CN103555391A - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
- Publication number
- CN103555391A CN103555391A CN201310473220.1A CN201310473220A CN103555391A CN 103555391 A CN103555391 A CN 103555391A CN 201310473220 A CN201310473220 A CN 201310473220A CN 103555391 A CN103555391 A CN 103555391A
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- Prior art keywords
- lubricating oil
- oil composition
- quality
- acid
- ester
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 65
- 239000003921 oil Substances 0.000 claims abstract description 61
- 150000002148 esters Chemical class 0.000 claims abstract description 35
- 239000000446 fuel Substances 0.000 claims abstract description 18
- -1 polyol ester Chemical class 0.000 claims description 111
- 229910052784 alkaline earth metal Chemical class 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000003925 fat Substances 0.000 claims description 24
- 229920005862 polyol Polymers 0.000 claims description 24
- 229920001748 polybutylene Polymers 0.000 claims description 23
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 229960002317 succinimide Drugs 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 150000001638 boron Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002480 mineral oil Substances 0.000 claims description 9
- 235000010446 mineral oil Nutrition 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 4
- 239000002199 base oil Substances 0.000 abstract description 18
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 230000001050 lubricating effect Effects 0.000 abstract description 3
- 235000014593 oils and fats Nutrition 0.000 abstract 4
- 150000007519 polyprotic acids Polymers 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 52
- 239000002253 acid Substances 0.000 description 29
- 239000002994 raw material Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 22
- 235000019197 fats Nutrition 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002551 biofuel Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000002632 lipids Chemical class 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 229960001860 salicylate Drugs 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 159000000007 calcium salts Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004519 grease Substances 0.000 description 6
- 239000010705 motor oil Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000013530 defoamer Substances 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical class CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003342 alkenyl 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
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 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
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
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- 239000000779 smoke Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
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- 235000013311 vegetables Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SZOLUXDHHKCYKT-ONEGZZNKSA-N (e)-but-1-en-1-amine Chemical compound CC\C=C\N SZOLUXDHHKCYKT-ONEGZZNKSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Polymers C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-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
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 1
- IJPXXOVHDMEUSR-UHFFFAOYSA-N 2-[2-hydroxyethyl(undecyl)amino]ethanol Chemical compound CCCCCCCCCCCN(CCO)CCO IJPXXOVHDMEUSR-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
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical class CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- GCVQVCAAUXFNGJ-UHFFFAOYSA-N 2-hexadecylbutanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)CC(O)=O GCVQVCAAUXFNGJ-UHFFFAOYSA-N 0.000 description 1
- MVDKKZZVTWHVMC-UHFFFAOYSA-N 2-hexadecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O MVDKKZZVTWHVMC-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/36—Esters of polycarboxylic acids
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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Abstract
在内燃机中使用的润滑油组合物,所述内燃机使用包含选自天然油脂、天然油脂的氢化处理物、天然油脂的酯交换物和天然油脂的酯交换物的氢化处理物中的至少一种的燃料,作为润滑油基油,以润滑油组合物总量为基准,配合5~30质量%的100℃运动粘度为3~8mm2/s的多元醇酯和/或100℃运动粘度为3~8mm2/s的多元酸酯而成。
Description
本申请是申请日为2008年10月17日、申请号为“200880112577.4”、发明名称为“润滑油组合物”的申请的分案申请。
技术领域
本发明涉及在使用来自天然油脂的燃料的内燃机中使用的润滑油组合物。
背景技术
现在,全球范围内对环境的规制变得越来越严格,特别是围绕汽车的状况的燃料效能限制、排气限制等变得越来越严格。其背景在于,地球温暖化等的环境问题和来自对于石油资源枯竭的担心的资源保护。
另一方面,地球上存在的植物吸收大气中的二氧化碳、水和太阳光进行光合作用,生成碳水化物和氧。因此,由以植物为原料的植物油制造的所谓的生物燃料在作为地球温暖化的主要原因的二氧化碳的削减、并且由汽车排出的大气污染物质的降低效果等方面广受关注。另外,还有观点认为:由植物生物质的燃烧生成的二氧化碳为不计入地球温暖化气体的增加的碳中和,今后,预料在烃类燃料中的生物燃料的混合比例会增加(参照例如非专利文献1)。
非专利文献1:山根浩二著“バイオディーゼル天ぷら鍋から燃料タンクヘ”东京图书出版会,2006年5月发行
发明内容
对于内燃机、特别是柴油发动机,用于减轻由煤烟等的颗粒物质(PM)、NOx等的排气成分导致的环境污染的对策成为重要的课题。作为其对策,在汽车上安装柴油颗粒过滤器(DPF)、排气净化催化剂(氧化或还原催化剂)等的排气净化装置是有效的。例如,在柴油发动机生成的煤烟附着于DPF之后,通过氧化、燃烧除去。
其中,在柴油发动机上安装DPF时,为了使过滤器中蓄积的煤烟燃烧,一般进行燃料的补充喷射。预想由于该补充喷射发动机油的燃料稀释增大,发动机油性能降低。特别是,生物燃料由于其物性而易蓄积在发动机油中,并且生物燃料在劣化分解时生成极性化合物,因此对发动机部件(活塞等)的清洁性的不良影响大。例如,发生由燃烧生成的金属氧化物、硫酸盐、碳酸盐等导致过滤器易阻塞的问题。另外,使用的发动机油的一部分燃烧并作为排气排出。因此,优选使润滑油中的金属份、硫份尽量低。而且,减少润滑油中的磷份和硫份从排气净化催化剂的劣化对策考虑也是优选的。
但是,迄今为止,未提供十分适合于生物燃料的润滑油。另外,如果单纯地减少润滑油中的金属份、磷份或硫份等的含量反而存在损害润滑性的可能。
因此,本发明的主要目的在于,提供即使将生物燃料、混合了生物燃料的燃料用于柴油发动机等内燃机,润滑性和发动机部件清洁性也优异的润滑油组合物。
为了解决上述课题,本发明提供下述的润滑油组合物。
(1)润滑油组合物,其是在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和天然油脂的酯交换物的氢化处理物中的至少一种的燃料的内燃机中使用的润滑油组合物,其特征在于,作为润滑油基油,以润滑油组合物总量为基准,配合5~30质量%的100℃运动粘度为3~8mm2/s的多元醇酯和/或100℃运动粘度为3~8mm2/s的多元酸酯。
(2)润滑油组合物,其是上述本发明的润滑油组合物,其特征在于,配合具有数均分子量为500~3500的聚丁烯基、硼(B)和氮(N)的质量比(B/N)为0.5以上的聚丁烯基琥珀酰亚胺化合物的硼衍生物和碱土金属类清净剂。
(3)润滑油组合物,其是上述本发明的润滑油组合物,其特征在于,硫酸灰分为1.1质量%以下。
(4)润滑油组合物,其是上述本发明的润滑油组合物,其特征在于,以组合物总量为基准,配合0.3质量%以上的酚类抗氧化剂和/或胺类抗氧化剂。
(5)润滑油组合物,其是上述本发明的润滑油组合物,其特征在于,以组合物总量为基准,配合换算为硼量为0.01质量%以上的上述聚丁烯基琥珀酰亚胺化合物的硼衍生物。
(6)润滑油组合物,其是上述本发明的润滑油组合物,其特征在于,以组合物总量为基准,硫含量为0.5质量%以下。
根据本发明的润滑油组合物,在使用由天然油脂等形成的所谓生物燃料的内燃机中,即使在发动机油中混入生物燃料,对活塞等发动机部件也表现出优异的清洁性。特别是,在发动机为高温时的高温清洁性优异。另外,在本发明的润滑油组合物中,由于能够减少残存于DPF的灰分,因此即使用于带有DPF的柴油发动机时,DPF的性能也不会降低。
应予说明,本发明的天然油脂,不限于源于植物的油脂,还包括源于动物的油脂。
具体实施方式
以下,详细说明本发明的实施方式。
本发明为在下述内燃机中使用的润滑油组合物,所述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和天然油脂的酯交换物的氢化处理物中的至少一种的燃料。
其中,作为天然油脂,可以使用在自然界广泛存在的各种动植物油脂,但优选使用以脂肪酸和甘油的酯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、蓖麻油、亚麻子油、橄榄油、桐油、山茶油、花生油、木棉籽油、可可油、木蜡、向日葵油、玉米油等。
天然油脂的氢化处理物是指,对上述油脂在适当的氢化催化剂存在下进行所谓的加氢而成的物质。
其中,作为氢化催化剂,可列举镍类催化剂、铂族(Pt、Pd、Rh、Ru)类催化剂、钴类催化剂、氧化铬类催化剂、铜类催化剂、锇类催化剂、铱类催化剂、钼类催化剂等。另外,作为氢化催化剂优选将两种以上上述催化剂组合进行使用。
天然油脂的酯交换物是指,在适当的酯合成催化剂存在下,对构成天然油脂的甘油三酯进行酯交换反应而得到的酯。例如,使低级醇和油脂在上述酯交换催化剂存在下进行酯交换反应,由此制造作为生物燃料的脂肪酸酯。低级醇用作酯化剂,可以列举甲醇、乙醇、丙醇、丁醇、戊醇等的碳原子数为5以下的醇,但从反应性和成本的角度考虑优选甲醇。这样的低级醇一般对于油脂以当量以上的量使用。
另外,天然油脂的酯交换物的氢化处理物是指,将上述的酯交换物在适当的氢化催化剂存在下进行加氢而成的物质。
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可以通过添加在由轻油等的烃构成的燃料中,作为混合燃料进行使用。
作为用于本发明的润滑油脂组合物中的润滑油基油,至少使用多元醇酯和/或多元酸酯。
作为多元醇酯,可以列举脂肪族多元醇与直链状或分支状的脂肪酸的酯。作为形成该多元醇酯的脂肪族多元醇,有新戊二醇、三羟甲基丙烷、二(三羟甲基)丙烷、三羟甲基乙烷、二(三羟甲基)乙烷、季戊四醇、二聚季戊四醇和三聚季戊四醇等。另外,作为脂肪酸,可以使用碳原子数为8~12的脂肪酸,作为特别优选的脂肪酸,列举壬酸、癸酸、十一烷酸、十二烷酸和十三烷酸。另外,还可以使用上述脂肪族多元醇与直链状或分支状的脂肪酸的偏酯。这些偏酯通过适当调节脂肪族多元醇与脂肪酸的反应摩尔数来进行反应而得到。
本发明的多元醇酯的100℃运动粘度为3~8mm2/s,优选为4~7mm2/s,更优选为5~6mm2/s。如果100℃运动粘度为3mm2/s以上,则蒸发损失减少,另外,如果运动粘度为8mm2/s以下,则粘性阻力导致的动力损失得到抑制,得到燃料效能改善效果。
作为本发明的多元酸酯,作为羧酸成分优选碳原子数为6~10的直链状或分支状的脂肪族二元酸,具体地可以列举己二酸、庚二酸、辛二酸、壬二酸、癸二酸和具有与它们相同的性状的酸。另外,作为醇成分,优选碳原子数为6~15的脂肪族醇,具体地可以列举己醇、庚醇、辛醇、壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇和十五烷醇和它们的异构体。
本发明的多元酸酯的100℃运动粘度为3~8mm2/s,优选为4~7mm2/s,更优选为5~6mm2/s。如果100℃运动粘度为3mm2/s以上,则蒸发损失减少,另外,如果运动粘度为8mm2/s以下,则粘性阻力导致的动力损失得到抑制,得到燃料效能改善效果。
上述多元醇酯、多元酸酯可以各自单独作为基油使用,或者也可以混合使用。例如,可以作为复合酯(complex ester)使用。复合酯是指,以多元酸和多元醇为原料合成的酯,通常,在原料中还含有一元酸。在本发明中,可以优选使用由脂肪族多元醇,和碳原子数为8~12的直链状或分支状的脂肪族单羧酸、直链状或分支状的脂肪族二元酸、或芳香族二元酸、三元酸、四元酸形成的复合酯。
作为用于复合酯的形成的脂肪族多元醇,可以使用三羟甲基丙烷、三羟甲基乙烷、季戊四醇和二聚季戊四醇等。另外,作为脂肪族单羧酸,可以列举碳原子数为8~12的脂肪族单羧酸,例如,可以列举十七烷酸、硬脂酸、十九烷酸、花生酸、二十二烷酸和二十四烷酸。作为脂肪族二元酸,可以列举琥珀酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、羧基十八烷酸、羧甲基十八烷酸、二十二烷二酸等。另外,作为芳香族二元酸,可以列举邻苯二甲酸、间苯二酸等,作为芳香族三元酸,可以列举偏苯三酸等,作为芳香族四元酸,可以列举1,2,4,5-苯四酸等。
即使使用复合酯作为用于本发明的润滑油组合物的润滑基油,优选的粘度范围也与上述多元醇酯、多元酸酯相同。
作为用于制备上述各种酯的酯化反应,例如,使醇(多元醇等)和羧酸(脂肪族多元酸或芳香族多元酸等)以规定比例反应即可。或者,也可以进行偏酯化,接着使该偏酯化物与羧酸反应,或者可以使酸的反应顺序颠倒,或者还可以将酸混合供给酯化反应。
上述多元醇酯和/或多元酸酯的含量以润滑油组合物总量为基准为5~30质量%,优选为10~25质量%,更优选为10~20质量%。在多元醇酯和/或多元酸酯的含量不足5质量%的情况下,达到高温的发动机内的清洁性不足,另一方面,如果超过30质量%,则对橡胶的影响变大,不优选。
另外,作为基油,可以在上述多元醇酯、多元酸酯中混合选自用作内燃机用润滑油的基油的矿物油、合成油中的任意的油。
作为矿物油,例如可以列举如下制备的矿物油:将常压蒸馏原油而得到的常压残留油进行减压蒸馏得到润滑油馏分,将该润滑油馏分进行溶剂脱沥青、溶剂萃取、氢化分解、溶剂脱蜡、催化脱蜡、氢化精炼等一种以上的处理而精炼的矿物油,或者通过将蜡、GTL(气液(gas-to-liquid))蜡异构化而制备的矿物油等。
另一方法,作为合成油,例如可以列举聚丁烯、聚烯烃(α-烯烃均聚物、共聚物等)、各种醚(例如,聚苯醚等)、聚乙二醇、烷基苯、烷基萘等。这些合成油中,从粘度特性和蒸发性角度考虑特别优选聚烯烃。
在本发明中,作为将多元醇酯、多元酸酯混合而使用的基油,可以使用1种上述矿物油,还可以将2种以上组合使用。另外,可以使用1种上述合成油,还可以将2种以上组合使用。而且,还可以将1种以上的矿物油和1种以上的合成油组合使用。即使将这些基油混合使用时,作为基油整体优选100℃运动粘度为3~8mm2/s的范围。如果100℃运动粘度为3mm2/s以上,则蒸发损失减少,另外,如果为8mm2/s以下,则粘性阻力导致的动力损失得到抑制,得到燃料效能改善效果。
作为将多元醇酯、多元酸酯混合使用的矿物油,优选使用利用环分析得到的%CA为3以下、硫份含量为50质量ppm以下的矿物油。其中,利用环分析得到的%CA是指,利用环分析n-d-M法算出的芳香族份的比例(百分率)。另外,硫份为根据JIS(Japanese IndustrialStandard,以下相同)K2541测定的值。
%CA为3以下、硫份为50质量ppm以下的基油可以提供表现出良好的氧化稳定性,能够抑制酸值的升高或淤渣的生成,同时对金属的腐蚀性少的润滑油组合物。更优选的是硫份为30质量ppm以下。另外,更优选的是%CA为1以下,进一步优选为0.5以下。
另外,多元醇酯、多元酸酯和将它们混合使用的基油的粘度指数优选为70以上,更优选为100以上,进一步优选为120以上。该粘度指数为70以上的基油由温度变化引起的粘度变化小。
优选在本发明的润滑油组合物中含有具有数均分子量为500~3500的聚丁烯基、硼(B)和氮(N)的质量比(B/N)为0.5以上的聚丁烯基琥珀酰亚胺化合物的硼衍生物和碱土金属类清净剂
这样的聚丁烯基琥珀酰亚胺化合物的硼衍生物例如如下得到:例如使(a)被数均分子量为500~3500的聚丁烯基取代的琥珀酸或其酸酐、(b)多亚烷基多胺、以及(c)硼化合物反应。
作为原料(a),使用被聚丁烯基取代的琥珀酸或其酸酐。该聚丁烯基的数均分子量(以下,有时略称为分子量或Mn)为500~3500,优选为1000~3000。如果该聚丁烯基的分子量不足500,则存在最终得到的琥珀酰亚胺化合物的硼衍生物在润滑油基油中不能充分溶解的情况,另外,如果分子量超过3500,则存在琥珀酰亚胺化合物变成高粘度,其处理变得困难的情况。
作为原料(a)的被聚丁烯基取代的琥珀酸或其酸酐,使符合该聚丁烯基的分子量的聚丁烯与马来酸酐以公知的方法反应即可。
作为原料(b),使用多亚烷基多胺,但优选使用全部的5摩尔%以上在末端具有环结构的多亚烷基多胺。原料(b)全部可以为在末端具有环结构的多亚烷基多胺,另外,还可以为在末端具有环结构的多亚烷基多胺与在末端不具有环结构的多亚烷基多胺的混合物。如果在末端具有环结构的多亚烷基多胺的比例为5摩尔%以上,则作为本发明目的的发动机部件的清洁性更加优异。如果多亚烷基多胺的比例为10摩尔%以上,进一步为20摩尔%以上,则清洁性进一步提高,特别是在高温下的清洁性优异。
作为原料(c),使用硼化合物。作为该硼化合物,例如可以列举硼酸、硼酸酐、硼酸酯、氧化硼、卤化硼等。其中,特别优选硼酸。
本发明中的聚丁烯基琥珀酰亚胺化合物的硼酸衍生物可以使上述原料(a)和原料(b)以及原料(c)反应而得到。该反应方法没有特别限定,可以使用公知的方法进行。例如,用以下方法使其反应,得到目的物。首先,使原料(a)和原料(b)反应,接着,使该反应生成物与原料(c)反应。对于原料(a)和原料(b)的反应中原料(a)和原料(b)的配合比例,优选为(a):(b)为0.1~10:1(摩尔比),更优选为0.5~2:1(摩尔比)。另外,对于原料(a)和原料(b)的反应温度,优选为约80~250℃,更优选为约100~200℃。在进行反应时,在原料的处理上、另外为了调整反应的需要可以使用溶剂,例如烃油等有机溶剂。
接着,使如上得到的原料(a)和(b)的反应生成物与原料(c)反应。作为该原料(c)的硼化合物的配合比例,相对于多亚烷基多胺,通常以摩尔比计优选1:0.5~10,更优选1:0.5~5。另外,对于反应温度,通常优选为约50~250℃,更优选为100~200℃。另外,在进行反应时,与原料(a)和原料(b)的反应相同地,在处理上以及为了调整反应的需要也可以使用溶剂,例如烃油等的有机溶剂。
通过上述反应,作为生成物得到被数均分子量为200~3500的聚丁烯基取代的琥珀酰亚胺化合物的硼衍生物。在本发明中,可以单独使用这样的1种硼衍生物,还可以将2种以上组合使用。
本发明的润滑油组合物的聚丁烯基琥珀酰亚胺化合物的硼衍生物的配合量,优选以组合物总量为基准,换算为硼(原子)为0.01质量%以上。更优选为0.01~0.2质量%,进一步优选为0.01~0.15质量%,最优选为0.01~0.1质量%。
另外,通过该硼衍生物中所含的硼以一定量以上存在,即使在润滑油组合物中混入生物燃料,在高温的内燃机中也可以得到高活塞清洁性。该硼衍生物的配合量不足0.01质量%的情况下,无法得到充分的高温清洁性。另外,即使硼含量超过0.2质量%,对高温清洁性也不表现进一步的提高,缺乏实用性。
并且,该硼衍生物中的硼(B)和氮(N)的质量比(B/N)优选为0.5以上,更优选为0.6以上,进一步优选为0.8以上。如果B/N为0.5以上,则在高温下的发动机部件的清洁性大幅提高。
应予说明,硼化琥珀酰亚胺类化合物如上所述,可以将原料(a)和原料(b)反应,接着将其反应生成物与原料(c)反应得到,但即使改变反应顺序,首先使原料(a)和(c)反应,之后,使其反应生成物与(b)反应,也能同样地得到目的的硼化琥珀酰亚胺类化合物。
优选在本发明的润滑油组合物中,与上述的聚丁烯基琥珀酰亚胺化合物的硼酸衍生物一起配合碱土金属类清净剂。
作为碱土金属类清净剂,例如优选碱土金属磺酸盐、碱土金属酚盐、碱土金属水杨酸盐和选自它们中的2种以上的混合物。
作为碱土金属硫酸盐,可以列举通过将分子量为300~1,500、优选400~700的烷基芳香族化合物磺化得到的烷基芳香族磺酸的碱土金属盐,特别是镁盐和/或钙盐等,其中优选使用钙盐。
作为碱土金属酚盐,可以列举烷基苯酚、烷基苯酚硫醚、烷基苯酚的曼尼希反应物的碱土金属盐,特别是镁盐和/或钙盐等,其中特别优选使用钙盐。
作为碱土金属水杨酸盐,可以列举烷基水杨酸的碱土金属盐,特别是镁盐和/或钙盐等,其中优选使用钙盐。作为构成上述碱土金属类清净剂的烷基,优选碳原子数为4~30的烷基,更优选6~18的直链或分支烷基,它们为直链或分支都可以。另外,它们还以是伯烷基、仲烷基或叔烷基。
另外,作为碱土金属磺酸盐、碱土金属酚盐和碱土金属水杨酸盐,不仅有使上述烷基芳香族磺酸、烷基苯酚、烷基苯酚硫醚、烷基苯酚的曼尼希反应物、烷基水杨酸等直接与镁和/或钙的碱土金属的氧化物、氢氧化物等的碱土金属碱反应,或通过首先形成钠盐、钾盐等的碱金属盐,然后与碱土金属盐进行置换等而得到的中性碱土金属磺酸盐、中性碱土金属酚盐和中性碱土金属水杨酸盐,还包含通过将中性碱土金属磺酸盐、中性碱土金属酚盐和中性碱土金属水杨酸盐与过量的碱土金属盐、碱土金属碱在水存在下加热而得到的碱性碱土金属磺酸盐、碱性碱土金属酚盐和碱性碱土金属水杨酸盐,或在二氧化碳存在下,通过将中性碱土金属磺酸盐、中性碱土金属酚盐和中性碱土金属水杨酸盐与碱土金属的碳酸盐或硼酸盐反应而得到的高碱性碱土金属磺酸盐、高碱性碱土金属酚盐和高碱性碱土金属水杨酸盐。
在本发明中,碱土金属类清净剂的优选的配合量换成为碱土金属的量,为0.35质量%以下,更优选为0.01~0.35质量%,进一步优选为0.1~0.35质量%。如果碱土金属类清净剂的配合量为0.01质量%以上,则形成氧化稳定性、碱值维持性和高温清洁性更加优异的润滑油组合物。另一方面,如果碱土金属类清净剂的配合量超过0.35质量%,则存在引起净化排气的催化剂的性能降低的可能。另外,在适用于带有DPF的柴油发动机时,存在DPF上的灰分附着量增多,DPF的寿命变短的可能。
在本发明的润滑油组合物中,作为抗氧化剂,优选配合酚类抗氧化剂和/或胺类抗氧化剂。
作为酚类抗氧化剂,例如可以列举3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、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’-异亚丙基双(2,6-二叔丁基苯酚)、2,2’-亚甲基双(4-甲基-6-壬基苯酚)、2,2’-异亚丁基双(4,6-二甲基苯酚)、2,2’-亚甲基双(4-甲基-6-环己基苯酚)、2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,4-二甲基-6-叔丁基苯酚、2,6-二叔戊基-p-甲酚、2,6-二叔丁基-4(N,N’-二甲基氨基甲基苯酚)、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、3-(4-羟基-3,5-二叔丁基苯基)丙酸正辛酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸十八烷基酯、2,2'-硫代[二乙基-双-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]等。其中,特别优选双酚类和含有酯基的酚类抗氧化剂。
另外,作为胺类抗氧化剂,例如可以列举单辛基二苯胺、单壬基二苯胺等的单烷基二苯胺类;4,4’-二丁基二苯胺、4,4’-二戊基二苯胺、4,4’-二己基二苯胺、4,4’-二庚基二苯胺、4,4’-二辛基二苯胺、4,4’-二壬基二苯胺等的二烷基二苯胺类;四丁基二苯胺、四己基二苯胺、四辛基二苯胺、四壬基二苯胺等的多烷基二苯胺类和萘胺类抗氧化剂,具体地可列举α-萘胺、苯基-α-萘胺、还有丁基苯基-α-萘胺、戊基苯基-α-萘胺、己基苯基-α-萘胺、庚基苯基-α-萘胺、辛基苯基-α-萘胺、壬基苯基-α-萘胺等的烷基取代苯基-α-萘胺等。这些中,优选二烷基二苯胺类和萘胺类抗氧化剂。
应予说明,作为其它抗氧化剂,还可以使用钼胺络合物类抗氧化剂。作为钼胺络合物类抗氧化剂,可以使用使6价的钼化合物,具体而言是三氧化钼和/或钼酸与胺化合物反应而成的化合物,例如用日本特开2003-252887号公报记载的制备方法得到的化合物。作为与6价的钼化合物反应的胺化合物没有特别限制,但具体可以列举单胺、二胺、聚胺和烷醇胺。更具体地,可以示例甲胺、乙胺、二甲胺、二乙胺、甲基乙基胺、甲基丙基胺等具有碳原子数为1~30的烷基(这些烷基可以为直链状也可以为分支状)的烷基胺;乙烯基胺、丙烯基胺、丁烯基胺、辛烯基胺和油胺等的具有碳原子数为2~30的烯基(这些烯基可以为直链状也可以为分支状)的烯基胺;甲醇胺、乙醇胺、甲醇乙醇胺、甲醇丙醇胺等的具有碳原子数为1~30的烷醇基(这些烷醇基可以为直链状也可以为分支状)的烷醇胺;亚甲基二胺、亚乙基二胺、亚丙基二胺和亚丁基二胺等的具有碳原子数为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、五亚乙基六胺等的多胺;十一烷基二乙基胺、十一烷基二乙醇胺、十二烷基二丙醇胺、油基二乙醇胺、油基亚丙基二胺、十八烷基四亚乙基五胺等在上述的单胺、二胺、多胺上具有碳原子数为8~20的烷基或烯基的化合物、咪唑啉等杂环化合物;这些化合物的环氧烷加合物以及它们的混合物等。另外,可以示例在日本特公平3-22438号公报和日本特开2004-2866号公报记载的琥珀酰亚胺的含硫钼络合物等。
上述抗氧化剂的配合量以组合物总量为基准,优选为0.3质量%以上,更优选为0.5质量%以上。另一方面,如果超过2质量%,则存在在润滑油基油中不溶的可能。因此,抗氧化剂的配合量以组合物总量为基准,优选为0.3~2质量%的范围。
在本发明的润滑油组合物中,在不损害本发明的效果的范围,根据需要还可以配合其它添加剂,例如粘度指数提高剂、倾点下降剂、耐磨损剂、无灰类摩擦减少剂、防锈剂、金属减活剂、表面活性剂和消泡剂等。
作为粘度指数提高剂,例如可以列举聚甲基丙烯酸酯、分散型聚甲基丙烯酸酯、烯烃类共聚物(例如,乙烯-丙烯共聚物等)、分散型烯烃类共聚物,苯乙烯类共聚物(例如,苯乙烯-二烯共聚物、苯乙烯-异戊二烯共聚物等)等。这些粘度指数提高剂的配合量由配合效果的角度考虑,以组合物总量为基准,为0.5~15质量%左右,优选为1~10质量%。
作为倾点下降剂,例如可以列举质均分子量为5000~50,000左右的聚甲基丙烯酸酯等。
作为耐磨损剂,可以列举二硫代磷酸锌、二硫代氨基甲酸锌、磷酸锌、二硫醚类、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(例如Mo-DTC)等的含硫化合物;亚磷酸酯类、磷酸酯类、膦酸酯类和它们的胺盐或金属盐等的含磷化合物;硫代亚磷酸酯类、硫代磷酸酯类(例如,Mo-DTP)、硫代膦酸酯类和它们的胺盐或金属盐等的含硫和磷的耐磨损剂。
作为无灰类摩擦减少剂,可以使用通常用作润滑油用的无灰类摩擦减少剂的任意的化合物,例如可以列举在分子中至少具有1个碳原子数为6~30的烷基或烯基的脂肪酸、脂肪族醇、脂肪族醚、脂肪族酯、脂肪族胺和脂肪族酰胺等。
作为防锈剂,列举石油磺酸盐、烷基苯磺酸盐、二壬基萘磺酸盐、烯基琥珀酸酯、多元醇酯等。由配合效果的角度考虑,这些防锈剂的配合量以组合物总量为基准,通常为0.01~1质量%左右,优选为0.05~0.5质量%。
作为金属减活剂(铜腐蚀防止剂),例如可以列举苯并三唑类、甲苯基三唑类、噻二唑类,咪唑类和嘧啶类化合物等。其中优选苯并三唑类化合物。通过配合金属减活剂能够抑制发动机部件的金属腐蚀和氧化劣化。从配合效果的角度考虑,这些金属减活剂的配合量以组合物总量为基准,优选为0.01~0.1质量%,更优选为0.03~0.05质量%。
作为表面活性剂,可以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的聚亚烷基二醇类非离子型表面活性剂等。
作为消泡剂,可以列举硅油、氟硅油和氟烷基醚等,由消泡效果与经济性平衡等的角度考虑,相对于组合物总量,优选配合0.005~0.1质量%左右。
在本发明的润滑油组合物中,优选硫含量以组合物总量为基准为0.5质量%以下,更优选为0.3质量%以下,进一步优选为0.2质量%以下。如果硫含量为0.5质量%以下,则可以有效地抑制净化排气的催化剂的性能降低。
在本发明的润滑油组合物中,优选磷含量以组合物总量为基准为0.12质量%以下,更优选为0.1质量%以下。如果磷含量为0.12质量%以下,则能够有效地抑制净化排气的催化剂的性能降低。
另外,在本发明的润滑油组合物中,优选硫酸灰分为1.1质量%以下,更优选为1质量%以下。如果硫酸灰分为1.1质量%以下,则能够有效地抑制净化排气的催化剂的性能降低。另外,在柴油发动机中,在DPF的过滤器上堆积的灰分量减少,该过滤器的灰分阻塞得到抑制,DPF的寿命变长。此外,该硫酸灰分是指,在将样品燃烧而生成的碳化残留物中加入硫酸并加热,达到恒量时的灰分,通常为了得知润滑油组合物中的金属类添加剂的大致的量而使用。具体来说,通过JISK2272的[5.硫酸灰分的试验方法]中规定的方法进行测定。
应予说明,在内燃机中润滑油的蒸发性增大,导致润滑油自身的消费量增加,由此导致润滑油寿命降低,进一步由于对排气催化剂的飞散量增大,导致催化能力·寿命降低。由此观点出发,在本发明的润滑油组合物中,优选根据JPI(Japan Petroleum Institute,以下相同)-5S-41-93测定的NOACK蒸发量为15质量%以下,更优选为13质量%以下,进一步优选为10质量%以下。
实施例
下面,通过实施例对本发明进行进一步详细地说明,但本发明不受这些实施例限定。
[实施例1~7、比较例1~4]
制备具有表1所示的配合组成的润滑油组合物,进行如下所示的热管试验。应予说明,用于润滑油组合物的制备的各成分的种类如下所示:
(1)基油A:氢化精炼基油,40℃运动粘度为21mm2/s,100℃运动粘度为4.5mm2/s,粘度指数为127,%CA为0.0,硫含量为不足20质量ppm,NOACK蒸发量为13.3质量%
(2)基油B:PAO,40℃运动粘度为17.5mm2/s,100℃运动粘度为3.9mm2/s,粘度指数为120,NOACK蒸发量为15质量%
(3)基油C:酯油(多元醇脂肪酸酯。多元醇成分为三羟甲基丙烷,脂肪酸成分使用将椰子油(C8~C12)精炼而成的脂肪酸),40℃运动粘度为19.8mm2/s,100℃运动粘度为4.3mm2/s,粘度指数为139,NOACK蒸发量为3质量%,皂化值为0.1mgKOH/g
(4)基油D:己二酸十三烷基酯,40℃运动粘度为27mm2/s,100℃运动粘度为5.3mm2/s,粘度指数为132,NOACK蒸发量为4质量%
(5)粘度指数提高剂:聚甲基丙烯酸酯,质均分子量为420,000,树脂量为39质量%
(6)倾点下降剂:聚烷基甲基丙烯酸酯,质均分子量为6,000
(7)金属类清净剂:高碱性水杨酸钙,碱值(高氯酸法)225mgKOH/g,钙含量为7.8质量%,硫含量为0.3质量%
(8)聚丁烯基琥珀酸单酰亚胺A:聚丁烯基的数均分子量为1000,氮含量为1.76质量%,硼含量为2.0质量%,B/N=1.1
(9)聚丁烯基琥珀酸双酰亚胺B:聚丁烯基的数均分子量为2000,氮含量为0.99质量%,B/N=0
(10)酚类抗氧化剂:3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯
(11)胺类抗氧化剂:二烷基二苯胺,氮含量为4.62质量%
(12)二烷基二硫代磷酸锌:Zn含量为9.0质量%,磷含量为8.2质量%,硫含量为17.1含量%,烷基:仲丁基与仲己基的混合物
(13)铜腐蚀防止剂:1-[N,N-双(2-乙基己基)氨基甲基]甲基苯并三唑
(14)生物柴油燃料:菜籽油甲基酯
(15)其它添加剂:防锈剂、表面活性剂和消泡剂
对各润滑油组合物的性状测定及热管试验进行如下:
(钙含量)
根据JIS-5S-38-92进行测定。
(硼含量)
根据JIS-5S-38-92进行测定。
(氮含量)
根据JIS K2609进行测定。
(磷含量)
根据JPI-5S-38-92进行测定。
(硫含量)
根据JIS K2541进行测定。
(硫酸灰分)
根据JIS K2272进行测定。
(Noack)
根据JPI-5S-41-93进行测定。
(热管试验)
作为试验用的润滑油组合物,设想内燃机中的燃料和润滑油的混合比例,使用相对于上述各润滑油组合物(新油)配合5质量%生物燃料(将菜籽油用甲醇进行酯交换得到的燃料)的混合油。试验温度设为280℃和320℃,对于其它条件,根据JPI-5S-55-99进行测定。另外,由于热管试验还存在粘度指数提高剂的量产生影响的情况,因此在各实施例·比较例中使粘度指数提高剂的配合量固定。试验后在玻璃管上的附着物量越少,则表明清洁性越好。
各润滑油组合物的性状和热管试验结果如表1所示。
[评价结果]
由表1的热管试验结果可知,在使用本发明的润滑油组合物的实施例1~7中,即使在新油中添加生物燃料,热管内的附着量也不是很多,可以认为发动机的清洁性也优异。另一方面,比较例1、2由于作为基油既没有使用多元醇酯也没有使用多元酸酯,因此附着量非常多。另外,如比较例3、4,即使将多元醇酯、多元酸酯用作基油,如果其配合量少,则基本上也未发现附着防止效果,无法期待对发动机的清洁性。
产业实用性
本发明的润滑油组合物适合用于使用生物燃料或含有生物燃料的燃料的内燃机。
Claims (6)
1.润滑油组合物,其是在下述内燃机中使用的润滑油组合物,所述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和天然油脂的酯交换物的氢化处理物中的至少一种的燃料,其特征在于,
作为润滑油基油,以润滑油组合物总量为基准,配合5~30质量%的100℃运动粘度为3~8mm2/s的多元醇酯和/或100℃运动粘度为3~8mm2/s的多元酸酯,
作为润滑油基油,在配合上述多元醇酯和/或上述多元酸酯的同时,还配合利用环分析得到的%CA为1以下的矿物油。
2. 根据权利要求1所述的润滑油组合物,其特征在于,
配合具有数均分子量为500~3500的聚丁烯基、硼(B)和氮(N)的质量比(B/N)为0.5以上的聚丁烯基琥珀酰亚胺化合物的硼衍生物、和
碱土金属类清洁剂。
3. 根据权利要求1所述的润滑油组合物,其特征在于,
硫酸灰分为1.1质量%以下。
4. 根据权利要求1~3中任一项所述的润滑油组合物,其特征在于,
以组合物总量为基准,配合0.3质量%以上的酚类抗氧化剂和/或胺类抗氧化剂。
5. 根据权利要求2所述的润滑油组合物,其特征在于,
以组合物总量为基准,配合换算为硼量为0.01质量%以上的上述聚丁烯基琥珀酰亚胺化合物的硼衍生物。
6. 根据权利要求1~3中任一项所述的润滑油组合物,其特征在于,
以组合物总量为基准,硫含量为0.5质量%以下。
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-
2007
- 2007-10-22 JP JP2007274080A patent/JP5198031B2/ja active Active
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2008
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- 2008-10-17 WO PCT/JP2008/068860 patent/WO2009054322A1/ja active Application Filing
- 2008-10-17 EP EP08841541.9A patent/EP2223992A4/en not_active Withdrawn
- 2008-10-17 CN CN200880112577.4A patent/CN101835880B/zh not_active Expired - Fee Related
- 2008-10-17 KR KR1020107011033A patent/KR20100087722A/ko active IP Right Grant
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WO2009054322A1 (ja) | 2009-04-30 |
TW200930805A (en) | 2009-07-16 |
JP2009102486A (ja) | 2009-05-14 |
EP2223992A4 (en) | 2014-09-10 |
CN101835880B (zh) | 2014-10-01 |
CN101835880A (zh) | 2010-09-15 |
JP5198031B2 (ja) | 2013-05-15 |
TWI447223B (zh) | 2014-08-01 |
EP2223992A1 (en) | 2010-09-01 |
KR20100087722A (ko) | 2010-08-05 |
US20100218740A1 (en) | 2010-09-02 |
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