical group 0.000 description 43
- 238000002156 mixing Methods 0.000 description 37
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 34
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 32
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 28
- 239000002184 metal Substances 0.000 description 27
- 229920001083 polybutene Polymers 0.000 description 26
- 239000002551 biofuel Substances 0.000 description 25
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 24
- 235000019197 fats Nutrition 0.000 description 22
- 239000002199 base oil Substances 0.000 description 20
- UIAFKZKHHVMJGS-UHFFFAOYSA-N beta-resorcylic acid Natural products OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 17
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 17
- 235000019253 formic acid Nutrition 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 150000001342 alkaline earth metals Chemical class 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000005864 Sulphur Substances 0.000 description 14
- 125000000913 palmityl 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])[H] 0.000 description 14
- 238000000746 purification Methods 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 13
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 229960002317 succinimide Drugs 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229960001860 salicylate Drugs 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 8
- 229920001748 polybutylene Polymers 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- 125000001204 arachidyl 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])[H] 0.000 description 7
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 239000010705 motor oil Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- SIFDSJCMINUPDM-UHFFFAOYSA-N 3-dodecyl-2-hydroxybenzoic acid Chemical compound CCCCCCCCCCCCC1=CC=CC(C(O)=O)=C1O SIFDSJCMINUPDM-UHFFFAOYSA-N 0.000 description 4
- RPEMQNHWDRJDHW-UHFFFAOYSA-N 3-hexadecyl-2-hydroxybenzoic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC(C(O)=O)=C1O RPEMQNHWDRJDHW-UHFFFAOYSA-N 0.000 description 4
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000005189 alkyl hydroxy group Chemical group 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000994 depressogenic effect Effects 0.000 description 4
- 239000011859 microparticle Substances 0.000 description 4
- 239000005078 molybdenum compound Substances 0.000 description 4
- 150000002752 molybdenum compounds Chemical class 0.000 description 4
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 3
- HPOHQPXRFJSLRG-UHFFFAOYSA-N 3-dodecyl-2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(O)C(CCCCCCCCCCCC)=CC2=C1 HPOHQPXRFJSLRG-UHFFFAOYSA-N 0.000 description 3
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 3
- SHYLJYPWTHGEIS-UHFFFAOYSA-N 3-hexadecyl-2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(O)C(CCCCCCCCCCCCCCCC)=CC2=C1 SHYLJYPWTHGEIS-UHFFFAOYSA-N 0.000 description 3
- ACFSYJJKCORIPD-UHFFFAOYSA-N 3-hexyl-2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(O)C(CCCCCC)=CC2=C1 ACFSYJJKCORIPD-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 150000001638 boron Chemical class 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
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- 239000004519 grease Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 2
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 2
- ZIHNKVLRTWFXPA-UHFFFAOYSA-N 2-hydroxy-3-nonylbenzoic acid Chemical compound CCCCCCCCCC1=CC=CC(C(O)=O)=C1O ZIHNKVLRTWFXPA-UHFFFAOYSA-N 0.000 description 2
- WJCRKKDULZQKDB-UHFFFAOYSA-N 3-hexyl-2-hydroxybenzoic acid Chemical compound CCCCCCC1=CC=CC(C(O)=O)=C1O WJCRKKDULZQKDB-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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- 235000020238 sunflower seed Nutrition 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
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 239000010496 thistle oil Substances 0.000 description 1
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- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-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
- MVWATEFMGRRVEL-UHFFFAOYSA-N tridecyl propanoate Chemical compound CCCCCCCCCCCCCOC(=O)CC MVWATEFMGRRVEL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002383 tung oil Substances 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
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- 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
- C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/087—Boron oxides, acids or salts
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- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2209/084—Acrylate; Methacrylate
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- C10M2215/064—Di- and triaryl amines
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- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C10M2215/28—Amides; Imides
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- C10M2223/045—Metal containing thio derivatives
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- C10M2227/09—Complexes with metals
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- C10M2229/02—Unspecified siloxanes; Silicones
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Abstract
本发明提供润滑油组合物,该润滑油组合物是在内燃机中使用的,该内燃机使用含有选自天然油脂的氢化处理物、天然油脂的酯交换物和该天然油脂的酯交换物的氢化处理物的至少1种的燃料,其特征在于:以组合物总量为基准,按碱金属换算量计,含有10-1000质量ppm碱金属硼酸盐或其水合物;即使混入上述燃料或者是低灰分,所述组合物也可以良好发挥清净性。
Description
技术领域
本发明涉及使用含有天然油脂的酯交换反应产物等的所谓生物燃料的内燃机用润滑油组合物。
背景技术
近年来,关于汽车尾气的污染,降低内燃机、特别是柴油发动机中颗粒物(PM:微粒)和NOx等的尾气成分导致的环境污染的对策成为重要课题。
目前,该对策是在汽车中安装微粒过滤器(DPF)或尾气净化催化剂(氧化或还原催化剂)等尾气净化装置。
但是,对安装了上述尾气净化装置的汽车使用以往的内燃机用润滑油时必须要解决以下问题。首先,煤烟附着在微粒过滤器上。该附着的煤烟虽然可通过氧化、燃烧除去,但是为了燃烧煤烟通常要进行燃料的后喷射。因此燃料对发动机油的稀释增大,发动机油的性能降低。
而且,因燃烧而生成的金属氧化物或硫酸盐、碳酸盐等会堵塞过滤器。因此,虽然优选润滑油中的金属成分尽量低,但该金属成分主要来自金属清净剂或抗氧化剂,因此很难既保持清净性、氧化稳定性又降低其掺混量。
为了解决上述问题,人们提出了很多方案,例如公开了一种带柴油机微粒除去装置的柴油发动机用润滑油组合物,它是可实现减少DPF中的灰分堵塞、同时可提高DPF捕集的PM的燃烧性、提高其除去效率、且实现DPF长寿命化的带DPF的柴油发动机用润滑油组合物,其特征在于:硫酸灰分为1.0%重量以下,硫分含量为0.3%重量以下,以及钼含量为100ppm以上(例如参照专利文献1)。
另一方面,对于汽车中使用的燃料,从削减造成地球暖化主要因素的二氧化碳的角度考虑,所谓的生物燃料受到关注。
该生物燃料是天然油脂的酯交换反应产物等含有来自天然油脂的化合物的燃料,作为天然油脂源的植物可通过光合作用吸收大气中的二氧化碳进行生长发育,因此有规定:由生物燃料生成的二氧化碳不被计算在地球暖化气体的增加中,属于碳中和。因此,生物燃料的利用有望进一步增加。
上述生物燃料用于安装了上述微粒过滤器的汽车中时,由于燃料对发动机油的稀释增大而导致发动机油性能降低,并且产生由于生物燃料劣化分解而生成的极性化合物,因此导致发动机油的氧化稳定性降低,并且对发动机部件的清净性有很大影响。为了避免过滤器堵塞而降低润滑油中金属成分时,这是更难以解决的问题。
专利文献1:日本特开2002-60776号公报
发明内容
发明所要解决的课题
本发明的目的在于提供润滑油组合物,该润滑油组合物用于使用生物燃料的内燃机,即使有生物燃料混入、或即使是低灰分也可以良好地发挥清净性。
解决课题的手段
本发明人发现:即使是在混入了生物燃料的润滑油中,掺混了特定化合物的润滑油组合物也具有抑制清净性等性能降低的效果,可实现本发明的目的。本发明基于所述认识完成。
即,本发明提供以下内容:
[1]润滑油组合物,其特征在于:该润滑油组合物是在内燃机中使用的,所述内燃机使用含有选自天然油脂的氢化处理物、天然油脂的酯交换物、以及天然油脂的酯交换物的氢化处理物中的至少一种的燃料,以组合物总量为基准,按碱金属换算量计,含有10-1000质量ppm碱金属硼酸盐或其水合物。
[2]上述[1]所述的润滑油组合物,该组合物含有(A)上述碱金属硼酸盐或其水合物,同时还含有选自以下(B)-(E)中的至少一种化合物:
(B)选自下述通式(I)和下述通式(II)所示的取代羟基芳族羧酸酯衍生物中的至少一种化合物:
[式中,R1和R2分别表示碳原子数6以上的有机基团,它们彼此相同或不同,a、b、c、d和e分别表示满足1≤a≤3,1≤b≤3,0≤c≤3,1≤d≤3,1≤e≤3,3≤(a+b+e)≤6,以及1≤(c+d)≤5的关系的整数,R1和R2为多个时,多个R1和R2彼此相同或不同。];
[式中,R3、R4和R5分别表示碳原子数6以上的有机基团,它们彼此相同或不同,f、g、h、i、j、k和m分别表示满足0≤f≤3,0≤g≤3,1≤(f+g)≤3,0≤h≤4,0≤i≤3,1≤(h+i)≤6,0≤j≤3,1≤k≤3,1≤m≤3,0≤(f+h)≤4,1≤(g+i+m)≤4,以及1≤(j+k)≤5的关系的整数,R3、R4和R5为多个时,多个R3、R4和R5彼此相同或不同。];
(C)酚系抗氧化剂,
(D)胺系抗氧化剂,
(E)钼系抗氧化剂。
[3]上述[1]或[2]所述的润滑油组合物,其中,硫酸灰分为1.2质量%以下。
发明效果
本发明的润滑油组合物是用于使用生物燃料的内燃机的润滑油组合物,可提供即使混入生物燃料、或者即使是低灰分也可以良好地发挥清净性的润滑油组合物。
实施发明的最佳方式
本发明是在内燃机中使用的润滑油组合物,该内燃机使用含有选自天然油脂、天然油脂的氢化处理物、天然油脂的酯交换物、以及天然油脂的酯交换物的氢化处理物中至少一种的燃料。
这里,作为天然油脂,可以使用在自然界中广泛存在的各种动植物油脂,优选使用以脂肪酸与甘油的酯作为主要成分的植物油,例如红花油、大豆油、菜籽油、棕榈油、棕榈仁油、棉籽油、椰子油、米糠油、芝麻油、蓖麻籽油、亚麻仁油、橄榄油、桐油、椿油、花生油、木棉油、可可油、木蜡油、葵花籽油、玉米油等。
天然油脂的氢化处理物是将上述油脂在适当的氢化催化剂的存在下进行所谓的氢化所得的。
这里,作为氢化催化剂,可列举:镍系催化剂、铂族(Pt、Pd、Rh、Ru)系催化剂、钴系催化剂、氧化铬系催化剂、铜系催化剂、锇系催化剂、铱系催化剂、钼系催化剂等。氢化催化剂优选将2种以上上述催化剂组合使用。
天然油脂的酯交换物是在适当的酯合成催化剂的存在下对构成天然油脂的三甘油进行酯交换反应所得到的酯。例如,将低级醇与油脂在上述酯合成催化剂的存在下进行酯交换反应,由此可以制备作为生物燃料的脂肪酸酯。低级醇是作为酯化剂使用的醇,可列举甲醇、乙醇、丙醇、丁醇、戊醇等碳原子数5以下的醇,从反应性和成本角度考虑优选甲醇。上述低级醇通常相对于油脂以当量以上的量使用。
天然油脂的酯交换物的氢化处理物是将上述酯交换物在适当的氢化催化剂的存在下进行氢化所得。
天然油脂、天然油脂的氢化处理物、天然油脂的酯交换物和天然油脂的酯交换物的氢化处理物添加到轻油等由烃构成的燃料中,适合作为混合燃料使用。
对于本发明的润滑油组合物中的基础油没有特别限定,可以从以往作为内燃机用润滑油的基础油所使用的矿物油或合成油中选择任意的基础油使用。
作为矿物油,例如可列举如下制备的矿物油等:将原油常压蒸馏,将得到的常压渣油进行减压蒸馏,将得到的润滑油馏分进行脱溶剂、溶剂萃取、氢解、溶剂脱蜡、催化脱蜡、加氢精制等一种以上的处理得到的精制的矿物油;或者将蜡或GTLWAX异构化制备的矿物油。
作为合成油,例如可列举:聚丁烯、聚烯烃[α-烯烃均聚物或共聚物(例如乙烯/α-烯烃共聚物)等]、各种酯(例如多元醇型酯、二元酸酯、磷酸酯等)、各种醚(例如聚苯醚等)、多元醇、烷基苯、烷基萘等。这些合成油中特别优选聚烯烃、多元醇型酯。
本发明中,基础油可以使用1种上述矿物油,也可以将2种以上组合使用。另外,可以使用1种上述合成油,也可以将2种以上组合使用。还可以将1种以上矿物油与1种以上合成油组合使用。
对于基础油的粘度没有特别限定,根据润滑油组合物的用途而不同,通常是100℃的运动粘度为2-30mm2/s,优选3-15mm2/s,更优选4-10mm2/s。如果100℃的运动粘度为2mm2/s以上,则蒸发损失少,如果为30mm2/s以下,则粘性阻力导致的动力的损失不会过大,可得到燃料消耗改善的效果。
作为基础油,优选使用环分析%CA为3.0以下、硫分含量为50质量ppm以下的基础油。这里,环分析%CA表示根据环分析n-d-M法计算的芳族成分的比例(百分率)。硫分是按照JIS K 2541测定的值。
%CA为3.0以下、硫分为50质量ppm以下的基础油具有良好的氧化稳定性,可以抑制酸值的升高或油泥的生成,同时可提供对金属的腐蚀性少的润滑油组合物。
更优选%CA为1.0以下,进一步优选0.5以下,更优选的硫分为30质量ppm。
而且,基础油的粘度指数优选70以上,更优选100以上,进一步优选120以上。该粘度指数为70以上的基础油由温度变化所导致的粘度变化小。
本发明的润滑油组合物需要含有碱金属硼酸盐或其水合物。
本发明所述的碱金属硼酸盐或其水合物通常以容易应用的微粒分散体形式利用。作为碱金属硼酸盐或其水合物的实例,可列举:按照美国专利3929650和4089790所述的方法合成的化合物等。例如可列举:在碱金属氢氧化物的存在下、优选进一步在琥珀酰亚胺等无灰性分散剂的共存下,将碱金属或碱土类金属中性磺酸盐进行碳酸化,得到过碱性(過塩基性perbasic)磺酸盐,使硼酸与其反应得到的碱金属硼酸盐的微粒分散体。这里,碱金属优选钾、钠等。
具体实例可列举:中性磺酸钙和分散在琥珀酰亚胺系中的组成式:KB3O5·H2O所示的碱金属硼酸盐的水合物的粒径约0.3μm以下的微粒分散体。
本发明中,以组合物总量为基准,按碱金属换算量计,必须含有10-1000质量ppm上述碱金属硼酸盐或其水合物。低于10质量ppm,则生物燃料混入时的清净性不足,而即使超过1000质量ppm掺混也未见与其相应的生物燃料混入时清净性效果的放大,并且可能使分散性降低。由于这些理由,该碱金属硼酸盐或其水合物的掺混量优选50-500质量ppm。
本发明的润滑油组合物优选含有上述碱金属硼酸盐或其水合物(“(A)成分”),同时掺混选自以下的(B)取代羟基芳族羧酸酯衍生物、(C)酚系抗氧化剂、(D)胺系抗氧化剂、以及(E)钼系抗氧化剂中的至少一种化合物。
该(B)成分是选自上述通式(I)和(II)所示的取代羟基芳族羧酸酯衍生物中的至少一种的化合物。
上述通式(I)、(II)中,R1、R2、R3、R4和R5分别表示碳原子数6以上的有机基团。该碳原子数6以上的有机基团优选碳原子数6-100、更优选碳原子数8-20的烃基。该烃基例如有烷基、链烯基、环烷基、环烯基、芳烷基等,它们可在非烃取代基以及链或环中具有杂原子。具体来说,可列举己基、辛基、壬基、癸基、十二烷基、十六烷基、三十烷基等的烃基,以及由聚乙烯、聚丙烯、聚丁烯等烯烃聚合物衍生的基团等。在希望为低粘度的取代羟基芳族羧酸酯衍生物时,该R1、R2、R3、R4和R5优选实质上为直链状的烃基。该R1和R2彼此相同或不同,R3、R4和R5彼此相同或不同。
上述通式(I)中,a、b、c、d和e分别表示1≤a≤3,1≤b≤3,0≤c≤3,1≤d≤3,1≤e≤3,3≤(a+b+e)≤6,以及1≤(c+d)≤5的关系的整数。d为2或3时,多个R1可以相同或不同,d为2或3时,多个R2可以相同或不同。
并且在上述通式(II)中,f、g、h、i、j、k和m表示分别满足0≤f≤3,0≤g≤3,1≤(f+g)≤3,0≤h≤4,0≤i≤3,1≤(h+i)≤6,0≤j≤3,1≤k≤3,1≤m≤3,0≤(f+h)≤4,1≤(g+i+m)≤4,以及1≤(j+k)≤5的关系的整数。h为2、3或4时,多个R3可以相同或不同,i为2或3时,多个R4可以相同或不同。k为2或3时,多个R5可以相同或不同。
作为上述通式(I)所示的取代羟基芳族羧酸酯衍生物的具体实例,可列举:(己基羟基苯甲酸)己基苯基酯、(己基羟基苯甲酸)十二烷基苯基酯、(辛基羟基苯甲酸)辛基苯基酯、(壬基羟基苯甲酸)壬基苯基酯、(壬基羟基苯甲酸)十六烷基苯基酯、(十二烷基羟基苯甲酸)壬基苯基酯、(十二烷基羟基苯甲酸)十二烷基苯基酯、(十二烷基羟基苯甲酸)十六烷基苯基酯、(十六烷基羟基苯甲酸)己基苯基酯、(十六烷基羟基苯甲酸)十二烷基苯基酯、(十六烷基羟基苯甲酸)十六烷基苯基酯、(二十烷基羟基苯甲酸)二十烷基苯基酯、(碳原子数11-15的混合烷基羟基苯甲酸)碳原子数11-15的混合烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯甲酸)十二烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]苯基酯、(己基羟基苯甲酸)己基羟基苯基酯、(辛基羟基苯甲酸)辛基羟基苯基酯、(十二烷基羟基苯甲酸)壬基羟基苯基酯、(十二烷基羟基苯甲酸)十二烷基羟基苯基酯、(十六烷基羟基苯甲酸)十二烷基羟基苯基酯、(十六烷基羟基苯甲酸)十六烷基羟基苯基酯、(二十烷基羟基苯甲酸)二十烷基羟基苯基酯、(碳原子数11-15的混合烷基羟基苯甲酸)碳原子数11-15的混合烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯甲酸)十二烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯基酯、(己基二羟基苯甲酸)己基苯基酯、(壬基二羟基苯甲酸)壬基苯基酯、(壬基二羟基苯甲酸)十二烷基苯基酯、(十二烷基二羟基苯甲酸)壬基苯基酯、(十二烷基二羟基苯甲酸)十二烷基苯基酯、(十六烷基二羟基苯甲酸)十六烷基苯基酯、(二十烷基二羟基苯甲酸)十六烷基苯基酯、(二十烷基二羟基苯甲酸)二十烷基苯基酯、(碳原子数11-15的混合烷基二羟基苯甲酸)碳原子数11-15的混合烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基苯甲酸)十二烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基苯甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]苯基酯、(己基二羟基苯甲酸)己基羟基苯基酯、(壬基二羟基苯甲酸)壬基羟基苯基酯、(壬基二羟基苯甲酸)十二烷基羟基苯基酯、(十二烷基二羟基苯甲酸)壬基羟基苯基酯、(十二烷基二羟基苯甲酸)十二烷基羟基苯基酯、(十六烷基二羟基苯甲酸)十六烷基羟基苯基酯、(二十烷基二羟基苯甲酸)十六烷基羟基苯基酯、(二十烷基二羟基苯甲酸)二十烷基羟基苯基酯、(碳原子数11-15的混合烷基二羟基苯甲酸)碳原子数11-15的混合烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基苯甲酸)十二烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基苯甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯基酯等。
而上述通式(II)所示的取代羟基芳族羧酸酯衍生物的具体实例可列举:(己基羟基萘甲酸)己基苯基酯、(己基羟基萘甲酸)十六烷基苯基酯、(壬基羟基萘甲酸)壬基苯基酯、(十二烷基羟基萘甲酸)十二烷基苯基酯、(十六烷基羟基萘甲酸)十六烷基苯基酯、(十二烷基羟基萘甲酸)二十烷基苯基酯、(二十烷基羟基萘甲酸)二十烷基苯基酯、(碳原子数11-15的混合烷基羟基萘甲酸)碳原子数11-15的混合烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基萘甲酸)十二烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基萘甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]苯基酯、(己基羟基萘甲酸)十二烷基羟基苯基酯、(辛基羟基萘甲酸)十二烷基羟基苯基酯、(十二烷基羟基萘甲酸)十二烷基羟基苯基酯、(十二烷基羟基萘甲酸)十六烷基羟基苯基酯、(十六烷基羟基萘甲酸)十六烷基羟基苯基酯、(十六烷基羟基萘甲酸)二十烷基羟基苯基酯、(碳原子数11-15的混合烷基羟基萘甲酸)碳原子数11-15的混合烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基萘甲酸)十二烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基萘甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯基酯、(己基二羟基萘甲酸)己基苯基酯、(己基二羟基萘甲酸)十六烷基苯基酯、(壬基二羟基萘甲酸)壬基苯基酯、(十二烷基二羟基萘甲酸)十二烷基苯基酯、(十二烷基二羟基萘甲酸)二十烷基苯基酯、(十六烷基二羟基萘甲酸)十六烷基苯基酯、(二十烷基二羟基萘甲酸)二十烷基苯基酯、(碳原子数11-15的混合烷基二羟基萘甲酸)碳原子数11-15的混合烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基萘甲酸)十二烷基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基萘甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]苯基酯、(己基二羟基萘甲酸)十二烷基羟基苯基酯、(辛基二羟基萘甲酸)十二烷基羟基苯基酯、(十二烷基二羟基萘甲酸)十二烷基羟基苯基酯、(十二烷基二羟基萘甲酸)十六烷基羟基苯基酯、(十六烷基二羟基萘甲酸)十六烷基羟基苯基酯、(十六烷基二羟基萘甲酸)二十烷基羟基苯基酯、(碳原子数11-15的混合烷基二羟基萘甲酸)碳原子数11-15的混合烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基萘甲酸)十二烷基羟基苯基酯、(长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]二羟基萘甲酸)长链烷基[例如由碳原子数30以上的聚癸烯衍生的基团、由数均分子量400以上的聚丁烯衍生的基团]羟基苯基酯等。
这些取代羟基芳族羧酸酯衍生物中,优选下述通式(III)或下述通式(III’)所示的化合物:
(式中,R1、R2、b、d和e与上述相同,d和e的合计为2-5);
(式中,R3、R4、R5、h、k和m与上述相同,n表示0、1或2,h和n的合计为1-6,m和n的合计为1-3)。
上述取代羟基芳族羧酸酯衍生物中,可以含有1种通式(I)所示的化合物,也可以含有2种以上。还可以含有1种上述通式(II)所示的化合物,也可以含有2种以上。并且还可以含有1种以上该通式(I)所示的化合物的和1种以上该通式(II)所示的化合物。该(B)成分的优选掺混量是以组合物总量为基准,优选0.5-30%重量,更优选1-10%重量。(B)成分的掺混量在上述范围,则即使在混入生物燃料时,也具有提高组合物的清净性、提高氧化稳定性的效果。
(C)成分的酚系抗氧化剂的优选的实例可列举:2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,4,6-三叔丁基苯酚、2,6-二叔丁基-4-羟基甲基苯酚、2,6-二叔丁基苯酚、2,4-二甲基-6-叔丁基苯酚、2,6-二叔丁基-4-(N,N-二甲基氨基甲基)苯酚、2,6-二叔戊基-4-甲基苯酚、4,4’-亚甲基双(2,6-二叔丁基苯酚)、4,4’-双(2,6-二叔丁基苯酚)、4,4’-双(2-甲基-6-叔丁基苯酚)、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、4,4’-亚丁基双(3-甲基-6-叔丁基苯酚)、4,4’-亚异丙基双(2,6-二叔丁基苯酚)、2,2’-亚甲基双(4-甲基-6-壬基苯酚)、2,2’-亚异丁基双(4,6-二甲基苯酚)、2,2’-亚甲基双(4-甲基-6-环己基苯酚)、2,4-二甲基-6-叔丁基苯酚、4,4’-硫代双(2-甲基-6-叔丁基苯酚)、4,4’-硫代双(3-甲基-6-叔丁基苯酚)、2,2’-硫代双(4-甲基-6-叔丁基苯酚)、双(3-甲基-4-羟基-5-叔丁基苄基)硫醚、双(3,5-二叔丁基-4-羟基苄基)硫醚、2,2’-硫代-二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、3-(3,5-二叔丁基-4-羟基苯基)丙酸十三烷基酯、四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、3-(3,5-二叔丁基-4-羟基苯基)丙酸辛基酯、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、3-(3-甲基-5-叔丁基-4-羟基苯基)丙酸辛基酯等。
(C)成分可以使用1种上述酚系抗氧化剂,也可以将2种以上组合使用。从效果和经济性的平衡等角度考虑,该(C)成分的掺混量基于润滑油组合物的总量优选在0.05-3.0质量%,更优选0.2-2.0质量%的范围内选择。
(D)成分的胺系抗氧化剂可以从以往作为润滑油的抗氧化剂使用的公知的胺系抗氧化剂中适当选择任意抗氧化剂使用。作为该胺系抗氧化剂,例如:二苯基胺系抗氧化剂,具体可列举:二苯基胺或一辛基二苯基胺、一壬基二苯基胺、4,4’-二丁基二苯基胺、4,4’-二己基二苯基胺、4,4’-二辛基二苯基胺、4,4’-二壬基二苯基胺、四丁基二苯基胺、四己基二苯基胺、四辛基二苯基胺、四壬基二苯基胺等具有碳原子数3-20的烷基的烷基化二苯基胺等,;以及萘基胺系抗氧化剂,具体可列举:α-萘基胺、苯基-α-萘基胺、以及丁基苯基-α-萘基胺、己基苯基-α-萘基胺、辛基苯基-α-萘基胺、壬基苯基-α-萘基胺等碳原子数3-20的烷基取代的苯基-α-萘基胺等。其中,从效果角度考虑,二苯基胺系比萘基胺系优选,特别优选具有碳原子数3-20的烷基的烷基化二苯基胺,尤其优选4,4’-二(C3-C20烷基)二苯基胺。
作为(D)成分,可以使用1种上述胺系抗氧化剂,也可以将2种以上组合使用。从效果和经济性的平衡等角度考虑,基于润滑油组合物总量,该(D)成分的掺混量优选在0.05-3.0质量%、更优选在0.2-2.0质量%的范围内选择。
作为(E)成分的钼系抗氧化剂,可列举优选的钼·胺络合物,该钼·胺络合物可以使用使6价钼化合物、具体来说可使用三氧化钼和/或钼酸与胺化合物反应得到的化合物,例如按照日本特开2003-252887号公报所述的制备方法得到的化合物。
作为与6价钼化合物反应的胺化合物没有特别限定,具体可列举一元胺、二元胺、多元胺和烷醇胺。更具体地可例示:甲基胺、乙基胺、丙基胺、丁基胺、戊基胺、己基胺、庚基胺、辛基胺、壬基胺、癸基胺、十一烷基胺、十二烷基胺、十三烷基胺、十四烷基胺、十五烷基胺、十六烷基胺、十七烷基胺、十八烷基胺、二甲基胺、二乙基胺、二丙基胺、二丁基胺、二戊基胺、二己基胺、二庚基胺、二辛基胺、二壬基胺、二癸基胺、二(十一烷基)胺、二(十二烷基)胺、二(十三烷基)胺、二(十四烷基)胺、二(十五烷基)胺、二(十六烷基)胺、二(十七烷基)胺、二(十八烷基)胺、甲基乙基胺、甲基丙基胺、甲基丁基胺、乙基丙基胺、乙基丁基胺和丙基丁基胺等具有碳原子数1-30的烷基(这些烷基可以是直链状也可以是支链状)的烷基胺,乙烯胺、丙烯胺、丁烯胺、辛烯胺以及油烯基胺等具有碳原子数2-30的链烯基(这些链烯基可以是直链状也可以是支链状)的链烯基胺,甲醇胺、乙醇胺、丙醇胺、丁醇胺、戊醇胺、己醇胺、庚醇胺、辛醇胺、壬醇胺、甲醇乙醇胺、甲醇丙醇胺、甲醇丁醇胺、乙醇丙醇胺、乙醇丁醇胺以及丙醇丁醇胺等具有碳原子数1-30的烷醇基(这些烷醇基可以是直链状也可以是支链状)的烷醇胺,甲二胺、乙二胺、丙二胺以及丁二胺等具有碳原子数1-30的亚烷基的亚烷基二胺,二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺等多元胺,十一烷基二乙基胺、十一烷基二乙醇胺、十二烷基二丙醇胺、油烯基二乙醇胺、油烯基丙二胺、硬脂基四亚乙基五胺等的在上述一元胺、二元胺、多元胺上具有碳原子数8-20的烷基或链烯基的化合物或咪唑啉等的杂环化合物,这些化合物的环氧烷烃加成产物,以及它们的混合物等。这些胺化合物中,优选伯胺、仲胺和烷醇胺。
这些胺化合物所具有的烃基的碳原子数优选4以上,更优选4-30,特别优选8-18。若胺化合物的烃基的碳原子数低于4,则有溶解性变差的倾向。通过使胺化合物的碳原子数为30以下,可以使钼-胺络合物中的钼含量相对提高,以少量的掺混即可以提高其效果。这些胺化合物可以单独使用1种,也可以将2种以上组合使用。
上述六价钼化合物与胺化合物的反应比如下:相对于1摩尔胺化合物,钼化合物的Mo原子的摩尔比优选0.7-5,更优选0.8-4,进一步优选1-2.5。关于反应方法没有特别限定,可以采用以往公知的方法,例如日本特开2003-252887号公报所述的方法。
本发明中,钼系抗氧化剂除上述钼-胺络合物之外,还可以使用日本特公平3-22438号公报、日本特开2004-2866号公报等中记载的琥珀酰亚胺的含硫钼络合物。
作为(E)成分,可以单独使用1种上述钼系抗氧化剂,也可以将2种以上组合使用。从效果和经济性的平衡等角度考虑,基于润滑油组合物总量,该(E)成分的掺混量优选在0.05-3.0质量%、更优选在0.1-2.0质量%,更优选在0.2-2.0质量%的范围内选择。
本发明的润滑油组合物中,优选与(A)成分一起含有选自上述(B)-(E)成分中的任意一种的化合物。由此可以进一步提高生物燃料混入时的清净性或氧化稳定性。
上文中,本发明的优选方案可列举如下。
(1)基础油+(A)
(2)基础油+(A)+(B)
(3)基础油+(A)+(C)和/或(D)
(4)基础油+(A)+(B)和/或(D)
(5)基础油+(A)+(B)+(C)和/或(D)+(E)
特别是从更为提高生物燃料混入时的清净性或氧化稳定性的角度考虑,优选(2)、(4)和(5)的形式,即,含有(B)成分的方案。
在不损害本发明的目的的范围内,本发明的润滑油组合物中可以根据需要适当掺混其它添加剂,例如:粘度指数增进剂、降凝剂、清净分散剂、其它抗氧化剂、耐磨损剂或极压剂、摩擦减少剂、分散剂、防锈剂、表面活性剂或抗乳化剂、消泡剂等。
作为粘度指数增进剂,例如可列举:聚甲基丙烯酸酯、分散型聚甲基丙烯酸酯、烯烃系共聚物(例如乙烯-丙烯共聚物等)、分散型烯烃系共聚物、苯乙烯系共聚物(例如苯乙烯-二烯共聚物、苯乙烯-异戊二烯共聚物等)等。
从掺混效果角度考虑,以润滑油组合物总量为基准,粘度指数增进剂的掺混量通常优选0.5-15质量%左右,更优选1-10质量%。
作为降凝剂,例如可列举重均分子量5000-50,000左右的聚甲基丙烯酸酯等。
从掺混效果的角度考虑,以润滑油总量为基准,降凝剂的掺混量通常优选0.1-2质量%左右,更优选0.1-1质量%。
作为清净分散剂,可以使用无灰分散剂、金属系清净剂。
作为无灰分散剂,可以使用润滑油中使用的任意的无灰分散剂,例如有:通式(IV)所示的一元琥珀酰亚胺化合物、或通式(V)所示的二元琥珀酰亚胺化合物。
通式(IV)、(V)中,R6、R8和R9分别为数均分子量500-4,000的链烯基或烷基,R8和R9可以相同或不同,R6、R8和R9的数均分子量优选1,000-4,000。
R7、R10和R11分别为碳原子数2-5的亚烷基,R10和R11可以相同或不同,r表示1-10的整数,s表示0或1-10的整数。
上述R6、R8和R9的数均分子量低于500,则对基础油的溶解性降低,而超过4,000则清净性降低,恐怕无法获得目标性能。
而且,上述r优选为2-5,更优选3-4。r低于1则清净性变差,r为11以上则对基础油的溶解性变差。
通式(V)中,s优选为1-4,更优选2-3。
如果在上述范围内,则在清净性以及对基础油的溶解性方面优选。
作为链烯基,可以列举含有聚丁烯基、聚异丁烯基、乙烯-丙烯共聚物的基团,作为烷基,可以是它们氢化形成的基团。
作为优选的链烯基的代表性实例,可列举:聚丁烯基或聚异丁烯基。
聚丁烯基可以将1-丁烯与异丁烯的混合物或高纯度的异丁烯聚合而获得。
优选的烷基的代表性实例是将聚丁烯基或聚异丁烯基氢化得到的基团。
上述链烯或烷基琥珀酰亚胺化合物通常通过将聚烯烃与马来酸酐反应得到的链烯基琥珀酸酐、或将其氢化得到的烷基琥珀酸酐与多元胺反应来制备。
上述一元琥珀酰亚胺化合物和二元琥珀酰亚胺化合物可通过改变链烯基琥珀酸酐或烷基琥珀酸酐与多元胺的反应比例来制备。
作为上述形成聚烯烃的烯烃单体,可以将碳原子数2-8的α-烯烃的1种或2种以上混合使用,优选使用异丁烯与丁烯-1的混合物。
作为多元胺,可列举:乙二胺、丙二胺、丁二胺、戊二胺等的单一二胺,二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺、二(甲基亚乙基)三胺、二亚丁基三胺、三亚丁基四胺、五亚戊基己胺等的亚烷基多元胺,氨基乙基哌嗪衍生物。
除上述链烯基或烷基琥珀酰亚胺化合物之外,还可以使用硼衍生物、和/或将它们用有机酸改性所得的化合物。
链烯基或烷基琥珀酰亚胺化合物的硼衍生物可以使用按照常规方法制备的物质。
例如,使上述聚烯烃与马来酸酐反应,制成链烯基琥珀酸酐,然后进一步与中间体反应,该中间体是上述多元胺与氧化硼、卤化硼、硼酸、硼酸酐、硼酸酯、硼酸的铵盐等硼化合物反应得到的,由此进行酰亚胺化获得。
该硼衍生物中的硼含量没有特别限定,硼通常为0.05-5质量%,优选0.1-3质量%。
以润滑油组合物为基准,通式(IV)所示的一元琥珀酰亚胺化合物或通式(V)所示的二元琥珀酰亚胺化合物的掺混量通常优选0.5-15质量%,更优选1-10质量%。
掺混量低于0.5质量%,则难以发挥其效果,而超过15质量%也得不到与其掺混量相应的效果。
琥珀酰亚胺化合物只要含有上述规定量即可,可以单独或将2种以上混合使用。
作为金属系清净剂,可以使用润滑油中使用的任意的碱土类金属系清净剂,例如可列举:碱土类金属磺酸盐、碱土类金属酚盐、碱土类金属水杨酸盐和选自其中2种以上的混合物等。
作为碱土类磺酸盐,可列举:将分子量300-1,500、优选400-700的烷基芳族化合物进行磺化得到的烷基芳族磺酸的碱土类金属盐,特别是镁盐和/或钙盐,其中优选使用钙盐。
作为碱土类金属酚盐,可列举:烷基苯酚、烷基苯酚硫化物、烷基苯酚的曼尼希反应物的碱土类金属盐、特别是镁盐和/或钙盐等,其中特别优选使用钙盐。
作为碱土类金属水杨酸盐,可列举:烷基水杨酸的碱土类金属盐、特别是镁盐或和/或钙盐等,其中优选使用钙盐。
作为构成上述碱土类金属系清净剂的烷基,优选碳原子数4-30、更优选碳原子数6-18的直链或支链烷基,它们可以是直链也可以是支链。
它们还可以是伯烷基、仲烷基或叔烷基。
作为碱土类金属的磺酸盐、碱土类金属的酚盐和碱土类金属的水杨酸盐,不仅是将上述烷基芳族磺酸、烷基苯酚、烷基苯酚硫化物、烷基苯酚的曼尼希反应物、烷基水杨酸等直接地或者与镁和/或钙的碱土类金属的氧化物或氢氧化物等碱土类金属碱反应,或者先制成钠盐或钾盐等的碱金属盐,然后通过与碱土类金属盐置换等而获得的中性碱土类金属磺酸盐、中性碱土类金属酚盐和中性碱土类金属水杨酸盐;还包含将中性碱土类金属磺酸盐、中性碱土类金属酚盐和中性碱土类金属水杨酸盐与过量的碱土类金属盐或碱土类金属碱在水的存在下加热得到的碱性碱土类金属磺酸盐、碱性碱土类金属酚盐和碱性碱土类金属水杨酸盐,或者是在二氧化碳存在下使中性碱土类金属磺酸盐、中性碱土类金属酚盐和中性碱土类金属水杨酸盐与碱土类金属的碳酸盐或硼酸盐反应得到的过碱性碱土类金属磺酸盐、过碱性碱土类金属酚盐和过碱性碱土类金属水杨酸盐。
本发明中,作为金属系清净剂,可以使用上述中性盐、碱性盐、过碱性盐以及它们的混合物等,特别是在清净性、耐磨损性方面优选过碱性水杨酸盐、过碱性酚盐、过碱性磺酸盐的一种以上与中性磺酸盐的混合。
本发明中,金属系清净剂的总碱值通常为10-500mgKOH/g,优选15-450mgKOH/g,优选使用选自其中的1种或将2种以上结合使用。
需说明的是,这里所谓的总碱值是按照JIS K 2501“石油产品和润滑油-中和值试验方法”之7.测定的、通过电位差滴定法(碱值·高氯酸法)得到的总碱值。
本发明的金属系清净剂的金属比没有特别限定,通常可以使用20以下的1种或将2种以上混合使用,优选以金属比为3以下、更优选1.5以下、特别优选1.2以下的金属系清净剂作为必须成分,这使得氧化稳定性或碱值保持性以及高温清净性等更为优异,因此优选。
需说明的是,这里所谓的金属比用金属系清净剂中金属元素的价数×金属元素含量(%mol)/皂基(せつけん基soap group)含有量(%mol)表示,金属元素是指钙、镁等,皂基是指磺酸基、酚基和水杨酸基等。
金属系清净剂通常是以用轻质润滑油基础油等稀释的状态等销售,可以购买获得,通常优选使用其金属含量为1.0-20质量%、优选2.0-16质量%的金属系清净剂。
以润滑油组合物总量为基准,金属系清净剂的掺混量通常优选0.01-20质量%,更优选0.1-10质量%。
掺混量低于0.01质量%则难以发挥其效果,而即使超过20质量%也得不到与该添加相应的效果。
金属系清净剂只要含有上述规定量即可,可以单独或将2种以上组合使用。
作为其它抗氧化剂,可列举硫系抗氧化剂等。
作为硫系抗氧化剂,例如可列举:酚噻嗪、四(3-月桂基硫代丙酸)季戊四醇酯、双十二烷基硫醚、双十八烷基硫醚、硫代二丙酸双十二烷基酯、硫代二丙酸双十八烷基酯、硫代二丙酸二肉豆蔻基酯、硫代二丙酸十二烷基十八烷基酯、2-巯基苯并咪唑等。
以润滑油组合物总量为基准,硫系抗氧化剂的掺混量通常优选0.1-5质量%,更优选0.1-3质量%。
作为耐磨损剂、极压剂,可列举:二硫代磷酸锌、磷酸锌、二硫代氨基甲酸锌、二硫化物类、硫化烯烃类、硫化油脂类、硫化酯类、硫代碳酸酯类、硫代氨基甲酸酯类、多硫化物类(ポリグルフアイド類polysulfide)等含硫化合物;亚硫酸酯类、磷酸酯类、膦酸酯类、以及它们的胺盐或金属盐等含磷化合物;硫代亚磷酸酯类、硫代磷酸酯类、硫代膦酸酯类、以及它们的胺盐或金属盐等含硫和磷的耐磨损剂。
作为摩擦减少剂,可以使用作为润滑油用的摩擦减少剂而通常使用的任意化合物,例如可列举:分子中至少具有一个碳原子数6-30的烷基或链烯基的脂肪酸酯、脂肪酸酰胺、脂肪酸、脂族醇、脂族胺、脂族醚等无灰摩擦减少剂。
以润滑油组合物总量为基准,摩擦减少剂的掺混量通常优选0.01-2质量%,更优选0.01-1质量%。
作为金属钝化剂,可列举:苯并三唑系、甲苯并三唑系、噻二唑系以及咪唑系化合物等。
以润滑油组合物总量为基准,金属钝化剂的掺混量通常优选0.01-3质量%,更优选0.01-1质量%。
作为防锈剂,可列举石油磺酸酯、烷基苯磺酸酯、二壬基萘磺酸酯、链烯基琥珀酸酯、多元醇型酯等。
从掺混效果的角度考虑,以润滑油组合物总量为基准,这些防锈剂的掺混量通常优选0.01-1质量%左右,更优选0.05-0.5质量%。
作为表面活性剂或抗乳化剂,可列举:聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚和聚氧乙烯烷基萘基醚等聚亚烷基二醇系非离子性表面活性剂等。
以润滑油组合物总量为基准,表面活性剂或抗乳化剂的掺混量通常优选0.01-3质量%,更优选0.01-1质量%。
作为消泡剂,可列举:硅油、氟硅油和氟烷基醚等,从消泡效果和经济性平衡角度考虑,以润滑油组合物总量为基准,优选0.0005-0.5质量%,更优选0.001-0.2质量%。
本发明的润滑油组合物中,硫酸灰分优选1.2质量%以下,更优选1.1质量%以下。若硫酸灰分为1.2质量%以下则可以抑制净化尾气的催化剂的性能降低。应用于带DPF的柴油发动机时,灰分对DPF的附着量少,可以使DPF的寿命延长。
本发明的润滑油组合物中,以组合物总量为基准,硫含量优选0.5质量%以下,更优选0.3质量%以下,进一步优选0.2质量%以下。若硫含量为0.5质量%以下则可以有效抑制净化尾气的催化剂的性能降低。
本发明的润滑油组合物中,以组合物总量为基准,磷含量优选为0.12质量%以下,更优选0.1质量%以下。若磷含量为0.12质量%以下则可以有效的抑制净化尾气的催化剂的性能降低。
本发明的润滑油组合物以规定量含有上述(A)成分,因此,即使应用于使生物燃料燃烧的方式的内燃机,其活塞等发动机部件的清净性也优异。特别是除(A)成分之外以规定量添加(B)成分,则高温时的清净性或氧化稳定性更为优异。
实施例
下面通过实施例和比较例进一步详细说明本发明,但本发明并不受这些实施例的限定。需说明的是,内燃机用润滑油组合物的现状和性能按照以下方法求出。
(1)运动黏度
按照JIS K2283测定。
(2)钙、钾、硼和磷的含量
按照JIS-5S-38-92测定。
(3)氮的含量
按照JIS K2609测定。
(4)钼、锌的含量
按照JIS-5S-38-92测定。
(5)硫含量
按照JIS K2541测定。
(6)硫酸灰分
按照JIS K2272测定。
(7)NOACK试验
按照ASTM D 5800测定。在250℃、1小时的条件下测定。
(8)热管试验
作为试验用的润滑油组合物,设定内燃机中的燃料与润滑油的混合比例,使用相对于上述各润滑油组合物(新油)掺混5质量%生物燃料(将菜籽油通过甲醇进行酯交换得到的燃料)所得到的混合油。试验温度设定为290℃,其它条件按照JPI-5S-55-99测定。试验后的评分是按照JPI-5S-55-99,以0分(黑色)-10分(无色)的11个等级对附着于测试管的漆膜(ラツカ一lacquer)进行评价,数字越大则堆积物少,显示清净性良好。需说明的是,作为参考,只使用新油进行同样的试验。另外,热管试验中,粘度指数增进剂的量有时对试验有影响,因此在各实施例、比较例中使粘度指数增进剂的掺混量一定。
(9)氧化稳定度试验
与上述(7)同样,使用对于润滑油组合物(新油)掺混5质量%生物燃料(将菜籽油通过甲醇进行酯交换得到的燃料)所得的混合油,按照JIS K2514-1996实施内燃机用润滑油氧化稳定度试验。在下述试验条件下氧化,测定试验前(新油)和试验后100℃下的运动粘度,求出粘度增加率%。黏度增加率越小则表示氧化稳定性优异。
(试验条件)
试验温度165.5℃,转数1300rpm,试验时间168小时,催化剂:铜板和铁板
实施例1-5、比较例1-3
按照表1所示的比例掺混表1所示的基础油和添加剂,制备润滑油组合物,该组合物的性状·组成和性能如表1所示。
[表1]
1)基础油:加氢精制基础油(40℃运动粘度=21mm2/s,100℃运动粘度=4.5mm2/s,粘度指数=127,%CA=0,硫分≤低于20质量ppm,NOACK试验蒸发量=13.3质量%)
2)碱金属硼酸盐水合物:微粒分散体(硼含量=6.8质量%,钾含量=4.0质量%)
3)芳族羧酸脂:十二烷基水杨酸十二烷基苯基酯
4)酚系抗氧化剂:3-(3,5-叔丁基-4-羟基苯基)丙酸十八烷基脂
5)胺系抗氧化剂:二烷基二苯胺(氮含量=4.62质量%)
6)钼系抗氧化剂:商品名“サクラル一ブ 710”(アデカ制备),钼含量=10质量%,氮含量=1.3质量%)
7)粘度指数增进剂:聚甲基丙烯酸酯(重均分子量=420000,树脂量39质量%)
8)降凝剂:聚甲基丙烯酸烷基酯(重均分子量=6000)
9)金属系清净剂:过碱性水杨酸钙(碱值(高氯酸法)=225mgKOH/g,Ca含量=7.8质量%,硫含量=0.3质量%)
10)聚丁烯基琥珀酰亚胺-1:一元酰亚胺(聚丁烯基的平均分子量=1000,氮含量=1.76质量%)
11)聚丁烯基琥珀酰亚胺-2:二元酰亚胺(聚丁烯基的平均分子量=2000,氮含量=0.99质量%)
12)二烷基二硫代磷酸锌:锌含量=9.0质量%,磷含量=8.2质量%,硫含量=17.1质量%,烷基=仲丁基和仲己基的混合物
13)抗铜腐蚀剂:1-[N,N-双(2-乙基己基)氨基甲基苯并三唑]
14)硅系消泡剂、防锈剂和表面活性剂等
根据表1可知,本发明的润滑油组合物在热管试验中,新油润滑油组合物的清净性优异,即使添加生物燃料其性能降低也小。与此相对,不含有本发明的(A)成分的比较例1-3即使是新油润滑油组合物,其清净性也降低,添加生物燃料后其性能显著降低。
产业实用性
本发明的润滑油组合物即使混入生物燃料、即使是低灰分,也可以良好地发挥清净性。因此,可有效地用作使用生物燃料的内燃机的润滑油组合物。
Claims (3)
1.润滑油组合物,其特征在于:该润滑油组合物是在内燃机中使用的,所述内燃机使用含有选自天然油脂的氢化处理物、天然油脂的酯交换物、以及天然油脂的酯交换物的氢化处理物中的至少一种的燃料,以组合物总量为基准,按碱金属换算量计,含有10-1000质量ppm碱金属硼酸盐或其水合物。
2.权利要求1所述的润滑油组合物,该组合物含有(A)上述碱金属硼酸盐或其水合物,同时还含有选自以下(B)-(E)中的至少一种化合物:
(B)选自下述通式(I)和下述通式(II)所示的取代羟基芳族羧酸酯衍生物中的至少一种化合物:
式中,R1和R2分别表示碳原子数6以上的有机基团,它们彼此相同或不同,a、b、c、d和e分别表示满足1≤a≤3,1≤b≤3,0≤c≤3,1≤d≤3,1≤e≤3,3≤(a+b+e)≤6,以及1≤(c+d)≤5的关系的整数,R1和R2为多个时,多个R1和R2彼此相同或不同;
式中,R3、R4和R5分别表示碳原子数6以上的有机基团,它们彼此相同或不同,f、g、h、i、j、k和m分别表示满足0≤f≤3,0≤g≤3,1≤(f+g)≤3,0≤h≤4,0≤i≤3,1≤(h+i)≤6,0≤j≤3,1≤k≤3,1≤m≤3,0≤(f+h)≤4,1≤(g+i+m)≤4,以及1≤(j+k)≤5的关系的整数,R3、R4和R5为多个时,多个R3、R4和R5彼此相同或不同;
(C)酚系抗氧化剂,
(D)胺系抗氧化剂,
(E)钼系抗氧化剂。
3.权利要求1或2所述的润滑油组合物,其中,硫酸灰分为1.2质量%以下。
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CN103597062A (zh) * | 2011-06-15 | 2014-02-19 | 卢布里佐尔公司 | 含有羧酸的盐的润滑组合物 |
CN103608440A (zh) * | 2011-06-15 | 2014-02-26 | 卢布里佐尔公司 | 含有芳族羧酸的酯的润滑组合物 |
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CN103597062A (zh) * | 2011-06-15 | 2014-02-19 | 卢布里佐尔公司 | 含有羧酸的盐的润滑组合物 |
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CN113597464B (zh) * | 2019-02-28 | 2022-10-14 | 雅富顿化学公司 | 用于柴油颗粒过滤器性能的润滑组合物 |
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EP2204438A1 (en) | 2010-07-07 |
WO2009050984A1 (ja) | 2009-04-23 |
US20130130954A1 (en) | 2013-05-23 |
KR20100061839A (ko) | 2010-06-09 |
US20100249000A1 (en) | 2010-09-30 |
JP5431947B2 (ja) | 2014-03-05 |
JPWO2009050984A1 (ja) | 2011-03-03 |
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CN105018181A (zh) | 2015-11-04 |
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