EP0524783A1 - Verwendung von Schmierölzusammensetzungen - Google Patents

Verwendung von Schmierölzusammensetzungen Download PDF

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Publication number
EP0524783A1
EP0524783A1 EP92306593A EP92306593A EP0524783A1 EP 0524783 A1 EP0524783 A1 EP 0524783A1 EP 92306593 A EP92306593 A EP 92306593A EP 92306593 A EP92306593 A EP 92306593A EP 0524783 A1 EP0524783 A1 EP 0524783A1
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EP
European Patent Office
Prior art keywords
lubricating oil
weight
polyether
units
oil composition
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.)
Ceased
Application number
EP92306593A
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English (en)
French (fr)
Inventor
Robert Brian Bp Chemicals Limited Cracknell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis Speciality Organics Far East Ltd
Original Assignee
BP Chemicals Ltd
Oceanfloor Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GB919115911A external-priority patent/GB9115911D0/en
Priority claimed from GB919115912A external-priority patent/GB9115912D0/en
Application filed by BP Chemicals Ltd, Oceanfloor Ltd filed Critical BP Chemicals Ltd
Publication of EP0524783A1 publication Critical patent/EP0524783A1/de
Ceased legal-status Critical Current

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    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
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    • C10M2209/107Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C10M2209/1075Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106 used as base material
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    • C10M2209/109Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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Definitions

  • the present invention relates to the use of lubricating oil compositions as inlet-valve deposit inhibitors, in particular the use of compositions comprising polyethers.
  • Multigrade lubricating oils for use in automotive engines comprise several components, in particular viscosity index improvers; these viscosity index improvers modify the viscometric properties of the lubricating oil; however, the problem with such additives is that they increase the deposits on the inlet valves of the engine and thereby impair the efficiency of the engine.
  • EP 246612 describes a lubricating oil based upon a mixture of mineral oil and a polyether. Whilst the description indicates that the polyether is freely soluble in the mineral oil, only compositions in which 5 to 60% by weight of the polyether is present are taught as being advantageous.
  • the polyether is one having the general formula R[(C n H 2n O) x (C m H 2m O) y H] z where R is a moiety derived from an organic starter, n is 2 to 4, m is 6 to 40, x and y are integers, z is 1 to 8 and the content of (C m H 2m O) groups in the polyether is 15 to 60% by weight.
  • EP 0355977 discloses an industrial or automobile lubricating oil, for use, eg as automotive or industrial gear lubricants, two-stroke engine lubricants, which comprises (a) 0 to 40% by weight of mineral oil(s) and (b) 100 to 60% by weight of a polyether having the general formula RX[(C x H 2x O) n (C y H 2y O) p H] m wherein R is C9 to C30 alkyl or alkylphenyl, X is O, S or N, x is 2 to 4, y is 6 to 30, m is 1 or 2 and n and p are such that the polyether contains between 1 and 35% by weight of (C y H 2y O) units and between 35 and 80% by weight of (C x H 2x O) units.
  • the polyether preferably has a molecular weight in the range 600 to 4000 and a viscosity in the range 32-460 mPa.s at 40°C.
  • a lubricating oil composition as an inlet-valve deposit inhibitor characterised in that the lubricating oil composition comprises a polyether of the formula RX[(C x H 2x O) n (C y H 2y O) p H] m wherein R is either an alkyl or alkylphenyl group having from 7 to 30 carbon atoms, X is selected from 0,S or N, or RX together represent H, x is an integer from 2 to 4, y is an integer from 6 to 30, m is 1 when X is O or S or when RX together represents H, or m is 2 when x is N, and n and p are such that the polyether contains between 0 and 40% by weight of (C y H 2y O) units and between 35 and 80% by weight of (C x H 2x O) units.
  • RX is either an alkyl or alkylphenyl group having from 7 to 30 carbon atoms
  • X is selected from 0,S or N, or RX together represent H
  • polyethers as defined above can be prepared as described in European Published Application EP 0355977.
  • compositions of the present invention overcome the problems of the prior art by improving inlet valve deposit inhibition of automotive engines in which the compositions are used. Furthermore, the viscometric properties of the compositions are superior to those of the prior art compositions.
  • R this is suitably an alkyl or alkylphenyl group having from 7 to 30 carbon atoms.
  • R is an alkyl group it is preferably a C10 to C24 alkyl group, such as might be obtained from a corresponding fatty acid alcohol, thiol or amine. Most preferred are alkyl groups having 12 to 18 carbon atoms.
  • R is alkylphenyl
  • R preferably has from 9 to 30 carbon atoms with phenyl groups substituted with one or more C6 to C12 alkyl groups being most preferred, preferably two, for example dinonyl phenol.
  • the polyether is comprised of one or two independent oxyalkylene backbones of formula [(C x H 2x O) n (C y H 2y 0) p H].
  • Such backbones are created by alkoxylating a starter molecule of formula RX(H) m with one or more alkylene oxides so that the backbone(s) formed comprise blocks of units of a given type.
  • the alkoxylation process can be carried out using a mixture of alkylene oxides in which case the backbones formed will comprise a random distribution of the units.
  • C x H 2x 0 and C y H 2y 0 For each of the two types of alkylene oxide, C x H 2x 0 and C y H 2y 0, one or more different alkylene oxides can be used.
  • the only constraint is that in the final polyether, the total number of units having the formula C x H 2x 0 should comprise between 35 and 80, preferably between 45 and 65% by weight and the total number of units having the formula C y H 2y O should comprise 0 to 40, preferably 1 to 30% by weight.
  • the polyethers described above suitably have a weight molecular weight as measured by Gel Permeation Chromatography using polystyrene standards, in the range 400 to 4000, preferably 700 to 3000, more preferably from 800 to 2,500. They are also characterised by having a viscosity in the range 32 to 460 mPas at 40°C.
  • the polyether has the formula defined above with n being in the range 5 to 30 and p being in the range 1 to 4.
  • the lubricating oil compositions of the present invention may consist essentially of a polyether as defined hereinabove; optionally the lubricating oil composition may further comprise an animal, vegetable or mineral oil or a synthetic lubricating oil, preferably a mineral oil or a synthetic lubricating oil.
  • a preferred combination is a polyether as defined hereinabove and a synthetic lubricating oil.
  • Suitable mineral oils include naphthenic and paraffinic oils.
  • Synthetic lubricating oils are synthesised by a chemical process as distinct from naturally occurring oils such as animal, vegetable or mineral oils.
  • the term "synthetic lubricating oil” is a term well-known in the art. Suitable synthetic lubricating oils include polyesters such as pentaerythritol tetraesters, and polyol esters, diesters of dibasic acids or polyesters of polybasic acids such as dioctyl adipate, dioctyl sebacate and tridecyladipate, polymeric hydrocarbons such as liquid polyisobutenes and polyalphaolefins.
  • the term synthetic lubricating oils will not encompass the polyethers as defined hereinabove.
  • compositions of the present invention must be compatible and the compositions must be storage stable, preferably for at least 1 year. Through routine testing the man skilled in the art would be able to formulate such compositions such that the above criteria are met.
  • Additives such as viscosity-index improvers, pour point depressants, detergent additives, anti-wear additives, extreme pressure additives, anti-oxidants, anti-corrosion and anti-foam agents etc may optionally be added to the compositions.
  • additives are comprised in the lubricating oil compositions of the present invention, such additives must be compatible in the composition and the compositions must be storage stable, preferably for at least 1 year. It is not necessary for all the components of the compositions to be independently compatible with one another so long as they are compatible in the final composition. Through routine testing the man skilled in the art woud be able to formulate such compositions such that the above criteria are met.
  • compositions of the present invention comprises polyether as defined hereinabove, and a synthetic lubricating oil
  • the ratio of polyether to synthetic lubricating oil is in the range 10:1 to 1:10, preferably 5:1 to 1:5.
  • the sum of the polyether and synthetic lubricating oil should be at least 10%, by weight of total weight of the composition, preferably greater than 30%, more preferably greater than 50%.
  • Example 1 (according to the invention) Comparative Test 2 (Parts by Weight) (Parts by Weight) Hitec 164 Polyalphaolefin (ex Ethyl) 50 50 Hitec 166 Polyalphaolefin (ex Ethyl) 25 25 Priolube 3932 (Polyol Ester) (ex Unichema) 10 25 Oil Soluble Polyalkylene Glycol 1769 15 VI Improver (Olefin Graft Copolymer of Polymethylmethacrylate) 10 8 Additive Package (ADX 11414 ex Adibis) 11 11 11
  • Example 1 The compositions of Example 1, Comparative Test 2 and a standard monograde lubricant were all tested using the Ford Pinto Inlet Valve Merit Rating Engine Test.
  • the test uses a standard fuel to assess the build up of deposits on the inlet valves derived from oil leaking down the valve stems.
  • the following lubricating oil composition was prepared: Parts 180 BHK (Hydrocracked Mineral Oil ex BP) 45 Priolube 3932 (Polyol Ester) (ex Unichema) 45 Oil Soluble Polyalkylene Glycol 1769 10 VI Improver (Polymethylmethacrylate) 4.8 SG/CD Additive Package 12.8
  • Example 3 The composition of Example 3 was tested in the M102E Engine Cleanliness (Sludge and Wear) test.
  • the multigrade CEC reference mineral oil RL 140 was used as a comparison. The results are given in Table I.
  • Table I Example 3 RL 140 Engine Cleanliness (maximum rating 10) 9.24 8.1 Average Cam Wear (microns) 57 70 Average Tappet Wear (microns) 3.6 2.7 Average Inlet Valve Rating (maximum rating 10 per valve) 8.63 8.5
  • Example 3 was also compared to a commercially available 10W-40 SG/CD lubricant based upon mineral oil and hydrocracked mineral oil. These results are given in Table II. Table II Example 3 Reference Oil Average Total Deposit per Valve (mg) 115 271 Average Tulip Deposit per Valve (mg) 95 214 Oil Consumption (g) 300 350
  • the Oil Soluble Polyalkylene Glycol 1769 was prepared as described in EP 355 977 and comprises 14% by weight dinonyl phenol, 73.1% propylene oxide, 12.9% C16 alpha olefin epoxide, the glycol has a viscosity at 100°C of 25.8 cSt, at 40°C of 191.0 cSt and a visocisty index of 172.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
EP92306593A 1991-07-23 1992-07-17 Verwendung von Schmierölzusammensetzungen Ceased EP0524783A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB919115911A GB9115911D0 (en) 1991-07-23 1991-07-23 Use of lubricating oil compositions
GB9115911 1991-07-23
GB919115912A GB9115912D0 (en) 1991-07-23 1991-07-23 Lubricants
GB9115912 1991-07-23

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EP0524783A1 true EP0524783A1 (de) 1993-01-27

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EP0551760A2 (de) * 1992-01-10 1993-07-21 Oceanfloor Limited Polyetherphosphatester
EP0692669A1 (de) * 1993-07-02 1996-01-17 Hydro-Quebec Beim Auswalzen von Lithiumbändern zu dünnen Folien zu verwendende Schmiermittelzusätze
FR2762005A1 (fr) * 1997-04-11 1998-10-16 Chevron Res & Tech Utilisation de surfactants de bas poids moleculaires comme agents ameliorant la filtrabilite dans des lubrifiants hydrauliques
WO2000023544A1 (en) * 1998-10-16 2000-04-27 Castrol Limited An engine oil comprising a polyalkylene glycol used in a direct injection engine
EP1000674A3 (de) * 1994-07-12 2000-11-29 Hydro-Quebec Herstellungsverfahren einer Metalldünnschicht aus einem Alkallimetall oder einer Alkallimetalllegierung durch Walzven eines Metallband in Gegenwart einer Schmiermittelzusammensetzung
EP1247858A1 (de) * 2001-04-02 2002-10-09 TonenGeneral Sekiyu K.K. Schmierölzusammensetzung für Brennkraftmaschinen
WO2013003405A1 (en) 2011-06-30 2013-01-03 Exxonmobil Research And Engineering Company Lubricating compositions containing polyalkylene glycol mono ethers
WO2013003392A1 (en) 2011-06-30 2013-01-03 Exxonmobil Research And Engineering Company Method of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers
WO2013003394A1 (en) 2011-06-30 2013-01-03 Exxonmobil Research And Engineering Company Lubricating compositions containing polyetheramines
WO2013010851A1 (en) * 2011-07-21 2013-01-24 Shell Internationale Research Maatschappij B.V. Two-phase lubricating oil composition
EP2633012A2 (de) * 2010-10-29 2013-09-04 Chevron Oronite Company LLC Schmierölzusammensetzungen
US8586520B2 (en) 2011-06-30 2013-11-19 Exxonmobil Research And Engineering Company Method of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers
US8969271B2 (en) 2009-07-23 2015-03-03 Dow Global Technologies Llc Polyakylene glycols useful as lubricant additives for groups I-IV hydrocarbon oils
US9850447B2 (en) 2013-05-23 2017-12-26 Dow Global Technologies Llc Polyalkylene glycols useful as lubricant additives for hydrocarbon base oils
JPWO2019160123A1 (ja) * 2018-02-16 2021-02-04 出光興産株式会社 潤滑油組成物
CN115443325A (zh) * 2020-04-27 2022-12-06 克鲁勃润滑剂慕尼黑两合欧洲公司 润滑剂组合物及其用途

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EP0551760A2 (de) * 1992-01-10 1993-07-21 Oceanfloor Limited Polyetherphosphatester
EP0551760A3 (en) * 1992-01-10 1993-12-08 Oceanfloor Ltd Polyether phosphate esters
US5414103A (en) * 1992-01-10 1995-05-09 Oceanfloor Limited Polyether phosphate esters
EP0692669A1 (de) * 1993-07-02 1996-01-17 Hydro-Quebec Beim Auswalzen von Lithiumbändern zu dünnen Folien zu verwendende Schmiermittelzusätze
EP1000674A3 (de) * 1994-07-12 2000-11-29 Hydro-Quebec Herstellungsverfahren einer Metalldünnschicht aus einem Alkallimetall oder einer Alkallimetalllegierung durch Walzven eines Metallband in Gegenwart einer Schmiermittelzusammensetzung
FR2762005A1 (fr) * 1997-04-11 1998-10-16 Chevron Res & Tech Utilisation de surfactants de bas poids moleculaires comme agents ameliorant la filtrabilite dans des lubrifiants hydrauliques
WO1998046708A1 (fr) * 1997-04-11 1998-10-22 Chevron Chemical S.A. Utilisation de surfactants de bas poids moleculaires comme agents ameliorant la filtrabilite dans des lubrifiants hydrauliques
WO2000023544A1 (en) * 1998-10-16 2000-04-27 Castrol Limited An engine oil comprising a polyalkylene glycol used in a direct injection engine
EP1247858A1 (de) * 2001-04-02 2002-10-09 TonenGeneral Sekiyu K.K. Schmierölzusammensetzung für Brennkraftmaschinen
US6750185B2 (en) 2001-04-02 2004-06-15 Tonengeneral Sekiyu K.K. Lubricating oil composition for internal combustion engines
AU783903B2 (en) * 2001-04-02 2005-12-22 Tonengeneral Sekiyu K.K. Lubricating oil composition for internal combustion engines
US8969271B2 (en) 2009-07-23 2015-03-03 Dow Global Technologies Llc Polyakylene glycols useful as lubricant additives for groups I-IV hydrocarbon oils
EP2633012A4 (de) * 2010-10-29 2014-07-23 Chevron Oronite Co Schmierölzusammensetzungen
EP2633012A2 (de) * 2010-10-29 2013-09-04 Chevron Oronite Company LLC Schmierölzusammensetzungen
WO2013003405A1 (en) 2011-06-30 2013-01-03 Exxonmobil Research And Engineering Company Lubricating compositions containing polyalkylene glycol mono ethers
WO2013003392A1 (en) 2011-06-30 2013-01-03 Exxonmobil Research And Engineering Company Method of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers
WO2013003394A1 (en) 2011-06-30 2013-01-03 Exxonmobil Research And Engineering Company Lubricating compositions containing polyetheramines
US8586520B2 (en) 2011-06-30 2013-11-19 Exxonmobil Research And Engineering Company Method of improving pour point of lubricating compositions containing polyalkylene glycol mono ethers
WO2013010851A1 (en) * 2011-07-21 2013-01-24 Shell Internationale Research Maatschappij B.V. Two-phase lubricating oil composition
CN103703112A (zh) * 2011-07-21 2014-04-02 国际壳牌研究有限公司 两相润滑油组合物
CN103703112B (zh) * 2011-07-21 2016-01-13 国际壳牌研究有限公司 两相润滑油组合物
RU2608736C2 (ru) * 2011-07-21 2017-01-23 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Двухфазная композиция смазочного масла
US9550956B2 (en) 2011-07-21 2017-01-24 Shell Oil Company Two-phase lubricating oil composition
US9850447B2 (en) 2013-05-23 2017-12-26 Dow Global Technologies Llc Polyalkylene glycols useful as lubricant additives for hydrocarbon base oils
JPWO2019160123A1 (ja) * 2018-02-16 2021-02-04 出光興産株式会社 潤滑油組成物
EP3754000A4 (de) * 2018-02-16 2021-09-29 Idemitsu Kosan Co., Ltd. Schmierölzusammensetzung
CN115443325A (zh) * 2020-04-27 2022-12-06 克鲁勃润滑剂慕尼黑两合欧洲公司 润滑剂组合物及其用途
CN115443325B (zh) * 2020-04-27 2024-07-09 克鲁勃润滑剂慕尼黑两合欧洲公司 润滑剂组合物及其用途

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