EP1046699A1 - Fluides fonctionnels non toxiques et biodégradables pour véhicules automobiles - Google Patents
Fluides fonctionnels non toxiques et biodégradables pour véhicules automobiles Download PDFInfo
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- EP1046699A1 EP1046699A1 EP00401044A EP00401044A EP1046699A1 EP 1046699 A1 EP1046699 A1 EP 1046699A1 EP 00401044 A EP00401044 A EP 00401044A EP 00401044 A EP00401044 A EP 00401044A EP 1046699 A1 EP1046699 A1 EP 1046699A1
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- toxic
- biodegradable
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- base fluid
- fluid
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Definitions
- the invention relates to non-toxic functional fluids and biodegradable for motor vehicles obtained by addition non-toxic and biodegradable functional additives to base type copolymer of ethylene oxide and propylene oxide or esters with fatty chains of neopolyols.
- Each motor vehicle currently contains a variety fluids fulfilling different functions such as lubricating oils engine and / or gear, hydraulic oils such as oil for power steering, brake fluid or shock absorber fluid, and coolant.
- Patent application DE A 196 47 554 discloses a refrigeration fluid and lifetime lubrication of an internal combustion engine consisting of a fluid carrier based on a copolymer of ethylene oxide and propylene oxide having an average molar mass of between 300 and 700 and a EO / PO weight ratio between 30/70 and 70/30, and a mixture additives.
- WO 97/30137 (corresponding to DE 196 05 162) (Elf Antar) describes a lubricating composition consisting of at least 70% by weight of at least one C 2-5 monoalkylene glycol , and up to 30% d '' a mixture of additives. This composition may also contain a small proportion, in particular from 0 to 15% by weight, of a polyalkylene glycol having a molar mass of less than 5000.
- the upper temperature limit for the use of these lubricants is at most equal to 165 ° C.
- a large part of the additives contained in these lubricants are also toxic and not very biodegradable.
- This use of the same basic fluid allows, when putting out of final use of the vehicle, to landfill with a single waste number or jointly reprocess all fluids functional made from it.
- the present invention therefore relates to the use of copolymers ethylene oxide (EO) and propylene oxide (PO) or esters with fatty neopolyol chains as one and the same base fluid for the manufacture of various functional fluids for motor vehicles by adding suitable non-toxic and biodegradable functional additives.
- EO ethylene oxide
- PO propylene oxide
- esters with fatty neopolyol chains as one and the same base fluid for the manufacture of various functional fluids for motor vehicles by adding suitable non-toxic and biodegradable functional additives.
- a functional fluid for vehicle automotive containing a base fluid consisting of oxide copolymers ethylene (EO) and propylene oxide (PO) or fatty chain esters neopolyols above, and various non-toxic functional additives and biodegradable.
- EO oxide copolymers ethylene
- PO propylene oxide
- fatty chain esters neopolyols neopolyols
- Copolymers of ethylene oxide and propylene oxide (hereinafter called EO / PO copolymers) used as base fluid for the production of functional liquids are random copolymers containing 30 to 90% by weight of units derived from ethylene oxide and from 70 to 10% by weight of units derived from propylene oxide and having a weight-average molar mass of between 300 and 1,200.
- the rapid biodegradability (according to CEC L-33-A-94) of these fluids is greater than 70%, or even sometimes greater than 80%.
- copolymers have a good lubricity which can be attribute to the formation of solidly adsorbed films on the surface of the parts subject to friction. They also have a very pour point low, below -20 ° C or even below -30 ° C. Their cooling power is better than that of mineral oils.
- the other group of compounds used according to the present invention as base fluid for motor vehicle functional liquids includes various fatty chain esters of neopolyols.
- neopolyols means alcohols containing at least three hydroxyl functions and having a neopentyl structure, that is to say a structure characterized by the absence of a hydrogen atom on the carbon atom in the ⁇ position of the carbons bearing hydroxyl functions. This absence of a hydrogen atom in position has alcoholic functions is of paramount importance because it gives the esters of these polyols a very high chemical stability, in particularly high stability to hydrolysis.
- neopolyols at the base of fatty chain esters include for example neopentylglycol (diol), trimethylolpropane (triol), pentaerythritol (tetraol) and dipentaerythritol (hexaol).
- polyols are esterified with long chain monoacids, that is to say C 8-36 fatty acids, with linear or branched chain, saturated or unsaturated, but preferably saturated, or with mixtures of such fatty acids .
- the esterification can be partial or complete. However, for obtain sufficient kinematic viscosity and a flash point fairly high, at least two hydroxyl functions must be esterified by fatty acids.
- Suitable saturated fatty acids caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and branched isomeric forms of these.
- Fatty acids can also have one or more double bonds, but these unsaturations are potential oxidation sites and affect the chemical stability of base fluids.
- the number of ethylenic unsaturations of the esters can be characterized by the iodine index, that is to say by the number of grams of iodine (I 2 ) which can be fixed per 100 g of material.
- the iodine index must be less than 10 and preferably less than 1.
- the fatty chain esters of neopolyols used as the base fluid in the present invention have a viscosity index at least 140.
- the basic fluids namely EO / PO copolymers or esters with fatty chains of neopolyols, used according to the present invention must have a volatility (Noack) of less than 7% and preferably less at 4%.
- pour point in English: for point
- pour point is meant the lowest temperature at which the oil still flows when it is cooled, without stirring, under standardized conditions (NF T 60-105 / ASTM D 97 / ISO 3016).
- EO / PO copolymers and fatty chain esters of neopolyols forming the basic fluids used according to the present invention must have a pour point below -20 ° C, and preferably below at -30 ° C, or even lower than -40 ° C.
- the present invention aims to solve the problems ecotoxicity and recycling posed by functional liquids prior art motor vehicles. For this it offers the use non-toxic and biodegradable base fluids described above in combination with additives that are also non-toxic and biodegradable.
- Additives used for the production of different fluids functional are chosen from antioxidants, anti-corrosion / anti-rust agents, pH regulating agents (buffer), agents anti-wear, anti-hydrolysis agents, dispersing agents and agents anti-foam, all non-toxic and biodegradable.
- the non-toxic and biodegradable antioxidants are chosen from zinc dialkyldithiocarbamates, alkyl dithiocarbamates such as methyl dithiocarbamate, vitamin E (tocopherol) and derivatives thereof, sterically hindered phenols such as 2,6-di- tert -butyl-4-methyl-phenol or similar hindered phenols in which the methyl group in position 4 is replaced by a higher aliphatic alkyl group, and the dialkyl trisulphides.
- Non-toxic and biodegradable anti-corrosion / anti-rust agents are chosen from succinic acid derivatives such as acids alkyl succinics and partial esters of succinic acid, and alkyl benzenesulfonates neutral calcium.
- Poly (aspartic acid) is a peptide polymer of acid aspartic capable of performing both the functions of dispersing agent, buffer agent (pH regulator) and antiwear agent.
- a poly (aspartic acid) having an average molar mass in weight between 1000 and 10 000.
- the basic fluid is a neopolyol ester
- an agent to protect it against hydrolysis.
- Such agents non-toxic and biodegradable are for example the carbodiimides sterically crowded.
- Non-toxic and biodegradable defoaming agents are example chosen from polydimethylsiloxanes.
- anti-wear agents are for example zinc dialkyldithiocarbamates, sulfurized olefins, esters of sulfurized unsaturated fatty acids, sulfurized jojoba oil and vegetable oils capable of being sulfurized by trapping and transfer sulfur from the fuel.
- the quantities of these various additives will of course depend the nature of the base fluid and the role of the additive.
- the oxidizing agent (s) are used in an amount of 0.2 to 3% by weight
- the or anti-corrosion / anti-rust agents are present at 0.05 to 1% by weight
- the anti-wear agent (s), if present, are added at a rate of 0.1 to 2% by weight
- the polypartic acid is present at a rate of 0.3 to 3% by weight
- the anti-foaming agent (s) are present in a lower amount at 0.02% by weight
- the anti-hydrolysis agent (s) are present at 0.2 to 2% by weight, all these values being related to the fluid basic.
- the total amount of functional additives added will depend on the chemical nature of the base fluid and the application of the final functional fluid. It is generally between 1 and 20% by weight, preferably between 2 and 12% by weight relative to the fluid based.
- the functional fluid produced by adding functional additives non-toxic and biodegradable to oxide copolymers ethylene and propylene oxide or neopolyol esters can be e.g. engine oil, gear oil, gear oil automatic transmission, power steering oil, fluid hydraulic for shock absorbers, brake fluid or coolant.
- the functional fluid of the present invention when it is an engine oil, is preferably used in engines whose parts friction - based on new ceramic or composite materials or surface treated with triboactive coatings - are less subject to wear by friction than metallic mechanical parts conventional internal combustion engines.
- the functional fluids used as engine oil allow lifetime or long term lubrication engine term because of functions conventionally assumed by additives gradually consumed (increase in the viscosity index and anti-wear) are now filled with the base liquid which is available in unlimited quantity.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Lubricants (AREA)
Abstract
Description
- les inhibiteurs de la corrosion/rouille des pièces métalliques du moteur,
- les agents anti-usure (AW) et extrême-pression (EP) réduisant le frottement par réaction chimique avec la surface métallique,
- les agents dispersants assurant la dispersion et l'évacuation de contaminants solides insolubles,
- les agents détergents évitant la formation de dépôt à la surface des pièces métalliques par dissolution des produits secondaires d'oxydation ou de la combustion,
- les agents augmentant l'indice de viscosité (VI), c'est-à-dire réduisant la diminution de la viscosité du lubrifiant en fonction de la température,
- les agents anti-oxydation inhibant la dégradation par oxydation du lubrifiant, et
- les agents abaissant le point d'écoulement.
Claims (17)
- Utilisation, pour différents fluides fonctionnels d'un véhicule automobile, d'un seul et même fluide de base comprenant un copolymère d'oxyde d'éthylène (EO) et d'oxyde de propylène (PO) de masse molaire moyenne en poids comprise entre 300 et 1200 et ayant un rapport en poids EO/PO compris entre 30/70 et 90/10, additionné d'un ou de plusieurs additifs fonctionnels non toxiques et biodégradables appropriés à la fonction spécifique.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée par le fait que lesdits copolymères EO/PO ont une volatilité (volatilité Noack mesurée selon DIN 51581) inférieure à 7 %, de préférence inférieure à 4 %.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée par le fait que lesdits copolymères EO/PO ont un indice de viscosité supérieur à 140.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée par le fait que lesdits copolymères EO/PO ont un point d'écoulement inférieur à -20 °C, de préférence inférieur à -30 °C, et tout particulièrement inférieur à -40 °C.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée par le fait que lesdits additifs fonctionnels sont choisis parmi les agents antioxydants, les agents anti-corrosion/anti-rouille, les agents régulateurs de pH (tampon), les agents anti-usure, les agents anti-hydrolyse, les agents anti-mousse et les agents dispersants, tous non toxiques et biodégradables.
- Utilisation selon la revendication 5, caractérisée par le fait que les agents anti-oxydants non toxiques et biodégradables sont choisis parmi les dialkyldithiocarbamates de zinc, les thiocarbamates d'alkyle tels que le dithiocarbamate de méthyle, la vitamine E (tocophérol) et les dérivés de celle-ci, les phénols stériquement encombrés tels que le 2,6-di-tert-butyl-4-méthyl-phénol ou des phénols encombrés similaires dans lesquels le groupe méthyle en position 4 est remplacé par un groupe alkyle aliphatique supérieur, et les trisulfures de dialkyle.
- Utilisation selon la revendication 5, caractérisée par le fait que le ou les agents anti-corrosion/anti-rouille non toxiques et biodégradables sont choisis parmi les dérivés d'acide succinique tels que les acides alkylsucciniques et les esters partiels d'acide succinique, et les alkylbenzènesulfonates de calcium neutres.
- Utilisation selon la revendication 5, caractérisée par le fait que l'on utilise comme agent dispersant, agent tampon (régulateur de pH) et agent anti-usure un poly(acide aspartique) ayant une masse molaire moyenne en poids comprise entre 1000 et 10 000.
- Utilisation selon la revendication 5, caractérisée par le fait que l'on utilise comme agent anti-usure des dialkyldithiocarbamates de zinc, des oléfines sulfurées, des esters d'acides gras insaturés sulfurées, l'huile de jojoba sulfurée et des huiles végétales susceptibles d'être sulfurées par piégeage et transfert de soufre en provenance du carburant.
- Utilisation selon la revendication 5, caractérisée par le fait que le ou les agents anti-mousse non toxiques et biodégradables sont choisis parmi les polydiméthylsiloxanes.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée par le fait que la teneur en additifs fonctionnels non toxiques et biodégradables des liquides fonctionnels préparés à partir du liquide de base est comprise entre 1 et 20 % en poids, de préférence entre 2 et 12 % en poids rapporté au fluide de base.
- Utilisation selon l'une quelconque des revendications précédentes, caractérisée par le fait que lesdits fluides fonctionnels préparés sont choisis parmi l'huile moteur, l'huile d'engrenage, l'huile pour transmission automatique, l'huile pour direction assistée, le fluide hydraulique pour amortisseurs, le liquide de frein et le liquide de refroidissement.
- Fluide fonctionel pour véhicule automobile, caractérisé par le fait qu'il contient un fluide de base constitué de copolymères d'oxyde d'éthylène (EO) et d'oxyde de propylène (PO) selon l'une quelconque des revendications 1 à 4, et des additifs fonctionnels non toxiques et biodégradables, dont au moins un agent anti-oxydant choisi parmi le dibutyldithiocarbamate de zinc, les thiocarbamates d'alkyle, la vitamine E (tocophérol) et les dérivés de celle-ci, les phénols stériquement encombrés et les trisulfures de dialkyle, lequel agent antioxydant est présent à raison de 0,2 à 3 % en poids rapporté au fluide de base.
- Fluide fonctionel pour véhicule automobile, caractérisé par le fait qu'il contient un fluide de base constitué de copolymères d'oxyde d'éthylène (EO) et d'oxyde de propylène (PO) selon l'une quelconque des revendications 1 à 4, et des additifs fonctionnels non toxiques et biodégradables, dont au moins un agent anti-corrosion choisi parmi les dérivés d'acide succinique et les alkylbenzènesulfonates de calcium neutres, lequel agent anti-corrosion est présent à raison de 0,05 à 1 % en poids rapporté au fluide de base.
- Fluide fonctionel pour véhicule automobile, caractérisé par le fait qu'il contient un fluide de base constitué de copolymères d'oxyde d'éthylène (EO) et d'oxyde de propylène (PO) selon l'une quelconque des revendications 1 à 6, et des additifs fonctionnels non toxiques et biodégradables, dont un poly(acide aspartique) ayant une masse molaire moyenne en poids comprise entre 1000 et 10 000, et qui est présent à raison de 0,3 à 3 % en poids rapporté au fluide de base.
- Fluide fonctionel pour véhicule automobile, caractérisé par le fait qu'il contient un fluide de base constitué de copolymères d'oxyde d'éthylène (EO) et d'oxyde de propylène (PO) selon l'une quelconque des revendications 1 à 6, et des additifs fonctionnels non toxiques et biodégradables, dont au moins un agent anti-usure choisi parmi les dialkyldithiocarbamates de zinc, des oléfines sulfurées, des esters d'acides gras insaturés sulfurés, l'huile de jojoba sulfurée et des huiles végétales susceptibles d'être sulfurées par piégeage et transfert de soufre en provenance du carburant, lequel agent anti-usure est présent à raison de 0,1 à 2,0 % en poids rapporté au fluide de base.
- Fluide fonctionel pour véhicule automobile, caractérisé par le fait qu'il contient un fluide de base constitué de copolymères d'oxyde d'éthylène (EO) et d'oxyde de propylène (PO) selon l'une quelconque des revendications 1 à 4, et des additifs fonctionnels non toxiques et biodégradables, dont au moins un agent anti-mousse choisi parmi les polydiméthylsiloxanes, présent en une quantité inférieure à 0,02 % en poids rapporté au fluide de base.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9904900 | 1999-04-19 | ||
| FR9904900A FR2792326B1 (fr) | 1999-04-19 | 1999-04-19 | Fluides fonctionnels non toxiques et biodegradables a base de copolymeres d'oxyde d'ethylene et d'oxyde de propylene pour vehicules automobiles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1046699A1 true EP1046699A1 (fr) | 2000-10-25 |
| EP1046699B1 EP1046699B1 (fr) | 2008-05-07 |
Family
ID=9544582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00401044A Expired - Lifetime EP1046699B1 (fr) | 1999-04-19 | 2000-04-14 | L'utilisation des fluides fonctionnels non toxiques et biodégradables pour véhicules automobiles |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1046699B1 (fr) |
| DE (1) | DE60038759D1 (fr) |
| FR (1) | FR2792326B1 (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009074664A1 (fr) * | 2007-12-12 | 2009-06-18 | Shell Internationale Research Maatschappij B.V. | Composition d'huile de graissage |
| WO2009134716A1 (fr) | 2008-04-28 | 2009-11-05 | Dow Global Technologies Inc. | Composition de lubrifiant à base de polyalkylèneglycol |
| WO2012129056A1 (fr) * | 2011-03-23 | 2012-09-27 | Dow Global Technologies Llc | Fluides de transfert de chaleur à base de polyalkylène glycol et huiles de moteur monofluides |
| CN103525531A (zh) * | 2013-09-27 | 2014-01-22 | 奥克化学扬州有限公司 | 一种用于蓝宝石晶体掏棒的冷却液 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140018273A1 (en) * | 2011-03-29 | 2014-01-16 | Dow Global Technologies Llc | Lubricant compositions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3876550A (en) * | 1974-04-15 | 1975-04-08 | Lubrizol Corp | Lubricant compositions |
| EP0572866A1 (fr) * | 1992-05-30 | 1993-12-08 | Fuchs Petrolub Ag Oel + Chemie | Fluide de travail non-polluant et rapidement biodégradable pour système de lubrification de moteurs et autres éléments de véhicules et de machines |
| US5401428A (en) * | 1993-10-08 | 1995-03-28 | Monsanto Company | Water soluble metal working fluids |
| DE19647554A1 (de) * | 1996-11-16 | 1998-05-28 | Daimler Benz Ag | Funktionsflüssigkeit für lebensdauergeschmierte Verbrennungsmotoren |
-
1999
- 1999-04-19 FR FR9904900A patent/FR2792326B1/fr not_active Expired - Fee Related
-
2000
- 2000-04-14 EP EP00401044A patent/EP1046699B1/fr not_active Expired - Lifetime
- 2000-04-14 DE DE60038759T patent/DE60038759D1/de not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3876550A (en) * | 1974-04-15 | 1975-04-08 | Lubrizol Corp | Lubricant compositions |
| EP0572866A1 (fr) * | 1992-05-30 | 1993-12-08 | Fuchs Petrolub Ag Oel + Chemie | Fluide de travail non-polluant et rapidement biodégradable pour système de lubrification de moteurs et autres éléments de véhicules et de machines |
| US5401428A (en) * | 1993-10-08 | 1995-03-28 | Monsanto Company | Water soluble metal working fluids |
| DE19647554A1 (de) * | 1996-11-16 | 1998-05-28 | Daimler Benz Ag | Funktionsflüssigkeit für lebensdauergeschmierte Verbrennungsmotoren |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009074664A1 (fr) * | 2007-12-12 | 2009-06-18 | Shell Internationale Research Maatschappij B.V. | Composition d'huile de graissage |
| WO2009134716A1 (fr) | 2008-04-28 | 2009-11-05 | Dow Global Technologies Inc. | Composition de lubrifiant à base de polyalkylèneglycol |
| US8357644B2 (en) | 2008-04-28 | 2013-01-22 | Dow Global Technologies Llc | Polyalkylene glycol lubricant composition |
| US8592357B2 (en) | 2008-04-28 | 2013-11-26 | Dow Global Technologies Llc | Polyalkylene glycol lubricant composition |
| WO2012129056A1 (fr) * | 2011-03-23 | 2012-09-27 | Dow Global Technologies Llc | Fluides de transfert de chaleur à base de polyalkylène glycol et huiles de moteur monofluides |
| CN103525531A (zh) * | 2013-09-27 | 2014-01-22 | 奥克化学扬州有限公司 | 一种用于蓝宝石晶体掏棒的冷却液 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2792326B1 (fr) | 2007-08-24 |
| DE60038759D1 (de) | 2008-06-19 |
| FR2792326A1 (fr) | 2000-10-20 |
| EP1046699B1 (fr) | 2008-05-07 |
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