WO2020204824A1 - Sulfur-free anti-wear, extreme pressure and anti-corrosion additives, and methods for producing and uses of the additives - Google Patents

Sulfur-free anti-wear, extreme pressure and anti-corrosion additives, and methods for producing and uses of the additives Download PDF

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Publication number
WO2020204824A1
WO2020204824A1 PCT/SG2020/050187 SG2020050187W WO2020204824A1 WO 2020204824 A1 WO2020204824 A1 WO 2020204824A1 SG 2020050187 W SG2020050187 W SG 2020050187W WO 2020204824 A1 WO2020204824 A1 WO 2020204824A1
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atoms
sulfur
metalloid
free composition
compound
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PCT/SG2020/050187
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French (fr)
Inventor
Alok CHAURASIA
Luv SHAH
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Polygel Innovations Pte. Ltd.
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Priority claimed from SG10201902887TA external-priority patent/SG10201902887TA/en
Application filed by Polygel Innovations Pte. Ltd. filed Critical Polygel Innovations Pte. Ltd.
Publication of WO2020204824A1 publication Critical patent/WO2020204824A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • the present invention relates generally to lubricants, and more specifically to sulfur-free anti wear, extreme pressure and anti-corrosion additives for lubricants oil compositions. More particularly, the invention relates to sulfur-free materials containing two or more kinds of metal and/or metalloid elements.
  • a lubricant is a substance introduced between two moving surfaces to reduce friction, minimize wear, distribute heat, remove contaminants, and improve efficiency. Modern equipment must be lubricated in order to prolong its lifetime and efficacy. Typically, lubricants contain 90% base oil and less than 10% additives.
  • lubricant additives may be added into lubricants, such as anti wear additives, extreme pressure additives, detergents, dispersants, friction modifiers, antifoam, antioxidant and rust inhibitor, pour point depressant and viscosity index improvers.
  • Zinc Dialkyldithiophosphate is a popular and universal extreme pressure additive used in lubricating oils because of its multifunctional extreme pressure, anti-wear and antioxidant properties 1 2 .
  • ZDDP is a ubiquitous additive used in engine oils for over 60 years as an effective extreme pressure, as well as an anti-oxidation, agent.
  • ZDDP is known to interfere with and to have adverse effect on the performance of modern catalytic converters, especially those used for Euro IV, V and VI Emission Norms due to the presence of sulfur atom in the molecule which is not compatible with palladium-, platinum- and titanium-based catalysts used in these converter systems 3 4 .
  • ZDDP also contains large amounts of sulfur and zinc, which damage the environment both directly and indirectly 5 .
  • ZDDP 5 11 Many attempts have already been made to find an alternative to ZDDP 5 11 .
  • phosphorothionates-based compounds can be used as antioxidant, anti-wear and extreme pressure additives in a lubricant composition.
  • the said additives are used for controlling wear on metal parts and enhancing the load carrying properties of lubricant 5 ’ 7 .
  • nano tungsten sulfide (WS2) particle may potentially be used to replace ZDDP.
  • WS2 nano tungsten sulfide
  • these potential replacements also contain sulfur 8 .
  • Zinc dialkylphosphate (ZP) is a sulfur-free analogue of ZDDP. However, anti wear performance of ZP is much worse than ZDDP at high speeds 1 1 .
  • the invention is directed to a process for synthesizing a sulfur-free composition; the process involves modification of a phosphorus compound using one or more functional group/s, and interaction of the modified phosphorus compound with a first metal compound or metalloid compound and a second metal compound or metalloid compound; and the sulfur-free composition contains:
  • a third or any further number of metal compound/s and/or metalloid compound/s is/are included in the interaction.
  • the phosphorus atoms, the metal atoms and/or the metalloid atoms are connected by carbon chain in the sulfur-free composition, and in some embodiments, at least one carbon atom in the carbon chain is replaced by one oxygen atom.
  • the phosphorus compound is diethylene glycol glycerine ester of triethyl phosphate (DEGGLYTEP) or diethylene glycol of triethyl phosphate (DEGTEP).
  • each of the one or more functional group/s may be -H, -OH, -OMe, -OEt, -COOH, -Me, -Et or any other carbon-containing functional group with two or more carbon atoms.
  • each of the first metal compound or metalloid compound, the second metal compound or metalloid compound, and the third or any further number of metal compound/s and/or metalloid compound/s includes at least one of -COOH, -OH and PO4 3 .
  • the metal in the metal compound is aluminum, titanium, hafnium, lanthanum, niobium, tantalum, tin, vanadium or zirconium; and the metalloid in the metalloid compound is antimony, germanium or silicon.
  • the metal compound is metal alkoxide and the metalloid compound is metalloid alkoxide.
  • the invention is directed to a sulfur- free composition
  • the sulfur-free composition is synthesized using the process as described above, the sulfur-free composition contains phosphorus atoms, M1 atoms and M2 atoms; M1 is different from M2, each of M1 and M2 is a metal element or metalloid element; and phosphorus atoms, M1 atoms and M2 atoms are connected by at least one chemical chain.
  • the sulfur-free composition includes M3 atoms, where M3 is different from M1 and M2, and M3 is a metal element or metalloid element; and phosphorus atoms, M1 atoms, M2 atoms and M3 atoms are connected by at least one chemical chain.
  • the sulfur-free composition includes M4 atoms, where M4 is different from any of M1 , M2 and M3, and M4 is a metal element or metalloid element; and phosphorus atoms, M1 atoms, M2 atoms, M3 atoms and M4 atoms are connected by at least one chemical chain.
  • the chemical chain is carbon chain, and in some embodiments, at least one carbon atom in the carbon chain is replaced by one oxygen atom.
  • each of the metal elements is aluminum, titanium, hafnium, lanthanum, niobium, tantalum, tin, vanadium or zirconium; and each of the metalloid elements is antimony, germanium or silicon.
  • the invention is directed to the use of the sulfur-free composition described above as an anti-wear additive in a lubricant.
  • the invention is directed to the use of the sulfur-free composition described above as an extreme pressure additive in a lubricant.
  • the invention is directed to the use of the sulfur-free composition described above as an anti-corrosion additive in a lubricant.
  • the lubricant includes the sulfur-free composition in an amount of 0.001 wt% to 10 wt%, preferably 2 wt%.
  • the invention is directed to the use of the sulfur-free composition described above as an anti-corrosion additive in a coating or paint.
  • Figure 1 depicts the outline of the synthesis process according to one embodiment of the present invention.
  • Figure 2 depicts the results of anti-corrosion test of some samples synthesized using the synthesis process according to one embodiment of the present invention.
  • Bi-Additive is a composition suitable to be used as an additive to lubricants, which contains at least two kinds of atoms in the molecular structure of the composition and each of such two kinds of atoms is metal or metalloid;
  • “Ter-Additive” is a composition suitable to be used as an additive to lubricants, which contains at least three kinds of atoms in the molecular structure of the composition and each of such three kinds of atoms is metal or metalloid;
  • FIG. 1 shows the outline of the synthesis process of the sulfur-free composition (III) according to one embodiment of the present invention.
  • Figure. 1 shows a process including at least two parts, one for modification of phosphorus compound, and another for interaction of the modified phosphorus compound with at least two metal compound/s and/or metalloid compound/s, to synthesize the sulfur-free composition (III).
  • the phosphorus compound is a compound containing phosphorus.
  • diethylene glycol glycerine ester of triethyl phosphate (DEGGLYTEP) is used as the phosphorus compound.
  • diethylene glycol of triethyl phosphate (DEGTEP) is used as the phosphorus compound.
  • DEGGLYTEP and DEGTEP are not the only two types of phosphorus compounds, and that the phosphorus compound can include other functional groups which will further be discussed below.
  • the phosphorus compound may include one or more functional group/s, and/or may be modified with one or more functional group/s.
  • Each of the one or more functional group/s may be -H, - OH, -OMe, -OEt, -COOH, -Me, -Et or any other carbon-containing functional group with two or more carbon atoms.
  • the interaction is preferably taking place in an inert environment.
  • the interaction of the phosphorus compound is with at least two metal compounds.
  • the interaction of the phosphorus compound is with at least two metalloid compounds.
  • the interaction of the phosphorus compound is with at least one metal compound and at least one metalloid compound.
  • the metal compound/s and/or metalloid compound/s may include one or more functional group/s, each of which may be -COOH, - OH or PO4 3 ⁇ .
  • each of the metal compounds may be metal alkoxide, and each of the metalloid compounds may be metalloid alkoxide.
  • the metal alkoxide may be aluminum alkoxide, titanium alkoxide, hafnium alkoxide, lanthanum alkoxide, niobium alkoxide, tantalum alkoxide, tin alkoxide, vanadium alkoxide, or zirconium alkoxide; and the metalloid alkoxide may be antimony alkoxide, germanium alkoxide or silicon alkoxide.
  • reaction vessel (1 ) Set up and clean reaction vessel. (2) Inject inert gas into the reaction vessel, to purge and remove air from the reaction vessel.
  • the inert gas is nitrogen.
  • the toluene is HPLC grade.
  • the metal compound or metalloid compound is aluminum isopropoxide.
  • the metal compound or metalloid compound is tetra isopropyl titanate (TiPT).
  • the process is not limited to the above steps. According to one embodiment of the present invention, the process may involve one or more additional step/s to add one or more further metal compound/s and/or metalloid compound/s to the mixture in the reaction vessel.
  • the sulfur-free composition synthesized using the process in the present invention has a new type of molecule, which is a kind of low molecular weight macromolecules.
  • the sulfur-free composition synthesized using two or more metal compound/s and/or metalloid compound/s has a molecular structure wherein metal atoms and/or metalloid atoms and phosphorus atoms are linked by chemical connection.
  • the molecular structure of the sulfur-free composition includes different metal atoms and/or metalloid atoms along with other functional groups.
  • the sulfur-free composition contains two kinds of metal element/s and/or metalloid element/s. If two metal compound/s and/or metalloid compound/s are used to synthesize the sulfur-free composition, the molecular structure of such sulfur-free composition would contain two kinds of metal atoms and/or metalloid atoms. The metal atoms and/or metalloid atoms are chemically connected in the molecular structure of the sulfur-free composition.
  • the sulfur-free composition which contains any two kinds of metal element/s and/or metalloid element/s is collectively called Bi-Additive in the present invention.
  • the molecular structure of Bi-Additive contains phosphorus, M1 and M2, wherein phosphorus atoms, M1 atoms and M2 atoms are connected by chemical chain.
  • Such chemical chain may be a carbon chain.
  • one or more carbon atom/s may be replaced by one or more oxygen atom/s.
  • Each of M1 and M2 is a metal element or metalloid element.
  • M1 is different from M2.
  • each of M1 and M2 is preferably aluminum, titanium, antimony, germanium, hafnium, lanthanum, niobium, tantalum, silicon, tin, vanadium or zirconium.
  • M1 and M2 are aluminum and titanium respectively.
  • the sulfur-free composition contains three kinds of metal element/s and/or metalloid element/s. If three metal compound/s and/or metalloid compound/s are used to synthesize the sulfur-free composition, the molecular structure of such sulfur-free composition would contain three kinds of metal atoms and/or metalloid atoms. The metal atoms and/or metalloid atoms are chemically connected in the molecular structure of the sulfur-free composition.
  • the sulfur-free composition which contains any three kinds of metal element/s and/or metalloid element/s is collectively called Ter-Additive in the present invention.
  • the molecular structure of Ter-Additive contains phosphorus, M1 , M2 and M3, wherein phosphorus atoms, M1 atoms, M2 atoms and M3 atoms are connected by chemical chain.
  • Such chemical chain may be a carbon chain.
  • one or more carbon atom/s may be replaced by one or more oxygen atom/s.
  • Each of M1 , M2 and M3 is a metal element or metalloid element.
  • Each of M1 , M2 and M3 is different from the other two.
  • each of M1 , M2 and M3 is preferably aluminum, titanium, antimony, germanium, hafnium, lanthanum, niobium, tantalum, silicon, tin, vanadium or zirconium.
  • M1 and M2 are aluminum and titanium respectively.
  • the sulfur-free composition contains four or more kinds of metal atoms and/or metalloid atoms. If four or more metal compound/s and/or metalloid compound/s are used to synthesize the sulfur-free composition, the molecular structure of such sulfur-free composition would contain four or more kinds of metal atoms and/or metalloid atoms. The metal atoms and/or metalloid atoms are chemically connected in the molecular structure of the sulfur-free composition.
  • the sulfur-free composition which contains any four or more kinds of metal element/s and/or metalloid element/s are collectively called Multi-Additive in the present invention.
  • the molecular structure of Multi- Additive contains phosphorus, M1 ... Mn, wherein phosphorus atoms, M1 atoms ... Mn atoms are connected by chemical chain.
  • Such chemical chain may be a carbon chain.
  • one or more carbon atom/s may be replaced by one or more oxygen atom/s.
  • Each of M1 ... Mn is a metal element or metalloid element.
  • Each of M1 ... Mn is different from the rest.
  • Mn is preferably aluminum, titanium, antimony, germanium, hafnium, lanthanum, niobium, tantalum, silicon, tin, vanadium or zirconium. According to one embodiment of the present invention, M1 and M2 are aluminum and titanium respectively.
  • At least two kinds of metal atoms and/or metalloid atoms are introduced to form the molecular structure of Bi-Additive, Ter- Additive and Multi-Additive.
  • the introduction of at least two kinds of metal atoms and/or metalloid atoms into the molecular structure of the sulfur-free composition contributes good anti-wear performance, anti-corrosion performance and extreme pressure performance.
  • Sulfur-free compositions synthesized using the process of the present invention may be of different molecular structures, depending on the reactant used and/or the prevailing condition/s affecting the process.
  • the sulfur-free composition synthesized using the process of the present invention contains phosphorus atoms, and at least two kinds of metal atoms and/or metalloid atoms, all of which are chemically connected.
  • formula (1 ) to formula (5) are five examples of different general molecular structures of such sulfur-free composition containing at least phosphorus atoms, titanium atoms and aluminum atoms.
  • composition samples have been synthesized using the process of the present invention, to test the performance of the sulfur-free composition synthesized through the process.
  • composition sample No. T-81 was synthesized using the process of the present invention, and using the following materials, wherein the phosphorus compound was DEGTEP:
  • a lubricant sample No. T-83 was prepared by adding the composition sample No. T-81 into base oil in an amount of 2 wt%.
  • the base oil was N-100 base oil.
  • composition sample No. T-85 was synthesized using the process of the present invention, and using the following materials, wherein the phosphorus compound was DEGTEP:
  • a lubricant sample No. T-86 was prepared by adding the composition sample No. T-85 into base oil in an amount of 2 wt%.
  • the base oil was N-100 base oil.
  • composition sample No. T-87 was synthesized using the process of the present invention, and using the following materials, wherein the phosphorus compound was DEGGLYTEP:
  • a lubricant sample No. T-88 was prepared by adding the composition sample No. T-87 into base oil in an amount of 2 wt%.
  • the base oil was N-100 base oil.
  • the DEGTEP (1 :1 ) contains DEG and TEP at a mole ratio of 1 :1 .
  • the DEGTEP (1 :1 ) may be prepared using the following materials and steps:
  • TEP Triethyl phosphate
  • the DEGGLYTEP (0.95:0.05:1 ) contains DEG, GLY and TEP at a mole ratio of 0.95:0.05:1 .
  • the DEGGLYTEP (0.95:0.05:1 ) may be prepared using the following materials and steps:
  • reaction vessel for a period of 30 minutes, until a homogeneous mixture is formed.
  • a lubricant was prepared by adding ZDDP into base oil in an amount of 2 wt%.
  • the base oil was N-100 base oil.
  • composition samples showed a good performance in terms of miscibility and dispensability in base oil.
  • the sulfur-free composition samples produced were found to be compatible with the commonly used lubricating N-100 base oil.
  • the lubricant includes the sulfur-free composition in an amount of 0.001 wt% to 10 wt%; in another embodiment, lubricant includes the sulfur-free composition in an amount of 2 wt%.
  • test results can be used to compare the anti-wear performance of the control sample ZDDP and that of the lubricant samples No. T-83 and No. T-88, which are indicated in Table. 2 below.
  • the test was conducted for a duration of one hour at a load of 15kgf, a temperature of 75 °C and a rotating speed of 1200 RPM.
  • composition produced by the process of the present invention will be of use in the lubrication industry to replace those additives containing sulfur, to resolve the issues due to sulfur.
  • EP1369469B1 An antioxidant additives combination for lubricants containing a molybdenum complex and analkylated phenothiazine.
  • EP1364955A1 Phosphorothionates.

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  • Organic Chemistry (AREA)
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Abstract

The present invention provides a sulfur-free composition containing phosphorous atoms, a first metal or metalloid element, and a second metal or metalloid element; and a process for synthesizing it comprising modification of a phosphorous compound using one or more functional groups, and interaction of the modified phosphorous compound with at least two kinds of metal compound and/or metalloid compounds. In specific embodiments, the phosphorous compound is diethylene glycol glycerine ester of triethyl phosphate (DEGGLYTEP) or diethylene glycol of triethyl phosphate (DEGTEP), the functional group is oleic acid, and the metal compounds are titanium alkoxide and aluminium alkoxide. Test results demonstrate that the sulfur-free composition synthesized using the process in the present invention is effective as anti-wear additive, extreme pressure additive and anti-corrosion additive in lubricants, and as anti-corrosion additive in coatings or paints.

Description

SULFUR-FREE ANTI-WEAR, EXTREME PRESSURE AND ANTI-CORROSION ADDITIVES, AND METHODS FOR PRODUCING AND USES OF THE ADDITIVES
FIELD OF THE INVENTION
[1 ] The present invention relates generally to lubricants, and more specifically to sulfur-free anti wear, extreme pressure and anti-corrosion additives for lubricants oil compositions. More particularly, the invention relates to sulfur-free materials containing two or more kinds of metal and/or metalloid elements.
BACKGROUND OF THE INVENTION
[2] A lubricant is a substance introduced between two moving surfaces to reduce friction, minimize wear, distribute heat, remove contaminants, and improve efficiency. Modern equipment must be lubricated in order to prolong its lifetime and efficacy. Typically, lubricants contain 90% base oil and less than 10% additives.
[3] Generally, various types of lubricant additives may be added into lubricants, such as anti wear additives, extreme pressure additives, detergents, dispersants, friction modifiers, antifoam, antioxidant and rust inhibitor, pour point depressant and viscosity index improvers.
[4] Zinc Dialkyldithiophosphate (ZDDP) is a popular and universal extreme pressure additive used in lubricating oils because of its multifunctional extreme pressure, anti-wear and antioxidant properties1 2. Particularly, ZDDP is a ubiquitous additive used in engine oils for over 60 years as an effective extreme pressure, as well as an anti-oxidation, agent.
[5] However, ZDDP is known to interfere with and to have adverse effect on the performance of modern catalytic converters, especially those used for Euro IV, V and VI Emission Norms due to the presence of sulfur atom in the molecule which is not compatible with palladium-, platinum- and titanium-based catalysts used in these converter systems3 4. ZDDP also contains large amounts of sulfur and zinc, which damage the environment both directly and indirectly5.
[6] Many attempts have already been made to find an alternative to ZDDP5 11. There are reports showing that phosphorothionates-based compounds can be used as antioxidant, anti-wear and extreme pressure additives in a lubricant composition. The said additives are used for controlling wear on metal parts and enhancing the load carrying properties of lubricant5 ’ 7. There is also report indicating that nano tungsten sulfide (WS2) particle may potentially be used to replace ZDDP. However, similar to ZDDP, these potential replacements also contain sulfur8. [7] Zinc dialkylphosphate (ZP) is a sulfur-free analogue of ZDDP. However, anti wear performance of ZP is much worse than ZDDP at high speeds1 1.
[8] In view of the above-mentioned issues, there is a clear need for novel materials and additives which show similar or better tribological performance than ZDDP and are compatible with the catalysts used in modern catalytic converters, especially those under the recently introduced Euro IV, V and VI Emission Norms.
[9] It is one object of the present invention to provide a sulfur-free additive for use as an anti wear additive in lubricants.
[10] It is another object of the present invention to provide a sulfur-free additive for use as an extreme pressure additive in lubricants.
[1 1 ] It is still another object of the present invention to provide a sulfur-free additive for use as an anti-corrosion additive in lubricants.
[12] It is still another object of the present invention to provide a zinc-free additive for use as an anti-wear, extreme pressure and/or anti-corrosion additive in lubricants.
[13] The above and other objects will become apparent in the following description and claims.
SUMMARY OF INVENTION
[14] According to one embodiment of the present invention, the invention is directed to a process for synthesizing a sulfur-free composition; the process involves modification of a phosphorus compound using one or more functional group/s, and interaction of the modified phosphorus compound with a first metal compound or metalloid compound and a second metal compound or metalloid compound; and the sulfur-free composition contains:
phosphorus atoms and metal atoms; or
phosphorus atoms and metalloid atoms; or
phosphorus atoms, metal atoms and metalloid atoms;
wherein said atoms are chemically connected in the sulfur-free composition.
[15] In some embodiments of the process invention for synthesizing a sulfur-free composition, a third or any further number of metal compound/s and/or metalloid compound/s is/are included in the interaction.
[16] In some embodiments of the process invention for synthesizing a sulfur-free composition, the phosphorus atoms, the metal atoms and/or the metalloid atoms are connected by carbon chain in the sulfur-free composition, and in some embodiments, at least one carbon atom in the carbon chain is replaced by one oxygen atom.
[17] In some embodiments of the process invention for synthesizing a sulfur-free composition, the phosphorus compound is diethylene glycol glycerine ester of triethyl phosphate (DEGGLYTEP) or diethylene glycol of triethyl phosphate (DEGTEP).
[18] In some embodiments of the process invention for synthesizing a sulfur-free composition, each of the one or more functional group/s may be -H, -OH, -OMe, -OEt, -COOH, -Me, -Et or any other carbon-containing functional group with two or more carbon atoms.
[19] In some embodiments of the process invention for synthesizing a sulfur-free composition, each of the first metal compound or metalloid compound, the second metal compound or metalloid compound, and the third or any further number of metal compound/s and/or metalloid compound/s includes at least one of -COOH, -OH and PO43 .
[20] In some embodiments of the process invention for synthesizing a sulfur-free composition, the metal in the metal compound is aluminum, titanium, hafnium, lanthanum, niobium, tantalum, tin, vanadium or zirconium; and the metalloid in the metalloid compound is antimony, germanium or silicon.
[21 ] In some embodiments of the process invention for synthesizing a sulfur-free composition, the metal compound is metal alkoxide and the metalloid compound is metalloid alkoxide.
[22] According to one embodiment of the present invention, the invention is directed to a sulfur- free composition, the sulfur-free composition is synthesized using the process as described above, the sulfur-free composition contains phosphorus atoms, M1 atoms and M2 atoms; M1 is different from M2, each of M1 and M2 is a metal element or metalloid element; and phosphorus atoms, M1 atoms and M2 atoms are connected by at least one chemical chain.
[23] In some embodiments of the sulfur-free composition invention, the sulfur-free composition includes M3 atoms, where M3 is different from M1 and M2, and M3 is a metal element or metalloid element; and phosphorus atoms, M1 atoms, M2 atoms and M3 atoms are connected by at least one chemical chain.
[24] In some embodiments of the sulfur-free composition invention, the sulfur-free composition includes M4 atoms, where M4 is different from any of M1 , M2 and M3, and M4 is a metal element or metalloid element; and phosphorus atoms, M1 atoms, M2 atoms, M3 atoms and M4 atoms are connected by at least one chemical chain. [25] In some embodiments of the sulfur-free composition invention, the chemical chain is carbon chain, and in some embodiments, at least one carbon atom in the carbon chain is replaced by one oxygen atom.
[26] In some embodiments of the sulfur-free composition invention, each of the metal elements is aluminum, titanium, hafnium, lanthanum, niobium, tantalum, tin, vanadium or zirconium; and each of the metalloid elements is antimony, germanium or silicon.
[27] According to one embodiment of the present invention, the invention is directed to the use of the sulfur-free composition described above as an anti-wear additive in a lubricant.
[28] According to one embodiment of the present invention, the invention is directed to the use of the sulfur-free composition described above as an extreme pressure additive in a lubricant.
[29] According to one embodiment of the present invention, the invention is directed to the use of the sulfur-free composition described above as an anti-corrosion additive in a lubricant.
[30] In some embodiments of the use invention, the lubricant includes the sulfur-free composition in an amount of 0.001 wt% to 10 wt%, preferably 2 wt%.
[31 ] According to one embodiment of the present invention, the invention is directed to the use of the sulfur-free composition described above as an anti-corrosion additive in a coating or paint.
BRIEF DESCRIPTION OF THE DRAWINGS
[32] Figure 1 depicts the outline of the synthesis process according to one embodiment of the present invention.
[33] Figure 2 depicts the results of anti-corrosion test of some samples synthesized using the synthesis process according to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[34] While the concepts of the present disclosure are susceptible to various modifications and alternative forms, specific embodiments will herein be described in detail. It should be understood, however, that there is no intent to limit the concepts of the present disclosure to the particular forms disclosed or terms used, but on the contrary, the intention is to cover all modifications, equivalents and alternatives consistent with the present disclosure and the appended claims. [35] In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, that the present invention may be practised without these specific details. Well-known methods, procedures, materials and conditions have not been described in detail so as not to unnecessarily obscure aspects of the implementations.
[36] It will be appreciated that the inclusion of a schematic element in a drawing is not meant to imply that such element is required in all embodiments or that the features represented by such element may not be included in or combined with other elements in some embodiments.
[37] Several features are described hereafter, each of which may be used independently of one another or with any combination of other features. However, any individual feature may not address any of the problems discussed above or might only address one of the problems discussed above. Some of the problems discussed above might not be fully addressed by any of the features described herein. Although headings are provided, information related to a particular heading, but not found in the section having that heading, may also be found elsewhere in the specification.
[38] In this specification:
(1) the terms“contain” and“include” and derivatives of these terms are not to be construed as being restricted or confined to the ensuing matters enumerated but as potentially encompassing other matters not so enumerated;
(2) words in the singular shall be construed to include the plural and vice versa, unless the context requires or indicates otherwise;
(3) unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art to which the present invention belongs;
(4) “Bi-Additive” is a composition suitable to be used as an additive to lubricants, which contains at least two kinds of atoms in the molecular structure of the composition and each of such two kinds of atoms is metal or metalloid;
(5) “Ter-Additive” is a composition suitable to be used as an additive to lubricants, which contains at least three kinds of atoms in the molecular structure of the composition and each of such three kinds of atoms is metal or metalloid;
(6)“Multi-Additive” is a composition suitable to be used as an additive to lubricants, which contains four or more kinds of atoms in the molecular structure of the composition and each of such four or more kinds of atoms is metal or metalloid. [39] Figure. 1 shows the outline of the synthesis process of the sulfur-free composition (III) according to one embodiment of the present invention. Figure. 1 shows a process including at least two parts, one for modification of phosphorus compound, and another for interaction of the modified phosphorus compound with at least two metal compound/s and/or metalloid compound/s, to synthesize the sulfur-free composition (III).
[40] For one part of the process involving modification of phosphorus compound, the phosphorus compound is a compound containing phosphorus. According to one embodiment of the present invention, diethylene glycol glycerine ester of triethyl phosphate (DEGGLYTEP) is used as the phosphorus compound. According to another embodiment of the present invention, diethylene glycol of triethyl phosphate (DEGTEP) is used as the phosphorus compound. Those skilled in the art would appreciate that DEGGLYTEP and DEGTEP are not the only two types of phosphorus compounds, and that the phosphorus compound can include other functional groups which will further be discussed below.
[41 ] The phosphorus compound may include one or more functional group/s, and/or may be modified with one or more functional group/s. Each of the one or more functional group/s may be -H, - OH, -OMe, -OEt, -COOH, -Me, -Et or any other carbon-containing functional group with two or more carbon atoms.
[42] For one part of the process involving interaction of the modified phosphorus compound with at least two metal compound/s and/or metalloid compound/s, the interaction is preferably taking place in an inert environment. According to one embodiment of the present invention, the interaction of the phosphorus compound is with at least two metal compounds. According to one embodiment of the present invention, the interaction of the phosphorus compound is with at least two metalloid compounds. According to one embodiment of the present invention, the interaction of the phosphorus compound is with at least one metal compound and at least one metalloid compound.
[43] According to one embodiment of the present invention, the metal compound/s and/or metalloid compound/s may include one or more functional group/s, each of which may be -COOH, - OH or PO43·. According to one embodiment of the present invention, each of the metal compounds may be metal alkoxide, and each of the metalloid compounds may be metalloid alkoxide. According to one embodiment of the present invention, the metal alkoxide may be aluminum alkoxide, titanium alkoxide, hafnium alkoxide, lanthanum alkoxide, niobium alkoxide, tantalum alkoxide, tin alkoxide, vanadium alkoxide, or zirconium alkoxide; and the metalloid alkoxide may be antimony alkoxide, germanium alkoxide or silicon alkoxide.
[44] According to one embodiment of the present invention, the following operational steps are taken to realize the process:
(1 ) Set up and clean reaction vessel. (2) Inject inert gas into the reaction vessel, to purge and remove air from the reaction vessel. According to one embodiment of the present invention, the inert gas is nitrogen.
(3) Pour toluene into the reaction vessel, and then inject nitrogen gas into the reaction vessel to purge and remove air and moisture, if any, from the toluene. According to one embodiment of the present invention, the toluene is HPLC grade.
(4) Add a metal compound or metalloid compound to reaction vessel and stir the mixture in the reaction vessel until a homogeneous mixture is formed. According to one embodiment of the present invention, the metal compound or metalloid compound is aluminum isopropoxide.
(5) Add another metal compound or metalloid compound to reaction vessel and stir the mixture in the reaction vessel until a homogeneous mixture is formed and allow the homogeneous mixture to stand in the reaction vessel for one hour. According to one embodiment of the present invention, the metal compound or metalloid compound is tetra isopropyl titanate (TiPT).
(6) Slowly add phosphorus compound, followed by oleic acid, to the mixture in the reaction
vessel, and then stir the contents in the reaction vessel until a homogeneous mixture is formed.
(7) Allow the mixture to stand in the reaction vessel, for a duration of one hour, at a temperature range of about 90 °C to about 130 °C, preferably 100 °C.
(8) Reduce temperature to about 70 °C, and remove liberated isopropyl alcohol by vacuum
distillation under a pressure of about 140mbar reduced from the standard atmosphere.
(9) Cool and pour the final product into air tight container under inert environment.
[45] Those skilled in the art would appreciate that the process is not limited to the above steps. According to one embodiment of the present invention, the process may involve one or more additional step/s to add one or more further metal compound/s and/or metalloid compound/s to the mixture in the reaction vessel.
[46] The sulfur-free composition synthesized using the process in the present invention has a new type of molecule, which is a kind of low molecular weight macromolecules. The sulfur-free composition synthesized using two or more metal compound/s and/or metalloid compound/s has a molecular structure wherein metal atoms and/or metalloid atoms and phosphorus atoms are linked by chemical connection. According to one embodiment of the present invention, the molecular structure of the sulfur-free composition includes different metal atoms and/or metalloid atoms along with other functional groups.
[47] According to one embodiment, the sulfur-free composition contains two kinds of metal element/s and/or metalloid element/s. If two metal compound/s and/or metalloid compound/s are used to synthesize the sulfur-free composition, the molecular structure of such sulfur-free composition would contain two kinds of metal atoms and/or metalloid atoms. The metal atoms and/or metalloid atoms are chemically connected in the molecular structure of the sulfur-free composition. For ease of reference, the sulfur-free composition which contains any two kinds of metal element/s and/or metalloid element/s is collectively called Bi-Additive in the present invention.
[48] According to one embodiment of the present invention, the molecular structure of Bi-Additive contains phosphorus, M1 and M2, wherein phosphorus atoms, M1 atoms and M2 atoms are connected by chemical chain. Such chemical chain may be a carbon chain. Along the carbon chain, one or more carbon atom/s may be replaced by one or more oxygen atom/s. Each of M1 and M2 is a metal element or metalloid element. M1 is different from M2. According to one embodiment of the present invention, each of M1 and M2 is preferably aluminum, titanium, antimony, germanium, hafnium, lanthanum, niobium, tantalum, silicon, tin, vanadium or zirconium. According to one embodiment of the present invention, M1 and M2 are aluminum and titanium respectively.
[49] According to one embodiment of the present invention, the sulfur-free composition contains three kinds of metal element/s and/or metalloid element/s. If three metal compound/s and/or metalloid compound/s are used to synthesize the sulfur-free composition, the molecular structure of such sulfur- free composition would contain three kinds of metal atoms and/or metalloid atoms. The metal atoms and/or metalloid atoms are chemically connected in the molecular structure of the sulfur-free composition. For ease of reference, the sulfur-free composition which contains any three kinds of metal element/s and/or metalloid element/s is collectively called Ter-Additive in the present invention.
[50] According to one embodiment of the present invention, the molecular structure of Ter-Additive contains phosphorus, M1 , M2 and M3, wherein phosphorus atoms, M1 atoms, M2 atoms and M3 atoms are connected by chemical chain. Such chemical chain may be a carbon chain. Along the carbon chain, one or more carbon atom/s may be replaced by one or more oxygen atom/s. Each of M1 , M2 and M3 is a metal element or metalloid element. Each of M1 , M2 and M3 is different from the other two. According to one embodiment of the present invention, each of M1 , M2 and M3 is preferably aluminum, titanium, antimony, germanium, hafnium, lanthanum, niobium, tantalum, silicon, tin, vanadium or zirconium. According to one embodiment of the present invention, M1 and M2 are aluminum and titanium respectively.
[51 ] According to one embodiment of the present invention, the sulfur-free composition contains four or more kinds of metal atoms and/or metalloid atoms. If four or more metal compound/s and/or metalloid compound/s are used to synthesize the sulfur-free composition, the molecular structure of such sulfur-free composition would contain four or more kinds of metal atoms and/or metalloid atoms. The metal atoms and/or metalloid atoms are chemically connected in the molecular structure of the sulfur-free composition. For ease of reference, the sulfur-free composition which contains any four or more kinds of metal element/s and/or metalloid element/s are collectively called Multi-Additive in the present invention.
[52] According to one embodiment of the present invention, the molecular structure of Multi- Additive contains phosphorus, M1 ... Mn, wherein phosphorus atoms, M1 atoms ... Mn atoms are connected by chemical chain. Such chemical chain may be a carbon chain. Along the carbon chain, one or more carbon atom/s may be replaced by one or more oxygen atom/s. Each of M1 ... Mn is a metal element or metalloid element. Each of M1 ... Mn is different from the rest. According to one embodiment of the present invention, each of M1 ... Mn is preferably aluminum, titanium, antimony, germanium, hafnium, lanthanum, niobium, tantalum, silicon, tin, vanadium or zirconium. According to one embodiment of the present invention, M1 and M2 are aluminum and titanium respectively.
[53] Those skilled in the art would appreciate from the above that, at least two kinds of metal atoms and/or metalloid atoms are introduced to form the molecular structure of Bi-Additive, Ter- Additive and Multi-Additive. The introduction of at least two kinds of metal atoms and/or metalloid atoms into the molecular structure of the sulfur-free composition contributes good anti-wear performance, anti-corrosion performance and extreme pressure performance.
[54] Sulfur-free compositions synthesized using the process of the present invention may be of different molecular structures, depending on the reactant used and/or the prevailing condition/s affecting the process. In any event, the sulfur-free composition synthesized using the process of the present invention contains phosphorus atoms, and at least two kinds of metal atoms and/or metalloid atoms, all of which are chemically connected. To illustrate, formula (1 ) to formula (5) are five examples of different general molecular structures of such sulfur-free composition containing at least phosphorus atoms, titanium atoms and aluminum atoms.
Figure imgf000010_0001
Formula (1 )
Figure imgf000011_0001
Formula (4)
Figure imgf000012_0001
Formula (5)
[55] Some composition samples have been synthesized using the process of the present invention, to test the performance of the sulfur-free composition synthesized through the process.
Example I
[56] A composition sample No. T-81 was synthesized using the process of the present invention, and using the following materials, wherein the phosphorus compound was DEGTEP:
Materials
• Toluene: 5 grams (HPLC grade)
• TiPT : 21 .3 grams (0.75M)
• Al-isopropoxide: 5 grams (0.25M)
• Oleic acid: 49.4 grams (1 .75M)
• DEGTEP (1 :1 ): 42.4 grams (1 .75M)
[57] A lubricant sample No. T-83 was prepared by adding the composition sample No. T-81 into base oil in an amount of 2 wt%. The base oil was N-100 base oil.
Example II
[58] A composition sample No. T-85 was synthesized using the process of the present invention, and using the following materials, wherein the phosphorus compound was DEGTEP:
Materials
• Toluene: 8.25 grams (HPLC grade)
• TiPT: 17.1 grams (0.6M)
• Al-isopropoxide: 8.25 grams (0.4M)
• Oleic acid: 49.4 grams (1 .75M)
• DEGTEP (1 :1 ): 42.4 grams (1 .75M) [59] A lubricant sample No. T-86 was prepared by adding the composition sample No. T-85 into base oil in an amount of 2 wt%. The base oil was N-100 base oil.
Example III
[60] A composition sample No. T-87 was synthesized using the process of the present invention, and using the following materials, wherein the phosphorus compound was DEGGLYTEP:
Materials
• Toluene: 5 grams (HPLC grade)
• TiPT: 21 .3 grams (0.75 M)
• Al-isopropoxide: 5 grams (0.25M)
• Oleic acid: 42.4 grams (1 .75M)
• DEGGLYTEP (0.95:0.05:1 ): 50.8 grams (1 .75M)
[61 ] A lubricant sample No. T-88 was prepared by adding the composition sample No. T-87 into base oil in an amount of 2 wt%. The base oil was N-100 base oil.
[62] The DEGTEP (1 :1 ) contains DEG and TEP at a mole ratio of 1 :1 . According to one embodiment of the present invention, the DEGTEP (1 :1 ) may be prepared using the following materials and steps:
Materials
• Diethylene glycol (DEG): 530 grams
• Triethyl phosphate (TEP): 91 1 grams
• Sodium ethoxide: 0.5 grams
Steps
(1 ) Set up and clean reaction vessel.
(2) Inject inert gas into the reaction vessel, such as nitrogen, to purge and remove air from the reaction vessel.
(3) Pour DEG and sodium ethoxide into the reaction vessel, and then stir the contents in the reaction vessel for a period of 30 minutes until a homogeneous mixture is formed.
(4) Slowly add TEP into reaction vessel, and then stir the contents in the reaction vessel until a homogeneous mixture is formed.
(5) Slowly heat up the mixture within the reaction vessel to a temperature range of 100 °C to 1 10 °C and perform reflux of the mixture for a period of 2 hours.
(6) Increase the temperature up to 120 °C to distill out liberated ethanol.
(7) Cool and pour the resultant DEGTEP into air tight container under inert environment. [63] The DEGGLYTEP (0.95:0.05:1 ) contains DEG, GLY and TEP at a mole ratio of 0.95:0.05:1 . According to one embodiment of the present invention, the DEGGLYTEP (0.95:0.05:1 ) may be prepared using the following materials and steps:
Materials
• DEG: 504 grams
• Glycerine (GLY): 23 grams
• TEP: 91 1 grams
• Sodium ethoxide: 0.5 grams
Steps
(1 ) Set up and clean the reaction vessel.
(2) Inject inert gas into the reaction vessel, such as nitrogen, to purge and remove air from the reaction vessel.
(3) Pour DEG and glycerine into the reaction vessel and then stir the contents in the
reaction vessel for a period of 30 minutes, until a homogeneous mixture is formed.
(4) Add sodium ethoxide into the reaction vessel and then stir the contents in the reaction vessel for a period of 30 minutes.
(5) Slowly add TEP into reaction vessel, and then stir the contents in the reaction vessel until a homogeneous mixture is formed.
(6) Slowly heat up the mixture within the reaction vessel to a temperature range of 100 °C to 1 10 °C and perform reflux of the mixture for a period of 2 hours.
(7) Increase the temperature up to 120 °C to distill out liberated ethanol.
(8) Cool and pour the resultant DEGGLYTEP into air tight container, under inert
environment.
Reference or Control Example
[64] As a reference or control example, a lubricant was prepared by adding ZDDP into base oil in an amount of 2 wt%. The base oil was N-100 base oil.
[65] Based on observations, all the composition samples showed a good performance in terms of miscibility and dispensability in base oil. The sulfur-free composition samples produced were found to be compatible with the commonly used lubricating N-100 base oil.
[66] According to one embodiment of the invention, the lubricant includes the sulfur-free composition in an amount of 0.001 wt% to 10 wt%; in another embodiment, lubricant includes the sulfur-free composition in an amount of 2 wt%. Extreme-Pressure Test
[67] The standard test method was conducted, under the protocol of ASTM-D2783-2003(2014), to test the extreme-pressure properties of lubricant samples No. T-83 and No. T-88. The test results can be used to compare the extreme-pressure properties of the lubricant containing ZDDP and the lubricants containing the sulfur-free composition as synthesized using the process in the present invention, which are indicated in Table. 1 below.
Table. 1 Extreme Pressure Test
Figure imgf000015_0001
[68] The test results indicated in Table. 1 show that the weld load test result of lubricant sample No. T-88 is the same as the test result of the control sample ZDDP, which are both 160 Kgf. Such results demonstrate that the sulfur-free composition synthesized using the process in the present invention, when used as extreme pressure additive for lubricants, is capable of good extreme pressure performance comparable to ZDDP.
Anti-Wear Performance Test
[69] The standard test method was conducted under the protocol of ASTM-D4172-1994(2016) to test anti-wear performance of lubricant samples No. T-83 and No. T-88. Under such test, those skilled in the art would appreciate that the anti-wear performance would generally be considered good if the resultant scar diameter meets a threshold of shorter than 2mm.
[70] The test results can be used to compare the anti-wear performance of the control sample ZDDP and that of the lubricant samples No. T-83 and No. T-88, which are indicated in Table. 2 below. The test was conducted for a duration of one hour at a load of 15kgf, a temperature of 75 °C and a rotating speed of 1200 RPM. Table. 2 Anti-wear Test
Figure imgf000016_0001
[71 ] Although the test results of the control sample ZDDP were slightly better, the performance of the two lubricant samples was comparable as indicated by the resultant scar diameters produced by both having been also significantly shorter than the threshold of 2mm. The test results indicated in Table. 2 demonstrate that the anti-wear performance of the sulfur-free composition synthesized using the process in the present invention is good for it to be used as anti-wear additive in lubricants. Therefore, the sulfur-free composition synthesized using the process in the present invention can be used as anti-wear additive in lubricants to replace ZDDP.
Anti-Corrosion Test
[72] The copper strip corrosion test, an Oil Analysis Method for Turbine, Gearbox and Hydraulic Lubricants, under the protocol of ASTM D130 was taken to test the sulfur-free composition synthesized using the process in the present invention. In such test, results are rated by comparing the stains on the copper strip to the ASTM color-match scale from 1 A to 4C. The rating of 1 A is given for appearance of freshly polished copper coupons with slight discoloration, but barely noticeable; 1 B indicates slight tarnish, and the ratings proceed further down the scale as corrosion staining of the test coupon increases, with 4C being the worst, typically appearing as severely corroded, blackened, and pitted coupon.
[73] The anti-corrosion performance of the three lubricant samples No. T-83, No. T-86 and No. T- 88 were tested, and the N-100 base oil itself was also tested as a reference or control sample, under the protocol of ASTM D130/IP 15. The test was conducted at the temperature of about 100 °C for a period of about 24 hours. Figure. 2 shows a photo of the copper strips after test of N-100, and samples No. T-83, No. T-86 and No. T-88, the results of which are indicated in Table. 3 below.
[74] As indicated in Table. 3, the change of color in each copper strip is barely noticeable, and the rating result of each copper strip is“1 A”. The test results demonstrate good performance of the sulfur- free composition synthesized using the process in the present invention being an additive for anti corrosion lubricants. The sulfur-free composition synthesized using the process in the present invention can also be used as an additive for anti-corrosion coatings and paints. Table. 3 Anti-Corrosion Test
Figure imgf000017_0001
[75] According to the above description of the present invention, those skilled in the art would appreciate that the sulfur-free composition synthesized using the process in the present invention is good to be applied in the following fields or areas:
(1 ) Extreme Pressure Additive for Lubricants
(2) Antioxidant
(3) Pour point Depressant
(4) Oxidation and corrosion resistance at elevated temperatures
(5) Anti-wear
(6) Cross-linker
(7) Precursor for hybrid-metal nonmaterial synthesis
(8) Plasticizer for polymer
(9) Coatings and paints
[76] The composition produced by the process of the present invention will be of use in the lubrication industry to replace those additives containing sulfur, to resolve the issues due to sulfur.
[77] While the disclosure contained herein has set forth some of the preferred embodiments of the present invention, as well as exemplary methods, materials, compositions, applications and uses of the present invention, it is not intended to limit or confine the present invention only to such embodiments or examples. It will be appreciated by those skilled in the art that variations to the steps and materials disclosed may be made without departing from the scope and spirit of the invention. Such variations may include, but are not limited to, selection of alternate practical steps, materials and practical conditions for reactions, and application of the process and application of the composition for other purposes or occasions that are not specifically mentioned above.
REFERENCES:
1 . Lubricants 2013, 7(4), 132-148; doi:3390/lubricants1 040132.
2. Spikes, H. ; The History and Mechanisms of ZDDP. Tribology Letters (2004) 17:
469. https://doi.Org/10.1023/B:TRIL.0000044495.26882.b5.
3. Spikes, H. A. ; Beyond ZDDP. Lubrication Science (2008) 20: 77-78. doi:10.1002/ls.60. 4. Paule Njiwa, Clotilde Minfray, Thierry Le Mogne, Beatrice Vacher, Jean-Michel Martin, Shigeki Matsui, Masaru Mishina; Zinc Dialkyl Phosphate (ZP) as an Anti-Wear Additive: Comparison with ZDDP. Tribology Letters (201 1 ). 44. 19-30. 10.1007/s1 1249-01 1 -9822-6.
5. Roman Heuberger, Antonella Rossi, Nicholas D. Spencer; Reactivity of alkylated phosphorothionates with steel : a tribological and surface-analytical study; Lubrication Science
2008; 20: 79-102; DOI : 10.1002/ls.56.
6. EP1369469B1 ; An antioxidant additives combination for lubricants containing a molybdenum complex and analkylated phenothiazine.
7. EP1364955A1 ; Phosphorothionates.
8. Monica Ratoi, Vlad Bogdan Niste, Jurgita Zekonyte; WS2 nanoparticles - potential replacement for
ZDDP and friction modifier additives; RSC Adv., 2014,4, 21238-21245.
9. B. Yu, D.G. Bansal, J. Qu, X. Sun, H. Luo, S. Dai, P.J. Blau, B.G. Bunting, G. Mordukhovich, D.J.
Smolenski; Oil-Miscible and Non-Corrosive Phosphonium-Based Ionic Liquids as Candidate Lubricant Additives, Wear (2012) 289: 58-64.
10. J. Qu, D.G. Bansal, B. Yu, J.Y. Howe, H. Luo, S. Dai, H. Li, P.J. Blau, B.G. Bunting, G.
Mordukhovich, D.J. Smolenski; Anti-Wear Performance and Mechanism of an Oil-Miscible Ionic Liquid as a Lubricant Additive, ACS Applied Materials & Interfaces 4 (2) (2012) 997-1002.
1 1 . Hoshino, K., Yagishita, K., Tagawa, K., and Spikes, H., "Tribological Properties of Sulphur-Free Antiwear Additives Zinc Dialkylphosphates (ZDPs)," SAE Int. J. Fuels Lubr. 5(1 ):504-510, 2012. https://doi.Org/10.4271 /201 1 -01 -2132.

Claims

1 . A process for synthesizing a sulfur-free composition, involving:
modification of a phosphorus compound using one or more functional group/s; and interaction of the modified phosphorus compound with a first metal compound or metalloid compound and a second metal compound or metalloid compound; wherein the sulfur-free composition contains:
phosphorus atoms and metal atoms; or
phosphorus atoms and metalloid atoms; or
phosphorus atoms, metal atoms and metalloid atoms;
wherein said atoms are chemically connected in the sulfur-free composition.
2. The process according to claim 1 , wherein a third metal compound or metalloid compound is included in the interaction.
3. The process according to claim 2, wherein any further number of metal compound/s and/or metalloid compound/s is/are included in the interaction.
4. The process according to any of claims 1 to 3, wherein the phosphorus atoms, the metal atoms and/or the metalloid atoms are connected by carbon chain in the sulfur-free composition.
5. The process according to claim 4, wherein at least one carbon atom in the carbon chain is replaced by one oxygen atom.
6. The process according to any of claims 1 to 5, wherein the phosphorus compound is diethylene glycol glycerine ester of triethyl phosphate (DEGGLYTEP) or diethylene glycol of triethyl phosphate (DEGTEP).
7. The process according to any of claims 1 to 6, wherein each of the one or more functional group/s is -H, -OH, -OMe, -OEt, -COOH, -Me, -Et or any other carbon-containing functional group with two or more carbon atoms.
8. The process according to any of claims 1 to 7, wherein each of the metal compounds and metalloid compounds includes at least one of -COOH, -OH and PO43 .
9. The process according to any of claims 1 to 8, wherein the metal in the metal compound is aluminum, titanium, hafnium, lanthanum, niobium, tantalum, tin, vanadium or zirconium;
10. The process according to any of claims 1 to 9, wherein the metalloid in the metalloid compound is antimony, germanium or silicon.
1 1 . The process according to any of claims 1 to 10, wherein the metal compound is metal alkoxide.
12. The process according to any of claims 1 to 1 1 , wherein the metalloid compound is metalloid alkoxide.
13. The process according to any of claims 1 to 12, wherein the first metal compound or metalloid compound is aluminum alkoxide, and the second metal compound or metalloid compound is titanium alkoxide.
14. A sulfur-free composition synthesized using the process according to any of claims 1 to 1 3, containing phosphorus atoms, M1 atoms and M2 atoms;
wherein M1 is different from M2; and
wherein each of M1 and M2 is a metal element or metalloid element; and
wherein phosphorus atoms, M1 atoms and M2 atoms are connected by at least one chemical chain.
15. The sulfur-free composition according to claim 14, wherein the sulfur-free composition further includes M3 atoms;
wherein M3 is different from M1 and M2; and
wherein M3 is a metal element or metalloid element; and
wherein phosphorus atoms, M1 atoms, M2 atoms and M3 atoms are connected by at least one chemical chain.
16. The sulfur-free composition according to claim 15, wherein the sulfur-free composition further includes M4 atoms;
wherein M4 is different from any of M1 , M2 and M3; and
wherein M4 is a metal element or metalloid element; and
wherein phosphorus atoms, M1 atoms, M2 atoms, M3 atoms and M4 atoms are connected by at least one chemical chain.
17. The sulfur-free composition according to any of claims 14 to 16, wherein the chemical chain is carbon chain.
18. The sulfur-free composition according to claim 17, wherein at least one carbon atom in the carbon chain is replaced by one oxygen atom.
19. The sulfur-free composition according to any of claims 14 to 18, wherein the metal element is aluminum, titanium, hafnium, lanthanum, niobium, tantalum, tin, vanadium or zirconium.
20. The sulfur-free composition according to any of claims 14 to 19, wherein the metalloid element is antimony, germanium or silicon.
21 . The sulfur-free composition according to any of claims 14 to 20, wherein M1 is aluminum, and M2 is titanium.
22. A use of the sulfur-free composition according to any of claims 1 4 to 21 as an anti-wear additive in a lubricant.
23. A use of the sulfur-free composition according to any of claims 14 to 21 as an extreme pressure additive in a lubricant.
24. A use of the sulfur-free composition according to any of claims 14 to 21 as an anti-corrosion additive in a lubricant.
25. The use according to any of claims 22 to 24, wherein the lubricant includes the sulfur-free composition in an amount of 0.001 wt% to 10 wt%.
26. The use according to claim 25, wherein the lubricant includes the sulfur-free composition in an amount of 2 wt%.
27. A use of the sulfur-free composition according to any of claims 14 to 21 as an anti-corrosion additive in a coating or paint.
PCT/SG2020/050187 2019-03-29 2020-03-27 Sulfur-free anti-wear, extreme pressure and anti-corrosion additives, and methods for producing and uses of the additives WO2020204824A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3334978A (en) * 1964-12-18 1967-08-08 Cities Service Oil Co Hydrocarbon fuel composition
US3491133A (en) * 1964-03-06 1970-01-20 Cities Service Res & Dev Co Metal organo phosphates and amine salts thereof
EP0010366A1 (en) * 1978-09-26 1980-04-30 Occidental Research Corporation Solid organometallic inorganic polymers and their application
US20110098375A1 (en) * 2008-07-25 2011-04-28 Tokuyama Dental Corporation Dental adhesive composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3491133A (en) * 1964-03-06 1970-01-20 Cities Service Res & Dev Co Metal organo phosphates and amine salts thereof
US3334978A (en) * 1964-12-18 1967-08-08 Cities Service Oil Co Hydrocarbon fuel composition
EP0010366A1 (en) * 1978-09-26 1980-04-30 Occidental Research Corporation Solid organometallic inorganic polymers and their application
US20110098375A1 (en) * 2008-07-25 2011-04-28 Tokuyama Dental Corporation Dental adhesive composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MARTINEZ-LARA, M. ET AL.: "Porous silica pillared ZrTi phosphate- phosphonates materials", SOLID STATE IONICS, vol. 73, 18 July 1994 (1994-07-18), pages 189 - 198, XP025754078, [retrieved on 20200825] *
ZHANG, X. ET AL.: "Hydrothermal synthesis of copper zirconium phosphate hydrate [Cu(OH)2Zr(HPO4)2.2H2O and an investigation of its lubrication properties in grease", APPLIED MATERIAL & INTERFACES, vol. 5, 29 July 2013 (2013-07-29), pages 7989 - 7994, [retrieved on 20200814] *

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