WO1999067347A2 - Oligodecenes produits par catalyse au metallocene, leur production et leur utilisation comme composants dans des lubrifiants - Google Patents

Oligodecenes produits par catalyse au metallocene, leur production et leur utilisation comme composants dans des lubrifiants Download PDF

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Publication number
WO1999067347A2
WO1999067347A2 PCT/EP1999/003809 EP9903809W WO9967347A2 WO 1999067347 A2 WO1999067347 A2 WO 1999067347A2 EP 9903809 W EP9903809 W EP 9903809W WO 9967347 A2 WO9967347 A2 WO 9967347A2
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Prior art keywords
oligodecenes
linear
decene
molecular weight
oils
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PCT/EP1999/003809
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German (de)
English (en)
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WO1999067347A3 (fr
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Hans Peter Rath
Helmut Mach
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Basf Aktiengesellschaft
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Priority to AU45046/99A priority Critical patent/AU4504699A/en
Priority to JP2000555993A priority patent/JP2002518582A/ja
Priority to EP99927838A priority patent/EP1088049A2/fr
Priority to KR1020007014401A priority patent/KR20010053003A/ko
Publication of WO1999067347A2 publication Critical patent/WO1999067347A2/fr
Publication of WO1999067347A3 publication Critical patent/WO1999067347A3/fr

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    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to the use of metallocene-catalyzed oligodecenes with a number-average molecular weight of 500 to 200,000 as components in lubricants, in particular in motor oils and gear oils, and to such lubricants themselves. Since some of these oligodecenes represent new substances, the invention relates to continue these new oligodecenes.
  • Hydrogenated short and medium chain oligoalkenes have long been used as components in synthetic lubricants, e.g. Motor oils, used. These are essentially di-, tri- and tetramers which are produced by oligomerization, for example using boron trifluoride as a catalyst and alcohols such as butanol or pentanol as promoters. However, this technology does not specifically lead to higher molecular weight oligomers terminated with vinylidene double bonds.
  • poly-1-olefins from C 3 - to co-olefins such as propene, 1-butene, 1-pentene or 1-hexene with a number average molecular weight of 300 to 10,000 are known, which by conventional Metallocene catalysis can be produced.
  • the 1-olefins mentioned are always used in a mixture with more volatile saturated and unsaturated hydrocarbons, for example a technical butane / butene stream or technical isobutene-containing butene streams (“raffinate 1/11” from the steam cracker) are used.
  • the poly-1-olefins obtained are also suitable, inter alia, as a constituent for lubricants.
  • EP-A 613 873 (2) describes metallocene-catalyzed oligomers made from linear ⁇ -olefins having 8 to 20 C atoms, e.g. technical 1-octene or technical 1-dodecene, with a number average molecular weight of 400 to 3000. According to (2), such oligomers are generally suitable as a base material for lubricants, but no longer with a number average molecular weight of 6000 or more.
  • WO-A 96/28486 (3) relates to copolymers of unsaturated dicarboxylic acids or their anhydrides and oligomers of 1-olefins having 3 to 14 carbon atoms, which can be prepared by metallocene catalysis. Among other things, n-decene is also mentioned as the 1-olefin. The average molecular weight of the olefin oligo- mere is 300 to 10,000.
  • the copolymers obtained from the unsaturated dicarboxylic acid (anhydrides) and the olefin oligomers are suitable as fuel and lubricant additives after derivatization with amines. 5
  • olefin oligomers produced by means of metallocene catalyst systems are known, which are based on linear and ring-shaped C 1 -C 1 -efins, for example 1-decene.
  • Their weight average molecular weight (M w ) is 100 to
  • these olefin oligomers can be functionalized with the usual chemical reactions such as hydroformylation and / or hydroamination
  • Process 15 connections which e.g. are suitable as fuel or lubricant additives.
  • the object of the present invention was to remedy the shortcomings of the prior art.
  • 35 can, with a number average molecular weight of 500 to 200,000, be found as components in lubricants, in particular in engine and gear oils, especially in multigrade engine oils and gear oils.
  • the areas of application for the oligodecenes mentioned are in particular hydraulic fluids, bed sheet oils, compressor oils, circulation oils, calender oils, rolling oils and lubricating greases.
  • the oligodecenes mentioned have a number average molecular weight (M N ) of 10,000 to 200,000, preferably 20,000 to 150,000, in particular from 25,000 to 100,000, especially from 30,000 to 80,000, particularly preferably from 35,000 to 60,000, the determination of M N usually being carried out by gel permeation chromatography (GPC), as a viscosity index improver in fully synthetic, partially synthetic and mineral motor oils, in particular in such multigrade engine oils, because they have a significantly more favorable flow behavior at high and especially at low temperatures.
  • GPC gel permeation chromatography
  • the engine oils remain more fluid; at high temperatures (operating temperature of the engine) they remain sufficiently viscous so that the lubricating film does not tear off.
  • (Fully) synthetic motor oils are to be understood in particular as those based on organic esters, synthetic hydrocarbons, poly- ⁇ -olefins and polyolefins (e.g. polyisobutene).
  • Semi-synthetic motor oils are mixtures of mineral oils with synthetic motor oils, especially with the above-mentioned synthetic motor oils.
  • the oligecenes mentioned can just as well be used in engine oils based only on mineral oils. Particularly interesting is the use in the so-called multi-grade engine oils, which are equally suitable for winter and summer operation of engines.
  • the engine oils mentioned can be used for a wide variety of applications, but in particular as four-stroke engine oils in automotive and two-wheel engines, locomotive diesel engines, etc.
  • the oligodecenes mentioned have a number average molecular weight (M N ) of 800 to 50,000, preferably from 1000 to 30,000, in particular from 1500 to 20,000, especially from 2000 to 15,000, the determination of M N usually by gel permeation - Chromatography (GPC) is used as a thickener or viscosity index improver in gear oils, especially in multigrade gear oils.
  • M N number average molecular weight
  • Thickeners” and “viscosity improvers” are synonyms when used in gear oils.
  • Gear oils are to be understood here in particular as gear oils for the automotive sector, especially manual and automatic gear oils.
  • the oligodecenes have a very good thickening effect as well as high shear stability and very low low-temperature viscosities.
  • the oligodecenes according to the application are clearly superior to the polymethacrylates normally used for such gear oils.
  • the said oligodecenes with a number average molecular weight (M N ) of 500 to 5000, preferably from 650 to 3500, in particular from 800 to 2500, the determination of M N usually being carried out by gel permeation chromatography (GPC) as synthetic Lubricant components in lubricants, especially in engine and gear oils, especially in multigrade engine and gear oils.
  • GPC gel permeation chromatography
  • the oligodecenes are characterized by particularly low low-temperature viscosities and are clearly superior to the poly- ⁇ -olefins commonly used for this purpose.
  • the oligodecenes according to the application are mostly used in their hydrogenated form, which, however, generally has no influence on the viscosimetic data.
  • the amount of the oligodecenes mentioned in the lubricants, in particular in the motor oils or gear oils, is usually 0.1 to 95% by weight, in particular 0.5 to 90% by weight, especially 1 to 85% by weight, based on the lubricant or the engine oil or gear oil.
  • the preferred amount used is 0.1 to 40% by weight, in particular 0.5 to 20% by weight, especially 1 to 10% by weight, based on the motor oil.
  • the preferred amount used as a thickener (viscosity index improver) in gear oils the preferred amount used is 0.5 to 70% by weight, in particular 1 to 50% by weight, especially 5 to 40% by weight, based on the gear oil.
  • the preferred amount is 1 to 95% by weight, in particular 5 to 90% by weight, especially 20 to 85% by weight, particularly preferably 30 to 85 % By weight, very particularly preferably 40 to 85% by weight, based on the lubricant.
  • Other customary additives such as dispersants, corrosion inhibitors, wear protection components, detergents, antioxidants, friction modifiers and / or defoamers (foam inhibitors) may also be present in the lubricants or engine or gear oils in the amounts customary for this.
  • the essential monomer component in the oligodecenes mentioned is linear 1-decene, which alone or in a mixture with up to 40 mol%, in particular up to 20 mol%, especially up to 5 mol%, based on the amount of 1- Decene, further linear CQ - until C ⁇ 2 -1-alkenes (1-octene, 1-nonen, 1-undecene and / or 1-dodecene) can be oligo erized.
  • These 1-alkenes can be in chemically pure form (purities of usually 99 to 99.9% by weight) or as industrial mixtures in purities of usually 90 up to 99% by weight are used, the remaining constituents of the technical mixtures normally being approximately equally volatile, polymerizable or non-polymerizable components (for example unsaturated isomers, homologs or saturated hydrocarbons).
  • the 1-alkenes used are practically free of volatile components, especially free of more volatile saturated or unsaturated hydrocarbons, in particular those with fewer than 8 carbon atoms; practically free means that at most a proportion of such volatile components of less than 1% by weight, in particular less than 0.5% by weight, can occur.
  • the systems of metallocene catalyst and active gate used for oligomerization are conventional catalyst systems.
  • the desired molecular weight ranges of the oligodecenes can be adjusted in a known manner by varying the structure of the metallocene.
  • the oligomerization is usually carried out in a suitable medium ("reaction mixture"), e.g. an organic solvent, under the usual conditions for this.
  • the reaction mixture is the mixture which is present in the time after all the reaction components have been combined until the catalyst system has been destroyed after the oligomerization reaction has taken place.
  • the solubility of the catalyst system in the reaction mixture is analogous by measuring the turbidity of the reaction mixture
  • the catalyst system is largely soluble if the turbidity number is in the range from 1 to 10, preferably in the range from 1 to 3.
  • the metallocene component of the catalyst system is a complex of titanium, zirconium and hafnium in which the metal atom M is sandwiched between two optionally substituted cyclopentadienyl groups, the remaining valences of the central atom M being replaced by easily exchangeable leaving atoms or leaving groups X 1 , X 2 are saturated.
  • Suitable metallocene complexes are those with the general formula Cp 2 MX 1 X 2 , in which M is titanium, zirconium or hafnium, preferably zirconium.
  • Cp 2 represent a pair of optionally substituted cyclopentadienyl ligands. Both cyclopentadienyl ligands or only one of the two can be substituted.
  • the cyclopentadienyl rings are usually substituted symmetrically. This means that the type, number and also the position of the alkyl substituents of one Cp ring is identical to the type, number and also position of the alkyl substituents of the second Cp ring.
  • the number of alkyl groups per cyclopentadienyl ring is 1 to 4.
  • Suitable C 5 - to C 3 o-alkyl radicals are the aliphatic radicals pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa-decyl, nonadecyl and eicosyl and their isomers , such as neo-pentyl, iso-octyl, and the cycloaliphatic radicals cyclopentyl and cyclohexyl. N-Octadecyl is particularly suitable.
  • the optionally C 5 - to C 3 o-alkyl-substituted cyclopentadienyl units can, however, also be substituted by 1 to 2 C 4 - to cio-alkylene units, which together with the cyclopentadienyl unit form a fused ring system, such as the tetrahydroindenyl system, form.
  • R 1 denotes a Ci to C 3 cr -organic group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl , i-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, cyclohexyl, phenyl or p-tolyl.
  • Preferred organosilyl radicals are trimethylsilyl and tert. -Butyldimethylsilyl, especially trimethylsilyl.
  • the symmetrical substitution pattern is not absolutely necessary, but is also not excluded.
  • Such metallocene catalysts in which the two cyclopentadienyl ligands are connected to one another via a bridge member.
  • Such bridging links mostly have 1 to 4 atoms (C atoms and / or heteroatoms such as Si, N, P, 0, S, Se or B) and optionally alkyl chains, for example 1,2-ethylidene, 1,3-propylidene or dialkylsilane -Bridges.
  • Easily exchangeable, formally negatively charged leaving atoms or leaving groups atoms or leaving groups X 1 , X 2 of the metallocene complexes of the general formula CpMX 1 X 2 may be mentioned: hydrogen, halogen such as fluorine, bromine, iodine and preferably chlorine.
  • alcoholates such as methanolate, ethanolate, n- and i-propanolate, phenolate, trifluoromethylphenolate, naphtholate and silanolate.
  • Ci to Cio alkyl radicals in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neo -Pentyl, hexyl, preferably methyl, tert-butyl and neo-pentyl, furthermore alicyclic C 3 - to -CC hydrocarbon radicals such as cyclopropyl, cyclobutyl, cyclopentyl and in particular cyclohexyl or C 5 - to C 2 Q-bicycloalkyl such as bicyclopentyl and especially bicycloheptyl and bicyclooctyl.
  • aliphatic Ci to Cio alkyl radicals in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pent
  • substituents X 1 , X 2 with aromatic structural units are C 6 - to cis-aryl, preferably phenyl or naphthyl, alkyl - aryl or arylalkyl, each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, such as for example tolyl and benzyl.
  • metallocene complexes are: bis (n-octadecylcyclopentadienyl) zirconium dichloride, bis (trimethylsilyl-cyclopentadienyl) zirconium dichloride, bis (tetrahydroindenyl) zirconium dichloride, bis [(tert-butyldimethyladilium) dichloride).
  • the metallocene complexes mentioned can be easily prepared by known processes, e.g. Brauer (ed.): Handbuch der Preparative Inorganic Chemistry, Volume 2, 3rd edition, pages 1395 to 1397, Enke, Stuttgart 1978.
  • a preferred process is based on the lithium salts of the appropriately substituted cyclopentadienyls, which are reacted with the transition metal halides.
  • the catalyst systems also contain activators which are known per se and are also called cocatalysts in the literature. They generally alkylate them Transition metal component of the catalyst system and / or abstract a ligand X from the transition metal component, so that ultimately a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can arise.
  • activators which are known per se and are also called cocatalysts in the literature. They generally alkylate them Transition metal component of the catalyst system and / or abstract a ligand X from the transition metal component, so that ultimately a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can arise.
  • Organometallic compounds of the 1st to 3rd main group or the 2nd subgroup of the periodic table are generally suitable for this task, but other acceptor compounds such as, for example, carbocation salts can also be used.
  • suitable activator compounds are organoaluminum and organoboron compounds as well as carbocation salts. Preference is given to open-chain or cyclic oligomeric alumoxane compounds which can be obtained by reacting aluminum tri-alkylene, in particular trimethyl or triethyl aluminum, with water.
  • R 2 is hydrogen, C 1 -C 4 -alkyl, preferably C 1 -C 4 -alkyl, in particular methyl, ethyl or butyl.
  • R 2 can also represent arylalkyl or alkylaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.
  • Aluminum alkyls Al (R 2 ) 3 are furthermore suitable, in which R 2 can mean fluorine, chlorine, bromine or iodine in addition to the radicals defined above, with the proviso that at least one radical R 2 is a C-organic radical or a hydrogen atom .
  • Particularly preferred compounds are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, di-isobutyl aluminum hydride and diethyl aluminum chloride.
  • organic boron compounds are also very suitable as activators, for example tris -arylboron compounds, preferably tris (pentafluoropheny1) boron, furthermore salts of carbonium ions, preferably triphenylmethyltetraarylborate, in particular triphenylmethyltetra (pentafluorophenyD orate.
  • tris -arylboron compounds preferably tris (pentafluoropheny1) boron
  • furthermore salts of carbonium ions preferably triphenylmethyltetraarylborate, in particular triphenylmethyltetra (pentafluorophenyD orate.
  • Al, B or C compounds mentioned are known or can be obtained in a manner known per se.
  • activators they can be used alone or as mixtures in the catalyst system.
  • the activator component is preferably used in a molar excess with respect to the metallocene complex.
  • the molar ratio of activator to metallocene complex is generally 100: 1 to 10,000: 1, preferably 100: 1 to 1,000: 1:
  • the constituents of the catalyst systems described can be introduced into the oligomerization reactor individually or as a mixture in any order.
  • the metallocene complex is preferably mixed with at least one activator component before it enters the reactor, that is to say preactivated.
  • the oligodecenes can be prepared in the customary reactors used for the oligomerization of olefins, either batchwise or preferably continuously. Suitable reactors include continuously operated stirred kettles, it also being possible to use a series of several stirred kettles connected in series.
  • the oligomerization can be carried out in a suspension, in liquid monomers and in inert solvents.
  • solvents in particular liquid organic hydrocarbons such as benzene, ethylbenzene or toluene are used.
  • the oligomerizations are preferably carried out in a reaction mixture in which the liquid monomer is present in excess.
  • the oligomerization is generally carried out at temperatures from -20 ° C to 200 ° C, in particular from 0 to 140 ° C, especially at 30 ° C to 110 ° C, it can usually be carried out using the low-pressure or medium-pressure process .
  • the amount of catalyst used is not critical.
  • the oligodecenes produced by metallocene catalysis contain unsaturated double bonds due to the oligomerization mechanism; the proportion of terminal vinylidene double bonds is particularly high. If these double bonds interfere when used as motor oil or lubricating oil components, they can be converted into saturated structures by conventional hydrogenation processes.
  • the oligodecenes used according to the invention have the above-mentioned number average molecular weight (M N ).
  • the number average molecular weight is usually determined by gel permeation chromatography (GPC).
  • the molecular weight distribution M W / M N (weight average / number average) is generally 1.3 to 5, a narrow distribution being more widely distributed, for example by extraction processes Samples are created and a broad distribution can also be obtained by mixing. If uniform catalyst systems are used, the distribution is generally from 1.5 to 3.0. Under certain circumstances, a broader distribution can be more advantageous, because the same thickening effect in the engine or lubricating oil usually requires more oligomer with a narrow distribution and the same molecular weight.
  • a wide distribution with a low-molecular flank in the molecular weight distribution can also be advantageous for an often additionally occurring dispersing action in the motor or lubricating oil.
  • bimodal distributions generated by blends can also have an advantageous effect.
  • Narrower distributions can also be advantageous due to better shear stability, especially with gear oils.
  • the present invention further relates to oligodecenes which are obtained by oligomerizing linear 1-decene, up to 40 mol%, based on the amount of linear 1-Decene, further linear Cs to C ⁇ -1 olefins can be polymerized in, are available in the presence of a titanium, zirconium or hafnium metal locene catalyst and an activator based on organoaluminum, organic boron or carbocationic compounds may have been hydrogenated after the oligomerization, with a number average molecular weight of 30,000 to 200,000, in particular from 35,000 to 150,000.
  • the present invention also relates to a process for the preparation of these oligodecenes, which is characterized in that linear 1-decene or a mixture of linear 1-decene and up to 40 mol%, based on the amount of linear 1-decene, further linear CQ - to C ⁇ 2 -1-alkenes metallocene-catalysed - as described above - oligomerized and, if desired, hydrogenated subsequently.
  • an oligodecene with an M N according to GPC of 3500 was produced using bis (n-octadecylcyclopentadienyl) zirconium dichloride / methylalumoxane.
  • an oligodecene with an M ⁇ according to GPC of 6450 was prepared using bis (n-octadecylcyclopentadienyl) zirconium dichloride / methylalumoxane.
  • Example 5
  • an oligodecene with an M N according to GPC of 850 was produced using bis (n-octadecylcyclopentadienyl) zirconium dichloride / methylalnmoxane.
  • Ashless dispersants 5.0% usual overbased sulfonate 2.8% zinc dithiophosphate 2.0% common antioxidant 0.4% common friction modifier 0.1% common foam inhibitor 0.002
  • M N 3500 from Example 3
  • Viscosity index improver Viscosity index improver
  • a fully synthetic multigrade motor oil (5W / 40) with the following composition:
  • Polyisobutene (M N 2300) as 3.85% thickener common polymethacrylate as 1.0% thickener common pour point improver 0.2%

Abstract

L'invention concerne des oligodécènes obtenus par oligomérisation de 1-décène linéaire, sachant que 40 % en mole maximum, par rapport à la quantité de 1-décène linéaire, d'autres 1-alcènes C8 à C12 linéaires peuvent être inclus par polymérisation, en présence d'un catalyseur de titane, de zirconium ou de hafnium et d'un activeur à base de composés aluminium-organiques, bore-organiques ou carbo-cationiques. Après oligomérisation, ces oligodécènes peuvent être hydrogénés. Ces oligodécènes ont un poids moléculaire moyen compris entre 500 et 200.000. L'invention concerne également leur utilisation comme composants de lubrifiants, notamment d'huiles pour moteurs et d'huiles à engrenages.
PCT/EP1999/003809 1998-06-19 1999-06-02 Oligodecenes produits par catalyse au metallocene, leur production et leur utilisation comme composants dans des lubrifiants WO1999067347A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU45046/99A AU4504699A (en) 1998-06-19 1999-06-02 Metallocene-catalyzed oligodecenes, their production and their use as component in lubricants
JP2000555993A JP2002518582A (ja) 1998-06-19 1999-06-02 メタロセン触媒を使用して製造されるオリゴデセン、その製造および潤滑剤における成分としてのその使用
EP99927838A EP1088049A2 (fr) 1998-06-19 1999-06-02 Oligodecenes produits par catalyse au metallocene, leur production et leur utilisation comme composants dans des lubrifiants
KR1020007014401A KR20010053003A (ko) 1998-06-19 1999-06-02 메탈로센 촉매 반응에 의해 제조된 올리고데켄 및 그 제조방법과, 윤활유 성분으로서의 그 용도

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19827323.1 1998-06-19
DE19827323A DE19827323A1 (de) 1998-06-19 1998-06-19 Verwendung von metallocenkatalysiert hergestellten Oligodecenen als Komponenten in Schmierstoffen

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WO1999067347A2 true WO1999067347A2 (fr) 1999-12-29
WO1999067347A3 WO1999067347A3 (fr) 2000-02-17

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JP (1) JP2002518582A (fr)
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AU (1) AU4504699A (fr)
DE (1) DE19827323A1 (fr)
WO (1) WO1999067347A2 (fr)

Cited By (19)

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WO2003070790A1 (fr) * 2002-02-21 2003-08-28 Idemitsu Petrochemical Co., Ltd. Polymere cristallin d'$g(a)-olefine d'ordre superieur et son procede de production
WO2003104292A1 (fr) * 2002-06-04 2003-12-18 Crompton Corporation Procede d'oligomerisation d'$g(a)-olefines a faible insaturation
US6713582B2 (en) 2001-12-14 2004-03-30 Uniroyal Chemical Company, Inc. Process for the oligomerization of α-olefins having low unsaturation, the resulting polymers, and lubricants containing same
JP2005501957A (ja) * 2001-08-31 2005-01-20 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ ポリ−α−オレフィンの合成及びその用途
WO2007011459A1 (fr) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Nouvelles compositions polyalphaolefiniques et procedes de realisation afferents
EP1950277A1 (fr) * 2005-11-15 2008-07-30 Idemitsu Kosan Co., Ltd. Composition de fluide de transmission
JP2009149911A (ja) * 2009-04-02 2009-07-09 Idemitsu Kosan Co Ltd α−オレフィン重合体の製造方法及び潤滑油
US7795194B2 (en) 2004-11-26 2010-09-14 Mitsui Chemicals, Inc. Synthetic lubricating oil and lubricating oil composition
WO2011079042A2 (fr) 2009-12-24 2011-06-30 Exxonmobil Chemical Patents Inc. Procédé de production d'huiles de base synthétiques inédites
WO2012027139A2 (fr) 2010-08-25 2012-03-01 Exxonmobil Chemical Patents Inc. Hydrocarbures synthétiques fluides pouvant être fonctionnalisés et leur procédé intégré de production
US8227392B2 (en) 2008-01-25 2012-07-24 Exxonmobil Research And Engineering Company Base stocks and lubricant blends containing poly-alpha olefins
WO2012134688A1 (fr) 2011-03-30 2012-10-04 Exxonmobil Chemical Patents Inc. Polyalpha-oléfines par oligomérisation et isomérisation
US8357829B2 (en) 2008-05-07 2013-01-22 Basf Se α-olefin/isobutene diblock copolymers
US8373011B2 (en) 2005-05-12 2013-02-12 Idemitsu Kosan Co., Ltd. Process for producing saturated aliphatic hydrocarbon compound, and lubricant composition
US8389625B2 (en) 2008-12-23 2013-03-05 Exxonmobil Research And Engineering Company Production of synthetic hydrocarbon fluids, plasticizers and synthetic lubricant base stocks from renewable feedstocks
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US9815915B2 (en) 2010-09-03 2017-11-14 Exxonmobil Chemical Patents Inc. Production of liquid polyolefins
US10968290B2 (en) 2017-03-28 2021-04-06 Exxonmobil Chemical Patents Inc. Metallocene-catalyzed polyalpha-olefins

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JP2005200452A (ja) * 2004-01-13 2005-07-28 Mitsui Chemicals Inc α−オレフィン（共）重合体の製造方法
JP2005200453A (ja) * 2004-01-13 2005-07-28 Mitsui Chemicals Inc α−オレフィン（共）重合体の製造方法
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JP5006788B2 (ja) * 2005-08-31 2012-08-22 出光興産株式会社 冷凍機油組成物
JP5390738B2 (ja) * 2005-11-15 2014-01-15 出光興産株式会社 内燃機関用潤滑油組成物
JP5330824B2 (ja) * 2006-03-10 2013-10-30 出光興産株式会社 冷凍機油組成物
US8535514B2 (en) 2006-06-06 2013-09-17 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst PAO novel base stock lubricant blends
US8299007B2 (en) 2006-06-06 2012-10-30 Exxonmobil Research And Engineering Company Base stock lubricant blends
US8501675B2 (en) 2006-06-06 2013-08-06 Exxonmobil Research And Engineering Company High viscosity novel base stock lubricant viscosity blends
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US9469704B2 (en) 2008-01-31 2016-10-18 Exxonmobil Chemical Patents Inc. Utilization of linear alpha olefins in the production of metallocene catalyzed poly-alpha olefins
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US6713582B2 (en) 2001-12-14 2004-03-30 Uniroyal Chemical Company, Inc. Process for the oligomerization of α-olefins having low unsaturation, the resulting polymers, and lubricants containing same
US7037974B2 (en) 2001-12-14 2006-05-02 Uniroyal Chemical Company, Inc. Process for the oligomerization of α-olefins having low unsaturation, the resulting polymers, and lubricants containing same
US7214755B2 (en) 2002-02-21 2007-05-08 Idemitsu Kosan Co., Ltd. Crystalline polymer of higher α-olefin and process for producing the same
WO2003070790A1 (fr) * 2002-02-21 2003-08-28 Idemitsu Petrochemical Co., Ltd. Polymere cristallin d'$g(a)-olefine d'ordre superieur et son procede de production
WO2003104292A1 (fr) * 2002-06-04 2003-12-18 Crompton Corporation Procede d'oligomerisation d'$g(a)-olefines a faible insaturation
US7129306B2 (en) 2002-06-04 2006-10-31 Crompton Corporation Process for the oligomerization of α-olefins having low unsaturation
US7795194B2 (en) 2004-11-26 2010-09-14 Mitsui Chemicals, Inc. Synthetic lubricating oil and lubricating oil composition
US8373011B2 (en) 2005-05-12 2013-02-12 Idemitsu Kosan Co., Ltd. Process for producing saturated aliphatic hydrocarbon compound, and lubricant composition
WO2007011459A1 (fr) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Nouvelles compositions polyalphaolefiniques et procedes de realisation afferents
EP2333034A1 (fr) * 2005-11-15 2011-06-15 Idemitsu Kosan Co., Ltd. Composition de fluide de transmission
US8268762B2 (en) 2005-11-15 2012-09-18 Idemitsu Kosan Co., Ltd. Transmission fluid composition
EP1950277A4 (fr) * 2005-11-15 2010-09-08 Idemitsu Kosan Co Composition de fluide de transmission
EP1950277A1 (fr) * 2005-11-15 2008-07-30 Idemitsu Kosan Co., Ltd. Composition de fluide de transmission
US8921290B2 (en) 2006-06-06 2014-12-30 Exxonmobil Research And Engineering Company Gear oil compositions
US8834705B2 (en) 2006-06-06 2014-09-16 Exxonmobil Research And Engineering Company Gear oil compositions
US8227392B2 (en) 2008-01-25 2012-07-24 Exxonmobil Research And Engineering Company Base stocks and lubricant blends containing poly-alpha olefins
US8357829B2 (en) 2008-05-07 2013-01-22 Basf Se α-olefin/isobutene diblock copolymers
US8389625B2 (en) 2008-12-23 2013-03-05 Exxonmobil Research And Engineering Company Production of synthetic hydrocarbon fluids, plasticizers and synthetic lubricant base stocks from renewable feedstocks
JP2009149911A (ja) * 2009-04-02 2009-07-09 Idemitsu Kosan Co Ltd α−オレフィン重合体の製造方法及び潤滑油
WO2011079042A2 (fr) 2009-12-24 2011-06-30 Exxonmobil Chemical Patents Inc. Procédé de production d'huiles de base synthétiques inédites
US9701595B2 (en) 2009-12-24 2017-07-11 Exxonmobil Chemical Patents Inc. Process for producing novel synthetic basestocks
WO2012027139A2 (fr) 2010-08-25 2012-03-01 Exxonmobil Chemical Patents Inc. Hydrocarbures synthétiques fluides pouvant être fonctionnalisés et leur procédé intégré de production
US8557902B2 (en) 2010-08-25 2013-10-15 Exxonmobil Chemical Patents Inc. Functionalizable synthetic hydrocarbon fluids and integrated method for production thereof
US9815915B2 (en) 2010-09-03 2017-11-14 Exxonmobil Chemical Patents Inc. Production of liquid polyolefins
WO2012134688A1 (fr) 2011-03-30 2012-10-04 Exxonmobil Chemical Patents Inc. Polyalpha-oléfines par oligomérisation et isomérisation
US10968290B2 (en) 2017-03-28 2021-04-06 Exxonmobil Chemical Patents Inc. Metallocene-catalyzed polyalpha-olefins

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Publication number Publication date
EP1088049A2 (fr) 2001-04-04
WO1999067347A3 (fr) 2000-02-17
KR20010053003A (ko) 2001-06-25
DE19827323A1 (de) 1999-12-23
AU4504699A (en) 2000-01-10
JP2002518582A (ja) 2002-06-25

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