JP2017014505A - Additive package for marine engine lubrication - Google Patents
Additive package for marine engine lubrication Download PDFInfo
- Publication number
- JP2017014505A JP2017014505A JP2016129827A JP2016129827A JP2017014505A JP 2017014505 A JP2017014505 A JP 2017014505A JP 2016129827 A JP2016129827 A JP 2016129827A JP 2016129827 A JP2016129827 A JP 2016129827A JP 2017014505 A JP2017014505 A JP 2017014505A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- additive
- engine
- composition
- additive package
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000654 additive Substances 0.000 title claims abstract description 60
- 230000000996 additive effect Effects 0.000 title claims abstract description 46
- 238000005461 lubrication Methods 0.000 title description 4
- 239000003921 oil Substances 0.000 claims abstract description 36
- 239000003599 detergent Substances 0.000 claims abstract description 27
- 230000001050 lubricating effect Effects 0.000 claims abstract description 16
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000344 soap Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000314 lubricant Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000010687 lubricating oil Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000005191 phase separation Methods 0.000 abstract description 5
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- 238000001879 gelation Methods 0.000 abstract description 3
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- 239000002585 base Substances 0.000 description 21
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- 238000012360 testing method Methods 0.000 description 8
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 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
- 239000010689 synthetic lubricating oil Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 238000010998 test method Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
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- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000010729 system oil Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 1
- RDAGYWUMBWNXIC-UHFFFAOYSA-N 1,2-bis(2-ethylhexyl)benzene Chemical compound CCCCC(CC)CC1=CC=CC=C1CC(CC)CCCC RDAGYWUMBWNXIC-UHFFFAOYSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- OZVKHOPICATTIK-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOCCO OZVKHOPICATTIK-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 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
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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
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
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- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/14—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring containing at least 2 hydroxy groups
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/16—Ethers
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
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- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- 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
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- 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
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- 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]
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/10—Running-in-oil ; Grinding
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Lubrication Of Internal Combustion Engines (AREA)
Abstract
Description
発明の分野
本発明は、2ストローク及び4ストローク船舶用ディーゼル内燃エンジン、すなわち前者は通常クロスヘッドエンジンと呼ばれ、後者はトランクピストンエンジンと呼ばれるエンジンの潤滑化に関する。これらの用途に適したそれぞれの潤滑剤は、一般的に船舶用ディーゼルシリンダ潤滑剤(「MDCL」)及びトランクピストンエンジン油(「TPEO」)として知られている。
The present invention relates to lubrication of two-stroke and four-stroke marine diesel internal combustion engines, i.e., the former commonly referred to as crosshead engines and the latter referred to as trunk piston engines. Each lubricant suitable for these applications is commonly known as marine diesel cylinder lubricant ("MDCL") and trunk piston engine oil ("TPEO").
発明の背景
クロスヘッドエンジンは、高出力から超高出力範囲を有する低速エンジンである。このエンジンは2つの別々に潤滑化される部品:高粘性油(MDCL)によって全損潤滑で潤滑化されるピストン/シリンダアセンブリ;及び通常はシステム油と呼ばれる低粘性潤滑剤によって潤滑化されるクランク軸を含む。
トランクピストンエンジンは、船舶、発電及び鉄道牽引用途で使用可能であり、クロスヘッドエンジンより高速である。クランクケース及びシリンダの潤滑化には単一の潤滑剤(TPEO)が用いられる。エンジンの全ての主要な可動部品、すなわちメインベアリング及びビッグエンドベアリング、カム軸及びバルブギアは、ポンプ式循環システムを用いて潤滑化される。シリンダライナは、一部ははねかけ式潤滑によって、一部は循環システムの油によって潤滑化され、該油は連接棒及びガジオンピンを介してピストンスカートの穴を通ってシリンダ壁にたどり着く。
BACKGROUND OF THE INVENTION A crosshead engine is a low speed engine having a high power to ultra high power range. This engine has two separately lubricated parts: a piston / cylinder assembly lubricated with high loss oil (MDCL) with full loss lubrication; and a crank lubricated with a low viscosity lubricant, usually called system oil Includes axis.
Trunk piston engines can be used in marine, power generation and railway traction applications and are faster than crosshead engines. A single lubricant (TPEO) is used to lubricate the crankcase and cylinder. All major moving parts of the engine, ie main and big end bearings, camshaft and valve gear, are lubricated using a pumped circulation system. The cylinder liner is lubricated partly by splash-type lubrication and partly by circulation system oil, which reaches the cylinder wall through the hole in the piston skirt via the connecting rod and the gudgeon pin.
船舶用潤滑剤は、日常的に金属清浄剤添加剤と配合される。この目的で清浄剤を使用することの実施上の問題は、サリチラート清浄剤とスルホナート清浄剤の特定の組み合わせが、ゲル又は相分離によって証明される安定性の問題を示すことである。
本発明の目的は、このような問題を軽減又は克服することである。
Marine lubricants are routinely blended with metal detergent additives. A practical problem of using detergents for this purpose is that certain combinations of salicylate detergents and sulfonate detergents exhibit stability problems that are evidenced by gel or phase separation.
The object of the present invention is to reduce or overcome such problems.
発明の概要
今やメチレン架橋アルキルフェノールにより例示される添加剤を用いて上記問題を克服できることが分かった。
従って、本発明は、一態様では、少量の潤滑粘度の油と、大量の(A)過塩基性金属ヒドロキシベンゾアート清浄剤添加剤及び(B)過塩基性金属スルホナート清浄剤添加剤と、(C)1〜10、好ましくは3〜5質量%の範囲の量の油溶性ヒドロカルビルフェノール-アルデヒド縮合物添加剤とを含む、2ストローク又は4ストローク船舶用エンジン潤滑油組成物のための添加剤パッケージであって、石鹸のミリモルとして表される(A)対(B)の比が90:10〜10:90、好ましくは80:20〜25:75の範囲内であり;かつ添加剤パッケージが、ASTM D2896を用いて好ましくは100〜450、さらに好ましくは150〜400のTBNを有する、添加剤パッケージを提供する。
Summary of the Invention It has now been found that the above problems can be overcome with additives exemplified by methylene bridged alkylphenols.
Accordingly, the present invention, in one aspect, comprises a small amount of an oil of lubricating viscosity and a large amount of (A) an overbased metal hydroxybenzoate detergent additive and (B) an overbased metal sulfonate detergent additive; C) Additive package for a two-stroke or four-stroke marine engine lubricating oil composition comprising an oil-soluble hydrocarbylphenol-aldehyde condensate additive in an amount ranging from 1 to 10, preferably 3 to 5% by weight. The ratio of (A) to (B) expressed as millimoles of soap is in the range of 90:10 to 10:90, preferably 80:20 to 25:75; and the additive package is An additive package is provided using ASTM D2896, preferably having a TBN of 100-450, more preferably 150-400.
第二態様では、少量の上記添加剤パッケージとブレンドされた、大量の潤滑粘度の油を含む、2ストローク又は4ストローク船舶用エンジン潤滑油組成物であって、2ストロークエンジン用組成物の場合はASTM D2896を用いて10〜120、好ましくは40〜100のTBNを有し、4ストロークエンジン用組成物の場合はASTM D2896を用いて25〜60のTBNを有する、組成物を提供する。
2ストロークエンジン用組成物を製造するためには添加剤パッケージを15〜30質量%の処理率で使用し、4ストロークエンジン用組成物を製造するためには添加剤パッケージを10〜20質量%の処理率で使用するのが好ましい。
潤滑油組成物は、2ストロークエンジン用組成物のためには0.15〜1.5質量%の油溶性ヒドロカルビルフェノール-アルデヒド縮合物添加剤を含み、4ストロークエンジンのためには0.1〜1質量%の油溶性ヒドロカルビルフェノール-アルデヒド縮合物添加剤を含むのが好ましい。
さらなる態様では、本発明は、
上記添加剤(A)及び(B)を上記比で含有する船舶用ディーゼルシリンダ潤滑剤において、該潤滑剤中における添加剤(A)及び(B)の安定性を改善するための、1〜10質量%の添加剤(C)の使用;並びに
クロスヘッド船舶用ディーゼルエンジンの潤滑化方法であって、エンジンの作動中にエンジンのピストン/シリンダに、本発明の上記態様の組成物を供給する工程を含む方法
を含む。
In a second embodiment, a two-stroke or four-stroke marine engine lubricating oil composition comprising a large amount of oil of lubricating viscosity blended with a small amount of the additive package, wherein the two-stroke engine composition is Compositions are provided having a TBN of 10 to 120, preferably 40 to 100 using ASTM D2896, and having a TBN of 25 to 60 using ASTM D2896 in the case of a four-stroke engine composition.
The additive package is used at a treatment rate of 15 to 30% by mass to produce a two-stroke engine composition, and the additive package is 10 to 20% by mass to produce a four-stroke engine composition. It is preferable to use at a treatment rate.
The lubricating oil composition contains 0.15-1.5 wt% oil-soluble hydrocarbylphenol-aldehyde condensate additive for 2-stroke engine compositions and 0.1-1 wt% oil-soluble for 4-stroke engines Preferably, a hydrocarbyl phenol-aldehyde condensate additive is included.
In a further aspect, the invention provides:
In a marine diesel cylinder lubricant containing the additives (A) and (B) in the above ratio, 1 to 10 for improving the stability of the additives (A) and (B) in the lubricant Use of a mass% additive (C); and a method of lubricating a crosshead marine diesel engine, wherein the composition of the above aspect of the invention is supplied to the piston / cylinder of the engine during engine operation. Including methods.
本明細書では、下記用語及び表現を使用する場合及び使用するとき、それらは以下に帰する意味を有する。
「活性成分」又は「(a.i.)」は、希釈剤又は溶媒でない添加剤材料を表し;
「含む」又はいずれの同種の用語も、規定した特徴、工程、又は整数若しくは成分の存在を特定するが、1つ以上の他の特徴、工程、整数、成分、又はそれらの群の存在又は付加を除外せず;「〜から成る」若しくは「本質的に〜から成る」という表現又は同種の表現は、「含む」又は同種の用語に包含され得る。ここで、「本質的に〜から成る」は、それが適用される組成物の特徴に物質的に影響を及ぼさない物質を含めることを許容し;
「ヒドロカルビル」は、分子の残部に直接付着した炭素原子及び主に炭化水素特性を有する置換基又は基(例えばアルキル基)を意味する。基の炭化水素特性を本質的に変えないとう条件でヘテロ原子が存在してもよく;
「大量」は、組成物の40又は50質量%以上、好ましくは60質量%以上、さらに好ましくは70質量%以上、最も好ましくは80質量%以上を意味し;
「少量」は、組成物の50質量%未満、好ましくは40質量%未満、さらに好ましくは30質量%未満、最も好ましくは20質量%未満、最も好ましくは10質量%を意味し;
「TBN」は、ASTM D2896により測定した場合の全塩基価を意味する。
As used herein, the following terms and expressions are used and when used, have the meaning ascribed to them below.
“Active ingredient” or “(ai)” represents an additive material that is not a diluent or solvent;
“Contains” or any similar term specifies the presence of a specified feature, step, or integer or component, but the presence or addition of one or more other features, steps, integers, components, or groups thereof The expression “consisting of” or “consisting essentially of” or like expressions may be encompassed by the term “including” or like terms. Here, “consisting essentially of” allows inclusion of substances that do not materially affect the characteristics of the composition to which it is applied;
“Hydrocarbyl” means a carbon atom directly attached to the rest of the molecule and a substituent or group having predominantly hydrocarbon character (eg, an alkyl group). Heteroatoms may be present provided that they do not substantially change the hydrocarbon character of the group;
“Major amount” means 40 or 50% by weight or more of the composition, preferably 60% by weight or more, more preferably 70% by weight or more, most preferably 80% by weight or more;
“Minor amount” means less than 50%, preferably less than 40%, more preferably less than 30%, most preferably less than 20%, most preferably less than 10% by weight of the composition;
“TBN” means the total base number as measured by ASTM D2896.
さらに本明細書では、使用する場合及び使用するとき、
「カルシウム含量」は、ASTM 4951により測定したものであり;
「リン含量」は、ASTM D5185により測定したものであり;
「硫酸灰分含量」は、ASTM D874により測定したものであり;
「硫黄含量」は、ASTM D2622により測定したものであり;
「KV100」は、100℃でASTM D445により測定した動粘度を意味する。
また、当然のことながら、必須のみならず最適及び慣例的な様々の使用成分は、配合、貯蔵又は使用の条件下で反応することがあり、本発明は、いずれの該反応の結果として得ることができるか又は得られた生成物をも提供する。
さらに、当然のことながら、本明細書で明記するいずれの上限及び下限の量、範囲及び比をも独立に組み合わせてよい。
Furthermore, in this specification, when using and when using,
“Calcium content” is measured by ASTM 4951;
“Phosphorus content” is measured by ASTM D5185;
“Sulfate ash content” is measured by ASTM D874;
"Sulfur content" is measured by ASTM D2622;
“KV100” means kinematic viscosity measured by ASTM D445 at 100 ° C.
Also, it will be appreciated that various components used, not only essential but also optimal and customary, may react under the conditions of formulation, storage or use, and the present invention may be obtained as a result of any such reaction. A product that can or is obtained is also provided.
Further, it will be appreciated that any upper and lower amount, range and ratio specified herein may be combined independently.
発明の詳細な説明
以下、本発明の特徴をさらに詳細に論じる。
<潤滑粘度の油>
潤滑剤組成物は、大きな割合の潤滑粘度の油を含有する。該潤滑油の粘度は、軽質留分鉱物油から重質潤滑油の粘度に及び得る。一般的に、油の粘度は、100℃で測定した場合に2〜40、例えば3〜15mm2/秒に及び、80〜100、例えば90〜95の粘度指数を有する。潤滑油は、組成物の60質量%より多く、典型的に70質量%より多くを構成し得る。
天然油には動物油及び植物油(例えば、ヒマシ油、ラード油);液体石油並びにパラフィン、ナフタレン及び混合パラフィン-ナフタレン型の水素化精製、溶媒処理又は酸処理された鉱物油がある。石炭又はシェール由来の潤滑粘度の油も有用な基油として役立つ。
合成潤滑油としては、炭化水素油及びハロ置換炭化水素油、例えば重合及び共重合オレフィン(例えば、ポリブチレン、ポリプロピレン、プロピレン-イソブチレンコポリマー、塩素化ポリブチレン、ポリ(1-ヘキセン)、ポリ(1-オクテン)、ポリ(1-デセン));アルキルベンゼン(例えば、ドデシルベンゼン、テトラデシルベンゼン、ジノニルベンゼン、ジ(2-エチルヘキシル)ベンゼン);ポリフェニル(例えば、ビフェニル、テルフェニル、アルキル化ポリフェノール);並びにアルキル化ジフェニルエーテル及びアルキル化ジフェニルスルフィド並びにその誘導体、類似体及び同族体が挙げられる。
DETAILED DESCRIPTION OF THE INVENTION The features of the present invention are discussed in further detail below.
<Oil of lubricating viscosity>
The lubricant composition contains a large proportion of oil of lubricating viscosity. The viscosity of the lubricating oil can range from a light cut mineral oil to a heavy lubricating oil. Generally, the viscosity of the oil ranges from 2 to 40, such as from 3 to 15 mm 2 / sec when measured at 100 ° C., and has a viscosity index of from 80 to 100, such as from 90 to 95. The lubricating oil may constitute more than 60%, typically more than 70% by weight of the composition.
Natural oils include animal and vegetable oils (eg, castor oil, lard oil); liquid petroleum and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffin, naphthalene and mixed paraffin-naphthalene type. 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 copolymerized olefins (e.g. polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly (1-hexene), poly (1-octene). ), Poly (1-decene)); alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene); polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenols); Examples include alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologues thereof.
アルキレンオキシドポリマー及びインターポリマー並びに末端ヒドロキシル基がエステル化、エーテル化等により修飾されたその誘導体は別分類の既知合成潤滑油を構成する。これらは、エチレンオキシド又はプロピレンオキシドの重合によって調製されるポリオキシアルキレンポリマー、並びにポリオキシアルキレンポリマーのアルキル及びアリールエーテル(例えば、1000の分子量を有するメチル-ポリイソプロピレングリコールエーテル又は1000〜1500の分子量を有するポリエチレングリコールのジフェニルエーテル);並びにそのモノカルボン酸エステル及びポリカルボン酸エステル、例えば、テトラエチレングリコールの酢酸エステル、混合C3-C8脂肪酸エステル及びC13オキソ酸ジエステルによって例示される。
別の適切な分類の合成潤滑油は、ジカルボン酸(例えば、フタル酸、コハク酸、アルキルコハク酸及びアルケニルコハク酸、マレイン酸、アゼライン酸、スベリン酸、セバシン酸、フマル酸、アジピン酸、リノール酸ダイマー、マロン酸、アルキルマロン酸、アルケニルマロン酸)と種々のアルコール(例えば、ブチルアルコール、ヘキシルアルコール、ドデシルアルコール、2-エチルヘキシルアルコール、エチレングリコール、ジエチレングリコールモノエーテル、プロピレングリコール)のエステルを含む。該エステルの具体例としては、アジピン酸ジブチル、セバシン酸ジ(2-エチルヘキシル)、フマル酸ジ-n-ヘキシル、セバシン酸ジオクチル、アゼライン酸ジイソオクチル、アゼライン酸ジイソデシル、フタル酸ジオクチル、フタル酸ジデシル、セバシン酸ジエイコシル、リノール酸ダイマーの2-エチルヘキシルジエステル、並びに1モルのセバシン酸を2モルのテトラエチレングリコール及び2モルの2-エチルヘキサン酸と反応させることによって形成される複合エステルが挙げられる。
Alkylene oxide polymers and interpolymers and derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These include polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having a molecular weight of 1000 or a molecular weight of 1000-1500. And the monocarboxylic and polycarboxylic acid esters thereof, such as tetraethylene glycol acetate, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diesters.
Another suitable class of synthetic lubricating oils are dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid. Dimers, malonic acids, alkylmalonic acids, alkenylmalonic acids) and esters of various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of the ester include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, sebacin Examples include dieicosyl acid, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid.
合成油として有用なエステルには、C5-C12モノカルボン酸と、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール及びトリペンタエリスリトール等のポリオール及びポリオールエステルとから作製されるものも含まれる。
ケイ素ベース油、例えばポリアルキル-、ポリアリール-、ポリアルコキシ-又はポリアリルオキシシリコーン油及びシリカート油は、合成潤滑油の別の有用な分類を構成し;該油としては、テトラエチルシリカート、テトライソプロピルシリカート、テトラ-(2-エチルヘキシル)シリカート、テトラ-(4-メチル-2-エチルヘキシル)シリカート、テトラ-(p-tert-ブチル-フェニル)シリカート、ヘキサ-(4-メチル-2-エチルヘキシル)ジシロキサン、ポリ(メチル)シロキサン及びポリ(メチルフェニル)シロキサンが挙げられる。他の合成潤滑油には、リン含有酸の液体エステル(例えば、リン酸トリクレジル、リン酸トリオクチル、デシルホスホン酸のジエチルエステル)及びポリマーテトラヒドロフランがある。
本発明の潤滑剤には未精製油、精製油及び再精製油を使用することができる。未精製油は、さらに精製処理することなく、天然又は合成源から直接得たものである。例えば、レトルト採収操作から直接得られるシェール油;蒸留から直接得られる石油;又はエステル化から直接得られ、さらに精製せずに用いられるエステル油は未精製油である。
Esters useful as synthetic oils include those made from C 5 -C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. included.
Silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyallyloxysilicone oils and silicate oils constitute 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) di Mention may be made of siloxanes, poly (methyl) siloxanes and poly (methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
Unrefined oil, refined oil and re-refined oil can be used for the lubricant of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly from retort harvesting operations; petroleum oil obtained directly from distillation; or ester oil obtained directly from esterification and used without further purification is an unrefined oil.
米国石油協会(API)出版物「エンジン油のライセンス供与及び認可システム(Engine Oil Licensing and Certification System)」(Industry Services Department,第14版,1996年12月,補遺1,1998年12月)は、ベースストックを以下のように分類している。
a)グループIベースストックは、90%未満の飽和物及び/又は0.03%を超える硫黄を含有し、かつ表E-1に特定した試験方法を用いて80以上120未満の粘度指数を有する。
b)グループIIベースストックは、90%以上の飽和物及び0.03%以下の硫黄を含有し、かつ表E-1に特定した試験方法を用いて80以上120未満の粘度指数を有する。
c)グループIIIベースストックは、90%以上の飽和物及び0.03%以下の硫黄を含有し、かつ表E-1に特定した試験方法を用いて120以上の粘度指数を有する。
d)グループIVベースストックは、ポリアルファオレフィン(PAO)である。
e)グループVベースストックは、グループI、II、III、又はIVに含まれない他の全てのベースストックを含む。
ベースストックの分析方法を以下に表にする。
The American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System” (Industry Services Department, 14th Edition, December 1996, Addendum 1, December 1998) Base stock is classified as follows.
a) Group I base stock contains less than 90% saturates and / or more than 0.03% sulfur and has a viscosity index of 80 to less than 120 using the test method specified in Table E-1.
b) Group II base stock contains 90% or more of saturates and 0.03% or less of sulfur and has a viscosity index of 80 or more and less than 120 using the test method specified in Table E-1.
c) Group III base stock contains 90% or more of saturates and 0.03% or less of sulfur and has a viscosity index of 120 or more using the test method specified in Table E-1.
d) Group IV base stock is polyalphaolefin (PAO).
e) Group V base stock includes all other base stocks not included in Group I, II, III, or IV.
The analysis method of base stock is shown in the table below.
表E-1 Table E-1
本発明は、好ましくは、潤滑粘度の油として90%以上の飽和物及び0.03%以下の硫黄を含有する上記油の当該ベースストック、例えばグループII、III、IV又はVを包含する。それらはフィッシャー・トロプシュ法によって合成された炭化水素由来のベースストックをも含む。フィッシャー・トロプシュ法では、一酸化炭素及び水素を含有する合成ガス(または「シンガス」)が最初に生成され、次にフィッシャー・トロプシュ触媒を用いて炭化水素に変換される。これらの炭化水素は、基油として役立つためには一般的にさらなる加工を必要とする。例えば、それらは技術上周知の方法によって水素異性化;水素化分解及び水素異性化;脱蝋;又は水素異性化及び脱蝋され得る。シンガスは、例えば、ベースストックをガス液化(gas-to-liquid)(「GTL」)基油と呼べるときには、水蒸気改質により天然ガス又は他のガス状炭化水素等のガスから;或いはベースストックをバイオマス液化(biomass-to-liquid)(「BTL」又は「BMTL」)基油と呼べるときには、バイオマスのガス化から;或いはベースストックを石炭液化(coal-to-liquid)(「CTL」)基油と呼べるときには石炭のガス化から製造可能である。
好ましくは、本発明における潤滑粘度の油は50質量%以上の前記ベースストックを含有する。該油は60質量%以上、例えば70、80又は90質量%以上の前記ベースストック又はその混合物を含有し得る。潤滑粘度の油は、実質的に全て前記ベースストック又はその混合物であってよい。
The present invention preferably includes such base stocks of the above oils containing, for example, greater than 90% saturates and less than 0.03% sulfur as oils of lubricating viscosity, such as Groups II, III, IV or V. They also include hydrocarbon-derived base stocks synthesized by the Fischer-Tropsch process. In the Fischer-Tropsch process, synthesis gas (or “syngas”) containing carbon monoxide and hydrogen is first produced and then converted to hydrocarbons using a Fischer-Tropsch catalyst. These hydrocarbons generally require further processing to serve as base oils. For example, they can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed by methods well known in the art. Syngas, for example, when the base stock can be referred to as a gas-to-liquid (“GTL”) base oil, is obtained from a gas such as natural gas or other gaseous hydrocarbons by steam reforming; Biomass-to-liquid (“BTL” or “BMTL”) base oil, when referred to as biomass gasification; or base stock from coal-to-liquid (“CTL”) base oil Can be produced from coal gasification.
Preferably, the oil of lubricating viscosity in the present invention contains 50% by mass or more of the base stock. The oil may contain 60% by weight or more, for example 70, 80 or 90% by weight or more of the base stock or mixtures thereof. The oil of lubricating viscosity may be substantially all of the base stock or a mixture thereof.
<添加剤(A)及び(B)>
これらはそれぞれ清浄剤、すなわち、エンジン内の堆積物、例えば高温ワニス及びラッカー堆積物の形成を減らす添加剤であり;清浄剤は酸中和特性を有し、微粉化固体を懸濁液中で保持することができる。清浄剤は金属「石鹸」、すなわち界面活性剤と呼ばれることもある酸性有機化合物の金属塩に基づいている。
清浄剤は、極性頭部と長い疎水性尾部を含む。過剰の金属化合物、例えば酸化物又は水酸化物を二酸化炭素等の酸性ガスと反応させることによって大量の金属塩基が含められて、金属塩基(例えば、カルボナート)ミセルの外層として中和した清浄剤を含む、過塩基性清浄剤が得られる。
清浄剤は、好ましくは酸から選択される界面活性剤の過塩基性の油溶性又は油分散性カルシウム、マグネシウム、ナトリウム又はバリウム塩等のアルカリ金属又はアルカリ土類金属添加剤であり、この過塩基性は、界面活性剤の油溶性塩によって油性希釈剤中で安定化される、油不溶性の金属塩、例えば炭酸塩、塩基性炭酸塩、酢酸塩、ギ酸塩、水酸化物又はシュウ酸塩によってもたらされる。油溶性界面活性剤塩の金属は、油不溶性塩の金属と同一又は異なっていてよい。油溶性塩であろうと油不溶性塩であろうと、金属はカルシウムであるのが好ましい。
清浄剤のTBNは、ASTM D2896によって測定した場合に、低い値、すなわち50mgKOH/g未満、中程度の値、すなわち50〜150mgKOH/g、又は高い値、すなわち150mgKOH/gを超える値であり得る。好ましくはTBNは、中程度又は高い値であり、すなわち50TBNを超える。さらに好ましくは、TBNは、ASTM D2896によって測定した場合に、少なくとも60mgKOH/g、さらに好ましくは少なくとも100mgKOH/g、さらに好ましくは少なくとも150mgKOH/gであり、かつ500mgKOH/gまで、例えば350mgKOH/gまでである。
清浄剤(A)においては、界面活性剤はヒドロキシ安息香酸から選択され、特定例はサリチル酸であり、塩はサリチラートである。サリチラート清浄剤は技術上周知である。
清浄剤(B)においては、界面活性剤はスルホン酸から選択され、塩はスルホナートである。スルホナート清浄剤も技術上周知である。
使用可能な清浄剤は、技術上周知なもののようにヒドロカルビル(例えばアルキル)置換されているものである。
上述したように、石鹸のミリモルとして表される(A)対(B)の比は、90:10〜10:90の範囲内である。範囲の上限の例として、80:20及び75:25を挙げることができる。範囲の下限の例として25:75を挙げることができる。前記上限及び下限を独立に組み合わせて下位範囲を与えることができる。
<Additives (A) and (B)>
Each of these is a detergent, i.e. an additive that reduces the formation of deposits in the engine, such as hot varnish and lacquer deposits; Can be held. Detergents are based on metal “soaps”, ie metal salts of acidic organic compounds, sometimes called surfactants.
The detergent includes a polar head and a long hydrophobic tail. A detergent that has been neutralized as an outer layer of a metal base (e.g., carbonate) micelle that includes a large amount of metal base by reacting excess metal compound, e.g., oxide or hydroxide, with an acidic gas such as carbon dioxide. An overbased detergent containing is obtained.
The detergent is 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 preferably selected from acids, the overbase Is stabilized by oil-insoluble metal salts, such as carbonates, basic carbonates, acetates, formates, hydroxides or oxalates, which are stabilized in oily diluents by oil-soluble salts of surfactants. Brought about. The metal of the oil-soluble surfactant salt may be the same as or different from the metal of the oil-insoluble salt. Whether it is an oil-soluble salt or an oil-insoluble salt, the metal is preferably calcium.
The TBN of the detergent can be low, i.e. less than 50 mg KOH / g, moderate, i.e. 50-150 mg KOH / g, or high, i.e. above 150 mg KOH / g, as measured by ASTM D2896. Preferably TBN is moderate or high, i.e. above 50TBN. More preferably, the TBN is at least 60 mg KOH / g, more preferably at least 100 mg KOH / g, more preferably at least 150 mg KOH / g, and up to 500 mg KOH / g, for example up to 350 mg KOH / g, as measured by ASTM D2896. is there.
In detergent (A), the surfactant is selected from hydroxybenzoic acid, a specific example is salicylic acid, and the salt is salicylate. Salicylate detergents are well known in the art.
In detergent (B), the surfactant is selected from sulfonic acids and the salt is a sulfonate. Sulfonate detergents are also well known in the art.
Detergents that can be used are those that are hydrocarbyl (eg alkyl) substituted, as is well known in the art.
As noted above, the ratio of (A) to (B) expressed as millimoles of soap is in the range of 90:10 to 10:90. Examples of the upper limit of the range include 80:20 and 75:25. An example of the lower limit of the range is 25:75. The lower limit can be given by combining the upper and lower limits independently.
<添加剤(C):例えばメチレン架橋アルキルフェノール(「MBAP」)>
これらは技術上周知であり、オキシアルキル化ヒドロカルビルフェノール縮合物の油溶性混合物を含み得る。ここで、フェノール官能基から調製されるオキシアルキル基は、式-(R'O)n-を有し、式中、R'はエチレン、プロピレン又はブチレン基であり;かつnは独立に0〜10であり;縮合物のフェノール官能基の45モル%未満、好ましくは30モル%未満はオキシアルキル化されず;縮合物のフェノール官能基の55モル%超えはモノオキシアルキル化されている。
該縮合物は、下記一般構造式で表すことができる。
<Additive (C): for example, methylene-bridged alkylphenol ("MBAP")>
These are well known in the art and may include oil-soluble mixtures of oxyalkylated hydrocarbyl phenol condensates. Where the oxyalkyl group prepared from the phenol functional group has the formula — (R′O) n —, where R ′ is an ethylene, propylene or butylene group; and n is independently from 0 to Less than 45 mol%, preferably less than 30 mol% of the phenol functionality of the condensate is not oxyalkylated; more than 55 mol% of the phenol functionality of the condensate is monooxyalkylated.
The condensate can be represented by the following general structural formula.
式中:
xは1〜50、好ましくは1〜40、さらに好ましくは1〜30であり;
R1及びR2は、H、1〜12個の炭素原子を有するヒドロカルビル基、又は1〜12個の炭素原子と少なくとも1個のヘテロ原子を有するヒドロカルビル基であり;かつ
Rは、9〜100個、好ましくは9〜70個、さらに好ましくは9〜50個の炭素原子を有するヒドロカルビル基である。
EP-A-2,374,866は、該縮合物についてさらに詳細に述べている。MBAPは、該縮合物の一実施形態を構成する。
上述したように、(C)は1〜10質量%、好ましくは3〜5質量%の範囲の量で存在する。下位範囲の例として、1〜7質量%及び1〜5質量%を挙げることもできる。
誤解を避けるため、本発明で使用するMBAPは、キャップされ(capped)ていてもキャップされていなくてもよいことを明記する。
In the formula:
x is 1 to 50, preferably 1 to 40, more preferably 1 to 30;
R 1 and R 2 are H, a hydrocarbyl group having 1 to 12 carbon atoms, or a hydrocarbyl group having 1 to 12 carbon atoms and at least one heteroatom; and
R is a hydrocarbyl group having 9 to 100, preferably 9 to 70, more preferably 9 to 50 carbon atoms.
EP-A-2,374,866 describes the condensate in more detail. MBAP constitutes one embodiment of the condensate.
As mentioned above, (C) is present in an amount ranging from 1 to 10% by weight, preferably from 3 to 5% by weight. Examples of the lower range may include 1 to 7% by mass and 1 to 5% by mass.
For the avoidance of doubt, it is clearly stated that the MBAP used in the present invention may be capped or uncapped.
<船舶用潤滑剤>
船舶用ディーゼルシリンダ潤滑剤(「MDCL」)
MDCLは、10〜35質量%、好ましくは13〜30質量%、最も好ましくは16〜24質量%の濃縮物又は添加剤パッケージを利用することができ、残りはベースストックである。MDCLは、MDCLの総質量に基づいて好ましくは少なくとも50質量%、さらに好ましくは少なくとも60質量%、さらに好ましくは少なくとも70質量%の潤滑粘度の油を含む。好ましくは、MDCLは、10〜100、例えば70〜100又は40〜100、好ましくは60〜90、さらに好ましくは70〜80の組成上のTBN(ASTM D2896を用いて)を有する。
MDCL中の添加剤の典型的な割合の例として以下のものを挙げることができる。
<Ship lubricant>
Marine diesel cylinder lubricant (MDCL)
The MDCL can utilize a 10-35 wt% concentrate, preferably 13-30 wt%, most preferably 16-24 wt% concentrate or additive package, with the remainder being base stock. The MDCL preferably comprises an oil having a lubricating viscosity of at least 50% by weight, more preferably at least 60% by weight, more preferably at least 70% by weight, based on the total weight of the MDCL. Preferably, the MDCL has a TBN (using ASTM D2896) with a composition of 10-100, such as 70-100 or 40-100, preferably 60-90, more preferably 70-80.
Examples of typical proportions of additives in MDCL include the following.
トランクピストンエンジン油(「TPEO」)
TPEOは、7〜35質量%、好ましくは10〜28質量%、さらに好ましくは12〜24質量%の濃縮物又は添加剤パッケージを利用することができ、残りはベースストックである。好ましくは、TPEOは、25〜60、例えば25〜55の組成物上のTBN(ASTM D2896を用いて)を有する。
TPEO中の添加剤の典型的な割合として以下のものを挙げることができる。
Trunk piston engine oil (TPEO)
The TPEO can utilize a concentrate or additive package of 7-35% by weight, preferably 10-28% by weight, more preferably 12-24% by weight, the rest being base stock. Preferably, the TPEO has a TBN (using ASTM D2896) on the composition of 25-60, such as 25-55.
The following can be mentioned as typical proportions of additives in TPEO.
本明細書で使用する用語「油溶性」又は「油分散性」は、化合物又は添加剤が全ての割合で油に可溶性、溶解性、混和性又は懸濁できることを必ずしも意味しない。しかしながら、これらの用語は、化合物又は添加剤が、油を利用する環境においてそれらの意図した効果を発揮するのに十分な程度まで油に、例えば、可溶又は安定分散性であることを意味する。さらに、必要に応じて、他の添加剤をさらに組み込むと、特定添加剤のより高いレベルの組み込みを可能にすることもある。
本発明の潤滑剤組成物は、定義された個々の(すなわち個別の)成分を含み、これらは混合の前後で化学的に同一のままであってもそうでなくてもよい。
必須ではないが、添加剤を含む1種以上の添加剤パッケージ又は濃縮物を調製し、それによって潤滑粘度の油に添加剤を同時に添加して潤滑油組成物を形成するのが望ましいことがある。溶媒によって及び穏やかに加熱しながら混合することによって、潤滑粘度の油への添加剤パッケージの分散を促進することができるが、これは必須ではない。一般的に、所望濃度をもたらすために適した量で添加剤を含有し、及び/又は添加剤パッケージをベース潤滑剤と併用するときに最終配合物において意図した機能を果たすように添加剤パッケージを配合することになる。
従って、添加剤を、他の望ましい添加剤と共に少量の基油又は他の相溶性溶媒と混合して、添加剤パッケージに基づいて、例えば、2.5〜90、好ましくは5〜75、最も好ましくは8〜60質量%の適切な割合の添加剤、残りは基油という量で活性成分を含有する添加剤パッケージを形成することができる。
最終配合物は、典型的に約5〜40質量%の添加剤パッケージを含有し、残りは基油であってよい。
As used herein, the term “oil-soluble” or “oil-dispersible” does not necessarily mean that the compound or additive can be soluble, soluble, miscible or suspended in oil in all proportions. However, these terms mean that the compound or additive is soluble or stable dispersible in the oil to a degree sufficient to exert their intended effect in the environment in which the oil is utilized. . Furthermore, if necessary, further incorporation of other additives may allow higher levels of incorporation of specific additives.
The lubricant composition of the present invention comprises defined individual (ie, individual) components that may or may not remain chemically the same before and after mixing.
Although not required, it may be desirable to prepare one or more additive packages or concentrates containing the additives, thereby simultaneously adding the additives to the oil of lubricating viscosity to form a lubricating oil composition. . Mixing with a solvent and with gentle heating can facilitate the dispersion of the additive package into the oil of lubricating viscosity, but this is not essential. In general, the additive package should contain the additive in an amount suitable to provide the desired concentration and / or perform the intended function in the final formulation when the additive package is used with the base lubricant. Will be blended.
Thus, the additive is mixed with a small amount of base oil or other compatible solvent along with other desirable additives, for example 2.5-90, preferably 5-75, most preferably 8 based on the additive package. Additive packages containing the active ingredient in an appropriate proportion of additives of ˜60% by weight, the remainder being base oil can be formed.
The final formulation typically contains about 5-40% by weight additive package with the remainder being base oil.
実施例
本発明を下記実施例によって説明するが、本発明をこれらに限定するものではない。
<安定性試験方法>
種々の割合のカルシウムサリチラート清浄剤(塩基度指数1.35)及びカルシウムスルホナート清浄剤(塩基度指数22.0)をスターラ及びホットプレートの助けを借りて単一段階で、1%の希釈油と共に75℃で30分間混合した。これにより一連の混合物を得た。
結果として生じた各混合物を目盛付きガラス安定性管中に注ぎ、室温及び60℃で12週間にわたって試験した。
毎週、添加剤の不安定性の証拠として、ゲル形成、相分離、管底に降下する沈降物の量、及び濁りについて安定性管を目視検証した。
試験は、メチレン架橋ドデシルフェノキシエタノール(キャップされていない「MBAP」)を含有する混合物及びそれを含有しない混合物について行なった。
<結果>
Examples The present invention is illustrated by the following examples, but the present invention is not limited thereto.
<Stability test method>
Various proportions of calcium salicylate detergent (basicity index 1.35) and calcium sulfonate detergent (basicity index 22.0) in a single step with the help of stirrer and hotplate, 75% with 1% diluent oil Mix at 30 ° C. for 30 minutes. This gave a series of mixtures.
Each resulting mixture was poured into a graduated glass stability tube and tested at room temperature and 60 ° C. for 12 weeks.
Each week, the stability tube was visually inspected for gel formation, phase separation, amount of sediment falling to the tube bottom, and turbidity as evidence of additive instability.
The test was performed on a mixture containing methylene bridged dodecylphenoxyethanol (uncapped “MBAP”) and a mixture containing no.
<Result>
キー:
OK:添加剤の安定性問題観察されず
ゲル/相分離n:添加剤不安定性(相分離よりひどいゲル形成)
数:安定性性能を観察及び報告した週数(最初の数は室温試験;2番目の数は60℃試験)
Key:
OK: Additive stability not observed, gel / phase separation n : Additive instability (gel formation worse than phase separation)
Number: Weeks in which stability performance was observed and reported (first number at room temperature test; second number at 60 ° C test)
上記データは、以下のことを示している。
1. 90/10比では、MBAPの非存在下でさえ、安定性問題は観察されなかった。
2. 75/25比では、MBAPの非存在下で安定性問題が観察され;室温試験は、1、3及び5質量%のMBAPで安定性問題を示さず;60℃試験は、1及び3質量%のMBAPで改善を示し、5質量%のMBAPで問題ないことを示した。
3. 50/50比では、MBAPの非存在下及び1質量%のMBAPで問題が観察され;3質量%のMBAP試験はいくらかの改善をもたらし;5質量%のMBAP試験は、室温でも60℃でも安定性問題を示さなかった。
4. 25/75比では、MBAPが無い場合に問題が観察され;1及び3質量%のMBAPでは、室温の結果は60℃の結果より悪く;5質量%のMBAP試験は、室温でも60℃でも安定性問題を示さなかった。
The above data shows the following.
1. At 90/10 ratio, no stability problem was observed even in the absence of MBAP.
2. At 75/25 ratio, stability problems are observed in the absence of MBAP; room temperature test shows no stability problems at 1, 3 and 5 wt% MBAP; 60 ° C test is 1 and 3 The mass% MBAP showed improvement, and 5% by mass MBAP showed no problem.
3. At 50/50 ratio, problems are observed in the absence of MBAP and 1% by weight MBAP; 3% by weight MBAP test provides some improvement; 5% by weight MBAP test is 60 ° C. even at room temperature But it showed no stability problems.
4. At 25/75 ratio, problems are observed in the absence of MBAP; with 1 and 3 wt% MBAP, room temperature results are worse than 60 ° C results; 5 wt% MBAP test is 60 ° C even at room temperature But it showed no stability problems.
Claims (8)
少量の潤滑粘度の油と、大量の(A)過塩基性金属ヒドロキシベンゾアート清浄剤添加剤及び(B)過塩基性金属スルホナート清浄剤添加剤と、(C)1〜10、好ましくは3〜6質量%の範囲の量の油溶性ヒドロカルビルフェノール-アルデヒド縮合物添加剤とを含み、
石鹸のミリモルとして表される(A)対(B)の比が90:10〜10:90、好ましくは80:20〜20:80の範囲内である、前記添加剤パッケージ。 An additive package for a two-stroke or four-stroke marine engine lubricating oil composition comprising:
A small amount of oil of lubricating viscosity, a large amount of (A) an overbased metal hydroxybenzoate detergent additive and (B) an overbased metal sulfonate detergent additive, and (C) 1-10, preferably 3 An oil soluble hydrocarbylphenol-aldehyde condensate additive in an amount in the range of 6% by weight;
Said additive package, wherein the ratio of (A) to (B) expressed as millimoles of soap is in the range of 90:10 to 10:90, preferably 80:20 to 20:80.
大量の潤滑粘度の油を含み、かつ少量の請求項1に記載の添加剤パッケージとブレンドされ、
2ストロークエンジン用組成物の場合はASTM D2896を用いて10〜120、好ましくは40〜100のTBNを有し、4ストロークエンジン用組成物の場合はASTM D2896を用いて25〜60のTBNを有する、前記組成物。 A two-stroke or four-stroke marine engine lubricating oil composition,
Comprising a large amount of oil of lubricating viscosity and a small amount blended with the additive package of claim 1;
2 stroke engine compositions have a TBN of 10-120, preferably 40-100 using ASTM D2896, and 4 stroke engines compositions have a TBN of 25-60 using ASTM D2896. , The composition.
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CN106318540B (en) | 2021-03-16 |
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