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WO2018136208A1 - Huiles de base lubrifiantes à stabilité élevée et leurs procédés de production - Google Patents

Huiles de base lubrifiantes à stabilité élevée et leurs procédés de production Download PDF

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Publication number
WO2018136208A1
WO2018136208A1 PCT/US2017/068457 US2017068457W WO2018136208A1 WO 2018136208 A1 WO2018136208 A1 WO 2018136208A1 US 2017068457 W US2017068457 W US 2017068457W WO 2018136208 A1 WO2018136208 A1 WO 2018136208A1
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Prior art keywords
alkyl group
base stock
lubricant base
formula
mol
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PCT/US2017/068457
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English (en)
Inventor
Kyle G. LEWIS
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Exxonmobil Chemical Patents Inc.
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Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to JP2019538427A priority Critical patent/JP2020504221A/ja
Priority to SG11201906221VA priority patent/SG11201906221VA/en
Priority to KR1020197020724A priority patent/KR20190097179A/ko
Priority to CA3050245A priority patent/CA3050245A1/fr
Priority to CN201780087163.XA priority patent/CN110325510A/zh
Priority to AU2017395027A priority patent/AU2017395027A1/en
Priority to BR112019014405A priority patent/BR112019014405A2/pt
Publication of WO2018136208A1 publication Critical patent/WO2018136208A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
    • C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • 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
    • C10M105/72—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing sulfur, selenium or tellurium
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/081—Thiols; Sulfides; Polysulfides; Mercaptals 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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

Definitions

  • This disclosure relates to sulfur-containing compounds, processes for producing the sulfur-containing compounds, and lubricating oil base stocks and lubricating oils including the sulfur-containing compounds with increased thermal and oxidative stability.
  • Lubricants in commercial use today are prepared from a variety of natural and synthetic base stocks admixed with various additive packages and solvents depending upon their intended application.
  • the base stocks typically include mineral oils, polyalpha-olefins (PAO), gas-to-liquid base oils (GTL), silicone oils, phosphate esters, diesters, polyol esters, and the like.
  • PCEOs passenger car engine oils
  • base stocks such as PAOs or GTL stocks.
  • PAOs and GTL stocks are an important class of lube base stocks with many excellent lubricating properties, including high viscosity index (VI), but may have lower thermal and oxidative stability. Thermal and oxidative stability is important because of a trend requiring smaller sump sizes that may result in more thermal and oxidative stress on the lubricants. Further, performance requirements for lubricants have become more stringent and the demand for longer drain intervals continues to grow.
  • VI viscosity index
  • Sulfur may be incorporated in the base stocks due to its anti-oxidant capabilities. While sulfurized PAO (S-PAO) base stocks can provide improved oxidative stability, improved durability during exposure to high temperatures and overall may extend the life of the lubricant, synthesis of S-PAO bases tocks may introduce a tertiary C-H bond in addition to the sulfur atom. For example, as shown in known scheme A below,
  • PAO oligomer thiol S-PAO
  • the sulfur addition follows the well-known "anti- Markovnikov addition,” wherein the sulfur atom bonds to the less substituted carbon atom of the double bond from the unhydrogenated PAO oligomer forming a tertiary C- H bond in the S-PAO.
  • This hydrogen atom of the C-H bond may be particularly labile to oxidative cleavage due to low tertiary C-H bond dissociation energy.
  • tertiary C-H bond can be prone to oxidative degradation thereby lowering the oxidative stability of the S-PAO.
  • this disclosure relates in part to a lubricant base stock comprising a compound having the formula (F-I below:
  • R 1 is a C1-C5000 alkyl group
  • R 2 is (i) a C4-C30 linear alkyl group or (ii) a C 4 - C5000 branched alkyl group having the formula (F-II) below:
  • R 5 and R 6 at each occurrence are each independently a hydrogen or a C1-C30 linear alkyl group and n is a positive integer, provided however, among all of R 5 and R 6 , at least one is a C1-C30 linear alkyl group; and R 7 is a hydrogen or a C1-C30 linear alkyl group; R 3 is hydrogen or a C1-C500 alkyl group; and R 4 is a C1-C50 alkyl group or an aromatic group.
  • This disclosure also relates in part to a process for making a compound of formula (F-I) and/or a base stock comprising a compound of formula (F-I), the process comprising reacting HS-R 4 with an olefin-containing material comprising a compound having the following formula:
  • This disclosure further relates in part to a formulated lubricant comprising one or more of the lubricant base stocks described herein.
  • FIG. 1 illustrates 3 ⁇ 4 NMR spectra of Product I.
  • FIG. 2 illustrates *H NMR spectra of Comparative Product 1.
  • a PAO molecule as obtained from the polymerization or oligomerization of alpha-olefin monomers, without further hydrogenation thereof, typically contains an ethylenically unsaturated C C double bond in the structure thereof.
  • An unhydrogenated PAO is sometimes referred to as a "uPAO" herein.
  • a uPAO material could comprise, among others, vinyls (F-A below, where R is an alkyl), 2,2-di-substituted olefins (F-B below, also-known-as vinylidenes, where RI and R2, the same or different, are alkyls), 1,2-di-substitued olefins (including the E- and Z-isomers of F-Cl and F-C2 below, also- known-as di-substituted vinylenes, where Ri and R2, the same or different, are alkyls), and tri-substituted olefins (F-D below, also-known-as tri-substituted vinylenes, where Ri, R2, and R3, the same or different, are alkyls).
  • the vinyls and vinylidenes are terminal olefins, while the di- and tri-substituted vinylene olefins are internal olefin
  • a uPAO can be hydrogenated in the presence of hydrogen and a hydrogenation catalyst to reduce the ethylenic unsaturation thereof and obtain a hydrogenated PAO.
  • Such hydrogenated PAO can be more stable compared to the corresponding uPAO, offering higher thermal and oxidative resistance.
  • lubricant refers to a substance that can be introduced between two or more moving surfaces and lowers the level of friction between two adjacent surfaces moving relative to each other.
  • a lubricant “base stock” is a material, typically a fluid at the operating temperature of the lubricant, used to formulate a lubricant by admixing with other components.
  • base stocks suitable in lubricants include API Group I, Group II, Group III, Group IV, Group V and Group VI base stocks.
  • PAOs, particularly hydrogenated PAOs have recently found wide use in lubricant formulations as a Group IV base stock.
  • NMR spectroscopy provides key structural information about the synthesized polymers.
  • Proton NMR ( ⁇ H-NMR) analysis of the uPAO gives a quantitative breakdown of the olefinic structure types (viz. vinyls, 1,2-di-substituted vinylenes, tri- substituted vinylenes, and vinylidenes).
  • compositions of mixtures of olefins comprising terminal olefins (vinyls and vinylidenes) and internal olefins (1,2-di- substituted vinylenes and tri- substituted vinylenes) are determined by using ⁇ -NMR.
  • a NMR instrument of at least a 500 MHz is run under the following conditions: a 30° flip angle RF pulse, 120 scans, with a delay of 5 seconds between pulses; sample dissolved in CDCb (deuterated chloroform); and signal collection temperature at 25 °C.
  • the following approach is taken in determining the concentrations of the various olefins among all of the olefins from an NMR graph.
  • peaks corresponding to different types of hydrogen atoms in vinyls (Tl), vinylidenes (T2), 1,2- di-substituted vinylenes (T3), and tri- substituted vinylenes (T4) are identified at the peak regions in TABLE I below.
  • Carbon-13 NMR ( 13 C-NMR) is used to determine tacticity of the PAOs of the present invention.
  • Carbon-13 NMR can be used to determine the concentration of the triads, denoted (m,m)-triads (i.e., meso, meso), (m,r)- (i.e., meso, racemic) and (r,r)- (i.e., racemic, racemic) triads, respectively.
  • concentrations of these triads defines whether the polymer is isotactic, atactic or syndiotactic.
  • the concentration of the (m,m)-triads in mol% is recorded as the isotacticity of the PAO material.
  • the calculation of tacticity is mm*100/(mm+mr+rr) for the molar percentages of (m,m)-triads, mr*100/(mm+mr+rr) for the molar percentages of (m,r)-triads, and rr*100/(mm+mr+rr) for the molar percentages of (r,r)-triads.
  • the (m,m)-triads correspond to 35.5 - 34.55 ppm, the (m,r)- triads to 34.55 - 34.1 ppm, and the (r,r)-triads to 34.1 - 33.2 ppm.
  • R 2 is (i) a C4-C30 linear alkyl group or (ii) a C4-C5000 branched alkyl having the formula F-II) below:
  • R 4 is a C1-C50 alkyl group or an aromatic group.
  • R 3 may be hydrogen, e.g. , when a uPAO used during synthesis is a vinylidene olefin.
  • R 1 or R 2 may be a C4-C5000 branched alkyl group represented by formula (F-II) above, and at least 50% (e.g., at least 60%, 70%, 80%, 90%, or even 95%) of R 6 are hydrogen, and at least 50% (e.g., at least 60%, 70%, 80%, 90%, or even 95%) of R 5 are independently a C1-C30 linear alkyl group.
  • R 6 and at least a portion of R 5 are alkyl groups
  • at least 80% of those R 6 that are alkyl groups are C1-C4 linear alkyl groups
  • at least 80% of R 5 are C4-C30 linear alkyl groups.
  • R 6 are hydrogen, and all R 5 , the same or different, are independently C1-C30 linear alkyl group. In certain variations, all R 6 are hydrogen, and all R 5 are identical C1-C30 linear alkyl groups.
  • R 4 may be a C1-C500 alkyl group, a C1-C300 alkyl group, a C1-C100 alkyl group, a C1-C50 alkyl group, a C1-C30 alkyl group or C1-C10 alkyl group.
  • the alkyl group may be linear or branched.
  • R 4 may be a Ci- C50 alkyl group, more particularly, a C1-C50 linear alkyl group or a C1-C30 linear alkyl group.
  • R 4 may be an aromatic group.
  • Suitable aromatic groups include, but are not limited to, one or more phenyl groups, optionally substituted with one or more alkyl groups, alkoxy groups or halogens (e.g. , F, CI, Br), hydroxyl groups, nitro group, and optionally containing a heteroatom (e.g. , N, O, S).
  • Processes for making the compounds of formula (F-I) are provided herein.
  • the process comprises reacting HS-R 4 (i.e., a thiol) with an olefin-containing material comprising a compound havin the following formula(F-Ia) below:
  • compounds of formula (F-I) (S-PAOs) with increased thermal and oxidative stability may be prepared by reacting uPAOs with thiol compounds under acid catalyzed conditions so that the sulfur atom bonds to the more highly substituted carbon atom of the double bond from the uPAO oligomer.
  • the balance of S-PAO compounds formed have the sulfur atom bonded to a primary or secondary carbon originating from the uPAO.
  • R 3 may be a C1-C5000 alkyl group, a C1-C4000 alkyl group, a C1-C3000 alkyl group, a C1-C2000 alkyl group, a C1-C1000 alkyl group, a C1-C900 alkyl group, a C1-C800 alkyl group, a C1-C700 alkyl group, a C1-C600 alkyl group, a C1-C500 alkyl group, a C1-C400 alkyl group, a C1-C300 alkyl group, a C1-C200 alkyl group, a Ci- Cioo alkyl group, a C1-C50 alkyl group, a C1-C30 alkyl group, or C1-C10 alkyl group.
  • the olefin-containing material may comprise one or more compounds of formula (F-Ia), where R 3 is an alkyl group (e.g., C1-C100 alkyl group), in an amount of at least about 1.0 wt%, at least about 10 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 75 wt%, at least about 80 wt%, at least about 90 wt%, at least about 99 wt%, or about 100 wt% based on the total weight of the olefin- containing material
  • the olefin-containing material may comprise a compound of formula (F-Ia), where R 3 is an alkyl group (e.g., C1-C100 alkyl group) in an amount of at least about
  • the olefin-containing material may comprise a compound of formula (F-Ia), where R 3 is an alkyl group (e.g., Ci-Cioo alkyl group), in an amount of about 1.0 wt% to about 100 wt%, 1.0 wt% to about 99 wt%, 1.0 wt% to about 90 wt%, about 10 wt% to about 60 wt%, about 10 wt% to about 50 wt% , about 10 wt% to about 40 wt% or about 10 wt% to about 25 wt%.
  • R 3 is an alkyl group (e.g., Ci-Cioo alkyl group)
  • the olefin-containing material may comprise a mixture of: (i) about 50 wt% to about 90 wt% or about 75 wt% to about 90 wt% of one or more olefin compounds of formula (F-Ia) wherein R 3 is hydrogen; and (ii) about 10 wt% to about 50 wt% or about 10 wt% to about 25 wt% of one or more olefin compounds of formula (F-Ia) wherein R 3 is an alkyl group (e.g. , Ci-Cioo alkyl group).
  • R 3 is an alkyl group (e.g. , Ci-Cioo alkyl group).
  • the olefin-containing materials used in the process may be PAO (mPAO, cPAO, and mixtures thereof) dimers (C4-C100), trimers (C6-C100), tetramers (Cs-Cioo) pentamer, hexamer, and higher oligomers, and the like, or alpha-olefins (e.g., C2-C30 alpha-olefin).
  • Suitable alpha-olefins include, for example, alkyl olefins such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, and the like.
  • the dimer can be from an alpha-olefin (e.g. , C2-C30 alpha-olefin), for example, 1-hexene, 1-octene, 1- decene, 1-dodecene, 1-tetradecene, 1-octadecene or a combination of alpha-olefins.
  • At least about 50 mol%, or at least about 60 mol%, or at least about 70 mol%, or at least about 75 mol%, or at least about 80 mol%, or at least about 90 mol%, or even about 95 mol%, of the olefin-containing materials described herein are isotactic.
  • at least about 60 mol%, or at least about 75 mol%, or at least about 80 mol% of the olefin-containing materials described herein are isotactic.
  • the cPAOs may be made by using conventional catalysts to form olefin- containing material having a formula (F-Ib).
  • suitable conventional catalysts include but are not limited to Lewis acid compounds, such as BF3, AICI3, aluminum trialkyls, or combinations thereof.
  • the resultant olefin-containing material tends to be a mixture of olefin compounds with highly varied R 1 , R 2 and R 3 .
  • At least one of R 1 , R 2 and R 3 may be an alkyl having a carbon backbone chain having multiple pendant groups attached thereto, many of which are short-chain alkyls such as methyl, ethyl, and the like.
  • Such unhydrogenated cPAOs obtained by using conventional catalysts typically may be atactic.
  • Processes for the production of cPAOs are disclosed, for example, in the following patents, each of which is incorporated herein by reference in its entirety: U.S. Patent Nos. 3, 149,178; 3,382,291 ; 3,742,082; 3,769,363; 3,780,128; 4,172,855; and 4,956,122; as well as in Shubkin, R. L. (Ed.) (1992) Synthetic Lubricants and High-Performance Functional Fluids (Chemical Industries) New York: Marcel Dekker Inc.
  • PAO lubricant compositions in which little double bond isomerization is found has resulted in different classes of high viscosity index PAO (HVI-PAO), which are also contemplated for use herein.
  • HVI-PAO high viscosity index PAO
  • a reduced chromium catalyst is reacted with an alpha-olefin monomer.
  • Such PAOs are described in U.S. Patent Nos. 4,827,073; 4,827,064; 4,967,032; 4,926,004; and 4,914,254, each of which is incorporated herein by reference in its entirety.
  • R 4 may be an alkyl group (e.g. , C1-C500 alkyl group, a C1-C300 alkyl group, a C1-C100 alkyl group, a C1-C50 alkyl group, etc.) or an aromatic group.
  • alkyl group e.g. , C1-C500 alkyl group, a C1-C300 alkyl group, a C1-C100 alkyl group, a C1-C50 alkyl group, etc.
  • illustrative thiols useful in the process describe herein include, for example, aliphatic thiols and aromatic thiols.
  • Illustrative aliphatic thiols include, for example, 1- butanethiol, 1-hexanethiol, 1-octanethiol, 1-decanehiol, 1-dodecanethiol, 1- hexadecanethiol, l-octadecanethiol, and the like.
  • Illustrative aromatic thiols include, for example, thiophenol, 4- methylbenzenethiol, 4-methoxythiophenol, benzyl mercaptan, 4-mercaptopyridine, 2- mercaptopyrimidine, 1-naphthalenethiol, 2-naphthalenethiol, and the like.
  • aromatic thiols useful in this disclosure include, for example, 2,3,4,5,6,- pentafluorothiophenol, 2,3,5,6-tetrafluorothiophenol, 2,3-dichlorothiophenol, 2,4- dichlorothiophenol, 2,5-dichlorothiophenol, 3,4-dichlorothiophenol, 3,5- dichlorothiophenol, 2,4-diflurothiophenol, 3,4-diflurothiophenol, 2-bromothiophenol, 3- bromothiophenol, 4-bromothiophenol, 2-chlorothiophenol, 3-chlorothiophenol, 4- chlorothiophenol, 2-fluorothiophenol, 3-fluorothiophenol, 4-fluorothiophenol, 2- chlorobenzenemethanethiol, 4-chlorobenzenemethanethiol, (3-nitrobenzyl) marcaptan, (4-nitrobenzyl)marcaptan, 2-mercaptobenze
  • Suitable acid catalysts that can be used in the processes described herein for making the compound having formula (F-I) include, for example, a Lewis acid.
  • the Lewis acid catalysts useful for coupling reactions include metal and metalloid halides conventionally used as Friedel-Crafts catalysts. Suitable examples include AlCh, BF3, AlBr3, T1CI3, and TiCU, either as such or with a protic promoter.
  • solid Lewis acid catalysts such as synthetic or natural zeolites; acid clays; polymeric acidic resins; amorphous solid catalysts, such as silica-alumina; and heteropoly acids, such as the tungsten zirconates, tungsten molybdates, tungsten vanadates, phosphotungstates and molybdotungstovanadogermanates (e.g., WOx/ZrC and WOx/MoCb). Beside these catalysts, acidic ionic liquid can also be used as catalysts for coupling reactions.
  • polymeric acidic resins such as Amberlyst 15, Amberlyst 36 are most preferred.
  • a compound having the formula (F-I) as described herein made by reacting HS-R 4 (i.e., a thiol) with an olefin-containing material comprising a compound having the following formula (F-Ia) as described herein in the presence of an acid catalyst is also provided herein.
  • HS-R 4 i.e., a thiol
  • an olefin-containing material comprising a compound having the following formula (F-Ia) as described herein in the presence of an acid catalyst
  • This disclosure provides lubricating oils useful as engine oils and in other applications characterized by excellent stability, solvency and dispersancy characteristics.
  • the lubricating oils are based on high quality base stocks including a major portion comprising one or more compounds corresponding in structure to formula (F-l) as described herein, also optionally, other components, such Group I, II and/or III mineral oil base stocks, GTL, Group IV (e.g. , PAO), Group V (e.g. , esters, alkylated aromatics, PAG) and combinations thereof,.
  • the lubricating oil base stock can be any oil boiling in the lube oil boiling range, typically between about 100 to about 450°C. In the present specification and claims, the terms base oil(s) and base stock(s) are used interchangeably.
  • Lubricating oils that are useful in the present disclosure are both natural oils and synthetic oils. Natural and synthetic oils (or mixtures thereof) can be used unrefined, refined, or re-refined (the latter is also known as reclaimed or reprocessed oil). Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve the at least one lubricating oil property.
  • Groups I, II, III, IV and V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
  • Group I base stocks generally have a viscosity index of from 80 to 120 and contain greater than 0.03% sulfur and less than 90% saturates.
  • Group II base stocks generally have a viscosity index of from 80 to 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
  • Group III stock generally has a viscosity index greater than 120 and contains less than or equal to 0.03% sulfur and greater than 90% saturates.
  • Group IV includes polyalpha- olefins (PAO).
  • Group V base stocks include base stocks not included in Groups I-IV. Table III below summarizes properties of each of these five groups.
  • Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present disclosure. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
  • Synthetic oils include hydrocarbon oil such as polymerized and interpolymerized olefins (polybutyl ones, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha-olefin copolymers, for example).
  • hydrocarbon oil such as polymerized and interpolymerized olefins (polybutyl ones, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha-olefin copolymers, for example).
  • Polyalpha-olefin (PAO) oil base stocks the Group IV API base stocks, are a commonly used synthetic hydrocarbon oil.
  • PAOs derived from C 8 , Cio, Ci2, Ci4 olefins or mixtures thereof may be utilized. See U.S. Patent Nos.
  • Group IV oils that is, the PAO base stocks have viscosity indices preferably greater than 130, more preferably greater than 135, still more preferably greater than 140.
  • lubricant base stock compositions provided herein may have an RPVOT break time of about 200 to about 1000 minutes, about 200 to about 900 minutes, about 300 to about 900 minutes, about 400 to about 900 minutes, about 500 to about 900 minutes, or about 400 to about 850 minutes.
  • compositions comprising compounds of formula (F-I), e.g. , lubricant base stock compositions provided herein may have a kinematic viscosity at 40°C (KV40), measured according to ASTM standard D-445, from about 5 to about 100 cSt, preferably from about 5 to about 75 cSt, preferably from about 5 to about 500 cSt, preferably from about 5 to about 35 cSt, preferably from about 9 to about 30 cSt, and more preferably from about 9 to about 25 cSt.
  • KV40 kinematic viscosity at 40°C
  • compositions comprising compounds of formula (F-I), e.g. , lubricant base stock compositions provided herein may have a pour point of less than about -30°C, less than about -40°C, less than about -50°C, less than about -60°C or -70°C.
  • the compositions provided herein may have a pour point of less than about -60°C.
  • the compositions provided herein may have a pour point of about -70°C to about -30°C, about -70°C to about -40°C, or about -70°C to about - 50°C.
  • Esters in a minor amount may be useful in the lubricating oils of this disclosure. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of monocarboxylic acids.
  • Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2- ethylhexyl alcohol, etc.
  • dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.
  • alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2- ethylhexyl alcohol, etc.
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
  • Particularly useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols such as the neopentyl polyols; e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-l,3-propanediol, trimethylol propane, pentaerythritol and dipentaerythritol with alkanoic acids containing at least 4 carbon atoms, preferably Cs to C30 acids such as saturated straight chain fatty acids including caprylic acid, capric acids, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.
  • the hindered polyols such as the neopentyl polyols;
  • Esters should be used in an amount such that the improved wear and corrosion resistance provided by the lubricating oils of this disclosure are not adversely affected.
  • Non-conventional or unconventional base stocks and/or base oils include one or a mixture of base stock(s) and/or base oil(s) derived from: (1) one or more Gas-to- Liquids (GTL) materials, as well as (2) hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oils derived from synthetic wax, natural wax or waxy feeds, mineral and/or non-mineral oil waxy feed stocks such as gas oils, slack waxes (derived from the solvent dewaxing of natural oils, mineral oils or synthetic oils; e.g., Fischer- Tropsch feed stocks), natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, foots oil or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials recovered from coal liquefaction or shale oil, linear or
  • GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon- containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
  • the GTL base stock(s) and/or base oils) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this materially especially suitable for the formulation of low SAP products.
  • GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity.
  • Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, Group V and Group VI oils and mixtures thereof, preferably API Group II, Group III, Group IV, Group V and Group VI oils and mixtures thereof, more preferably the Group III to Group VI base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • Minor quantities of Group I stock such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier oil for additives used on an "as received" basis.
  • Even in regard to the Group II stocks it is preferred that the Group II stock be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range 100 ⁇ VI ⁇ 120.
  • the sulfur and nitrogen content of GTL, base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this material especially suitable for the formulation of low sulfur, sulfated ash, and phosphorus (low SAP) products.
  • the base stock component of the present lubricating oils will typically be from about 50 wt% to about 99 wt% of the total composition (all proportions and percentages set out in this specification are by weight unless the contrary is stated) and more usually in the range of about 80 wt% to about 99 wt%.
  • the formulated lubricating oil useful in the present disclosure may additionally contain one or more of the other commonly used lubricating oil performance additives including but not limited to dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other anti-wear agents and/or extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, other friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
  • dispersants including but not limited to dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other anti-wear agents and/or extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity
  • Viscosity improvers also known as Viscosity Index modifiers, and VI improvers
  • Viscosity Index modifiers also known as Viscosity Index modifiers, and VI improvers
  • VI improvers increase the viscosity of the oil composition at elevated temperatures which increases film thickness, while having limited effect on viscosity at low temperatures.
  • Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant.
  • Typical molecular weights of these polymers are from 10,000 to 1,000,000, more typically 20,000 to 500,000, and even more typically from 50,000 and 200,000.
  • suitable viscosity improvers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutylene is a commonly used viscosity index improver.
  • Another suitable viscosity index improver is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants.
  • Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene- butadiene based polymers of 50,000 to 200,000 molecular weight.
  • the amount of viscosity modifier may range from zero to 8 wt %, preferably zero to 4 wt %, more preferably zero to 2 wt % based on active ingredient and depending on the specific viscosity modifier used.
  • Typical antioxidant include phenolic antioxidants, aminic antioxidants and oil-soluble copper complexes. Detailed description of such antioxidants and their quantities of use can be found, e.g., in WO2015/060984 Al, the relevant portions thereof are incorporated herein by reference in their entirety.
  • alkali or alkaline earth metal salicylate detergent which is an essential component in the present disclosure
  • other detergents may also be present. While such other detergents can be present, it is preferred that the amount employed be such as to not interfere with the synergistic effect attributable to the presence of the salicylate. Therefore, most preferably such other detergents are not employed.
  • additional detergents can include alkali and alkaline earth metal phenates, sulfonates, carboxylates, phosphonates and mixtures thereof.
  • These supplemental detergents can have total base number (TBN) ranging from neutral to highly overbased, i.e. TBN of 0 to over 500, preferably 2 to 400, more preferably 5 to 300, and they can be present either individually or in combination with each other in an amount in the range of from 0 to 10 wt %, preferably 0.5 to 5 wt % (active ingredient) based on the total weight of the formulated lubricating oil. As previously stated, however, it is preferred that such other detergent not be present in the formulation.
  • Such additional other detergents include by way of example and not limitation calcium phenates, calcium sulfonates, magnesium phenates, magnesium sulfonates and other related components (including borated detergents).
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants may be ashless or ash-forming in nature.
  • the dispersant is ashless.
  • So called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • metal-containing detergents discussed above form ash upon combustion.
  • Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • the polar group typically contains at least one element of nitrogen, oxygen, or phosphorus.
  • Typical hydrocarbon chains contain 50 to 400 carbon atoms.
  • a particularly useful class of dispersants are the alkenylsuccinic derivatives, typically produced by the reaction of a long chain substituted alkenyl succinic compound, usually a substituted succinic anhydride, with a polyhydroxy or polyamino compound.
  • the long chain group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group.
  • Exemplary patents describing such dispersants are U.S. Patent Nos. 3, 172,892; 3,219,666; 3,316, 177 and 4,234,435.
  • Other types of dispersants are described in U.S. Patent Nos. 3,036,003; and 5,705,458.
  • Hydrocarbyl-substituted succinic acid compounds are popular dispersants.
  • succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful.
  • Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of an alkenyl succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between alkenyl succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated poly alky lpoly amines, propoxylated polyalkylpolyamines and poly alkenylpoly amines such as polyethylene poly amines.
  • propoxylated hexamethylenediamine is propoxylated hexamethylenediamine.
  • the molecular weight of the alkenyl succinic anhydrides will typically range between 800 and 2,500.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, and boron compounds such as borate esters or highly borated dispersants.
  • the dispersants can be borated with from 0.1 to 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. [00110] Typical high molecular weight aliphatic acid modified Mannich condensation products can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HN(R)2 group-containing reactants.
  • propylene polyamines such as propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamines are also suitable reactants.
  • the alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes.
  • the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene polyamine reactants.
  • Such additives may be used in an amount of 0.1 to 20 wt %, preferably 0.1 to 8 wt %, more preferably 1 to 6 wt % (on an as-received basis) based on the weight of the total lubricant.
  • pour point depressants also known as lube oil flow improvers
  • Pour point depressant may be added to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include alkylated naphthalenes polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties.
  • Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 percent, preferably 0.001 to 0.5 wt %, more preferably 0.001 to 0.2 wt %, still more preferably 0.0001 to 0.15 wt % (on an as-received basis) based on the total weight of the lubricating oil composition.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants.
  • One type of antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non- reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of 0.01 to 5 wt %, preferably 0.01 to 1.5 wt % on an as-received basis.
  • anti-wear additives which are essential components of the present disclosure
  • other anti-wear additives can be present, including zinc dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, other organo molybdenum-nitrogen complexes, sulfurized olefins, etc.
  • organo molybdenum-nitrogen complexes embraces the organo molybdenum-nitrogen complexes described in U.S. Patent No. 4,889,647.
  • the complexes are reaction products of a fatty oil, diethanolamine and a molybdenum source. Specific chemical structures have not been assigned to the complexes.
  • U.S. Patent No. 4,889,647 reports an infrared spectrum for a typical reaction product of that disclosure; the spectrum identifies an ester carbonyl band at 1740 cm -1 and an amide carbonyl band at 1620 cm "1 .
  • the fatty oils are glyceryl esters of higher fatty acids containing at least 12 carbon atoms up to 22 carbon atoms or more.
  • the molybdenum source is an oxygen- containing compound such as ammonium molybdates, molybdenum oxides and mixtures.
  • organo molybdenum complexes which can be used in the present disclosure are tri-nuclear molybdenum- sulfur compounds described in EP 1 040 115 and WO 99/31113 and the molybdenum complexes described in U.S. Patent No. 4,978,464.
  • the lube properties of the products produced in Examples 1 and 2 were evaluated as provided.
  • the kinematic viscosity (KV) of the products was measured using ASTM standard D-445 and reported at temperatures of 100°C (KV100) or 40°C (KV40).
  • the viscosity index (VI) was measured according to ASTM standard D-2270 using the measured kinematic viscosities for each product.
  • the Noack volatility of the products was measured according to ASTM standard D-5800.
  • the pour point of the products was measured according to ASTM D5950.
  • the *H NMR spectra of Product I shown in FIG. 1 shows the singlet peak at 1.14 ppm, indicating the presence of Compound-I. It also shows a small doublet peak at 2.85 ppm, indicating the presence of a small amount of Compound-II. Normalized integration values show that the Compound-I to Compound-II molar ratio in this product was approximately 97.7 to 2.5.
  • a C20 uPAO dimer was alkylated with 4-methylbenzenethiol (obtained from Sigma-Aldrich) by acid catalyst as shown below in Scheme 2 to form Product II containing Compound- III and Compound-IV.
  • a C16 uPAO dimer was alkylated with 1-octanethiol by acid catalyst as shown below in Scheme 3 to form Product III containing Compound-V and Compound- VI.
  • a C20 uPAO dimer was alkylated with 1-octanethiol by acid catalyst as shown below in Scheme 4 to form Product IV containing Compound- VII and Compound- VIII.
  • a glass reactor under N2 atmosphere was charge with C20 uPAO dimer (887.1 g, 3.16 mol), 1-octanethiol (554.3 g, 3.79 mol) (obtained from Sigma- Aldrich), and Amberlyst-15H (30.1 g, 3.3 wt%) (obtained from Sigma- Aldrich) to form a mixture.
  • the mixture was heated to 120°C for 20 hours. Additional Amberlyst-15H (15.0 g, 1.6 wt%) was added and the reaction continued for 8 hours.
  • the mixture was filtered through Celite to remove catalyst. The filtrate was distilled under vacuum to 100°C to remove unreacted thiol and then to 250°C to remove unreacted olefin.
  • the 3 ⁇ 4 NMR spectra of Product IV was determined and is shown in FIG. 4. Further, the 3 ⁇ 4 NMR structural assignments of compounds VII and VIII are shown in FIG. 5. As shown, in FIG. 5, the molecular structure of compound VII includes a methyl group positioned adjacent to the aliphatic C-S bond. The methyl group was identifiable as a singlet peak with a chemical shift of 1.20 ppm. The carbon atom of the aliphatic C- S bond from the PAO moiety has no hydrogen atoms and was thus featureless by ⁇ NMR. The carbon atom of the aliphatic C-S bond from the aliphatic thiol moiety has two hydrogen atoms which were recognizable as a triplet peak with a chemical shift of 2.39 ppm.
  • both S-containing aromatic base stocks from Product I and Comparative Product 1 have even longer RPVOT break times than SynessticTM 5, demonstrating that the S atom can contribute additional oxidative stability to an aromatic-containing base stock.
  • the presence of sulfur atom in an otherwise aliphatic base stock molecule can improve oxidative stability.
  • the base stock of Product III has a longer RPVOT break time compared to a hydrocarbon base stock, such as PAO 4.

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Abstract

L'invention concerne des composés ayant la formule (F-I) suivante, dans laquelle : R1 représente un groupe alkyle en C1-C5000; R2 représente (i) un groupe alkyle linéaire en C4-C30 (ii) un alkyle ramifié en C4-C5000 ayant la formule (F-II) suivante, dans laquelle, R5 et R6 à chaque occurrence sont chacun indépendamment de l'hydrogène ou un groupe alkyle linéaire en C1-C30 et n est un nombre entier positif, à condition que, parmi tous les groupes R5 et R6, au moins l'un est un groupe alkyle linéaire en C1-C30; et R7 représente l'hydrogène ou un groupe alkyle linéaire en C1-C30 ; R3 représente l'hydrogène ou un groupe alkyle en C1-C5000; et R4 représente un groupe alkyle en C1-C50 ou un groupe aromatique. L'invention concerne également des procédés de préparation de composés de formule (F-I) ainsi que des compositions de base et des compositions lubrifiantes contenant des composés de formule (F-I).
PCT/US2017/068457 2017-01-17 2017-12-27 Huiles de base lubrifiantes à stabilité élevée et leurs procédés de production WO2018136208A1 (fr)

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