EP3739026A1 - Polyaziridine polymers as lubricating oil additives - Google Patents
Polyaziridine polymers as lubricating oil additives Download PDFInfo
- Publication number
- EP3739026A1 EP3739026A1 EP19174838.3A EP19174838A EP3739026A1 EP 3739026 A1 EP3739026 A1 EP 3739026A1 EP 19174838 A EP19174838 A EP 19174838A EP 3739026 A1 EP3739026 A1 EP 3739026A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating oil
- oil composition
- polymer
- polyaziridine
- fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 50
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 45
- 239000000654 additive Substances 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 239000012530 fluid Substances 0.000 claims abstract description 70
- 230000005540 biological transmission Effects 0.000 claims abstract description 20
- 238000009472 formulation Methods 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000012208 gear oil Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000010705 motor oil Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000005069 Extreme pressure additive Substances 0.000 claims description 3
- 230000002929 anti-fatigue Effects 0.000 claims description 3
- 239000007866 anti-wear additive Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- 239000010722 industrial gear oil Substances 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZTQBHLJFTXXKAA-UHFFFAOYSA-N O=S(=O)NCC1=CC=CC=C1 Chemical compound O=S(=O)NCC1=CC=CC=C1 ZTQBHLJFTXXKAA-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001541 aziridines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000010551 living anionic polymerization reaction Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920001391 sequence-controlled polymer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VBNWSEVVMYMVLC-UHFFFAOYSA-N 1-(4-methylphenyl)sulfonylaziridine Chemical class C1=CC(C)=CC=C1S(=O)(=O)N1CC1 VBNWSEVVMYMVLC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006362 organocatalysis Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 synthetic or natural Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Images
Classifications
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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
- C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
- C10M151/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the invention relates to a lubricating oil composition
- a lubricating oil composition comprising a polyaziridine polymer, a process for preparing such lubricating oil composition and the use thereof as a lubricating oil additive for reducing friction in a transmission fluid, an engine oil formulation, a gear oil formulation, an axle fluid or in a hydraulic fluid.
- Lubricants are compositions that reduce friction between surfaces. In addition to allowing freedom of motion between two surfaces and reducing mechanical wear of the surfaces, a lubricant also may inhibit corrosion of the surfaces and/or may inhibit damage to the surfaces due to heat or oxidation. Examples of lubricant compositions include, but are not limited to, engine oils, transmission fluids, gear oils, industrial lubricating oils, greases and metalworking oils.
- a typical lubricant composition includes a base fluid and optionally one or more additives.
- Conventional base fluids are hydrocarbons, such as mineral oils.
- base oil or base fluid is commonly used interchangeably.
- base fluid is used as a general term.
- lubricant additives include, but are not limited to, viscosity index improvers, thickeners, oxidation inhibitors, corrosion inhibitors, dispersing agents, high pressure additives, anti-foaming agents and metal deactivators.
- Friction modifiers are used to protect the metal surfaces as they build up a protective film at the metal surfaces and in addition help to reduce friction.
- the downsizing of the hardware leads to additional hurdles.
- the transmission and hydraulic pump are smaller, cooling is more difficult, and gears and bearings have to handle higher loads.
- the tribological contact between two moving surfaces exhibits a reduced film thickness of the lubricant.
- the applied additives have to ensure a low friction loss and to protect the surface from wear and fatigue in these boundary conditions.
- Typical classes of friction modifiers are (i) oxygen-containing organic compounds that have a polar head group capable of adsorption at surfaces including alcohols, esters and carboxylic acids, (ii) organic compounds which contain nitrogen groups either in combination with (i) or (iii), (iii) organic sulphur compounds which can form reacted films at surfaces, (iv) organic phosphorus compounds which can form reacted films at surfaces, (v) organic boron compounds which may form reacted films at surfaces, (vi) organic molybdenum compounds which can form MoS 2 film on surfaces, or (vii) ZDDPs which can form polymeric films on surfaces ( R.M. Mortier et al. (eds.), Chemistry and Technology of Lubricants, 3rd edn., DOI 10.1023/
- the inventors of the present invention have surprisingly found that the polyaziridine polymers as defined in claim 1 provide excellent friction reduction performances when added to a lubricant oil composition.
- a first object of the present invention is a lubricating oil composition
- a lubricating oil composition comprising at least one base fluid and at least one polyaziridine polymer as defined in claim 1 and its dependent claims.
- a second object of the present invention relates to a process for preparing the lubricating oil composition according to the present invention.
- a third object of the present invention is the use of a polyaziridine polymer in a lubricating oil composition as defined in claim 1 or its dependent claims as a lubricating oil additive in an automatic transmission fluid, a manual transmission fluid, a continuously variable transmission fluid, a dual clutch transmission fluid, a dedicated hybrid transmission fluid, an engine oil formulation, a gear oil formulation, an industrial gear oil formulation, an axle fluid or in a hydraulic fluid.
- the present invention is directed to the use of a polyaziridine polymer according to the present invention as a friction modifier for reducing friction in a lubricating oil composition.
- Figure 1 is a graph comparing the Stribeck curve obtained with a pure naphthenic API Group V base fluid and the Stribeck curve obtained with the same base fluid (API group V base fluid) treated with the polymer 2 according to the present invention.
- the invention relates to a lubricating oil composition
- a lubricating oil composition comprising at least one base fluid; and at least one polyaziridine polymer obtainable by polymerizing a monomer composition consisting of one or more aziridine monomer of formula (I) wherein R is a linear or branched alkyl group with 15 to 30 carbon atoms.
- the lubricating oil composition comprises between 95 and 99.95 % by weight of the at least one base fluid and between 0.05 and 5 % by weight of the at least one polyaziridine polymer, based on the total weight of the lubricating composition.
- the lubricating oil composition may further comprise an additive selected from the group consisting of a viscosity index improver, a pour point improver, a dispersant, a demulsifier, a lubricity additive, a detergent, a defoamer, a corrosion inhibitor, an antioxidant, an antiwear additive, an extreme pressure additive, an antifatigue additive, a dye, an odorant or a mixture thereof.
- an additive selected from the group consisting of a viscosity index improver, a pour point improver, a dispersant, a demulsifier, a lubricity additive, a detergent, a defoamer, a corrosion inhibitor, an antioxidant, an antiwear additive, an extreme pressure additive, an antifatigue additive, a dye, an odorant or a mixture thereof.
- the polyaziridine polymer as defined in claim 1 bares a nitrogen in every monomer unit of the linear or branched polymer backbone, thus enabling good adhesion to the metal surface.
- they work as multidentate compound giving good adhesion also under high load.
- the polyaziridine polymer may be prepared by cationic ring opening polymerization, in which case the polyaziridine polymer according to the present invention has a branched polymer backbone.
- the polymer backbone of the polyaziridine polymer corresponds to the longest series of covalently bonded atoms that together create the continuous chain of the polyaziridine polymer.
- the polyaziridine polymer may also be prepared by anionic ring opening polymerization, in which case the polyaziridine polymer according to the present invention has a linear polymer backbone.
- the polyaziridine polymers of the invention can be prepared for example according to the process as described in Section B of the supporting information of the publication " Sequence-Controlled Polymers via Simultaneous Living Anionic Copolymerization of Competing Monomers", E. Rieger, Macromol. Rapid Commun., 2016, 37, 833-839 .
- the aziridine monomer has two sites where side groups can be attached: the nitrogen atom or one of the carbon atoms. This allows to tailor the properties and also to attach long carbon side-chains making this structure oil soluble. It was found that the polyaziridine polymers according to the invention must be prepared using aziridine monomers of formula (I) with an alkyl group R having between 15 and 30 carbon atoms, preferably between 15 and 20 carbon atoms, more preferably 16 carbon atoms. This seems to ensure oil solubility in the lubricating oil composition as shown in the experimental part.
- lubricating oil compositions comprising at least one oil-soluble polyaziridine polymer according to the present invention have an improved friction coefficient compared to a pure base fluid.
- the oil-soluble polyaziridine polymer according to the present invention can be used as friction modifier in lubricating oil compositions.
- the oil-soluble polyaziridine polymer is poly-2-methyl-N-hexadecasylaziridin, in which case the alkyl group R of the aziridine monomer is a linear alkyl group having 16 carbon atoms.
- the at least one polyaziridine polymer has a linear polymer backbone.
- the at least one polyaziridine polymer has a number-average molecular weight comprised in the range between 1,000 g/mol and 20,000 g/mol, preferably in the range between 1,000 g/mol and 10,000 g/mol, more preferably in the range between 2,000 g/mol and 8,000 g/mol, even more preferably in the range between 3,000 g/mol and 6,000 g/mol.
- all number-average molecular weights are calculated by measuring the ratio of 1 H NMR absorptions of the polymer chain and the initiator signals.
- Nuclear magnetic resonance (NMR) measurements were conducted on a Bruker AVANCE 300 spectrometer operating with 300 MHz frequencies at 298 K.
- the at least one polyaziridine polymer is obtainable by polymerizing a monomer composition consisting of one or more aziridine monomer of formula (I), wherein R is a linear alkyl group with 15 to 20 carbon atoms, preferably 16 carbon atoms.
- the present invention relates to a lubricating oil composition
- a lubricating oil composition comprising a base fluid and at least one polyaziridine polymer of the present invention as defined in claim 1.
- the base fluids correspond to lubricant base fluids, mineral, synthetic or natural, animal or vegetable oils suited to their use/chosen depending on the intended use.
- the base fluids used in formulating the lubricating oil compositions according to the present invention include, for example, conventional base stocks selected from API (American Petroleum Institute) base stock categories known as Group I, Group II, Group III, Group IV and Group V.
- the Group I and II base stocks are mineral oil materials (such as paraffinic and naphthenic oils) having a viscosity index (or VI) of less than 120.
- Group I is further differentiated from Group II in that the latter contains greater than 90% saturated materials and the former contains less than 90% saturated material (that is more than 10% unsaturated material).
- Group III is considered the highest level of mineral base fluid with a VI of greater than or equal to 120 and a saturates level greater than or equal to 90%.
- Group IV base fluids are polyalphaolefins (PAO).
- Group V base fluids are esters and any other base fluids not included in Group I to IV base fluids. These base fluids can be used individually or as a mixture.
- the lubricant composition comprises an API Group V
- the lubricating oil compositions according to the present invention may also further comprise any other additional additives suitable for use in the formulations.
- additives are selected from the group consisting of a viscosity index improver, a pour point improver, a dispersant, a demulsifier, a lubricity additive, a detergent, a defoamer, a corrosion inhibitor, an antioxidant, an antiwear additive, an extreme pressure additive, an antifatigue additive, a dye, an odorant or a mixture thereof.
- the invention also relates to a process for preparing a lubricating oil composition comprising at least one polyaziridine polymer as defined above, wherein the process comprises:
- the invention also relates to the use of the polymer as described in detail above as a lubricating oil additive in a lubricating oil composition.
- the invention relates to the use of the polymer as described in detail above as a friction modifier for a lubricating oil composition.
- the lubricating oil compositions are, among others, an automatic transmission fluid, a manual transmission fluid, a continuously variable transmission fluid, a dedicated hybrid transmission fluid, a dual clutch transmission fluid, a gear oil formulation, an industrial gear oil formulation, an axle fluid, an engine oil formulation or a hydraulic fluid.
- the lubricating oil compositions show excellent antifriction properties.
- the polymers were dissolved with a treat rate of 0.5 wt% in a naphthenic API Group V base fluid and the friction coefficient measured on a Mini Traction Machine with the following conditions: scanning from 2500 to 5 mm/s at 30N, 80° C and 50% Slide-Roll-Ratio (SRR) with 4 repeats per sample.
- SRR Slide-Roll-Ratio
- both polymers were added to a naphthenic base fluid with a treat rate of 0.5 wt%, based on the total weight of the lubricating oil composition.
- Polymer 1 with a C8 side chain was not soluble in oil.
- inventive Polymer 2 with a C16 side chain was soluble in oil at elevated temperatures (80 to 100 °C).
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
- The invention relates to a lubricating oil composition comprising a polyaziridine polymer, a process for preparing such lubricating oil composition and the use thereof as a lubricating oil additive for reducing friction in a transmission fluid, an engine oil formulation, a gear oil formulation, an axle fluid or in a hydraulic fluid.
- The present invention relates to the field of lubrication. Lubricants are compositions that reduce friction between surfaces. In addition to allowing freedom of motion between two surfaces and reducing mechanical wear of the surfaces, a lubricant also may inhibit corrosion of the surfaces and/or may inhibit damage to the surfaces due to heat or oxidation. Examples of lubricant compositions include, but are not limited to, engine oils, transmission fluids, gear oils, industrial lubricating oils, greases and metalworking oils.
- A typical lubricant composition includes a base fluid and optionally one or more additives. Conventional base fluids are hydrocarbons, such as mineral oils. The terminology base oil or base fluid is commonly used interchangeably. Here, base fluid is used as a general term.
- A wide variety of additives may be combined with the base fluid, depending on the intended use of the lubricant. Examples of lubricant additives include, but are not limited to, viscosity index improvers, thickeners, oxidation inhibitors, corrosion inhibitors, dispersing agents, high pressure additives, anti-foaming agents and metal deactivators.
- The currently biggest challenge for lube manufacturers and OEMs in the automotive industry are more and more stringent fuel economy targets. Two levers are used to improve the fuel economy of, e.g., transmissions: the use of lubricants with lower viscosities and downsizing of the hardware.
- The use of low viscosity lubricants leads to a thinner oil film between the contact surfaces in e.g. gearings and roller bearings especially at high temperatures, thus leading to an increased level of damage caused by excessive local stress. Friction modifiers are used to protect the metal surfaces as they build up a protective film at the metal surfaces and in addition help to reduce friction.
- The downsizing of the hardware leads to additional hurdles. The transmission and hydraulic pump are smaller, cooling is more difficult, and gears and bearings have to handle higher loads. Thus, the tribological contact between two moving surfaces exhibits a reduced film thickness of the lubricant. The applied additives have to ensure a low friction loss and to protect the surface from wear and fatigue in these boundary conditions.
- As of today, typical oil soluble friction modifiers in lubricants either adsorb at the metal surface of the tribological contact e.g. via van-der-Waals interactions or build up reacted layers. Typical classes of friction modifiers are (i) oxygen-containing organic compounds that have a polar head group capable of adsorption at surfaces including alcohols, esters and carboxylic acids, (ii) organic compounds which contain nitrogen groups either in combination with (i) or (iii), (iii) organic sulphur compounds which can form reacted films at surfaces, (iv) organic phosphorus compounds which can form reacted films at surfaces, (v) organic boron compounds which may form reacted films at surfaces, (vi) organic molybdenum compounds which can form MoS2 film on surfaces, or (vii) ZDDPs which can form polymeric films on surfaces (R.M. Mortier et al. (eds.), Chemistry and Technology of Lubricants, 3rd edn., DOI 10.1023/b105569_3, Springer Science+Business Media B.V. 2010).
- For the class of absorbing compounds, several factors are important such as they have to show a strong interaction with the surface also under high loads, they have to build up a protective film layer at the surface, they have to be oil-soluble in case they desorb from the surface, their tendency to interact with the surface must be higher than the interaction with the surrounding oil.
- The synthesis of polyaziridine polymers is described in detail in many publications, such as "The living anionic polymerization of activated aziridines: a systematic study of reaction conditions and kinetics", Polym. Chem. 2017, 8, 2824-2832; "Multihydroxy Polyamines by Living Anionic Polymerization of Aziridines" ACS Macro Lett., 2016, 5, 195-198; or "Organocatalytic Ring-Opening Polymerization of N-Tosyl Aziridines by a N-Heterocyclic Carbene" Chem. Commun., 2016, 72, 9719-9722. These publications are silent on the problems of lubrication and oil solubility.
- Based on the foregoing, there is still the need to find additional lubricating oil additives, in particular, new friction modifiers with excellent friction performances while having good oil compatibility with the lubricating oil compositions.
- After an exhaustive investigation, the inventors of the present invention have surprisingly found that the polyaziridine polymers as defined in
claim 1 provide excellent friction reduction performances when added to a lubricant oil composition. - Thus, a first object of the present invention is a lubricating oil composition comprising at least one base fluid and at least one polyaziridine polymer as defined in
claim 1 and its dependent claims. - A second object of the present invention relates to a process for preparing the lubricating oil composition according to the present invention.
- A third object of the present invention is the use of a polyaziridine polymer in a lubricating oil composition as defined in
claim 1 or its dependent claims as a lubricating oil additive in an automatic transmission fluid, a manual transmission fluid, a continuously variable transmission fluid, a dual clutch transmission fluid, a dedicated hybrid transmission fluid, an engine oil formulation, a gear oil formulation, an industrial gear oil formulation, an axle fluid or in a hydraulic fluid. In a preferred embodiment, the present invention is directed to the use of a polyaziridine polymer according to the present invention as a friction modifier for reducing friction in a lubricating oil composition. - For better illustrating the advantages and properties of a lubricating oil composition comprising the polyaziridine polymer of the invention, a graph is attached as a non-limiting example:
Figure 1 is a graph comparing the Stribeck curve obtained with a pure naphthenic API Group V base fluid and the Stribeck curve obtained with the same base fluid (API group V base fluid) treated with the polymer 2 according to the present invention. - According to a first aspect of the invention, the invention relates to a lubricating oil composition comprising at least one base fluid; and at least one polyaziridine polymer obtainable by polymerizing a monomer composition consisting of one or more aziridine monomer of formula (I)
- According to a preferred embodiment of the invention, the lubricating oil composition comprises between 95 and 99.95 % by weight of the at least one base fluid and between 0.05 and 5 % by weight of the at least one polyaziridine polymer, based on the total weight of the lubricating composition.
- According to another preferred embodiment of the invention, the lubricating oil composition may further comprise an additive selected from the group consisting of a viscosity index improver, a pour point improver, a dispersant, a demulsifier, a lubricity additive, a detergent, a defoamer, a corrosion inhibitor, an antioxidant, an antiwear additive, an extreme pressure additive, an antifatigue additive, a dye, an odorant or a mixture thereof.
- According to the present invention, the polyaziridine polymer as defined in
claim 1 bares a nitrogen in every monomer unit of the linear or branched polymer backbone, thus enabling good adhesion to the metal surface. In contrast to the existing carbon acid compound friction modifiers, they work as multidentate compound giving good adhesion also under high load. - The polyaziridine polymer may be prepared by cationic ring opening polymerization, in which case the polyaziridine polymer according to the present invention has a branched polymer backbone. The polymer backbone of the polyaziridine polymer corresponds to the longest series of covalently bonded atoms that together create the continuous chain of the polyaziridine polymer.
- The polyaziridine polymer may also be prepared by anionic ring opening polymerization, in which case the polyaziridine polymer according to the present invention has a linear polymer backbone. The polyaziridine polymers of the invention can be prepared for example according to the process as described in Section B of the supporting information of the publication "Sequence-Controlled Polymers via Simultaneous Living Anionic Copolymerization of Competing Monomers", E. Rieger, Macromol. Rapid Commun., 2016, 37, 833-839.
- The nitrogen atom in every monomer unit makes the structure very polar. The inventors of the present invention surprisingly came to the conclusion that this structure favors to attach to the metal surface, rather than staying in the oil phase. It seems to favor a fast and strong adhesion of the polymer to the surface, which allows to reduce the friction between metal parts.
- The aziridine monomer has two sites where side groups can be attached: the nitrogen atom or one of the carbon atoms. This allows to tailor the properties and also to attach long carbon side-chains making this structure oil soluble. It was found that the polyaziridine polymers according to the invention must be prepared using aziridine monomers of formula (I) with an alkyl group R having between 15 and 30 carbon atoms, preferably between 15 and 20 carbon atoms, more preferably 16 carbon atoms. This seems to ensure oil solubility in the lubricating oil composition as shown in the experimental part.
- The inventors of the present invention have surprisingly found that lubricating oil compositions comprising at least one oil-soluble polyaziridine polymer according to the present invention have an improved friction coefficient compared to a pure base fluid. Thus, the oil-soluble polyaziridine polymer according to the present invention can be used as friction modifier in lubricating oil compositions.
- According to a preferred embodiment of the present invention, the oil-soluble polyaziridine polymer is poly-2-methyl-N-hexadecasylaziridin, in which case the alkyl group R of the aziridine monomer is a linear alkyl group having 16 carbon atoms.
- According to a preferred embodiment of the invention, the at least one polyaziridine polymer has a linear polymer backbone.
- According to another preferred embodiment of the invention, the at least one polyaziridine polymer has a number-average molecular weight comprised in the range between 1,000 g/mol and 20,000 g/mol, preferably in the range between 1,000 g/mol and 10,000 g/mol, more preferably in the range between 2,000 g/mol and 8,000 g/mol, even more preferably in the range between 3,000 g/mol and 6,000 g/mol.
- In the present invention, all number-average molecular weights are calculated by measuring the ratio of 1H NMR absorptions of the polymer chain and the initiator signals. Nuclear magnetic resonance (NMR) measurements were conducted on a Bruker AVANCE 300 spectrometer operating with 300 MHz frequencies at 298 K.
- According to a preferred embodiment of the invention, the at least one polyaziridine polymer is obtainable by polymerizing a monomer composition consisting of one or more aziridine monomer of formula (I), wherein R is a linear alkyl group with 15 to 20 carbon atoms, preferably 16 carbon atoms.
- As indicated above, the present invention relates to a lubricating oil composition comprising a base fluid and at least one polyaziridine polymer of the present invention as defined in
claim 1. - The base fluids correspond to lubricant base fluids, mineral, synthetic or natural, animal or vegetable oils suited to their use/chosen depending on the intended use.
- The base fluids used in formulating the lubricating oil compositions according to the present invention include, for example, conventional base stocks selected from API (American Petroleum Institute) base stock categories known as Group I, Group II, Group III, Group IV and Group V. The Group I and II base stocks are mineral oil materials (such as paraffinic and naphthenic oils) having a viscosity index (or VI) of less than 120. Group I is further differentiated from Group II in that the latter contains greater than 90% saturated materials and the former contains less than 90% saturated material (that is more than 10% unsaturated material). Group III is considered the highest level of mineral base fluid with a VI of greater than or equal to 120 and a saturates level greater than or equal to 90%. Group IV base fluids are polyalphaolefins (PAO). Group V base fluids are esters and any other base fluids not included in Group I to IV base fluids. These base fluids can be used individually or as a mixture. Preferably, the lubricant composition comprises an API Group V base fluid.
- The lubricating oil compositions according to the present invention may also further comprise any other additional additives suitable for use in the formulations. These additives are selected from the group consisting of a viscosity index improver, a pour point improver, a dispersant, a demulsifier, a lubricity additive, a detergent, a defoamer, a corrosion inhibitor, an antioxidant, an antiwear additive, an extreme pressure additive, an antifatigue additive, a dye, an odorant or a mixture thereof.
- The invention also relates to a process for preparing a lubricating oil composition comprising at least one polyaziridine polymer as defined above, wherein the process comprises:
- (i) preparing one or more polyaziridine polymer, and
- (ii) mixing with one or more base fluid.
- Reference is made to the base fluids as described above.
- The invention also relates to the use of the polymer as described in detail above as a lubricating oil additive in a lubricating oil composition.
- The invention relates to the use of the polymer as described in detail above as a friction modifier for a lubricating oil composition.
- The lubricating oil compositions are, among others, an automatic transmission fluid, a manual transmission fluid, a continuously variable transmission fluid, a dedicated hybrid transmission fluid, a dual clutch transmission fluid, a gear oil formulation, an industrial gear oil formulation, an axle fluid, an engine oil formulation or a hydraulic fluid.
- As shown in the experimental part, due to the presence of the polyaziridine polymer as defined in the present invention, the lubricating oil compositions show excellent antifriction properties.
- The invention is illustrated by the following examples.
-
- Mn
- number-average molecular weight
- MTM
- mini traction machine
- Poly(HDsMAz)
- Poly-2-methyl-N-hexadecasylaziridine
- Poly(OsMAz)
- Poly-2-methyl-N-octasylaziridine
- SRR
- Slide-Roll-Ratio
- The polymers were dissolved with a treat rate of 0.5 wt% in a naphthenic API Group V base fluid and the friction coefficient measured on a Mini Traction Machine with the following conditions: scanning from 2500 to 5 mm/s at 30N, 80° C and 50% Slide-Roll-Ratio (SRR) with 4 repeats per sample.
- Two polyaziridine polymers were used, both provided by the Max-Planck-Institute for Polymer Research in Mainz and prepared via anionic polymerization according to the process as described on page 14 in Section B of the supporting information of the publication "Sequence-Controlled Polymers via Simultaneous Living Anionic Copolymerization of Competing Monomers", E. Rieger, Macromol. Rapid Commun., 2016, 37, 833-839:
- Polymer 1: Poly-2-methyl-N-octasylaziridine (Poly(OsMAz)) with 14 repeat units
Starting material: 2-methyl-N-octasylaziridine monomer (12.5 g, 64.28 mmol), N-benzyl-sulfonamide as initiator (1.00 g, 5.40 mmol), potassium bis(trimethylsilyl)amide as a deprotonation agent (969.57 mg, 4.86 mmol)
Mn (NMR) = 3,400 g/mol - Polymer 2: Poly-2-methyl-N-hexadecasylaziridine (Poly(HDsMAz)) with 15 repeat units
Starting material: 2-methyl-N-hexadecasylaziridine monomer (250 mg, 725 µmol), N-benzyl-sulfonamide as initiator (8.93 mg, 36.15 µmol), potassium bis(trimethylsilyl)amide as a deprotonation agent (6.5 mg, 33 µmol)
Mn (NMR) = 5,400 g/mol - To test the solubility in oil which is the key criteria for an application in lubricants, both polymers were added to a naphthenic base fluid with a treat rate of 0.5 wt%, based on the total weight of the lubricating oil composition.
Polymer 1 with a C8 side chain was not soluble in oil. In contrast, inventive Polymer 2 with a C16 side chain was soluble in oil at elevated temperatures (80 to 100 °C). - Thus, for the further evaluation of the friction modifier properties only Polymer 2 was used.
- In
Figure 1 , a comparison of the Stribeck curves measured with the MTM of the pure naphthenic API Group V fluid and of the same base fluid comprising polymer 2 is shown. It can be seen that the friction coefficient for the base fluid comprising polymer 2 is lower over the full speed range compared to the pure base fluid, thus proving a positive effect of the polyaziridine structure on friction and a possible application as friction modifier in lubricants.
Claims (13)
- The lubricating oil composition according to claim 1, wherein the at least one polyaziridine polymer has a linear polymer backbone.
- The lubricating oil composition according to claim 1 or 2, wherein the at least one polyaziridine polymer has a number-average molecular weight comprised in the range between 1,000 g/mol and 20,000 g/mol.
- The lubricating oil composition according to claim 3, wherein the at least one polyaziridine polymer has a number-average molecular weight comprised in the range between 1,000 g/mol and 10,000 g/mol.
- The lubricating oil composition according to claim 3, wherein the at least one polyaziridine polymer has a number-average molecular weight comprised in the range between 2,000 g/mol and 8,000 g/mol.
- The lubricating oil composition according to claim 3, wherein the at least one polyaziridine polymer has a number-average molecular weight comprised in the range between 3,000 g/mol and 6,000 g/mol.
- The lubricating oil composition according to any one of claims 1 to 6, wherein the at least one polyaziridine polymer is obtainable by polymerizing a monomer composition consisting of one or more aziridine monomer of formula (I), wherein R is a linear alkyl group with 15 to 20 carbon atoms, preferably 16 carbon atoms.
- The lubricating oil composition according to any one of claims 1 to 7, wherein the lubricating oil composition comprises between 95 and 99.95 % by weight of the base fluid and between 0.05 and 5 % by weight of the at least one polyaziridine polymer, based on the total weight of the lubricating composition.
- The lubricating oil composition according to any one of claims 1 to 8, wherein the lubricating oil composition further comprises an additive selected from the group consisting of a viscosity index improver, a pour point improver, a dispersant, a demulsifier, a lubricity additive, a detergent, a defoamer, a corrosion inhibitor, an antioxidant, an antiwear additive, an extreme pressure additive, an antifatigue additive, a dye, an odorant or a mixture thereof.
- The lubricating oil composition according to any one of claims 1 to 9, wherein the at least one base fluid is selected from the group consisting of API Group I base fluid, API Group II base fluid, API Group III base fluid, API Group IV base fluid, API Group V base fluid or a mixture thereof, preferably an API Group V base fluid.
- Process for preparing the lubricating oil composition comprising the at least one polyaziridine polymer as defined in any one of claims 1 to 10, wherein the process comprises:(i) preparing one or more polyaziridine polymer, and(ii) mixing with one or more base fluid.
- Use of a polyaziridine polymer in a lubricating oil composition as defined in any one of claims 1 to 10 as a lubricating oil additive in an automatic transmission fluid, a manual transmission fluid, a continuously variable transmission fluid, a dual clutch transmission fluid, a dedicated hybrid transmission fluid, an engine oil formulation, a gear oil formulation, an industrial gear oil formulation, an axle fluid, or in a hydraulic fluid.
- Use of a polyaziridine polymer according to claim 12 as a friction modifier for reducing friction in a lubricating oil composition.
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CN202010405525.9A CN111944584B (en) | 2019-05-16 | 2020-05-14 | Polyaziridine polymers as lubricating oil additives |
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US20070027046A1 (en) | 2005-08-01 | 2007-02-01 | The Lubrizol Corporation | Novel Dispersants |
GB201003579D0 (en) | 2010-03-04 | 2010-04-21 | Croda Int Plc | Friction reducing additive |
EP3164473A4 (en) * | 2014-07-02 | 2018-01-03 | Basf Se | Sulfonate esters to improve fluoropolymer seal compatibility of lubricant compositions |
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