EP1621601A1 - Process for producing a lubricating grease from a vegetable oil and grease obtained - Google Patents

Process for producing a lubricating grease from a vegetable oil and grease obtained Download PDF

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Publication number
EP1621601A1
EP1621601A1 EP05300622A EP05300622A EP1621601A1 EP 1621601 A1 EP1621601 A1 EP 1621601A1 EP 05300622 A EP05300622 A EP 05300622A EP 05300622 A EP05300622 A EP 05300622A EP 1621601 A1 EP1621601 A1 EP 1621601A1
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EP
European Patent Office
Prior art keywords
oil
lubricating grease
acid
manufacturing
grease according
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.)
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Application number
EP05300622A
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German (de)
French (fr)
Inventor
Hervé Grignou
Lê Chiên Hoang
Lydia Moigner
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Christol Grease
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Christol Grease
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Publication of EP1621601A1 publication Critical patent/EP1621601A1/en
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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
    • C10M121/00—Lubricating compositions characterised by the thickener being a compound of unknown or incompletely defined constitution
    • C10M121/04—Reaction products
    • 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
    • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
    • C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
    • C10M117/04—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen containing hydroxy groups
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2205/003—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/24—Epoxidised acids; Ester derivatives thereof
    • C10M2207/246—Epoxidised acids; Ester derivatives thereof used as thickening agents
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2020/065—Saturated 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
    • C10N2020/067—Unsaturated 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
    • C10N2020/081—Biodegradable 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
    • C10N2030/64—Environmental friendly compositions
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the present invention relates to a method of manufacturing a lubricating grease from oil, especially from sunflower oil.
  • the invention also covers the fat obtained.
  • Industrial lubricating greases are currently obtained from 12-hydroxystearic acid by a saponification reaction in the presence of an alkali metal hydroxide selected from lithium, calcium or aluminum, to name but a few.
  • 12-hydroxystearic acid obtained from castor oil, is its high number of carbons in its hydrocarbon chain and the presence of a hydroxyl group on the carbon 12 of the hydrocarbon chain, which leads to additional interactions by hydrogen bonds, at the level of soap fibers obtained which cause the formation of a gel.
  • vegetable oil is intended to mean any extract of oleaginous plant seeds, derivatives such as fatty acids, fatty acid esters, whatever the viscosity, the purity and the chemical composition.
  • the object of the present invention is to find another vegetable oil and a method for obtaining a fat from this new vegetable oil, capable of substituting for acids 12 derived from castor oil.
  • sunflower oil there is a variety called "sunflower classic” whose seeds provide an oil rich in linoleic acid (C18: 2). This variety is widely spread.
  • Oleic sunflower varieties now exist on the market whose seeds contain an oil rich in oleic acid 75% to 90% oleic acid (C18: 1).
  • Oleic acid is a fatty acid of 18 carbon atoms with a double bond in the 9-position.
  • oleic sunflower oil available from large oil suppliers having an oleic acid content of 75 to 85%.
  • the first step is the transformation of the sunflower oil to obtain an intermediate product capable of being associated with an oil-based matrix in order to obtain a fat having satisfactory properties, by the saponification reaction in the presence of a neutralizing base. .
  • the present invention provides for producing an intermediate product by subjecting the retained vegetable oil to an epoxidation reaction.
  • the two vegetable oils used have, before epoxidation, the following fatty acid compositions: Fatty acids Oleic sunflower oil Classic Sunflower Oil Oleic acid 79.16% 27.77% Linoleic acid 11.41% 60.14% Other * 9.43% 12.09% other fatty acids are for example: palmitic acid, stearic acid, linolenic acid, arachidic acid, acosenoic acid or behenic acid.
  • a first means for epoxidation is to use a peracid such as performic or peracetic acid, obtained from the corresponding acid, treated with hydrogen peroxide.
  • the four intermediate compounds according to the invention show that the epoxidized fatty acids of conventional sunflower oil C and the epoxidized fatty acids of oleic sunflower oil D have parameters close to those of 12-hydroxystearic acid. whose acid, saponification and iodine values are respectively 175 mg of KOH / g, 180 to 190 mg of KOH / g and 5 g of I 2 / 100g
  • the four intermediate compounds according to the invention are tested for the manufacture of a fat by a saponification reaction according to a given manufacturing process.
  • This process consists in using a matrix composed of oil of petroleum, vegetable or synthetic origin.
  • the example used requires about 90% for the matrix, 8% of one of the four intermediate products according to the invention A, B, C or D and 2% of a neutralizing base chosen from hydroxides. calcium or sodium, but in this case it is chosen lithium hydroxide LiOH about 2%.
  • a fat is produced under the same conditions with 12-hydroxystearic acid as intermediate product.
  • Part of the matrix is introduced into a cooker and then is added the amount of intermediate compound A, B, C or D according to the invention or the amount of control 12 hydroxystearic acid, with stirring with appropriate temperature rise.
  • the neutralizing base is introduced into the mixture so as to form a soap.
  • the reaction with acid 12 is as follows: CH 3 - (CH 2 ) 5 -CHOH- (CH 2 ) 10 -COOH + LiOH ⁇ CH 3 - (CH 2 ) 5 -CHOH- (CH 2 ) 10 -COOLi + H 2 O
  • the soap has a creamy and smooth texture with a drop point greater than 190 ° C.
  • the penetration measurements are of the order of 280 tenths of a millimeter.
  • the saponification reaction does not seem to occur and especially the resulting mixture has crystals that makes it unusable industrially as a lubricant.
  • the measured drop points of the order of 210 ° C are higher than that of the control fat.
  • compound B makes it possible to reach stable penetration measurements of the order of 280 tenths of millimeters. Static test behavior is therefore better.
  • This compound B oleic sunflower oil epoxidized, can be used as an intermediate product to allow the formation of a fat since the qualities of the fat obtained are greater than that of the control fat.
  • sunflower oil can be replaced by oil from other oleaginous varieties such as rapeseed or soy or a combination thereof .
  • the fats obtained by saponification of a matrix in the presence of a neutralizing base and of an intermediate compound obtained by hydroxylation of soybean oil makes it possible to achieve results comparable to those obtained with sunflower oil.

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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)
  • Fats And Perfumes (AREA)

Abstract

Producing a lubricating grease comprises epoxidizing a vegetable oil, adding the epoxidized vegetable oil to a mineral, vegetable or synthetic oil, mixing and heating while adding a neutralizing base, and cooling the mixture when saponification is complete. An independent claim is also included for lubricating grease produced as above, with a dropping point of about 210[deg]C and a penetration of about 280 tenths of a millimeter.

Description

La présente invention concerne un procédé de fabrication d'une graisse lubrifiante à partir d'huile, notamment à partir d'huile de tournesol.The present invention relates to a method of manufacturing a lubricating grease from oil, especially from sunflower oil.

L'invention couvre aussi la graisse obtenue.The invention also covers the fat obtained.

Les graisses lubrifiantes industrielles sont actuellement obtenues à partir d'acide 12-hydroxystéarique par une réaction de saponification en présence d'un hydroxyde de métal alcalin, choisi parmi le lithium, le calcium ou l'aluminium pour ne citer que ceux-là.Industrial lubricating greases are currently obtained from 12-hydroxystearic acid by a saponification reaction in the presence of an alkali metal hydroxide selected from lithium, calcium or aluminum, to name but a few.

L'acide 12-hydroxystéarique est obtenu à partir d'huile de ricin par un procédé complexe avec trois étapes :

  • hydrogénation totale de l'huile de ricin,
  • transformation de l'huile hydrogénée en savon par la soude, et
  • transformation du savon sodique en acide 12-hydroxystéarique par l'acide chlorhydrique.
12-hydroxystearic acid is obtained from castor oil by a complex process with three steps:
  • total hydrogenation of castor oil,
  • conversion of the hydrogenated oil to soap with sodium hydroxide, and
  • conversion of sodium soap to 12-hydroxystearic acid by hydrochloric acid.

Les approvisionnements de l'acide 12-hydroxystéarique, obtenu à partir de l'huile de ricin, sont liés à des productions dans des pays étrangers lointains avec les aléas de prix, de délai, de quantité. De plus, il faut tenir compte des paramètres de production liés aux conditions météorologiques qui conduisent à des quantités et à des qualités variables. De plus, un industriel se doit de disposer d'une diversification des sources d'approvisionnement.The supplies of 12-hydroxystearic acid, obtained from castor oil, are related to production in distant foreign countries with the vagaries of price, time, quantity. In addition, meteorological production parameters that lead to variable quantities and qualities must be taken into account. In addition, an industrialist must have a diversification of sources of supply.

La particularité de l'acide 12-hydroxystéarique, obtenu à partir de l'huile de ricin, est son nombre élevé de carbones dans sa chaîne hydrocarbonée et la présence d'un groupement hydroxyle sur le carbone 12 de la chaîne hydrocarbonée, qui conduit à des interactions supplémentaires par des liaisons hydrogènes, au niveau des fibres de savon obtenues qui provoquent la formation d'un gel.The particularity of 12-hydroxystearic acid, obtained from castor oil, is its high number of carbons in its hydrocarbon chain and the presence of a hydroxyl group on the carbon 12 of the hydrocarbon chain, which leads to additional interactions by hydrogen bonds, at the level of soap fibers obtained which cause the formation of a gel.

On entend pour la suite de la description par "huile végétale" tout extrait de graines de plantes oléagineuses, les dérivés tels que les acides gras, les esters d'acide gras, quelles que soient la viscosité, la pureté et la composition chimique.For the rest of the description, the term "vegetable oil" is intended to mean any extract of oleaginous plant seeds, derivatives such as fatty acids, fatty acid esters, whatever the viscosity, the purity and the chemical composition.

Le but de la présente invention est de trouver une autre huile végétale et un procédé permettant d'obtenir une graisse à partir de cette nouvelle huile végétale, apte à se substituer aux acides 12 issus de l'huile de ricin.The object of the present invention is to find another vegetable oil and a method for obtaining a fat from this new vegetable oil, capable of substituting for acids 12 derived from castor oil.

L'approvisionnement de cette nouvelle matière grasse doit permettre un approvisionnement stable, indépendant des conditions météorologiques, contrairement à l'approvisionnement en huile de ricin.The supply of this new fat must allow a stable supply, independent of weather conditions, contrary to the supply of castor oil.

Les prix doivent aussi être plus stables.Prices must also be more stable.

La description qui va suivre explicite un exemple particulier, non limitatif, recourant à de l'huile de tournesol. En effet, il existe une variété dite "tournesol classique" dont les graines fournissent une huile riche en acide linoléique (C18:2). Cette variété est fortement répandue.The description which follows explains a particular, non-limiting example, using sunflower oil. Indeed, there is a variety called "sunflower classic" whose seeds provide an oil rich in linoleic acid (C18: 2). This variety is widely spread.

Des variétés de tournesols dites oléiques existent maintenant sur le marché dont les graines contiennent une huile riche en acide oléique 75% à 90% d'acide oléique (C18:1). L'acide oléique est un acide gras de 18 atomes de carbone avec une double liaison en position 9.So-called oleic sunflower varieties now exist on the market whose seeds contain an oil rich in oleic acid 75% to 90% oleic acid (C18: 1). Oleic acid is a fatty acid of 18 carbon atoms with a double bond in the 9-position.

Dans le cadre de la présente invention, sans aucun caractère limitatif, il est utilisé une huile de tournesol oléique disponible auprès des grands fournisseurs d'huile ayant une teneur en acide oléique de 75 à 85%.In the context of the present invention, without any limiting character, it is used an oleic sunflower oil available from large oil suppliers having an oleic acid content of 75 to 85%.

Le procédé d'obtention d'une graisse lubrifiante selon la présente invention est maintenant décrit en détail et les tableaux intégrés regroupent les différents résultats obtenus au cours de ce procédé.The process for obtaining a lubricating grease according to the present invention is now described in detail and the integrated tables group together the different results obtained during this process.

La première étape est la transformation de l'huile de tournesol pour obtenir un produit intermédiaire apte à être associé à une matrice à base d'huile pour obtenir une graisse ayant des propriétés satisfaisantes, ceci par réaction de saponification en présence d'une base neutralisante.The first step is the transformation of the sunflower oil to obtain an intermediate product capable of being associated with an oil-based matrix in order to obtain a fat having satisfactory properties, by the saponification reaction in the presence of a neutralizing base. .

La présente invention prévoit de réaliser un produit intermédiaire en faisant subir à l'huile végétale retenue une réaction d'époxydation.The present invention provides for producing an intermediate product by subjecting the retained vegetable oil to an epoxidation reaction.

Les deux huiles végétales utilisées ont, avant époxydation, les compositions en acides gras suivantes : Acides gras Huile Tournesol oléique Huile Tournesol classique Acide oléique 79,16 % 27,77 % Acide linoléique 11,41 % 60,14 % Autres * 9,43 % 12,09 % * on entend par autres acides gras par exemple : acide palmitique, stéarique, linolénique, arachidique, acosénoïque ou béhénique. The two vegetable oils used have, before epoxidation, the following fatty acid compositions: Fatty acids Oleic sunflower oil Classic Sunflower Oil Oleic acid 79.16% 27.77% Linoleic acid 11.41% 60.14% Other * 9.43% 12.09% other fatty acids are for example: palmitic acid, stearic acid, linolenic acid, arachidic acid, acosenoic acid or behenic acid.

Un premier moyen pour l'époxydation est de recourir à un peracide tel que l'acide performique ou peracétique, obtenu à partir de l'acide correspondant, traité au peroxyde d' hydrogène.A first means for epoxidation is to use a peracid such as performic or peracetic acid, obtained from the corresponding acid, treated with hydrogen peroxide.

Cette réaction d'époxydation de l'huile, en présence de peracide formique fabriqué in situ, consiste en la succession des étapes suivantes :

  • chauffage de cette huile de tournesol à une température comprise entre 45 et 65°C,
  • ajout de 1 à 10% en poids d'acide formique de très grande pureté tout en homogénéisant sous agitation le mélange,
  • addition progressive de l'agent peroxydant, dans le mode préféré de réalisation, l'eau oxygénée avec une concentration en peroxyde d'hydrogène situé entre 30 et 70% ; la température est maintenue à 70°C environ,
  • maintien sous agitation jusqu'à époxydation complète,
  • refroidissement, décantation des phases organique et huileuse, neutralisation, lavage et séchage de la phase huileuse constituée de l'huile de tournesol oléique époxydée,
ceci avec un rapport molaire constant de H2O2/C=C compris entre 0,2 et 4, c'est-à-dire en faisant varier la quantité de peroxyde d'hydrogène en fonction du taux d'époxydation désiré.This epoxidation reaction of the oil, in the presence of formic peracid produced in situ, consists of the following succession of steps:
  • heating this sunflower oil to a temperature between 45 and 65 ° C,
  • addition of 1 to 10% by weight of formic acid of very high purity while homogenizing with stirring the mixture,
  • progressive addition of the peroxidizing agent, in the preferred embodiment, oxygenated water with a hydrogen peroxide concentration of between 30 and 70%; the temperature is maintained at about 70 ° C.
  • keeping stirring until complete epoxidation,
  • cooling, decantation of the organic and oily phases, neutralization, washing and drying of the oily phase consisting of epoxidized oleic sunflower oil,
this with a constant molar ratio of H 2 O 2 / C = C between 0.2 and 4, that is to say by varying the amount of hydrogen peroxide depending on the desired epoxidation rate.

Le taux d'époxydation varie ainsi de façon sensiblement proportionnelle à celui du rapport H2O2/C=C 0,2 à 4 correspondant à une variation de 20 à 100% du taux d'époxydation.The epoxidation rate thus varies substantially proportionally to that of the ratio H 2 O 2 / C = C 0.2 to 4 corresponding to a variation of 20 to 100% of the epoxidation rate.

Pour réaliser les essais comparatifs qui vont suivre, on reproduit cette réaction d'époxydation sur de l'huile de tournesol classique, sur de l'huile de tournesol oléique et sur les acides gras de ces deux huiles, classique et oléique, pour obtenir quatre composés selon l'invention :

  • A. huile de tournesol classique époxydée,
  • B. huile de tournesol oléique époxydée,
  • C. acides gras époxydés de l'huile de tournesol classique,
  • D. acides gras époxydés de l'huile de tournesol oléique.
To carry out the comparative tests which follow, this epoxidation reaction is reproduced on conventional sunflower oil, on oleic sunflower oil and on the fatty acids of these two oils, conventional and oleic, to obtain four compounds according to the invention:
  • A. Epoxidized Classic Sunflower Oil,
  • B. epoxidized oleic sunflower oil,
  • C. epoxidized fatty acids of conventional sunflower oil,
  • D. epoxidized fatty acids of oleic sunflower oil.

On obtient les caractéristiques suivantes pour ces composés intermédiaires : Paramètres A B C D Indice d'acide (mg KOH/g) 0,5 0,5 145 154 Indice saponification (mg KOH/g) 180 185 205 203 Indice d'iode (g I2/100g) 3,2 1,0 2,6 3,6 The following characteristics are obtained for these intermediate compounds: Settings AT B VS D Acid number (mg KOH / g) 0.5 0.5 145 154 Saponification index (mg KOH / g) 180 185 205 203 Iodine number (g I 2 / 100g) 3.2 1.0 2.6 3.6

Les quatre composés intermédiaires selon l'invention ainsi obtenus montrent que les acides gras époxydés de l'huile de tournesol classique C et les acides gras époxydés de l'huile de tournesol oléique D ont des paramètres proches de ceux de l'acide 12-hydroxystéarique dont les indices d'acide, de saponification et d'iode sont respectivement de 175 mg de KOH/g, de 180 à 190 mg de KOH/g et de 5 g d'I2/100gThe four intermediate compounds according to the invention thus obtained show that the epoxidized fatty acids of conventional sunflower oil C and the epoxidized fatty acids of oleic sunflower oil D have parameters close to those of 12-hydroxystearic acid. whose acid, saponification and iodine values are respectively 175 mg of KOH / g, 180 to 190 mg of KOH / g and 5 g of I 2 / 100g

Les quatre composés intermédiaires selon l'invention sont testés pour la fabrication d'une graisse par une réaction de saponification suivant un procédé de fabrication donné.The four intermediate compounds according to the invention are tested for the manufacture of a fat by a saponification reaction according to a given manufacturing process.

Ce procédé consiste à utiliser une matrice composée d'huile d'origine pétrolière, végétale ou de synthèse. Dans le cas présent, l'exemple retenu requiert 90% environ pour la matrice, 8% de l'un des quatre produits intermédiaires selon l'invention A, B, C ou D et 2% d'une base neutralisante choisie parmi les hydroxydes de calcium ou de sodium, mais en l'occurrence il est choisi l'hydroxyde de lithium LiOH pour 2% environ.This process consists in using a matrix composed of oil of petroleum, vegetable or synthetic origin. In the present case, the example used requires about 90% for the matrix, 8% of one of the four intermediate products according to the invention A, B, C or D and 2% of a neutralizing base chosen from hydroxides. calcium or sodium, but in this case it is chosen lithium hydroxide LiOH about 2%.

En témoin, une graisse est réalisée dans les mêmes conditions avec l'acide 12-hydroxystéarique comme produit intermédiaire.As a control, a fat is produced under the same conditions with 12-hydroxystearic acid as intermediate product.

Une partie de la matrice est introduite dans un cuiseur puis est ajoutée la quantité du composé intermédiaire A, B, C ou D selon l'invention ou la quantité d'acide 12 hydroxystéarique témoin, sous agitation avec montée en température adaptée.Part of the matrix is introduced into a cooker and then is added the amount of intermediate compound A, B, C or D according to the invention or the amount of control 12 hydroxystearic acid, with stirring with appropriate temperature rise.

Enfin, la base neutralisante est introduite dans le mélange en sorte de former un savon.Finally, the neutralizing base is introduced into the mixture so as to form a soap.

La réaction avec l'acide 12 est la suivante :

         CH3-(CH2)5-CHOH-(CH2)10-COOH + LiOH → CH3-(CH2)5-CHOH-(CH2)10-COOLi + H2O
The reaction with acid 12 is as follows:

CH 3 - (CH 2 ) 5 -CHOH- (CH 2 ) 10 -COOH + LiOH → CH 3 - (CH 2 ) 5 -CHOH- (CH 2 ) 10 -COOLi + H 2 O

Il se produit la formation d'un savon et d'eau.There is a formation of soap and water.

Le savon est de texture onctueuse et lisse avec un point de goutte supérieur à 190°C.The soap has a creamy and smooth texture with a drop point greater than 190 ° C.

Les mesures de pénétration sont de l'ordre de 280 dixièmes de millimètres.The penetration measurements are of the order of 280 tenths of a millimeter.

La réaction avec l'huile végétale époxydée est la suivante :

Figure imgb0001
The reaction with the epoxidized vegetable oil is as follows:
Figure imgb0001

Il se produit la formation d'un savon et du glycérol qui subsiste dans le savon. La réaction provoque l'ouverture des ponts époxydes en formant des groupements hydroxyles.There is the formation of a soap and glycerol which remains in the soap. The reaction causes the opening of the epoxide bridges forming hydroxyl groups.

On constate que cette réaction de saponification menée avec les produits :

  • C/ acides gras époxydés de l'huile de tournesol classique, ou
  • D/ acides gras époxydés de l'huile de tournesol oléique,
forme des cristaux.It is found that this saponification reaction carried out with the products:
  • C / epoxidized fatty acids of conventional sunflower oil, or
  • D / epoxidized fatty acids of oleic sunflower oil,
form crystals.

Il apparaît même que la formation d'un savon n'a pas lieu.It even appears that the formation of a soap does not take place.

La réaction de saponification ne semble pas se produire et surtout le mélange obtenu comporte des cristaux qui le rende inexploitable industriellement à titre de lubrifiant.The saponification reaction does not seem to occur and especially the resulting mixture has crystals that makes it unusable industrially as a lubricant.

L'accent doit être porté sur les composés issus des deux produits selon l'invention, sélectionnés, à savoir :

  • A/ huile de tournesol classique époxydée, et
  • B/ huile de tournesol oléique époxydée.
The focus must be on the compounds from the two products according to the invention, selected, namely:
  • A / epoxidized conventional sunflower oil, and
  • B / Epoxidized Oleic Sunflower Oil.

Ces deux composés conduisent à l'obtention de savons ayant une texture adaptée, lisse et onctueuse, très semblable à celle du savon obtenu avec le témoin.These two compounds lead to obtaining soaps having a suitable texture, smooth and unctuous, very similar to that of the soap obtained with the control.

Il ne se produit pas de formation de cristaux.There is no formation of crystals.

Les points de goutte mesurés de l'ordre de 210°C sont supérieurs à celui de la graisse témoin.The measured drop points of the order of 210 ° C are higher than that of the control fat.

Quant aux mesures de pénétration, elles sont moins bonnes pour le composé A que celles obtenues avec le témoin puisqu'elles sont de l'ordre de 340 dixièmes de millimètres.As for the penetration measurements, they are less good for compound A than those obtained with the control since they are of the order of 340 tenths of millimeters.

Par contre, le composé B permet d'atteindre des mesures de pénétration stables de l'ordre de 280 dixièmes de millimètres. Le comportement aux tests statiques est donc meilleur.On the other hand, compound B makes it possible to reach stable penetration measurements of the order of 280 tenths of millimeters. Static test behavior is therefore better.

Ce composé B, l'huile de tournesol oléique époxydé, peut être utilisé comme produit intermédiaire pour permettre la formation d'une graisse puisque les qualités de la graisse obtenue sont supérieures à celle de la graisse témoin.This compound B , oleic sunflower oil epoxidized, can be used as an intermediate product to allow the formation of a fat since the qualities of the fat obtained are greater than that of the control fat.

Afin d'améliorer la qualité des tests dynamiques, il est possible d'agir sur la structure de la graisse issue de l'huile de tournesol oléique époxydée à travers les paramètres du procédé de fabrication.In order to improve the quality of the dynamic tests, it is possible to act on the structure of the grease resulting from the oleic sunflower oil epoxidized through the parameters of the manufacturing process.

On constate qu'il est possible de réaliser une graisse à partir d'huile de tournesol époxydée et plus particulièrement une graisse optimisée à partir d'huile de tournesol oléique époxydée.It is found that it is possible to produce a fat from epoxidized sunflower oil and more particularly an optimized fat from epoxidized oleic sunflower oil.

Les essais ont été conduits à partir d'un exemple particulier non limitatif mais l'huile de tournesol peut être remplacée par de l'huile issue d'autres variétés oléagineuses telles que le colza ou le soja ou d'une combinaison de celles-ci.The tests were conducted from a particular nonlimiting example but the sunflower oil can be replaced by oil from other oleaginous varieties such as rapeseed or soy or a combination thereof .

En effet, les graisses obtenues par saponification d'une matrice en présence d'une base neutralisante et d'un composé intermédiaire obtenu par hydroxylation d'huile de soja permet d'atteindre des résultats comparables à ceux obtenus avec l'huile de tournesol.In fact, the fats obtained by saponification of a matrix in the presence of a neutralizing base and of an intermediate compound obtained by hydroxylation of soybean oil makes it possible to achieve results comparable to those obtained with sunflower oil.

Ainsi les problèmes d'approvisionnement, de qualité variable, de quantités tributaires des climats, les problèmes de fluctuation de prix sont résolus.Thus the problems of supply, of variable quality, of quantities dependent on climates, the problems of fluctuation of prices are solved.

Claims (10)

Procédé de fabrication d'une graisse lubrifiante, caractérisé en ce qu'il comprend les étapes suivantes : - phase d'époxydation d'une huile végétale, - ajout d'un volume de cette huile végétale époxydée à une matrice à base d'huile d'origine pétrolière, végétale ou de synthèse, - mélange et mise en température avec ajout d'une base neutralisante, et - refroidissement après réaction complète de saponification. A method of manufacturing a lubricating grease, characterized in that it comprises the following steps: epoxidation phase of a vegetable oil, adding a volume of this epoxidized vegetable oil to a matrix based on oil of petroleum, vegetable or synthetic origin, - mixing and heating with the addition of a neutralizing base, and - cooling after complete saponification reaction. Procédé de fabrication d'une graisse lubrifiante selon la revendication 1, caractérisé en ce que l'huile est issue de tournesol.A method of manufacturing a lubricating grease according to claim 1, characterized in that the oil is derived from sunflower. Procédé de fabrication d'une graisse lubrifiante selon la revendication 1 ou 2, caractérisé en ce que l' huile est issue de tournesol oléique.Process for producing a lubricating grease according to claim 1 or 2, characterized in that the oil is derived from oleic sunflower. Procédé de fabrication d'une graisse lubrifiante selon la revendication 3, caractérisé en ce que l'huile est issue de tournesol oléique comprenant au moins 75 à 85% d'acide oléique.Process for producing a lubricating grease according to Claim 3, characterized in that the oil is derived from oleic sunflower comprising at least 75 to 85% oleic acid. Procédé de fabrication d'une graisse lubrifiante selon la revendication 1, caractérisé en ce que l'huile est issue de soja.Process for producing a lubricating grease according to Claim 1, characterized in that the oil is derived from soya beans. Procédé de fabrication d'une graisse lubrifiante selon l'une quelconque des revendications précédentes, caractérisé en ce que la base neutralisante est un hydroxyde d'alcalin.A method of manufacturing a lubricating grease according to any one of the preceding claims, characterized in that the neutralizing base is an alkaline hydroxide. Procédé de fabrication d'une graisse lubrifiante selon la revendication 6, caractérisé en ce que l'hydroxyde d'alcalin est l'hydroxyde de lithium.A method of manufacturing a lubricating grease according to claim 6, characterized in that the alkali hydroxide is lithium hydroxide. Procédé de fabrication d'une graisse lubrifiante selon l'une quelconque des revendications précédentes, caractérisé en ce que la phase d' époxydation de l'huile végétale comprend les étapes suivantes : - chauffage de cette huile à une température comprise entre 45 et 65°C, - ajout de 1 à 10% en poids d'un acide tout en homogénéisant sous agitation le mélange, - addition progressive d'un agent peroxydant, - maintien sous agitation jusqu'à époxydation complète, - refroidissement, décantation des phases organique et huileuse, neutralisation, lavage et séchage de la phase huileuse. Process for manufacturing a lubricating grease according to any one of the preceding claims, characterized in that the epoxidation phase of the vegetable oil comprises the following steps: heating this oil to a temperature of between 45 and 65.degree. adding 1 to 10% by weight of an acid while homogenizing the mixture with stirring, progressive addition of a peroxidizing agent, - keeping stirring until complete epoxidation, - cooling, decantation of the organic and oily phases, neutralization, washing and drying of the oily phase. Procédé de fabrication d'une graisse lubrifiante selon la revendication 8, caractérisé en ce que l'acide ajouté est de l'acide formique.A method of manufacturing a lubricating grease according to claim 8, characterized in that the added acid is formic acid. Graisse lubrifiante obtenue par mise en oeuvre du procédé selon l'une quelconque des revendications 1 à 4 et 7, caractérisée en ce qu'elle présente les propriétés suivantes : - point de goutte de 210°C environ, et - mesures de pénétration de l'ordre de 280 dixièmes de millimètres. Lubricating grease obtained by carrying out the process according to any one of Claims 1 to 4 and 7, characterized in that it has the following properties: - drop point of about 210 ° C, and - penetration measurements of the order of 280 tenths of a millimeter.
EP05300622A 2004-07-30 2005-07-26 Process for producing a lubricating grease from a vegetable oil and grease obtained Withdrawn EP1621601A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009149902A1 (en) * 2008-06-13 2009-12-17 KLüBER LUBRICATION MüNCHEN KG Lubricant composition based on natural and renewable raw materials
CN103288627A (en) * 2013-05-22 2013-09-11 山东天兴生物科技有限公司 Method for preparing 12-hydroxy stearic acid through utilizing hydrogenerated castor oil as raw material
DE102015210097B3 (en) * 2015-06-01 2016-09-08 Ahmad Azhdari Process for the preparation of a lubricant, lubricant and use of a lubricant

Citations (4)

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Publication number Priority date Publication date Assignee Title
US3009878A (en) * 1954-07-12 1961-11-21 Texaco Inc Lubricating greases prepared from epoxy fatty acid materials
GB987573A (en) * 1960-07-01 1965-03-31 Otto Hoesch Strengthened lithium greases
DE4436760A1 (en) * 1994-10-14 1996-04-18 Henkel Kgaa Process for the preparation of organic compounds containing epoxy groups
EP0806470A2 (en) * 1996-05-08 1997-11-12 The Lubrizol Corporation A biodegradable vegetable oil grease

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009878A (en) * 1954-07-12 1961-11-21 Texaco Inc Lubricating greases prepared from epoxy fatty acid materials
GB987573A (en) * 1960-07-01 1965-03-31 Otto Hoesch Strengthened lithium greases
DE4436760A1 (en) * 1994-10-14 1996-04-18 Henkel Kgaa Process for the preparation of organic compounds containing epoxy groups
EP0806470A2 (en) * 1996-05-08 1997-11-12 The Lubrizol Corporation A biodegradable vegetable oil grease

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009149902A1 (en) * 2008-06-13 2009-12-17 KLüBER LUBRICATION MüNCHEN KG Lubricant composition based on natural and renewable raw materials
CN102066536B (en) * 2008-06-13 2013-07-24 慕尼黑克吕伯尔润滑器两合公司 Lubricant composition based on natural and renewable raw materials
CN103288627A (en) * 2013-05-22 2013-09-11 山东天兴生物科技有限公司 Method for preparing 12-hydroxy stearic acid through utilizing hydrogenerated castor oil as raw material
DE102015210097B3 (en) * 2015-06-01 2016-09-08 Ahmad Azhdari Process for the preparation of a lubricant, lubricant and use of a lubricant

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FR2873712B1 (en) 2006-11-24

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