EP3935145A1 - Use of polymers as additives for lubricant oil compositions - Google Patents
Use of polymers as additives for lubricant oil compositionsInfo
- Publication number
- EP3935145A1 EP3935145A1 EP20707685.2A EP20707685A EP3935145A1 EP 3935145 A1 EP3935145 A1 EP 3935145A1 EP 20707685 A EP20707685 A EP 20707685A EP 3935145 A1 EP3935145 A1 EP 3935145A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- building blocks
- use according
- polymer
- weight
- alkyl groups
- 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.)
- Withdrawn
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000000314 lubricant Substances 0.000 title claims abstract description 32
- 239000000654 additive Substances 0.000 title claims abstract description 25
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 239000003921 oil Substances 0.000 claims description 37
- 239000002199 base oil Substances 0.000 claims description 34
- 230000009021 linear effect Effects 0.000 claims description 26
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 5
- 239000011976 maleic acid Substances 0.000 abstract description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 description 22
- 150000001298 alcohols Chemical class 0.000 description 19
- 239000012530 fluid Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229940044603 styrene Drugs 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229940044600 maleic anhydride Drugs 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- CAYHVMBQBLYQMT-UHFFFAOYSA-N 2-decyltetradecan-1-ol Chemical compound CCCCCCCCCCCCC(CO)CCCCCCCCCC CAYHVMBQBLYQMT-UHFFFAOYSA-N 0.000 description 1
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 description 1
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- 102100028626 4-hydroxyphenylpyruvate dioxygenase Human genes 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- -1 anticorrosives Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920002469 poly(p-dioxane) polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/069—Linear chain compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
-
- 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
- C10N2030/68—Shear stability
-
- 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
- C10N2040/08—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 present invention is concerned with the use of polymers as additives for lubri cant oil compositions, wherein the polymers comprise styrene and maleic acid di alkyl ester building blocks and increase the shear stability of the compositions.
- VI index index improv ers Vll-treated lubricants
- Polymer containing fluids exhibit less reduction in viscosity with increase in tem perature than the corresponding base fluids containing no polymer.
- the hydrody namic volume of the polymer in the fluid increases with increase in temperature thereby resulting in an increase in viscosity, which greatly compensates the oppos ing effect of commonly observed reduction in viscosity of a fluid with rise in tem perature.
- the shear stability of the additive has strong influence on multigrade engine oil’s ability to retain its viscosity under shearing conditions, experienced by the lubricant while in use.
- the loss of viscosity of a lubricant under shear can be of two kinds, namely a temporary viscosity loss or a permanent viscosity loss.
- One of the major problems with many of the VII is their tendency to undergo permanent reduction of viscosity as a result of mechanical shearing which occurs in most of the mechanical system.
- lubricant oil compositions have increased in recent years and will increase even further due to more demanding environmental and governmental standards.
- Many functional fluids like hydraulic oils, gear oils, transmission oils and crankcase oils comprise VII and/or pour point depressants (PPD) in order to main tain a certain viscosity and flowability over a wide temperature regime.
- Those ad ditives are marketed based upon features such as cold temperature deposit con trol, stable viscosity and fluid durability. While VII improve the viscosity index of a lubricant oil, PPDs are applied to maintain low temperature flowability (pour point) and cold filterability (cold filter plugging point).
- the polymers are usually based on polyolefins and polymethacrylates, acrylates or sty rene-maleic anhydride co-polymers and esterified derivatives thereof. These poly mers can be altered in their structures by using different alcohols for their produc tion. Especially, poly(alkylmethacrylates) (PAMA) and poly-styrene-maleic anhy drides (PSMA) represent a class of VII or PPD which have been used for many years in lubricant oil compositions.
- PAMA poly(alkylmethacrylates)
- PSMA poly-styrene-maleic anhy drides
- Base oils are produced by means of refining crude oils via distillation. While the lighter oils are used for fuels, the heavier cuts are suitable as base oils. By hydro processing sulfur and aromatics are removed using hydrogen under high pressure in order to obtain, purified base oils, which are desired when quality requirements are particularly stringent. Depending on the properties and the refining methods, base oils can be classified into 5 groups according to the American Petroleum In stitute (API). Group I
- API defines group I as "base stocks contain less than 90 percent saturates and/or greater than 0.03 percent sulfur and have a vis cosity index greater than or equal to 80 and less than 120".
- API de fines group II as "base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120".
- API defines group III as "base stocks contain(ing) greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120". This group may be described as synthetic technology oils or hydro-cracked synthetic oil.
- PAO poly-alpha-olefins
- Group V oils include, among others, naphthenic oils and esters.
- US8343900 B2 suggested to use OXO based alcohols (linear and branched) in combination with 2-alkyl branched Guerbet type alcohols to improve PSMA addi tives with respect to shear stability and viscosity index. It is said that the PSMA additives provide an acceptable/improved shear stability, but this is not demon strated.
- US2570846 A discloses the use of esters of styrene/maleic acid-copolymers to reduce the pour point and to increase the viscosity index of lubricating oils.
- the alcohol moieties are based on linear C6- to C18- alkanols.
- US3574575 A discloses esters of styrene/maleic acid-copolymers as fluidity im provers in liquid hydrocarbons.
- the alcohol moieties of the ester groups are based on alcohols having at least 20 carbon atoms in the alkyl portion.
- US5703023 A discloses polymeric viscosity index improvers made from sty rene/maleic anhydride copolymers esterified with C8- to C18- alcohols, of which 50-90% are linear and the balance being branched (preferably 2-ethylhexanol).
- US8293689 B2 discloses lubricating compositions containing styrene/maleic anhy dride copolymers esterified with 2-decyltetradecanol (lsofol24) or 2-ethylhexanol and linear C12-15-alcohols (Neodol25) further comprising an anti-wear agent.
- paraffin-containing fluids have a much higher viscosity and are mostly crude oils, whereas base oils are already refined fractions, from which the long-chain paraffins (wax) have been removed by dewaxing steps (see above).
- the efficiency of depressing the pour point in crude oils is greatly in fluenced by the side chains of the polymer, respectively their carbon chain length and branching.
- the pour point is determined by ASTM D5985 and mainly caused by the precipitation of wax crystals in the liquid, whereas in base oils much shorter alkanes tend to pour out and the pour point is determined ac cording to ASTM D97. Therefore, the pour point of crude oils is usually at much higher temperatures than the one of base oils. Therefore, W02017/012716 A1 teaches away from using the polymer additives in base oils.
- shear sta bility does not play any role for additives that are exclusively pour point depres sants.
- the object of the present invention is to provide a polymer as an additive for use as shear stable viscosity index improvers with a high thickening efficiency and at the same time increased low temperature performance (pour point).
- polystyrene-maleic anhydride (PSMA) based copolymers having lin ear alkyl and branched alkyl moieties, in particular 2-alkyl branched, generate high shear stable polymers with high thickening efficiency and increased low tempera ture performance (pour point) in a lubricant oil composition.
- PSMA polystyrene-maleic anhydride
- the present invention relates to a) the use of styrene-maleic acid dialkyl ester pol ymers in lubricant oil compositions, b) to a method for improving the shear stability of a lubricant oil composition and c) to styrene-maleic acid dialkyl ester polymers each according to the respective independent claims.
- the further optional defini tions of claims 2 to 17 also apply to b) and c) as defined in claims 18 and 19.
- the invention relates to the use of styrene-maleic acid alkyl ester polymers, where the ester groups are made from mixtures of long-chain linear and branched fatty alcohols.
- the styrene-maleic acid alkyl ester polymers comprise at least the following building blocks:
- R1 , R2 are independent from each other a C10- to C50- alkyl group, the alkyl group being branched or linear;
- the ratio of the linear alkyl groups to the branched alkyl groups is in the range from 95:5 to 5:95, preferably 90:10 to 10:90, more preferably 80:20 to 20:80, most preferably 70:30 (all in weight%); particular preferred embodiments are for example 90: 10 to 50:50; or 80:20 to 50:50; or 70:30 to 50:50 or 80:20 to 60:40 (all in weight%); alternatively, particular preferred embodiments are for example 10:90 to 50:50 or 20:80 to 50:50 or 30:70 to 50:50 or 20:80 to 40:60 (all in weight%);
- the building blocks a) and b) are present in the polymer in a (number) ratio of from 80:20 to 20:80, relative to each other, or according to preferred em bodiments 75:25 to 50:50, preferably 60:40 to 50:50, more preferably 50:50.
- the linear alkyl groups R1 , R2 preferably have 12 to 20, more preferably 12 to 14, carbon atoms.
- the branched alkyl groups preferably have 10 to 32, more prefera bly 12 to 26 and most preferably 12 to 20, carbon atoms, including those branched at the 2 position.
- the branched alkyl groups R1 , R2 are preferably branched at the 2 position.
- Ac cording to a further embodiment the alkyl groups R1 , R2 that are branched at the 2 position have at least one additional branching, wherein the at least one addi tional branching is preferably at least a methyl branching.
- R1 , R2 as defined above comprise branched alkyl groups as follows:
- branched alkyl groups that are branched at the 2 position, comprising at least one additional branching, wherein the at least one additional branching is at least a methyl branching.
- the branched alkyl groups R1 , R2 having an alkyl branch at the 2 position are preferably alkyl groups with a main chain (including any other branching at the main chain) that has 4 carbon atoms more than as in the side chain at the 2 position wherein both the alkyl branch at the 2 position and the main chain preferably com prise no further branching.
- the polymer preferably has an acid value of less than 2 mg KOH/g, measured according to DIN EN 14104.
- the polymer chain preferably comprises in total 50 to 150 building blocks a) and b) per polymer chain plus optionally other building blocks or end groups.
- the styrene-maleic acid dialkyl ester polymers preferably have a molecular weight (mass) Mw in the range of 30,000 to 75,000 g/mol, more preferably 30,000 to 60,000 g/mol and most preferably of 40,000 to 52,000 g/mol.
- the polydispersity index (PDI) M w /M n thereof preferably is between 1 .5 and 2.5, more preferably be tween 1 .8 and 2.2. Both are determined by gel permeation chromatography (GPC) as defined below.
- the lubricant oil composition of the present invention is a composition comprising at least one base oil and at least one styrene-maleic acid dialkyl ester polymer as defined herein.
- the lubricant oil composition may comprise further additives cus tomary in the lubricant industry such as thickeners, antioxidants, antiwear agents, anticorrosives, metal deactivators, detergents, dyes, lubricity improvers, friction modifiers and high-pressure additives.
- the base oil can be a mineral oil or a syn thetic oil.
- the base oil may have a kinematic viscosity of 20 to 2500 mm 2 /s, in particular of 40 to 500 mm 2 /s, at 40°C.
- the base oil is at least one Group l-V base oil, preferably Group l-IV base oil, as well as mixtures thereof.
- the base oil may also be at least one oil with a viscosity class according to ISO 3448 in the range of VG10 to VG320, preferably VG15 to VG68.
- the base oil may have a pour point according to ASTM D97 equal to or below -10° C.
- the polymers defined above are used to improve the Permanent Shear Stability Index (PSSI) of the lubricant oil composition at 100° C after 20 h to a value below 40%, preferably below 30%.
- PSSI Permanent Shear Stability Index
- the polymer may also increase the permanent shear stability of the lubricant oil composition and/or act as viscosity index improver and/or pour point depressant therein.
- the polymers used are not uniform compounds but a mixture of compounds com prising above building blocks a) and b) and in so far above values refer to a mixture of compounds or in other words the overall composition of the polymers is defined by above values.
- the polymer may comprise building blocks other than a) or b), for example maleic acid anhydride, or maleic acid mono-esters.
- the invention makes use of styrene-maleic acid alkyl ester polymers having the following building block:
- R1 and R2 alkyl, without that the sequence of building blocks resulting from styrene a) and maleic acid dialkyl ester b) necessarily need to be of an alternating nature ( a)b) a)b) a)b) .... ).
- the building blocks can also have a random distribution or a block structure.
- R1 and R2 may be different for each b.
- reaction scheme below illustrates the synthesis of styrene-maleic acid dialkyl ester polymers with an alternating structure.
- the product can also be syn thesized via alternative synthetic pathways (such as performing the esterification of maleic anhydride before copolymerising with styrene).
- the completion of the polymerization to the desired level was measured by the acid number of the unreacted maleic anhydride in the filtered polymerisation solu tion.
- the acid value is preferably less than 2 mg KOH/g.
- the copolymer average molecular weight (mass) Mw was determined by using GPC analysis (MZGel SDplus 100 A 5 pm 300x8 mm/ MZ-Gel SDplus 1000 A 5pm 300x8mm/Agilent polyPore 5pm 300x7.5 mm equipped with a pre-column Mz-Gel SDplus linear 5pm 20 50x8mm, injection volume 20 pL, solvent THF, flow rate 1 ml/m in, detection via UV (254 nm) and refractive index).
- Methane sulfonic acid (0.13 mol) was charged as catalyst and the reactor was heated up until the reflux of xylene started. The esterification reaction was carried out until the theoretical amount of water was collected.
- the polystyrene-maleic anhydride copolymer ester solution was treated with acti vated carbon and filtrated before removal of xylene. Xylene was removed by dis tillation to obtain the neat copolymer ester.
- the fatty alcohols / fatty alcohol mixtures specified in below table were used in the esterification step for preparation of the polymers described in table 1 .
- ISOFOL alcohols are branched Guerbet alcohols, more specifically, saturated pri mary alcohols with defined branching at the two position of the carbon chain.
- the Guerbet alcohols can chemically be described as 2-alkyl-1 -alkanols, with the alkyl and the alkanol group both being linear.
- ISOFOL 2426S is an example for a branched alkyl group having one 2-alkyl branching and additionally at least one methyl branching.
- NAFOL 1214 refers to a C12-14 synthetic linear alcohol mixture
- NAFOL 1620 re fers to a C16-20 synthetic linear alcohol mixture
- NAFOL 1218 refers to a C12-18 synthetic linear alcohol mixture
- LIALCHEM 25/75 refers to a C12-25 essen tially linear alcohol mixture (75-79 weight% linear content), which is essentially identical in composition to NEODOL 25 from Shell.
- the number of carbon atoms given above refers to the complete molecule and not only to the backbone of the alcohol.
- PSMA-1214 The alcohol NAFOL 1214 was used to esterify the
- PSMA-25/I24 A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 65 weight% LIALCHEM 25/75 and 35 weight% ISOFOL 24. Molecular weight: 16,402 g/mol (example reflecting preparative example 4 of US 8,343,900 B2).
- LW A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 70 weight% NAFOL 1214 and 30 weight% ISOFOL 12. Molecular weight: 19,229 g/mol. PSMA-1214/I2426S
- LW A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 70 weight% NAFOL 1214 and 30 weight% ISOFOL 2426S. Molecular weight: 21 ,364 g/mol.
- PSMA-1214/112 (90/10): A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 90 weight% NAFOL 1214 and 10 weight% ISOFOL 12. Molecular weight: 40,588 g/mol.
- PSMA-1214/112 A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 70 weight% NAFOL 1214 and 30 weight% ISOFOL 12. Molecular weight: 46,502 g/mol.
- PSMA-1214/112 (30/70): A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 30 weight% NAFOL 1214 and 70 weight% ISOFOL 12. Molecular weight: 42,061 g/mol.
- PSMA-1214/116 A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 70 weight% NAFOL 1214 and 30 weight% ISOFOL 16.
- PSMA-1214/120 A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 70 weight% NAFOL 1214 and 30 weight% ISOFOL 20.
- PSMA-1214/124 A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 70 weight% NAFOL 1214 and 30 weight% ISOFOL 24.
- PSMA-1214/I2426S A mixture of alcohols esterified with styrene-maleic an hydride copolymer: 70 weight% NAFOL 1214 and 30 weight% ISOFOL 2426S.
- PAMA-1214 The alcohol NAFOL 1214 esterified with alkylmethac- rylates copolymer.
- PAMA-1214/1620 A mixture of alcohols esterified with alkylmethacrylates copolymer: 70 weight% NAFOL 1214 and 30 weight% NAFOL 1620.
- PSMA Styrene-maleic anhydride copolymer containing 50 mol% maleic acid di alkyl ester
- PAM A Poly(alkylmethacrylates)
- inventive polymeric additives were tested by addition of 10 wt% neat polymer to different base oils with regard to the pour point depression (PP), thickening effi ciency (TE) and viscosity index (VI). The results are listed in table 3.
- the polymers as defined in claim 1 improve the pour point depression, thickening efficiency and the viscosity index compared to existing PAMA-additives or PSMA with only linear alkyl chains.
- PSSI Permanent Shear Stability Index
- the 20h shear stability of the inventive PSMA based polymeric additive is higher than the PSMA based polymeric additives of the state of the art and at least in the same range as PAMA based ones. It has been sur prisingly found that introducing a Guerbet structured alcohol in the PSMA-polymer led to improved shear stability.
Abstract
Description
Claims
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EP19161442.9A EP3705557A1 (en) | 2019-03-07 | 2019-03-07 | Use of polymers as additives for lubricant oil compositions |
PCT/EP2020/056278 WO2020178460A1 (en) | 2019-03-07 | 2020-03-09 | Use of polymers as additives for lubricant oil compositions |
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EP3935145A1 true EP3935145A1 (en) | 2022-01-12 |
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EP19161442.9A Withdrawn EP3705557A1 (en) | 2019-03-07 | 2019-03-07 | Use of polymers as additives for lubricant oil compositions |
EP20707685.2A Withdrawn EP3935145A1 (en) | 2019-03-07 | 2020-03-09 | Use of polymers as additives for lubricant oil compositions |
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EP19161442.9A Withdrawn EP3705557A1 (en) | 2019-03-07 | 2019-03-07 | Use of polymers as additives for lubricant oil compositions |
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EP (2) | EP3705557A1 (en) |
CN (1) | CN113544242A (en) |
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NL68496C (en) | 1947-03-20 | |||
US3574575A (en) | 1969-04-21 | 1971-04-13 | Mobil Oil Corp | Liquid hydrocarbon oil compositions containing esters of styrene-maleic anhydride copolymers as fluidity improvers |
CA1275403C (en) * | 1985-06-07 | 1990-10-23 | Albert Rossi | Lubricating oil composition containing dual additive combination for lowtemperature viscosity improvement |
US5703023A (en) | 1991-12-24 | 1997-12-30 | Ethyl Corporation | Lubricants with enhanced low temperature properties |
US6013735A (en) * | 1998-02-13 | 2000-01-11 | Ethyl Corporation | Process for the preparation of acrylate and methacrylate polymers |
JP2003504487A (en) * | 1999-07-09 | 2003-02-04 | ザ ルブリゾル コーポレイション | Nitrogen-containing esterified carboxy-containing interpolymers with improved oxidative stability and lubricants containing the same |
US6475963B1 (en) * | 2001-05-01 | 2002-11-05 | Infineum International Ltd. | Carboxylate-vinyl ester copolymer blend compositions for lubricating oil flow improvement |
DE102005031244A1 (en) * | 2005-07-01 | 2007-02-15 | Rohmax Additives Gmbh | Oil-soluble comb polymers |
JP2009536685A (en) | 2006-05-08 | 2009-10-15 | ザ ルブリゾル コーポレイション | Lubricating composition containing a polymer and an antiwear agent |
CA2651901C (en) | 2006-05-08 | 2014-11-18 | The Lubrizol Corporation | Novel polymers and methods of controlling viscosity |
US20150232781A1 (en) * | 2012-08-20 | 2015-08-20 | The Lubrizol Corporation | Lubricating Composition Including Esterified Copolymer And Method |
JP2014169426A (en) * | 2013-03-05 | 2014-09-18 | Sanyo Chem Ind Ltd | Viscosity index improving agent and lubricant composition including the same |
EP3121204A1 (en) | 2015-07-23 | 2017-01-25 | Sasol Performance Chemicals GmbH | Polymeric additives for paraffin-containing fluids |
-
2019
- 2019-03-07 EP EP19161442.9A patent/EP3705557A1/en not_active Withdrawn
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2020
- 2020-03-09 CN CN202080019113.XA patent/CN113544242A/en active Pending
- 2020-03-09 WO PCT/EP2020/056278 patent/WO2020178460A1/en active Application Filing
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EP3705557A1 (en) | 2020-09-09 |
CN113544242A (en) | 2021-10-22 |
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