EP2607462B1 - Lubrification de moteur marin - Google Patents
Lubrification de moteur marin Download PDFInfo
- Publication number
- EP2607462B1 EP2607462B1 EP12196639.4A EP12196639A EP2607462B1 EP 2607462 B1 EP2607462 B1 EP 2607462B1 EP 12196639 A EP12196639 A EP 12196639A EP 2607462 B1 EP2607462 B1 EP 2607462B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- acid
- polyisobutylene
- mass
- range
- 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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- 238000005461 lubrication Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims description 50
- 239000000654 additive Substances 0.000 claims description 28
- 229920002367 Polyisobutene Polymers 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 17
- 239000010705 motor oil Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 230000001050 lubricating effect Effects 0.000 claims description 8
- -1 for example Substances 0.000 description 48
- 239000003599 detergent Substances 0.000 description 32
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- 229910052751 metal Inorganic materials 0.000 description 24
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- 239000000314 lubricant Substances 0.000 description 23
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- 239000002253 acid Substances 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 150000007513 acids Chemical class 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
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- 125000000217 alkyl group Chemical group 0.000 description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
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- 238000000034 method Methods 0.000 description 9
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
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- 125000001424 substituent group Chemical group 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000007866 anti-wear additive Substances 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
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- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- WLLCYXDFVBWGBU-UHFFFAOYSA-N bis(8-methylnonyl) nonanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC(C)C WLLCYXDFVBWGBU-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 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 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical class CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 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 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 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 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical class CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZAGXLQIHXTXRFW-UHFFFAOYSA-N tris(2-ethyl-4-methylhexyl)-tris(2-ethyl-4-methylhexyl)silyloxysilane Chemical compound CCC(C)CC(CC)C[Si](CC(CC)CC(C)CC)(CC(CC)CC(C)CC)O[Si](CC(CC)CC(C)CC)(CC(CC)CC(C)CC)CC(CC)CC(C)CC ZAGXLQIHXTXRFW-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
- F01M9/00—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
- F01M9/02—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00 having means for introducing additives to lubricant
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
Definitions
- This invention concerns reducing deposit formation in a centrifuge system in a trunk piston diesel engine.
- Trunk piston diesel engines are used in marine, power generation and rail traction applications and may have a rated speed of between 300 and 1000 rpm.
- trunk piston diesel engines a single lubricant composition is used for crankcase and cylinder lubrication. All major moving parts of the engine, i.e. the main and big end bearings, camshaft and valve gear, are lubricated by a pumped circulation system.
- the cylinder liners are lubricated partially by splash lubrication and partially by oil from the circulation system which finds its way to the cylinder wall through holes in the piston skirt via the connecting rod and gudgeon pin.
- Trunk piston diesel engines use a centrifuge system to remove contaminants such as, for example, soot or water, from the lubricant composition.
- the centrifuge system relies on the use of a sealing medium that is heavier than the lubricant.
- the sealing medium is generally water.
- the lubricant composition passes through the centrifuge system, it comes into contact with the water.
- the lubricant therefore needs to be capable of shedding the water and remaining stable in the presence of water. If the lubricant is unable to shed the water, the water builds up in the lubricant forming an emulsion, which leads to deposits building up in the centrifuge system and prevents the centrifuge system from working properly.
- the centrifuge system normally operates at temperatures of less than 100°C, such as less than 95°C, e.g. around 90°C.
- the aim of the present invention is to provide for the reduction of deposit formation in a centrifuge system in a trunk piston diesel engine.
- US2005/0119140A concerns a method of reducing deposit formation in a centrifuge system in a trunk piston diesel engine.
- the method includes the step of lubricating the trunk piston diesel engine with a composition including at least one detergent and at least 1.5 mass% of phenol, based on the total amount of the lubricant compositions.
- US-A-2008/0287329 A1 (“'329”) describes a lubricant oil for a marine four-stroke engine that includes 1 to 20 % by weight of at least one polyisobutylene. '329 states that the increase of viscosity of such lubricant oils is slowed down. However, '329 makes no mention of the above-mentioned deposit formation problem in the centrifuge of trunk piston engines.
- the present invention provides the use of a polyisobutylene of number-average molecular weight in the range of 400 to 8000, such as 1,300 to 2,225, and having a kinematic viscosity at 100°C in the range of 50 to 50,000, such as 630 to 2,500, mm 2 /sec, as an additive constituting 1-25 mass % of a trunk piston diesel engine lubricant composition to reduce deposit formation in a centrifuge in a trunk piston diesel engine when the composition is lubricating the engine during its operation.
- the trunk piston diesel engine lubricant composition contains little or no brightstock.
- the trunk piston diesel engine lubricant composition is substantially free of brightstock. Even more preferably, the trunk piston diesel engine lubricant composition contains no brightstock.
- the lubricant of composition contains a major proportion of an oil of lubricating viscosity.
- Such lubricating oils may range in viscosity from light distillate mineral oils to heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to 40, such as 3 to 15, mm 2 /sec, as measured at 100°C, and a viscosity index of 80 to 100, such as 90 to 95.
- the lubricating oil may comprise greater than 60, typically greater than 70. mass % of the composition.
- the oil may include 'brightstock' which refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C of from 28 to 36 mm 2 s -1 . It is, however, preferred that little or no brightstock is included, for example less than 5, 4, 3, 2 or 1 mass %, based on the mass of the composition. Brightstock may be completely or substantially absent.
- Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
- Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivative, analogues and homologues thereof.
- Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diester of tetraethylene glycol.
- polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
- alkyl and aryl ethers of polyoxyalkylene polymers e.
- Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
- dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linole
- esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles oftetraethylene glycol and two moles of 2-ethylhexanoic acid.
- Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
- Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
- oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
- Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
- Unrefined, refined and re-refined oils can be used in lubricants of the present invention.
- Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations; petroleum oil obtained directly from distillation; or ester oil obtained directly from esterification and used without further treatment are unrefined oils.
- the polyisobutylene additive may be present in the following proportions: 1 to 20, or 1 to 15, such as 1-10, such as 1-6, such as 1-5, such as 1-4 mass percent.
- the polyisobutylene has a number-average weight in the range of 400 to 8,000, such as 1,300 to 2,225. Among other ranges that may be used, the following may be mentioned: 900 - 3,000, 1,000 - 8,000, 1,500 - 6,000 and 2,000 - 5,000, and also a lower limit of 500.
- the polyisobutylene has a kinematic viscosity at 100°C in the range of 50 to 50,000, such as 630 to 2,500, mm 2 /sec. Among other ranges that may be used, the following may be mentioned: 2,000 - 6,000, 2,000 - 5,000, and 3,000 - 4,500, mm 2 /stc.
- Polyisobutylene also embraces mixtures of several polyisobutylenes, synthesised separately and possibly having molecular weights outside the ranges of values indicated above, provided that the mixture of the various polyisobutylenes has a molecular weight lying within said ranges.
- Polyisobutylene is commercially available.
- a detergent is an additive that reduces formation of deposits, for example, high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
- a detergent comprises a polar head with a long hydrophobic tail.
- Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
- a metal compound such as an oxide or hydroxide
- an acidic gas such as carbon dioxide
- the detergent is preferably an alkali metal or alkaline earth metal additive such as an overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salt of a surfactant selected from phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid, wherein the overbasing is provided by an oil-insoluble salt of the metal, e.g. carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilised by the oil-soluble salt of the surfactant.
- the metal of the oil-soluble surfactant salt may be the same or different from that of the metal of the oil-insoluble salt.
- the metal, whether the metal of the oil-soluble or oil-insoluble salt is calcium.
- the TBN of the detergent may be low, i.e. less than 50 mg KOH/g, medium, i.e. 50-150 mg KOH/g, or high, i.e. over 150 mg KOH/g, as determined by ASTM D2896.
- the TBN is medium or high, i.e. more than 50 TBN.
- the TBN is at least 60, more preferably at least 100, more preferably at least 150, and up to 500, such as up to 350 mg KOH/g, as determined by ASTM D2896.
- Surfactants for the surfactant system of the overbased detergent preferably contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
- hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
- hydrocarbyl groups in surfactants for use in accordance with the invention are aliphatic groups, preferably alkyl or alkylene groups, especially alkyl groups, which may be linear or branched. The total number of carbon atoms in the surfactants should be at least sufficient to impart the desired oil-so lubility.
- Phenols, for use in preparing the detergents may be non-sulphurized or, preferably, sulphurized.
- phenol as used herein includes phenols containing more than one hydroxyl group (for example, alkyl catechols) or fused aromatic rings (for example, alkyl naphthols) and phenols which have been modified by chemical reaction, for example, alkylene-bridged phenols and Mannich base-condensed phenols; and saligenin-type phenols (produced by the reaction of a phenol and an aldehyde under basic conditions).
- Preferred phenols may be derived from the formula where R represents a hydrocarbyl group and y represents 1 to 4. Where y is greater than 1, the hydrocarbyl groups may be the same or different.
- Sulphurized hydrocarbyl phenols may typically be represented by the formula: where x is generally from 1 to 4. In some cases, more than two phenol molecules may be linked by S x bridges.
- hydrocarbyl groups represented by R are advantageously alkyl groups, which advantageously contain 5 to 100, preferably 5 to 40, especially 9 to 12, carbon atoms, the average number of carbon atoms in all of the R groups being at least 9 in order to ensure adequate solubility in oil.
- Preferred alkyl groups are nonyl (tripropylene) groups.
- hydrocarbyl-substituted phenols will for convenience be referred to as alkyl phenols.
- a sulphurizing agent for use in preparing a sulphurized phenol or phenate may be any compound or element which introduces -(S) x - bridging groups between the alkyl phenol monomer groups, wherein x is generally from 1 to about 4.
- the reaction may be conducted with elemental sulphur or a halide thereof, for example, sulphur dichloride or, more preferably, sulphur monochloride. If elemental sulphur is used, the sulphurization reaction may be effected by heating the alkyl phenol compound at from 50 to 250, preferably at least 100, °C.
- the sulphurization reaction may be effected by treating the alkyl phenol at from -10 to 120, preferably at least 60, °C.
- the reaction may be conducted in the presence of a suitable diluent.
- the diluent advantageously comprises a substantially inert organic diluent, for example mineral oil or an alkane.
- the reaction is conducted for a period of time sufficient to effect substantial reaction. It is generally preferred to employ from 0.1 to 5 moles of the alkyl phenol material per equivalent of sulphurizing agent.
- a basic catalyst for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
- sulphurized alkyl phenols useful in preparing overbased detergents generally comprise diluent and unreacted alkyl phenols and generally contain from 2 to 20 mass %, preferably 4 to 14 mass %, and most preferably 6 to 12 mass%, sulphur based on the mass of the sulphurized alkyl phenol.
- phenol as used herein includes phenols that have been modified by chemical reaction with, for example, an aldehyde, and Mannich base-condensed phenols.
- Aldehydes with which phenols may be modified include, for example, formaldehyde, propionaldehyde and butyraldehyde.
- the preferred aldehyde is formaldehyde.
- Aldehyde-modified phenols suitable for use are described in, for example, US-A-5 259 967 .
- Mannich base-condensed phenols are prepared by the reaction of a phenol, an aldehyde and an amine. Examples of suitable Mannich base-condensed phenols are described in GB-A-2 121 432 .
- the phenols may include substituents other than those mentioned above provided that such substituents do not detract significantly from the surfactant properties of the phenols.
- substituents are methoxy groups and halogen atoms.
- Salicylic acids used in accordance with the invention may be non-sulphurized or sulphurized, and may be chemically modified and/or contain additional substituents, for example, as discussed above for phenols. Processes similar to those described above may also be used for sulphurizing a hydrocarbyl-substituted salicylic acid, and are well known to those skilled in the art. Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol.
- Preferred substituents in oil-soluble salicylic acids from which overbased detergents in accordance with the invention may be derived are the substituents represented by R in the above discussion of phenols.
- the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms.
- Sulphonic acids used in accordance with the invention are typically obtained by sulphonation of hydrocarbyl-substituted, especially alkyl-substituted, aromatic hydrocarbons, for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
- alkyl-substituted aromatic hydrocarbons for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
- alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives for example, chlorobenzene, chlorotoluene or chloronaphthalene.
- Alkylation of aromatic hydrocarbons may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 100 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, and polyolefins, for example, polymers of ethylene, propylene, and/or butene.
- alkylaryl sulphonic acids usually contain from 7 to 100 or more carbon atoms. They preferably contain from 16 to 80, or 12 to 40, carbon atoms per alkyl-substituted aromatic moiety, depending on the source from which they are obtained.
- hydrocarbon solvents and/or diluent oils may also be included in the reaction mixture, as well as promoters and viscosity control agents.
- Such sulphonic acids can be sulphurized. Whether sulphurized or non-sulphurized these sulphonic acids are believed to have surfactant properties comparable to those of sulphonic acids, rather than surfactant properties comparable to those of phenols.
- Sulphonic acids suitable for use in accordance with the invention also include alkyl sulphonic acids, such as alkenyl sulphonic acids.
- alkyl sulphonic acids such as alkenyl sulphonic acids.
- the alkyl group suitably contains 9 to 100, advantageously 12 to 80, especially 16 to 60, carbon atoms.
- Carboxylic acids that may be used in accordance with the invention include mono- and dicarboxylic acids.
- Preferred monocarboxylic acids are those containing 1 to 30, especially 8 to 24, carbon atoms. (Where this specification indicates the number of carbon atoms in a carboxylic acid, the carbon atom(s) in the carboxylic group(s) is/are included in that number.)
- Examples of monocarboxylic acids are iso-octanoic acid, stearic acid, oleic acid, palmitic acid and behenic acid. Iso-octanoic acid may, if desired, be used in the form of the mixture of C 8 acid isomers sold by Exxon Chemicals under the trade name "Cekanoic".
- Suitable acids are those with tertiary substitution at the ⁇ -carbon atom and dicarboxylic acids with more than 2 carbon atoms separating the carboxylic groups. Further, dicarboxylic acids with more than 35, for example, 36 to 100, carbon atoms are also suitable. Unsaturated carboxylic acids can be sulphurized. Although salicylic acids contain a carboxylic group, for the purposes of the present invention they are considered to be a separate group of surfactants, and are not considered to be carboxylic acid surfactants. (Nor, although they contain a hydroxyl group, are they considered to be phenol surfactants.)
- naphthenic acids especially naphthenic acids containing one or more alkyl groups
- dialkylphosphonic acids dialkylthiophosphonic acids
- dialkyldithiophosphoric acids dialkyldithiophosphoric acids
- high molecular weight (preferably ethoxylated) alcohols preferably ethoxylated) alcohols
- dithiocarbamic acids thiophosphines
- dispersants of these types are well known to those skilled in the art.
- detergents useful in the present invention are optionally sulphurized alkaline earth metal hydrocarbyl phenates that have been modified by carboxylic acids such as stearic acid, for examples as described in EP-A- 271 262 (LZ-Adibis); and phenolates as described in EP-A- 750 659 (Chevron ).
- overbased metal compounds preferably overbased calcium detergents, that contain at least two surfactant groups, such as phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid, that may be obtained by manufacture of a hybrid material in which two or more different surfactant groups are incorporated during the overbasing process.
- surfactant groups such as phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid
- hybrid materials are an overbased calcium salt of surfactants phenol and sulphonic acid; an overbased calcium salt of surfactants phenol and carboxylic acid; an overbased calcium salt of surfactants phenol, sulphonic acid and salicylic acid; and an overbased calcium salt of surfactants phenol and salicylic acid.
- any suitable proportions by mass may be used, preferably the mass to mass proportion of any one overbased metal compound to any other metal overbased compound is in the range of from 5:95 to 95:5; such as from 90:10 to 10:90; more preferably from 20:80 to 80:20; especially from 70:30 to 30:70; advantageously from 60:40 to 40:60.
- the hybrid detergent preferably includes at least 5 mass% of salicylate, more preferably at least 10 mass% of salicylate.
- the hybrid detergent preferably includes at least 5 mass% of phenate.
- the amount of salicylate and phenate in the hybrid detergent can be determined using techniques such as chromatography, spectroscopy and/or titration, well known to persons skilled in the art.
- the hybrid detergent may also include other surfactants such as sulphonate, sulphurized phenate, thiophosphate, naphthenate, or oil-soluble carboxylate.
- the hybrid detergent may include at least 5 mass% of sulphonate.
- the surfactant groups are incorporated during the overbasing process.
- hybrid materials include, for example, those described in WO-A- 97/46643 ; WO-A- 97/46644 ; WO-A- 97/46645 ; WO-A- 97/46646 ; and WO-A- 97/46647 .
- an “overbased calcium salt of surfactants” is meant an overbased detergent in which the metal cations of the oil-insoluble metal salt are essentially calcium cations. Small amounts of other cations may be present in the oil-insoluble metal salt, but typically at least 80, more typically at least 90, for example at least 95, mole %, of the cations in the oil-insoluble metal salt, are calcium ions. Cations other than calcium may be derived, for example, from the use in the manufacture of the overbased detergent of a surfactant salt in which the cation is a metal other than calcium.
- the metal salt of the surfactant is also calcium.
- the TBN of the hybrid detergent is at least 300 mg KOH/g, such as at least 330 mg KOH/g, more preferably at least 350 mg KOH/g, more preferably at least 400 mg KOH/g, most preferably in the range of from 400 to 600 mg KOH/g, such as up to 500 mg KOH/g, as determined by ASTM D2896.
- the amount of overbased metal detergent in the lubricant is at least 0.5, preferably in the range of from 5 to 50, more preferably from 10 to 50, mass % based on the total amount of the lubricant composition.
- the overbased metal detergents may or may not be borated, and typically the boron contributing compound, e.g the metal borate, is considered to form part of the overbasing.
- the detergent may include both a non-borated detergent and a borated detergent.
- the overbased metal detergents preferably have a sulphated ash content (as determined by ASTM D874) of at least 0.85%, more preferably at least 1.0% and even more preferably at least 1.2%.
- the detergent or detergents may include phenol as an unreacted component and, if so, the amount of phenol contributes to the total phenol content present in the trunk piston diesel engine lubricant composition. All of the phenol present in the trunk piston diesel engine lubricant composition may come from the detergent or detergents.
- the trunk piston engine oil preferably also includes at least one dispersant, anti-wear additive or anti-oxidant.
- the trunk piston diesel engine lubricant composition may include at least one dispersant.
- a dispersant is an additive for a lubricating composition whose primary function is to improve engine cleanliness.
- Ashless dispersants comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g. an O, P or N atom.
- the hydrocarbon is an oleophilic group that confers oil-solubility, having for example 40 to 500 carbon atoms.
- ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
- ashless dispersants are succinimides, e.g. polyisobutene succinic anhydride; and polyamine condensation products that may be borated or unborated.
- the dispersant is preferably present in an amount from 0.5 to 5 mass %, based on the total amount of the lubricant composition.
- the trunk piston diesel engine lubricant composition may include at least one anti-wear additive.
- the anti-wear additive may be metallic or non-metallic, preferably the former.
- Dihydrocarbyl dithiophosphate metal salts are examples of the anti-wear additives.
- the metal in the dihydrocarbyl dithiophosphate may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.
- Zinc salts are preferred, preferably in the range of 0.1 to 1.5, preferably 0.5 to 1.3, mass %, based upon the total mass of the lubricating oil composition. They may be prepared in accordance with known techniques by firstly forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
- DDPA dihydrocarbyl dithiophosphoric acid
- a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
- multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary.
- any basic or neutral zinc compound may be used but the oxides, hydroxides and carbonates are most generally employed.
- Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
- the preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: [(RO)(R 1 O)P(S)S] 2 Zn where R and R 1 may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R 1 groups are alkyl groups of 2 to 8 carbon atoms.
- the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, I-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
- the total number of carbon atoms (i.e. in R and R 1 ) in the dithiophoshoric acid will generally be 5 or greater.
- the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
- the anti-wear additive is preferably present in an amount from 0.10 to 3.0 mass %, based on the total amount of the lubricant composition.
- the trunk piston diesel engine lubricant composition may include at least one anti-oxidant.
- the anti-oxidant may be aminic or phenolic.
- secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms.
- anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
- the anti-oxidant if present, is provided in the composition in an amount of up to 3 mass %, based on the total amount of the lubricant composition.
- pour point depressants such as pour point depressants, anti-foamants, metal rust inhibitors, pour point depressants and/or demulsifiers may be provided, if necessary.
- 'oil-soluble' or 'oil-dispersable' do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
- the lubricant compositions of this invention comprise defined individual (i.e. separate) components that may or may not remain the same chemically before and after mixing.
- additive package(s) may be prepared, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby the additives can be added simultaneously to the oil of lubricating viscosity to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
- the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
- the additives may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass % of additives in the appropriate proportions, the remainder being base oil.
- the final formulations may typically contain about 5 to 40 mass % of the additive packages(s), the remainder being base oil.
- the following examples use a centrifuge water shedding test which evaluates the ability of an oil to shed water from a prepared test mixture of oil and water.
- the test uses an Alfa Laval MAB103B 2.0 centrifuge coupled to a Watson Marlow peristaltic pump. The centrifuge is sealed with 2 litres of water. A measurement is made of the amount of deposits formed in the centrifuge during the test. The test is carried out at 87°C. Pre-measured amounts of water and the test oil are mixed together and then passed through the centrifuge at a rate of 2 litres/min. The test is run for an hour and a half, allowing the mixture to pass through the centrifuge about 10 times. The centrifuge is weighed before and after the test. A poor trunk piston diesel engine lubricant composition will produce a larger amount of deposits in the centrifuge system.
- Trunk piston engine oils were prepared having TBNs of about 40.
- the TPEOs were subjected to the centrifuge water shedding test. Details of the TPEOs and the test results are shown below in Table 1.
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Claims (17)
- Utilisation d'un polyisobutylène ayant une moyenne en nombre du poids moléculaire dans l'intervalle de 400 à 8000 et ayant une viscosité cinématique à 100°C dans l'intervalle de 50 à 50 000 m2/s comme additif représentant 1 à 25 % en masse d'une composition de lubrifiant pour moteur diesel à piston-fourreau afin de réduire la formation de dépôts dans une centrifugeuse dans un moteur diesel à piston-fourreau lorsque la composition lubrifie le moteur pendant son fonctionnement.
- Utilisation suivant la revendication 1, dans laquelle la composition comprend moins de 0,5 % en masse d'huile lubrifiante de base à haute viscosité "brightstock".
- Utilisation suivant la revendication 2, dans laquelle la composition comprend moins de 0,1 % en masse d'huile lubrifiante de base à haute viscosité "brightstock".
- Utilisation suivant la revendication 1, dans laquelle la composition est substantiellement dépourvue d'huile lubrifiante de base à haute viscosité "brightstock".
- Utilisation suivant la revendication 1, dans laquelle la composition ne contient aucune huile lubrifiante de base à haute viscosité "brightstock".
- Utilisation suivant l'une quelconque des revendications 1 à 5, dans laquelle la moyenne en nombre du poids moléculaire du polyisobutylène est comprise dans l'intervalle de 900 à 8000.
- Utilisation suivant la revendication 6, dans laquelle la moyenne en nombre du poids moléculaire du polyisobutylène est comprise dans l'intervalle de 1000 à 6000.
- Utilisation suivant la revendication 7, dans laquelle la moyenne en nombre du poids moléculaire du polyisobutylène est comprise dans l'intervalle de 1300 à 5000.
- Utilisation suivant la revendication 8, dans laquelle la moyenne en nombre du poids moléculaire du polyisobutylène est comprise dans l'intervalle de 1500 à 2225.
- Utilisation suivant la revendication 9, dans laquelle la viscosité cinématique à 100°C du polyisobutylène est comprise dans l'intervalle de 200 à 6000.
- Utilisation suivant la revendication 10, dans laquelle la viscosité cinématique à 100°C du polyisobutylène est comprise dans l'intervalle de 630 à 5000 mm2/s.
- Utilisation suivant la revendication 11, dans laquelle la viscosité cinématique à 100°C du polyisobutylène est comprise dans l'intervalle de 2000 à 5000 mm2/s.
- Utilisation suivant la revendication 12, dans laquelle la viscosité cinématique à 100°C du polyisobutylène est comprise dans l'intervalle de 3000 à 4500 mm2/s.
- Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle l'indice de basicité total (TBN) de la composition est égal ou supérieur à 30.
- Utilisation suivant la revendication 14, dans laquelle le TBN est égal ou supérieur à 35.
- Utilisation suivant la revendication 15, dans laquelle le TBN est égal ou supérieur à 45.
- Utilisation suivant la revendication 16, dans laquelle le TBN est égal ou supérieur à 50.
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EP12196639.4A EP2607462B1 (fr) | 2011-12-20 | 2012-12-12 | Lubrification de moteur marin |
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EP (1) | EP2607462B1 (fr) |
KR (1) | KR102052209B1 (fr) |
CN (1) | CN103173263B (fr) |
AU (1) | AU2012268784B2 (fr) |
CA (1) | CA2799383C (fr) |
DK (1) | DK2607462T3 (fr) |
ES (1) | ES2463417T3 (fr) |
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WO2024086554A1 (fr) * | 2022-10-17 | 2024-04-25 | Chevron Oronite Company Llc | Compositions d'huile lubrifiante pour moteur marin |
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FR3053697B1 (fr) * | 2016-07-07 | 2019-08-16 | Total Marketing Services | Composition lubrifiante pour moteur a gaz |
Family Cites Families (15)
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US4708809A (en) | 1982-06-07 | 1987-11-24 | The Lubrizol Corporation | Two-cycle engine oils containing alkyl phenols |
GB8628609D0 (en) | 1986-11-29 | 1987-01-07 | Bp Chemicals Additives | Lubricating oil additives |
US5259967A (en) | 1992-06-17 | 1993-11-09 | The Lubrizol Corporation | Low ash lubricant composition |
FR2717491B1 (fr) | 1994-03-17 | 1996-06-07 | Chevron Chem Sa | Additifs détergents-dispersants pour huiles lubrifiantes du type alkylsalicylates-alkylphénates, alcalino-terreux, sulfurisés et suralcalinisés. |
GB9611318D0 (en) | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
GB9611317D0 (en) | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
GB9611316D0 (en) | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
GB9611424D0 (en) | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
GB9611428D0 (en) | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
ATE491775T1 (de) * | 1999-09-13 | 2011-01-15 | Infineum Int Ltd | Eine methode zum schmieren für zweitakt- schiffsdieselmotoren |
GB0011733D0 (en) * | 2000-05-16 | 2000-07-05 | Infineum Int Ltd | Additives for improved engine operation |
US20050119140A1 (en) * | 2003-10-30 | 2005-06-02 | Laurent Chambard | Method of reducing deposit formation in a centrifuge system in a trunk piston diesel engine |
FR2879621B1 (fr) * | 2004-12-16 | 2007-04-06 | Total France Sa | Huile pour moteur marin 4-temps |
ES2731475T3 (es) * | 2006-08-08 | 2019-11-15 | Infineum Int Ltd | Composición de aceite lubricante que contiene aditivos detergentes |
US20090203559A1 (en) * | 2008-02-08 | 2009-08-13 | Bera Tushar Kanti | Engine Lubrication |
-
2012
- 2012-12-12 ES ES12196639.4T patent/ES2463417T3/es active Active
- 2012-12-12 EP EP12196639.4A patent/EP2607462B1/fr active Active
- 2012-12-12 DK DK12196639.4T patent/DK2607462T3/da active
- 2012-12-18 KR KR1020120148391A patent/KR102052209B1/ko active IP Right Grant
- 2012-12-19 SG SG2012093837A patent/SG191537A1/en unknown
- 2012-12-20 CA CA2799383A patent/CA2799383C/fr active Active
- 2012-12-20 AU AU2012268784A patent/AU2012268784B2/en active Active
- 2012-12-20 CN CN201210558788.9A patent/CN103173263B/zh active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024086554A1 (fr) * | 2022-10-17 | 2024-04-25 | Chevron Oronite Company Llc | Compositions d'huile lubrifiante pour moteur marin |
Also Published As
Publication number | Publication date |
---|---|
AU2012268784B2 (en) | 2014-03-13 |
DK2607462T3 (da) | 2014-03-31 |
CA2799383C (fr) | 2019-12-31 |
EP2607462A1 (fr) | 2013-06-26 |
CN103173263B (zh) | 2017-03-01 |
SG191537A1 (en) | 2013-07-31 |
KR102052209B1 (ko) | 2019-12-04 |
AU2012268784A1 (en) | 2013-07-04 |
CN103173263A (zh) | 2013-06-26 |
ES2463417T3 (es) | 2014-05-27 |
CA2799383A1 (fr) | 2013-06-20 |
KR20130071384A (ko) | 2013-06-28 |
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