FR2753986A1 - HYPERCOMPRESSOR LUBRICANT AND PROCESS FOR OBTAINING THE SAME - Google Patents

HYPERCOMPRESSOR LUBRICANT AND PROCESS FOR OBTAINING THE SAME Download PDF

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Publication number
FR2753986A1
FR2753986A1 FR9611892A FR9611892A FR2753986A1 FR 2753986 A1 FR2753986 A1 FR 2753986A1 FR 9611892 A FR9611892 A FR 9611892A FR 9611892 A FR9611892 A FR 9611892A FR 2753986 A1 FR2753986 A1 FR 2753986A1
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Prior art keywords
sep
lubricating oil
oil according
polymers
oils
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FR9611892A
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French (fr)
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FR2753986B1 (en
Inventor
Raymond Barbarin
Jean Marie Thiebaux
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Elf Antar France
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Elf Antar France
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Priority to FR9611892A priority Critical patent/FR2753986B1/en
Application filed by Elf Antar France filed Critical Elf Antar France
Priority to KR1019990702702A priority patent/KR20000048728A/en
Priority to AU44650/97A priority patent/AU4465097A/en
Priority to BR9711578A priority patent/BR9711578A/en
Priority to CA002267098A priority patent/CA2267098A1/en
Priority to JP10516281A priority patent/JP2001501660A/en
Priority to ZA9708699A priority patent/ZA978699B/en
Priority to PCT/FR1997/001716 priority patent/WO1998014537A1/en
Priority to ARP970104490A priority patent/AR009102A1/en
Publication of FR2753986A1 publication Critical patent/FR2753986A1/en
Application granted granted Critical
Publication of FR2753986B1 publication Critical patent/FR2753986B1/en
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular 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
    • C10M145/12Macromolecular 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 monocarboxylic
    • C10M145/14Acrylate; Methacrylate
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    • C10M101/00Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02Petroleum fractions
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    • C10M101/04Fatty oil fractions
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    • C10M143/00Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
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    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/06Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/041Mixtures of base-materials and additives the additives being macromolecular compounds only
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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)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention concerns a lubricating oil for superchargers containing at least one lubricating base characterised in that it contains 0.3 to 30 wt. % of at least one polymer of the group consisting of polyolefines obtained from ethylene and propylene, and the copolymers of these olefins, said polymer being in the form of powder, granules or microsized particles in solid state dispersed in said base at room temperature.

Description

La présente invention concerne une huile lubrifiante pour hypercompresseur d'oléfine, et son procédé d'obtention, cette huile lubrifiante étant particulièrement adaptée à la fabrication de polyéthylène basse densité homopolymères et copolymères. The present invention relates to a lubricating oil for olefin hypercompressor, and to its method of production, this lubricating oil being particularly suitable for the manufacture of low-density polyethylene homopolymers and copolymers.

Les hypercompresseurs utilisés dans la fabrication des polyéthylènes basse densité sont constitués d'un piston (plongeur) dans une chemise, une lubrification étant nécessaire au contact de ces deux éléments pour éviter le grippage. Dans ces hypercompresseurs, on compresse l'éthylène ou un mélange d'éthylène avec une autre monomère pour former de nombreux copolymères, et cela à une pression supérieure à 100 bars. Le lubrifiant, injecté à graissage perdu entre en contact avec le monomère ou les monomères et, par conséquent, avec le polymère en formation. Or, le ou les monomères présents peuvent avoir une action délavante vis-à vis de l'huile lubrifiante dans le cylindre de l'hypercompresseur. Un tel délavage en supprimant le film lubrifiant conduit au grippage du contact chemise/piston. The hypercompressors used in the manufacture of low density polyethylenes consist of a piston (plunger) in a jacket, lubrication being necessary in contact with these two elements to prevent galling. In these hypercompressors, ethylene or a mixture of ethylene with another monomer is compressed to form many copolymers, and this at a pressure greater than 100 bar. The lubricant injected with lost lubricant comes into contact with the monomer or monomers and, therefore, with the forming polymer. However, the monomer or monomers present may have a defatting action with respect to the lubricating oil in the cylinder of the hypercompressor. Such washing by removing the lubricant film leads to seizing the contact shirt / piston.

Pour compenser cet effet, le lubrifiant utilisé doit pouvoir résister au lavage par le ou les monomères. Ainsi, on préfère utiliser un lubrifiant très peu soluble dans le ou les monomère(s) et efficace vis-à-vis de la lubrification du contact chemise/piston.To compensate for this effect, the lubricant used must be resistant to washing with the monomer or monomers. Thus, it is preferred to use a lubricant which is very slightly soluble in the monomer (s) and effective with respect to the lubrication of the liner / piston contact.

Parmi les lubrifiants connus pour les hypercompresseurs utilisés pour la fabrication de polyéthylène, les huiles synthétiques sont généralement préférées. D'une part, il est connu de prendre des huiles synthétiques telles que les polyglycols purs non additivés ou encore les huiles blanches dites codex, épaissies par des polybutènes. Les polyglycols présentent l'avantage d'avoir une faible solubilité dans l'éthylène procurant ainsi une durée de vie cylindre/piston importante. Cependant ils présentent des inconvénients liés à leurs caractéristiques physicochimiques : problème d'odeur du produit fini, collage des films de polyéthylène (blocking), diminution des propriétés diélectriques du polyéthylène (gêne pour leur utilisation dans les câbles électriques notamment) et enfin leur coût généralement supérieur aux huiles minérales. Among the lubricants known for the hypercompressors used for the manufacture of polyethylene, synthetic oils are generally preferred. On the one hand, it is known to take synthetic oils such as pure polyglycols not additives or white oils called codex, thickened by polybutenes. Polyglycols have the advantage of having a low solubility in ethylene thus providing a significant cylinder / piston life. However, they have drawbacks related to their physicochemical characteristics: odor problem of the finished product, bonding of the polyethylene films (blocking), reduction of the dielectric properties of the polyethylene (discomfort for their use in electric cables in particular) and finally their cost generally. superior to mineral oils.

La présente invention vise donc à résoudre ces inconvénients, notamment à limiter le coût de la lubrification, à supprimer l'odeur et surtout à limiter la formation de film d'huile en surface des sacs de polyéthylène, à garder de bonnes propriétés diélectriques au produit fini tout en maintenant une durée de vie chemise piston importante. The present invention therefore aims to overcome these disadvantages, in particular to limit the cost of lubrication, to eliminate the odor and especially to limit the formation of oil film on the surface of the polyethylene bags, to keep good dielectric properties to the product finished while maintaining a significant piston shirt life.

La présente invention a donc pour objet une huile lubrifiante pour hypercompresseur contenant au moins une base lubrifiante caractérisée en ce qu'elle contient de 0,3 à 30 W en poids d'au moins un polymère du groupe constitué par les polyoléfines obtenues à partir d'éthylène, de propylène et des copolymères de ces oléfines. The subject of the present invention is therefore a lubricating oil for a hyper-compressor containing at least one lubricating base, characterized in that it contains from 0.3 to 30 W by weight of at least one polymer from the group consisting of polyolefins obtained from ethylene, propylene and copolymers of these olefins.

Par base lubrifiante on entend le composé hydrocarboné majeur de l'huile lubrifiante qui sera additivé. By lubricating base is meant the major hydrocarbon compound of the lubricating oil which will be additive.

Les bases lubrifiantes selon l'invention sont choisies parmi les huiles minérales d'origine pétrolière, les huiles synthétiques du groupe constitué par les polyglycols, leurs esters et les poly-a-oléfines, les huiles végétales et leur mélange. Dans un mode préféré de l'invention, ces bases minérales sont des huiles minérales blanches codex et des poly-a-oléfines.  The lubricating bases according to the invention are chosen from mineral oils of petroleum origin, synthetic oils from the group consisting of polyglycols, their esters and poly-α-olefins, vegetable oils and their mixture. In a preferred embodiment of the invention, these inorganic bases are codex white mineral oils and poly-α-olefins.

Comme les huiles lubrifiantes contiennent des polymères de l'éthylène et du propylène dans leur composition, elles présentent de faibles coefficients de frottement, sont partiellement insolubles dans les monomères et elles résistent au délavage par ces monomères. En outre, ces huiles n'ajoutent pas d'odeur au produit fini. Since the lubricating oils contain polymers of ethylene and propylene in their composition, they have low coefficients of friction, are partially insoluble in the monomers and they resist fading by these monomers. In addition, these oils do not add odor to the finished product.

Les polymères de l'invention sont des polymères de densité voisine des huiles dans lesquelles ils sont dispersés, de masse molaire moyenne en poids comprise entre 20.000 et 100.000. Ils se présentent sous la forme de poudre, de granulés ou de particules micronisées. The polymers of the invention are polymers of density close to the oils in which they are dispersed, with a weight average molecular weight of between 20,000 and 100,000. They are in the form of powder, granules or micronized particles.

Dans un mode préféré de l'invention, ces polymères sont choisis parmi les polyéthylènes, les polypropylènes, les polyéthylènevinylacétates (EVA), les éthylènevinylacrylates, les éthylènevinylméthacrylates (EVM) et les polyéthylèneacrylates (EDA ou éthylène dérivé acrylique). In a preferred embodiment of the invention, these polymers are chosen from polyethylenes, polypropylenes, polyethylenevinylacetates (EVA), ethylenevinylacrylates, ethylenevinylmethacrylates (EVM) and polyethyleneacrylates (EDA or ethylene acrylic derivative).

Dans un mode de réalisation de l'invention, l'huile lubrifiante est constituée de 80 à 99% en poids d'une huile minérale blanche codex et de 1 à 20% en poids de polyéthylène basse densité. In one embodiment of the invention, the lubricating oil consists of 80 to 99% by weight of a codex white mineral oil and 1 to 20% by weight of low density polyethylene.

Selon la présente invention, on peut rajouter à la dite huile lubrifiante les additifs classiquement utilisés notamment des additifs anti-usures, anti-rouille, des passivateurs des métaux jaunes et des inhibiteurs de polymérisation (KILLER). According to the present invention, it is possible to add to the said lubricating oil the conventionally used additives, in particular anti-wear, anti-rust additives, yellow metal passivators and polymerization inhibitors (KILLER).

Un deuxième objet de l'invention est le procédé de fabrication de l'huile lubrifiante qui consiste à faire fondre, sous agitation, le polymère dans l'huile à une température supérieure ou égale à 100 OC, à faire refroidir le mélange ainsi constitué à température ambiante. Dans un mode préféré du procédé selon l'invention, la température de fusion est choisie supérieure à 140 OC.  A second object of the invention is the method of manufacturing the lubricating oil which consists of melting, with stirring, the polymer in the oil at a temperature greater than or equal to 100 OC, to cool the mixture thus formed to ambient temperature. In a preferred embodiment of the process according to the invention, the melting temperature is chosen to be greater than 140 OC.

Pour expliciter les avantages de la présente invention, des exemples sont donnés ci-après à titre illustratif mais non limitatif. To explain the advantages of the present invention, examples are given below by way of illustration but not limitation.

EXEMPLE I
Le présent exemple vise à montrer la supériorité des huiles lubrifiantes de l'invention au regard du grippage comparés au produits de l'art antérieur.
EXAMPLE I
The present example aims to show the superiority of the lubricating oils of the invention with respect to galling compared to the products of the prior art.

Plusieurs échantillons selon l'invention ont été préparés et sont référencés par X ; les échantillons comparatifs de l'art antérieur sont appelés C. Le tableau I ci-après donne la composition des différents échantillons testés.  Several samples according to the invention have been prepared and are referenced by X; the comparative samples of the prior art are called C. Table I below gives the composition of the various samples tested.

TABLEAU I

Figure img00040001
TABLE I
Figure img00040001

<tb> Echantillon <SEP> Composition
<tb> T <SEP> = <SEP> témoin <SEP> Huile <SEP> blanche <SEP> ELF <SEP> la) <SEP>
<tb> <SEP> X1 <SEP> Huile <SEP> blanche <SEP> ELF(a( <SEP> + <SEP> 1% <SEP> polyéthylène
<tb> <SEP> X2 <SEP> Huile <SEP> blanche <SEP> ELF(a( <SEP> + <SEP> 2% <SEP> polyéthylène
<tb> <SEP> X3 <SEP> Huile <SEP> blanche <SEP> ELF(a) <SEP> + <SEP> 6% <SEP> polyéthylène
<tb> <SEP> X4 <SEP> Huile <SEP> blanche <SEP> ELF(a) <SEP> + <SEP> 20% <SEP> polyéthylène
<tb> <SEP> C1 <SEP> Huile <SEP> blanche <SEP> ELF(a) <SEP> + <SEP> 40% <SEP> polybutène <SEP>
<tb> <SEP> C2 <SEP> Huile <SEP> blanche <SEP> A(b) <SEP> + <SEP> 40% <SEP> polybutène
<tb> <SEP> C3 <SEP> Huile <SEP> blanche <SEP> B(b) <SEP> + <SEP> 40% <SEP> polybutène
<tb> <SEP> C4 <SEP> Huile <SEP> polybutène <SEP> de <SEP> grade <SEP> ISO <SEP> 220
<tb> (a) Huiles blanches ELF = huiles blanches paraffiniques
codex/grade 68 (b) Huiles blanches A et B = huiles du commerce
Tous ces échantillons ont été testés sur une machine FALEX extrême pression, dérivée de la méthode FORD
EUBJI 1A. Cet essai consiste à faire tourner un cylindre à 290 tours/mn entre deux mors qui l'enserrent, et à mesurer le couple de frottement à chaque palier de 445 Newton jusqu'au grippage.
<tb> Sample <SEP> Composition
<tb> T <SEP> = <SEP> control <SEP> Oil <SEP> white <SEP> ELF <SEP> la) <SEP>
<tb><SEP> X1 <SEP> Oil <SEP> white <SEP> ELF (a (<SEP> + <SEP> 1% <SEP> polyethylene
<tb><SEP> X2 <SEP> Oil <SEP> white <SEP> ELF (a (<SEP> + <SEP> 2% <SEP> polyethylene
<tb><SEP> X3 <SEP> Oil <SEP> white <SEP> ELF (a) <SEP> + <SEP> 6% <SEP> polyethylene
<tb><SEP> X4 <SEP> Oil <SEP> white <SEP> ELF (a) <SEP> + <SEP> 20% <SEP> polyethylene
<tb><SEP> C1 <SEP> White <SEP> Oil <SEP> ELF (a) <SEP> + <SEP> 40% <SEP> Polybutene <SEP>
<tb><SEP> C2 <SEP> Oil <SEP> white <SEP> A (b) <SEP> + <SEP> 40% <SEP> polybutene
<tb><SEP> C3 <SEP> Oil <SEP> white <SEP> B (b) <SEP> + <SEP> 40% <SEP> polybutene
<tb><SEP> C4 <SEP> Oil <SEP> polybutene <SEP> from <SEP> grade <SEP> ISO <SEP> 220
<tb> (a) White oils ELF = paraffinic white oils
codex / grade 68 (b) White oils A and B = commercial oils
All these samples were tested on a FALEX extreme pressure machine, derived from the FORD method
EUBJI 1A. This test consists of rotating a cylinder at 290 rpm between two jaws that surround it, and measuring the friction torque at each level of 445 Newton until seizing.

Chaque palier, maintenu pendant 60 secondes, correspond à un coefficient de frottement ; on retient la valeur du palier avant grippage.  Each bearing, maintained for 60 seconds, corresponds to a coefficient of friction; the value of the bearing before seizure is retained.

Le tableau II ci-après rassemble les résultats des tests. Table II below collates the results of the tests.

TABLEAU II

Figure img00050001
TABLE II
Figure img00050001

<tb> Echantillon <SEP> Palier <SEP> avant <SEP> Couple <SEP> de <SEP> frottement
<tb> <SEP> grippage <SEP> (N) <SEP> avant <SEP> grippage <SEP> (Ncm)
<tb> <SEP> T <SEP> 445 <SEP> 80
<tb> <SEP> X1 <SEP> 890 <SEP> 76
<tb> <SEP> X2 <SEP> 1335 <SEP> 90
<tb> <SEP> X3 <SEP> 1780 <SEP> 126
<tb> <SEP> X4 <SEP> 1780 <SEP> 118
<tb> <SEP> C1 <SEP> 890 <SEP> 112
<tb> <SEP> C2 <SEP> 890 <SEP> 108
<tb> <SEP> C3 <SEP> 890 <SEP> 110
<tb> <SEP> C4 <SEP> 445 <SEP> 96
<tb>
Pour des concentrations inférieures en polymères, les produits selon l'invention montrent une meilleure lubrification et un coefficient de frottement plus faible.
<tb> Sample <SEP> Tier <SEP> before <SEP> Couple <SEP> of <SEP> Friction
<tb><SEP> seizure <SEP> (N) <SEP> before <SEP> seizure <SEP> (Ncm)
<tb><SEP> T <SEP> 445 <SEP> 80
<tb><SEP> X1 <SEP> 890 <SEP> 76
<tb><SEP> X2 <SEP> 1335 <SEP> 90
<tb><SEP> X3 <SEP> 1780 <SEP> 126
<tb><SEP> X4 <SEP> 1780 <SEP> 118
<tb><SEP> C1 <SEP> 890 <SEP> 112
<tb><SEP> C2 <SEP> 890 <SEP> 108
<tb><SEP> C3 <SEP> 890 <SEP> 110
<tb><SEP> C4 <SEP> 445 <SEP> 96
<Tb>
For lower polymer concentrations, the products according to the invention show a better lubrication and a lower coefficient of friction.

Claims (8)

REvENnTcATTON RREvENnTcATTON R 1 - Huile lubrifiante pour hypercompresseur contenant au moins une base lubrifiante caractérisée en ce qu'elle contient de 0,3 à 30 % en poids d'au moins un polymère du groupe constitué par les polyoléfines obtenues à partir d'éthylène et de propylène, et les copolymères de ces oléfines.1 - lubricating oil for a hyper-compressor containing at least one lubricating base, characterized in that it contains from 0.3 to 30% by weight of at least one polymer from the group consisting of polyolefins obtained from ethylene and propylene, and copolymers of these olefins. 2 - Huile lubrifiante selon la revendication 1 caractérisée en ce que au moins une base lubrifiante est choisie parmi les huiles minérales d'origine pétrolière, les huiles synthétiques du groupe constitué par les polyglycols, les esters et les poly-a-oléfines, et les huiles végétales et leur mélange.2 - lubricating oil according to claim 1 characterized in that at least one lubricating base is selected from mineral oils of petroleum origin, synthetic oils of the group consisting of polyglycols, esters and poly-α-olefins, and vegetable oils and their mixtures. 3 - Huile lubrifiante selon le revendication 2 caractérisée en ce que les bases lubrifiantes sont des huiles minérales blanches codex, et les poly-a-oléfines. 3 - lubricating oil according to claim 2 characterized in that the lubricating bases are codex white mineral oils, and poly-α-olefins. 4 - Huile lubrifiante selon les revendications 1 à 3 caractérisée en ce que les polymères l'invention sont des polymères de densité voisine à celle des huiles dans lesquelles ils sont solubilisés, de masse molaire moyenne en poids comprise entre 20.000 et 100.000.4 - lubricating oil according to claims 1 to 3 characterized in that the polymers of the invention are polymers of density close to that of the oils in which they are solubilized, with a weight average molar mass of between 20,000 and 100,000. 5 - Huile lubrifiante selon les revendications 1 à 4 caractérisée en ce que les polymères se présentent sous la forme de poudre, de granulés ou de particules micronisées.5 - lubricating oil according to claims 1 to 4 characterized in that the polymers are in the form of powder, granules or micronized particles. 6 - Huile lubrifiante selon les revendications 1 à 5 caractérisée en ce que les polymères sont choisis parmi les polymères et copolymères de l'éthylène et du propylène, éventuellement substitués, plus particulièrement les polyéthylènes, les polypropylènes, les polyéthylènevinylacétates (EVA), les éthylènevinylacrylates, les éthylènevinylméthacrylates (EVM) et les polyéthylèneacrylates (EDA).6 - lubricating oil according to claims 1 to 5 characterized in that the polymers are chosen from polymers and copolymers of ethylene and propylene, optionally substituted, more particularly polyethylenes, polypropylenes, polyethylenevinylacétates (EVA), ethylenevinylacrylates ethylenevinyl methacrylates (EVM) and polyethyleneacrylates (EDA). 7 - Huile lubrifiante selon les revendications 1 à 6 caractérisée en ce qu'elle est constituée de 80 à 99 % en poids d'une huile minérale blanche codex et de 1 à 20% en poids de polyéthylène basse densité.7 - lubricating oil according to claims 1 to 6 characterized in that it consists of 80 to 99% by weight of a codex white mineral oil and 1 to 20% by weight of low density polyethylene. 8 - Procédé de fabrication de l'huile lubrifiante selon les revendications 1 à 7 consistant à faire fondre, sous agitation, le polymère dans l'huile à une température supérieure ou égale à 100 OC, de préférence supérieure à 1400c, et à faire refroidir le mélange ainsi constitué à température ambiante. 8 - A method of manufacturing the lubricating oil according to claims 1 to 7 of melting, with stirring, the polymer in the oil at a temperature greater than or equal to 100 OC, preferably greater than 1400c, and to cool the mixture thus formed at room temperature.
FR9611892A 1996-09-30 1996-09-30 LUBRICANT FOR HYPERCOMPRESSOR AND PROCESS FOR OBTAINING SAME Expired - Fee Related FR2753986B1 (en)

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FR9611892A FR2753986B1 (en) 1996-09-30 1996-09-30 LUBRICANT FOR HYPERCOMPRESSOR AND PROCESS FOR OBTAINING SAME
AU44650/97A AU4465097A (en) 1996-09-30 1997-09-29 Lubricant for supercharger and method for obtaining same
BR9711578A BR9711578A (en) 1996-09-30 1997-09-29 Hypercompressant lubricant and process
CA002267098A CA2267098A1 (en) 1996-09-30 1997-09-29 Lubricant for supercharger and method for obtaining same
KR1019990702702A KR20000048728A (en) 1996-09-30 1997-09-29 Lubricant for supercharger and method for obtaining same
JP10516281A JP2001501660A (en) 1996-09-30 1997-09-29 Lubricant for hyper compressor and method for producing the same
ZA9708699A ZA978699B (en) 1996-09-30 1997-09-29 Lubricant for a high pressure compressor and process for obtaining it.
PCT/FR1997/001716 WO1998014537A1 (en) 1996-09-30 1997-09-29 Lubricant for supercharger and method for obtaining same
ARP970104490A AR009102A1 (en) 1996-09-30 1997-09-30 LUBRICATING OIL FOR HYPERCOMPRESSOR AND PROCEDURE FOR ITS MANUFACTURE

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CA2267098A1 (en) 1998-04-09
KR20000048728A (en) 2000-07-25

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