EP2342312B1 - Low pour point lubricant base stock - Google Patents
Low pour point lubricant base stock Download PDFInfo
- Publication number
- EP2342312B1 EP2342312B1 EP09823893.4A EP09823893A EP2342312B1 EP 2342312 B1 EP2342312 B1 EP 2342312B1 EP 09823893 A EP09823893 A EP 09823893A EP 2342312 B1 EP2342312 B1 EP 2342312B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- propanediol
- base stock
- lubricant base
- substituted
- engine
- 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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- 239000000314 lubricant Substances 0.000 title claims description 51
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 30
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 30
- 150000002148 esters Chemical class 0.000 claims description 29
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical class C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 17
- 239000000539 dimer Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000013638 trimer Substances 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- RXGPYPPCEXISOV-UHFFFAOYSA-N 2-propylheptanoic acid Chemical compound CCCCCC(C(O)=O)CCC RXGPYPPCEXISOV-UHFFFAOYSA-N 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical group CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 7
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 claims description 6
- 150000005691 triesters Chemical class 0.000 claims description 6
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 6
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000001735 carboxylic acids Chemical class 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- 241001550224 Apha Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- -1 ester compounds Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/34—Esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- 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
- 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
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
- C10M2209/1095—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified used as base material
-
- 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
- C10N2020/011—Cloud point
-
- 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
- C10N2020/071—Branched chain compounds
-
- 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
- C10N2030/02—Pour-point; 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/74—Noack Volatility
-
- 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
- C10N2040/12—Gas-turbines
- C10N2040/13—Aircraft turbines
-
- 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
-
- 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
- C10N2040/255—Gasoline 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
- C10N2040/255—Gasoline engines
- C10N2040/26—Two-strokes or two-cycle engines
Definitions
- the present invention refers to an automotive, an aeronautic, a marine or a stationary engine or turbine lubricant base stock comprising at least one ester between 2-propylheptanoic acid and at least one 2,2-substituted 1,3-propanediol and/or at least one dimer, trimer or polymer thereof and/or at least one alkoxylated species of a said 2,2-substituted 1,3-propanediol or a said dimer, trimer or polymer thereof, and to the use of said lubricant base stock for internal combustion engines and turbine engines.
- a lubricant comprising a lubricant base stock formulated with appropriate performance additives, must comprehensively comply with the requirements of a specific application and it is typically not enough to comply with one specific parameter, such as viscosity, only, but compliance is required for the whole set of application properties, often comprising specific demands for parameters such as viscosity, viscosity stability, flash point, pour point, volatility etc.
- Lubricant base stocks are classified according to API (American Petroleum Institute, API Publication 1509) into five categories according to their chemical composition: Groups I to III consisting of different grades of mineral oil base stocks, Group IV being defined for Poly( ⁇ -olefins) and Group V being reserved for all other base stocks, including ester base stocks. It is known in the art that base stocks of different groups contribute to certain typical lubricant performance, such as low temperature properties, oxidation stability and/or compatibility properties. It is also known in the art, when formulating a final lubricant product for a specific application, that two or more base stocks of one or more groups can be combined. Synthetic esters are known to be combined with base stocks from other groups, such as poly( ⁇ -olefin) of API Group IV as disclosed in US 5,151,205 or with mineral oils, API Groups 1 to 3 as disclosed in US 5,665,683 .
- a lubricant is typically formulated by combining a lubricant base stock, or a mixture of lubricant base stocks, of suitable inherent properties with additives and other optional formulation aids.
- Esters of diols, triols, tetrols and polyols are frequently used lubricant base stocks in a number of high-performance lubricant applications. Said esters are obtained from an alcohol, having two or more hydroxyl groups, which alcohol is esterified with a carboxylic acid or acid mixture. During the esterification process the hydroxyl groups of said alcohol are converted partially or fully into ester groups, by means of having an acid component attached to them.
- Formulation of a lubricant meeting specific end-properties typically involves the step of selecting a base-stock inherently exhibiting properties being close to the ones required. It is known in the art, that the final fine-tuning of the desired properties can be made by means of blending the base-stock with other components, capable of modifying the properties in accordance to the specification and other demands. Blending is, however, not always preferred, as this introduces complexity to the system, at least in the form of an increased number of components included in the lubricant.
- ester product may, for instance, be composed of a mixture of said alcohols esterified with a carboxylic acid or a said alcohol can be esterified with a mixture of carboxylic acids in order to obtain for instance improved compatibility and cold-flow properties. In even more general terms this may apply when combing a mixture of said alcohols with a mixture of carboxylic acids in order to obtain a statistical mixture of ester end-products.
- Esters based on said mixtures of raw materials are not, however, desired in all cases. They induce a degree of composition uncertainty to the system, and one or more of the statistically formed ester compounds may contribute to undesired and/or adverse performance. There are thus needs and demands for a range of different, essentially single reactants esters showing advantageous inherent properties.
- Pour point is a lubricant property, which characterises the cold flow properties of a lubricant. Pour point is reported as the reading of the lowest temperature where a test lubricant shows a defined degree of fluidity. A more detailed description is given in the standard ASTM D5950. Low pour point is desired in lubricants aimed for use at low temperature conditions, occurring for instance at the startup of engines in cold climate and/or winter conditions. Examples of applications requiring good cold properties include, but are not limited to, automotive and aviation lubricants, lubricants for automotive, stationary and 2-stroke engines, hydraulic fluids, refrigeration lubricants, dielectric fluids and greases.
- Esters of branched carboxylic acids are known to contribute to reduced pour point, as disclosed in for instance US 4,514,314 . So far, however, reported and used branched carboxylic acids are either neo or iso-branched. 2-ethylhexanoic acid is the only used 2-branched carboxylic acid having more than four carbons and in the literature disclosed carboxylic acids having 10 or more carbon atoms are either linear acids, iso-acids or neo-acids.
- the present invention accordingly refers to an automotive, an aeronautic, a marine or a stationary engine or turbine lubricant base stock comprising at least one ester obtained by esterifying 2-propylheptanoic acid with (i) at least one 2,2-substituted 1,3-propanediol and/or at least one dimer, trimer or polymer thereof, wherein said 2,2-substituted 1,3-propanediol is neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolethane or trimethylolbutane, and/or (ii) at least one alkoxylated species of a said 2,2-substituted 1,3-propanediol or a said dimer, trimer or polymer thereof.
- the present invention refers to the use of a lubricant base stock comprising at least one ester between 2-propylheptanoic acid and at least one 2,2-substituted 1,3 - propanediol and/or at least one dimer, trimer or polymer thereof and/or at least one alkoxylated species of a said 2,2-substituted 1,3-propanediol or a said dimer, trimer or polymer thereof in production of a lubricant for internal combustion engines and turbine engines, such as automotive engines, aeronautic engines, marine engines and stationary engines. Said engines can suitably be exemplified by for instance otto, diesel, wanckel and jet engines, including 2-stroke engines.
- the herein most preferred lubricant base stock comprises a triester of trimethylolpropane or a tetraester of pentaerythritol and/or di-trimethylolpropane.
- Said 2,2-substituted 1,3-propanediol is in preferred embodiments of the present invention a 2,2-dialkyl-1,3-propanediol, a 2-alkyl-2-hydroxyalkyl-1,3-propanediol or a 2,2-dihydroxyalkyl-1,3-propanediol, wherein said alkyl preferably is a C 1 -C 8 alkyl.
- the most preferred embodiments of said 2,2-substituted 1,3-propanediol and said dimer, trimer and polymer thereof include neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolethane, trimethylolbutane, trimethylolpropane, pentaerythritol, di-trimethylolpropane and di-pentaerythritol.
- Said alkoxylated species are preferably selected from the group consisting of ethoxylated and/or propoxylated trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, di-trimethylolpropane and di-pentaerythritol.
- Said ester is in especially preferred embodiments of the present invention a triester or tetraester of a said 2-alkyl-2-hydroxyalkyl-1,3-propanediol or a said 2,2-dihydroxyalkyl-1,3-propanediol or a said dimer, trimer of polymer thereof, such as an esterification product, between 2-propylheptanoic acid and pentaerythritol, trimethylolpropane or di-trimethylolpropane, having a triester or tetraster content of at least 95%, such as at least 97%, by weight.
- Example 1 was repeated with the difference that pentaerythritol was replaced by the same amount of trimethylolpropane and that 561.5 g of 2-propylheptanoic acid was charged instead of 733.8 g, yielding pale yellow ester product having following properties.
- Example 1 was repeated with the difference that 2-propylheptanoic acid was replaced by 613.4 g of 2-ethylhexanoic acid, yielding pale yellow ester product having following properties.
- ester products lubricant base stocks
- the ester products according to embodiments of the present invention exhibited substantially improved properties.
- the result is given in Table 1 below.
- Example 1 The ester products obtained in Example 1 and Example 3 (comparative) were over night placed in a freezer at -18-20°C.
- the product of Example 1 was after said time a clear high viscous liquid, while the product of Example 3 was an opaque waxy solid.
- Table 1 Property Viscosity at 40°C, cSt Viscosity at 100°C, cSt Viscosity index value Pour point °C Flash point closed cup °C NOACK evaporation %-w/w ENISO3104 ENISO 3104 ASTM D 2270 ASTM D 5950 ENISO2492 CEC L40-93-B Ex. 1 57.2 7.83 110 ⁇ -56 270 1.7 Ex. 2 34.4 5.44 89 ⁇ -52 244 5.0 Ex. 3 46.2 6.39 82 -6 178 3.4
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- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
- The present invention refers to an automotive, an aeronautic, a marine or a stationary engine or turbine lubricant base stock comprising at least one ester between 2-propylheptanoic acid and at least one 2,2-substituted 1,3-propanediol and/or at least one dimer, trimer or polymer thereof and/or at least one alkoxylated species of a said 2,2-substituted 1,3-propanediol or a said dimer, trimer or polymer thereof, and to the use of said lubricant base stock for internal combustion engines and turbine engines. Qualifying for a specific application, a lubricant, comprising a lubricant base stock formulated with appropriate performance additives, must comprehensively comply with the requirements of a specific application and it is typically not enough to comply with one specific parameter, such as viscosity, only, but compliance is required for the whole set of application properties, often comprising specific demands for parameters such as viscosity, viscosity stability, flash point, pour point, volatility etc.
- Lubricant base stocks are classified according to API (American Petroleum Institute, API Publication 1509) into five categories according to their chemical composition: Groups I to III consisting of different grades of mineral oil base stocks, Group IV being defined for Poly(α-olefins) and Group V being reserved for all other base stocks, including ester base stocks. It is known in the art that base stocks of different groups contribute to certain typical lubricant performance, such as low temperature properties, oxidation stability and/or compatibility properties. It is also known in the art, when formulating a final lubricant product for a specific application, that two or more base stocks of one or more groups can be combined. Synthetic esters are known to be combined with base stocks from other groups, such as poly(α-olefin) of API Group IV as disclosed in
US 5,151,205 or with mineral oils, API Groups 1 to 3 as disclosed inUS 5,665,683 . - A lubricant is typically formulated by combining a lubricant base stock, or a mixture of lubricant base stocks, of suitable inherent properties with additives and other optional formulation aids. Esters of diols, triols, tetrols and polyols are frequently used lubricant base stocks in a number of high-performance lubricant applications. Said esters are obtained from an alcohol, having two or more hydroxyl groups, which alcohol is esterified with a carboxylic acid or acid mixture. During the esterification process the hydroxyl groups of said alcohol are converted partially or fully into ester groups, by means of having an acid component attached to them.
- Formulation of a lubricant meeting specific end-properties typically involves the step of selecting a base-stock inherently exhibiting properties being close to the ones required. It is known in the art, that the final fine-tuning of the desired properties can be made by means of blending the base-stock with other components, capable of modifying the properties in accordance to the specification and other demands. Blending is, however, not always preferred, as this introduces complexity to the system, at least in the form of an increased number of components included in the lubricant.
- It is, furthermore, known in the art that certain ester properties can be strongly influenced by selecting mixtures of starting materials instead of single reactants. The ester product may, for instance, be composed of a mixture of said alcohols esterified with a carboxylic acid or a said alcohol can be esterified with a mixture of carboxylic acids in order to obtain for instance improved compatibility and cold-flow properties. In even more general terms this may apply when combing a mixture of said alcohols with a mixture of carboxylic acids in order to obtain a statistical mixture of ester end-products. Esters based on said mixtures of raw materials are not, however, desired in all cases. They induce a degree of composition uncertainty to the system, and one or more of the statistically formed ester compounds may contribute to undesired and/or adverse performance. There are thus needs and demands for a range of different, essentially single reactants esters showing advantageous inherent properties.
- Pour point is a lubricant property, which characterises the cold flow properties of a lubricant. Pour point is reported as the reading of the lowest temperature where a test lubricant shows a defined degree of fluidity. A more detailed description is given in the standard ASTM D5950. Low pour point is desired in lubricants aimed for use at low temperature conditions, occurring for instance at the startup of engines in cold climate and/or winter conditions. Examples of applications requiring good cold properties include, but are not limited to, automotive and aviation lubricants, lubricants for automotive, stationary and 2-stroke engines, hydraulic fluids, refrigeration lubricants, dielectric fluids and greases.
- Esters of branched carboxylic acids are known to contribute to reduced pour point, as disclosed in for instance
US 4,514,314 . So far, however, reported and used branched carboxylic acids are either neo or iso-branched. 2-ethylhexanoic acid is the only used 2-branched carboxylic acid having more than four carbons and in the literature disclosed carboxylic acids having 10 or more carbon atoms are either linear acids, iso-acids or neo-acids. - It has now quite surprisingly been found that introduction of 2-propylheptanoic acid as the acid component in an ester, intended as a lubricant base stock, significantly reduces the pour point of the ester. The, according to the present invention, obtained combination of high flash point, low evaporation loss, high viscosity and the unexpected and exceptionally low pour point and the high viscosity index value imply new technological opportunities in adjusting the properties of presently known lubricants. Neither 2-branched carboxylic acids, besides the in the art well known 2-ethylhexanoic acid, as starting material, nor any correlation between the molecular weight of the ester and the pour point of the lubricant, has so far been reported for ester lubricants and/or lubricant base stocks. The present invention accordingly refers to an automotive, an aeronautic, a marine or a stationary engine or turbine lubricant base stock comprising at least one ester obtained by esterifying 2-propylheptanoic acid with (i) at least one 2,2-substituted 1,3-propanediol and/or at least one dimer, trimer or polymer thereof, wherein said 2,2-substituted 1,3-propanediol is neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolethane or trimethylolbutane, and/or (ii) at least one alkoxylated species of a said 2,2-substituted 1,3-propanediol or a said dimer, trimer or polymer thereof. Furthermore, the present invention refers to the use of a lubricant base stock comprising at least one ester between 2-propylheptanoic acid and at least one 2,2-substituted 1,3 - propanediol and/or at least one dimer, trimer or polymer thereof and/or at least one alkoxylated species of a said 2,2-substituted 1,3-propanediol or a said dimer, trimer or polymer thereof in production of a lubricant for internal combustion engines and turbine engines, such as automotive engines, aeronautic engines, marine engines and stationary engines. Said engines can suitably be exemplified by for instance otto, diesel, wanckel and jet engines, including 2-stroke engines. The herein most preferred lubricant base stock comprises a triester of trimethylolpropane or a tetraester of pentaerythritol and/or di-trimethylolpropane.
- Said 2,2-substituted 1,3-propanediol is in preferred embodiments of the present invention a 2,2-dialkyl-1,3-propanediol, a 2-alkyl-2-hydroxyalkyl-1,3-propanediol or a 2,2-dihydroxyalkyl-1,3-propanediol, wherein said alkyl preferably is a C1-C8 alkyl. The most preferred embodiments of said 2,2-substituted 1,3-propanediol and said dimer, trimer and polymer thereof include neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolethane, trimethylolbutane, trimethylolpropane, pentaerythritol, di-trimethylolpropane and di-pentaerythritol. Said alkoxylated species are preferably selected from the group consisting of ethoxylated and/or propoxylated trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, di-trimethylolpropane and di-pentaerythritol.
- Said ester is in especially preferred embodiments of the present invention a triester or tetraester of a said 2-alkyl-2-hydroxyalkyl-1,3-propanediol or a said 2,2-dihydroxyalkyl-1,3-propanediol or a said dimer, trimer of polymer thereof, such as an esterification product, between 2-propylheptanoic acid and pentaerythritol, trimethylolpropane or di-trimethylolpropane, having a triester or tetraster content of at least 95%, such as at least 97%, by weight.
- Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilise the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following Examples 1 and 2 refer to preparation of esters oils according to embodiments of the present invention and Example 3 to a comparative ester oil outside the scope of said invention. Example 4 and 5 and Table 1 present evaluations of prepared esters.
- 120.9 g of pentaerythritol, 733.8 g of 2-propylheptanoic acid, 2.5 g of p-toluenesulphonic as catalyst and 43.0 g of n-octane as azeotropic solvent were charged in a reaction vessel equipped with mechanical agitator, nitrogen purge, heating device, condensers and a Dean-Stark water trap. The reaction mixture was rapidly heated to 170°C and heating was subsequently continued at a gradient of 20°C/min until an esterification temperature of 235°C was reached. The esterification was now allowed to continue until GC analysis evidenced less than 1% triester (ester having one unreacted hydroxyl group) in the reaction mixture. 15.6 g of active carbon was then added for control of discoloration and vacuum was applied for evaporation of the azeotropic solvent and excess of carboxylic acid. The mixture was, when a reaction product having an acid value of less than 3 mg KOH/g was obtained, cooled to 50°C and 14.6 g of 10% (aq.) NaOH solution was now added to the reaction mixture. Vacuum was once more applied and the reaction mixture was re-heated to 100°C for dehydration. The resulting reaction product was finally filtered yielding pale yellow ester product having following properties.
Colour: 144 APHA Acid value: 0.04 mg KOH/g Hydroxyl value: 0.23 mg KOH/g Pentaerythritol tetraester content: 97% by weight. - Example 1 was repeated with the difference that pentaerythritol was replaced by the same amount of trimethylolpropane and that 561.5 g of 2-propylheptanoic acid was charged instead of 733.8 g, yielding pale yellow ester product having following properties.
Colour: 44 APHA Acid value: 0.02 mg KOH/g Hydroxyl value: 0.52 mg KOH/g Trimethylolpropane triester content: 97% by weight. - Example 1 was repeated with the difference that 2-propylheptanoic acid was replaced by 613.4 g of 2-ethylhexanoic acid, yielding pale yellow ester product having following properties.
Colour: 5 APHA Acid value: 0.03 mg KOH/g Hydroxyl value: 0.52 mg KOH/g Pentaerythritol tetraester content: 98.7% by weight. - The in Examples 1,2 and 3 (comparative) obtained ester products (lubricant base stocks) were evaluated with regard to properties important in lubricants. The ester products according to embodiments of the present invention exhibited substantially improved properties. The result is given in Table 1 below.
- The ester products obtained in Example 1 and Example 3 (comparative) were over night placed in a freezer at -18-20°C. The product of Example 1 was after said time a clear high viscous liquid, while the product of Example 3 was an opaque waxy solid.
Table 1 Property Viscosity at 40°C, cSt Viscosity at 100°C, cSt Viscosity index value Pour point °C Flash point closed cup °C NOACK evaporation %-w/w ENISO3104 ENISO 3104 ASTM D 2270 ASTM D 5950 ENISO2492 CEC L40-93-B Ex. 1 57.2 7.83 110 < -56 270 1.7 Ex. 2 34.4 5.44 89 < -52 244 5.0 Ex. 3 46.2 6.39 82 -6 178 3.4
Claims (15)
- Use of a lubricant base stock, comprising at least one ester obtained by esterifying 2-propylheptanoic acid with at least one 2,2-substituted 1,3-propanediol and/or at least one dimer, trimer or polymer thereof and/or at least one alkoxylated species of a said 2,2-substituted 1,3-propanediol or a said dimer, trimer or polymer thereof, in the production of a lubricant for internal combustion engines and turbine engines.
- Use of a lubricant base stock according to Claim 1 characterised in that said 2,2-substituted 1,3-propanediol is a 2,2-dialkyl-1,3-propanediol, a 2-alkyl-2-hydroxyalkyl-1,3-propanediol or a 2,2-dihydroxyalkyl-1,3-propanediol.
- Use of a lubricant base stock according to Claim 2 characterised in that said alkyl is a C1-C8 alkyl.
- Use of a lubricant base stock according to any of the Claims 1-3 characterised in that said 2,2-substituted 1,3-propanediol is neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolethane, trimethylolbutane, trimethylolpropane or pentaerythritol.
- Use of a lubricant base stock according to Claim 1 characterised in that said dimer is di-trimethylolpropane or di-pentaerythritol.
- Use of a lubricant base stock according to Claim 1 characterised in that said alkoxylated species is an ethoxylated and/or propoxylated trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, di-trimethylolpropane or di-pentaerythritol.
- Use of a lubricant base stock according to any of the Claims 2-6 characterised in that said lubricant base stock comprises a triester of 2-alkyl-2-hydroxyalkyl-1,3-propanediol or a tetraester of a dimer thereof.
- Use of a lubricant base stock according to any of the Claims 2-6 characterised in that said lubricant base stock comprises a tetraester of 2,2-dihydroxyalkyl-1,3-propanediol.
- Use of a lubricant base stock according to any of the Claims 1-8 characterised in that said lubricant base stock comprises a triester of trimethylolpropane or a tetraester of pentaerythritol or di-trimethylolpropane.
- Use of a lubricant base stock according to any of the Claims 1-9, said engine being an automotive engine, an aeronautic engine, a marine engine or a stationary engine.
- Use according to Claim 10, said engine being an otto, a diesel, a wanckel or a jet engine.
- Use according to Claim 10, said engine being a 2-stroke engine.
- A lubricant base stock characterised in that it is an automotive, an aeronautic, a marine or a stationary engine or turbine lubricant base stock, comprising at least one ester obtained by esterifying 2-propylheptanoic acid with (i) at least one 2,2-substituted 1,3-propanediol and/or at least one dimer, trimer or polymer thereof, wherein said 2,2-substituted 1,3-propanediol is neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolethane or trimethylolbutane, and/or (ii) at least one alkoxylated species of a 2,2-substituted 1,3-propanediol or a dimer, trimer or polymer thereof.
- A lubricant base stock according to Claim 13 characterised in that said alkoxylated species of a 2,2-substituted 1,3-propanediol is an alkoxylated 2,2-dialkyl-1,3-propanediol, an alkoxylated 2-alkyl-2-hydroxyalkyl-1,3-propanediol or an alkoxylated 2,2-dihydroxyalkyl-1,3-propanediol.
- A lubricant base stock according to Claim 14 characterised in that said alkyl is a C1-C8 alkyl.
Applications Claiming Priority (2)
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SE0802280A SE532942C2 (en) | 2008-10-27 | 2008-10-27 | Low lubricant base lubricant |
PCT/SE2009/000463 WO2010050871A1 (en) | 2008-10-27 | 2009-10-16 | Low pour point lubricant base stock |
Publications (3)
Publication Number | Publication Date |
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EP2342312A1 EP2342312A1 (en) | 2011-07-13 |
EP2342312A4 EP2342312A4 (en) | 2012-04-18 |
EP2342312B1 true EP2342312B1 (en) | 2017-11-29 |
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EP09823893.4A Active EP2342312B1 (en) | 2008-10-27 | 2009-10-16 | Low pour point lubricant base stock |
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US (2) | US20110247578A1 (en) |
EP (1) | EP2342312B1 (en) |
JP (1) | JP5406931B2 (en) |
CN (1) | CN102203225B (en) |
ES (1) | ES2659370T3 (en) |
SE (1) | SE532942C2 (en) |
WO (1) | WO2010050871A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102020102162A1 (en) | 2020-01-29 | 2021-07-29 | Oq Chemicals Gmbh | TCD ester for low temperature lubricant applications |
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JP6135017B2 (en) * | 2012-02-01 | 2017-05-31 | Khネオケム株式会社 | Mixed ester |
US9523058B2 (en) | 2012-03-23 | 2016-12-20 | Kh Neochem Co., Ltd. | Mixed ester |
JPWO2015016314A1 (en) * | 2013-07-31 | 2017-03-02 | Khネオケム株式会社 | Refrigerating machine oil and working fluid composition for refrigerating machine using the same |
CN105130799A (en) * | 2015-06-30 | 2015-12-09 | 百川化工(如皋)有限公司 | Method for producing ditrimethylolpropane oleate |
CN105037146A (en) * | 2015-06-30 | 2015-11-11 | 百川化工(如皋)有限公司 | Ditrimethylolpropane laurate and preparation method thereof |
CN106329626B (en) * | 2016-08-31 | 2019-02-26 | 浙江腾腾电气有限公司 | A kind of photovoltaic charged control system of MPPT |
US11680218B2 (en) | 2018-06-04 | 2023-06-20 | Tetramer Technologies, Llc | Biodegradable lubricant with tailored hydrolytic stability and improved thermal stability through alkoxylation of glycerol |
CA3102545A1 (en) * | 2018-06-04 | 2019-12-12 | Tetramer Technologies, Llc | Lubricating base oils from esterified alkoxylated polyols using saturated long-chain fatty acids |
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JP2000072715A (en) * | 1998-08-31 | 2000-03-07 | Idemitsu Kosan Co Ltd | Polyhydric alcohol ester compound and lubricating oil composition containing the same |
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- 2009-10-16 ES ES09823893.4T patent/ES2659370T3/en active Active
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- 2009-10-16 WO PCT/SE2009/000463 patent/WO2010050871A1/en active Application Filing
- 2009-10-16 US US13/125,240 patent/US20110247578A1/en not_active Abandoned
- 2009-10-16 EP EP09823893.4A patent/EP2342312B1/en active Active
- 2009-10-16 CN CN200980143018.4A patent/CN102203225B/en active Active
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- 2013-12-09 US US14/100,955 patent/US20140100149A1/en not_active Abandoned
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DE102020102162A1 (en) | 2020-01-29 | 2021-07-29 | Oq Chemicals Gmbh | TCD ester for low temperature lubricant applications |
WO2021152001A1 (en) | 2020-01-29 | 2021-08-05 | Oq Chemicals Gmbh | Tcd-esters for low temperature liquid applications |
Also Published As
Publication number | Publication date |
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SE0802280A1 (en) | 2010-04-28 |
SE532942C2 (en) | 2010-05-18 |
US20140100149A1 (en) | 2014-04-10 |
JP2012506942A (en) | 2012-03-22 |
EP2342312A4 (en) | 2012-04-18 |
ES2659370T3 (en) | 2018-03-15 |
WO2010050871A1 (en) | 2010-05-06 |
US20110247578A1 (en) | 2011-10-13 |
JP5406931B2 (en) | 2014-02-05 |
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EP2342312A1 (en) | 2011-07-13 |
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