WO1996023751A1 - Procede de preparation d'oligomeres d'olefine - Google Patents
Procede de preparation d'oligomeres d'olefine Download PDFInfo
- Publication number
- WO1996023751A1 WO1996023751A1 PCT/EP1996/000235 EP9600235W WO9623751A1 WO 1996023751 A1 WO1996023751 A1 WO 1996023751A1 EP 9600235 W EP9600235 W EP 9600235W WO 9623751 A1 WO9623751 A1 WO 9623751A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- olefin oligomers
- alkyl
- catalyst systems
- substituents
- range
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
- C07C2/34—Metal-hydrocarbon complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Definitions
- the present invention relates to an improved process for the preparation of olefin oligomers with a molecular weight distribution Mw / Mn in the range from 1.0 to 2.4 by oligomerization of olefins in the presence of metallocene catalyst systems.
- the invention further relates to olefin oligomers obtainable by a process according to claims 1 to 4, and to the use of the olefin oligomers for the production of lubricants or fuel additives.
- Olefin oligomers are valuable starting products for the production of fuel and oil additives, lubricants and plasticizers. They can also be used as macromonomers.
- the modified products obtainable from the olefin oligomers such as, for example, lubricants or fuel additives, have a narrow, monomodal molecular weight distribution. If, on the other hand, the molecular weight distribution is relatively broad, the relatively high molecular weight oligomer fractions can have an adverse effect on the shear stability or valve cleaning characteristics.
- EP-A 0 268 214 describes the oligomerization of propylene with five-fold alkyl-substituted cyclopentadienyl complexes (metallocene complexes) without the molecular weight distribution Mw / Mn of the propylene oligomers being disclosed.
- EP-A 0 596 553 describes olefin oligomerizations with metallocene catalysts, the cyclopentadienyl ligands of which are substituted by different alkyls.
- Mw / Mn of the oligomers is not mentioned.
- EP-A 0 540 108 describes the preparation of olefin oligomers having a molecular weight distribution of 1.1 to 5.0. However, very special preparative, complex metallocene complexes are also used as catalyst components, the productivity and solubility of which leave something to be desired.
- the olefins are linear and ring-shaped with 2 to 12 carbon atoms, for example ⁇ -olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methylpentene-1 or vinylcyclohexane are suitable, and also olefins with an internal double bond such as E- and Z-2-butene, E- and Z-2-pentene, E- and Z- 3-witches.
- ⁇ -olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methylpentene-1 or vinylcyclohexane are suitable, and also ole
- Cyclopropanes, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclonones, cyclodecene and norbornene are suitable as cycloolefins.
- C 2 - to C - ⁇ -01efins, such as ethylene, propene, 1-butene and in particular propene, are preferably used.
- oligomerize mixtures of different olefins having 2 to 12 carbon atoms In addition to the pure olefins, it is of course also possible to oligomerize mixtures of different olefins having 2 to 12 carbon atoms.
- the molar ratio of the individual olefin components to one another is generally not critical if one observes that the amount of ethylene units in the cooligomers is generally 0.01 to 5 mol%, preferably 0.01 to 3 mol%, in total is particularly 0.01 to 2 mol%.
- the reaction mixture is the mixture which is present in the time after all 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 determined by measuring the turbidity of the reaction mixture analogously to DIN 38404.
- the catalyst system is largely soluble in the sense of the invention 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 so-called titanocene-zirconocene and hafnocene derivative, hence complexes of titanium, zirconium and hafnium, in which the metal atom M is bonded between two optionally substituted cyclopentadienyl groups, the remaining valences of Central atom M are saturated by easily exchangeable leaving atoms or leaving groups X 1 , X 2 .
- Suitable metallocene complexes are those with the general formula Cp 2 MX x X 2 in which M is titanium, zirconium or hafnium, preferably zirconium.
- Cp represent a pair of optionally substituted cyclopentadienyl ligands.
- the cyclopentadienyl rings are substituted symmetrically.
- the type, number and also the position of the alkyl substituents of the 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 C5 to C3c alkyl radicals for the purposes of the invention are the aliphatic pentyl, hexyl, heptyl, octyl, nonyl, decyl,
- N-Octadecyl is particularly suitable.
- C 5 - to C 3 o-alkyl-substituted cyclopentadienyl units can also be substituted by 1 to 2 C - to Cio-alkylene units, which together with the cyclopen- tadienyl unit form a fused ring system, such as the tetrahydroindenyl system.
- substituted cyclopentadienyl ligands are also possible in pairs in which at least one cyclopentadienyl unit is substituted with at least one organosilyl group -Si (R 1 ) 3 .
- R 1 then denotes a Ci to C 3 o-carbon 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, p-tolyl.
- Preferred organosilyl radicals are trimethylsilyl and tert-butyldimethylsilyl, in particular trimethylsilyl.
- the symmetrical substitution pattern is not absolutely necessary, but is also not excluded.
- X 1 , X 2 of the metallocene complexes of the general formula I are: hydrogen, halogen such as fluorine, bromine, iodine and preferably chlorine.
- alcoholates such as methanolate, ethanolate, n- and i-propanolate, phenolate, trifluoromethylphenolate, naphtholate, silanolate may be mentioned.
- 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.
- alicyclic C 3 to C 2 hydrocarbon radicals such as cyclopropyl, cyclobutyl, cyclopentyl and in particular cyclohexyl or C 5 to C 2 o-bicycloalkyl, such as bicyclopentyl, and in particular bicycloheptyl and bicyclooctyl.
- substituents X 1 , X 2 with aromatic structural units are C ⁇ - 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 tolyl, benzyl.
- metallocene complexes I are: bis (n-oetadecylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (tetrahydroindenyl) zirconium dichloride, bis [(tert.-butyldimethylsilydichlorodichlorodichloride) dichloride -butylcyclopentadienyl) zirconium dichloride.
- the metallocene complexes of the general formula I can be synthesized in a simple manner by known processes, for example Brauer (ed.): Handbuch der preparative inorganic chemistry, volume 2, 3rd editions, 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 according to the invention also contain activators B) which are known per se and are also called cocatalysts in the literature. In general, they alkylate the transition metal component A) of the catalyst system and / or abstract a ligand X from the transition metal component, so that a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can ultimately result.
- activators B which are known per se and are also called cocatalysts in the literature. In general, they alkylate the transition metal component A) of the catalyst system and / or abstract a ligand X from the transition metal component, so that a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can ultimately result.
- 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.
- activator compounds are aluminum organyl, boron organyle and carbocation salts.
- Open-chain or cyclic alumoxane compounds of the general formula II or III are preferred, which can be obtained according to US Pat. No. 4,794,096 by reacting aluminum trialkyls with water.
- R represents a Ci to C ß alkyl group, preferably Methyl ⁇ or ethyl group, and m is an integer from 5 to 30, preferably 10 to 25th
- the oligomeric alumoxane compounds are present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
- R 2 is hydrogen, C 1 - to C 10 -alkyl, preferably C 1 to C 4 -alkyl, in particular methyl, ethyl, 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 A1 (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 is a hydrogen atom.
- Particularly preferred compounds are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, di-isobutyl aluminum hydride, diethyl aluminum chloride.
- organic boron compounds are also very suitable as activators, for example tris-arylboron compounds, preferably tris (pentafluorophenyl) boron, furthermore salts of carbonium ions, preferably triphenylmethyl tetraaryl borate, in particular triphenylmethyl tetra (pentafluoropheny dborate).
- tris-arylboron compounds preferably tris (pentafluorophenyl) boron
- furthermore salts of carbonium ions preferably triphenylmethyl tetraaryl borate, in particular triphenylmethyl tetra (pentafluoropheny dborate).
- Al, B or C compounds mentioned are known or can be obtained in a manner known per se.
- the activators can be used alone or as mixtures in the catalyst system.
- the activator component B) is preferably used in a molar excess with respect to the metal complex A).
- the molar ratio of activator B) to metal complex A) is generally 100: 1 to 10000: 1, preferably 100: 1 to 1000: 1.
- the constituents of the catalyst systems according to the invention 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.
- a particular advantage of the catalyst systems of the process according to the invention is their substantial solubility in the reaction mixture.
- the oligomers according to the invention can be prepared in the conventional reactors used for the oligomerization of olefins, either batchwise or preferably continuously.
- Suitable reactors include Konuierlich operated stirred kettle, where it is also possible to use a number of several stirred kettles connected in series.
- the oligomerization can be carried out in the gas phase, in a suspension, in liquid monomers and in inert solvents.
- solvents in particular liquid 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, preferably more than 60% by volume absolute and in particular more than 80% by volume absolute.
- the oligomeric aluminoxane compound preferably as a solution in toluene
- the olefin with 2 to 12 carbon atoms is added and the temperature is increased.
- oligomerization is carried out for 20 to 800 minutes, preferably 50 to 200 minutes.
- the temperatures here are from 0 to 250 ° C., preferably from 20 to 200 ° C., and the work is carried out at pressures from 100 to 300,000 kPa, preferably in the range from 100 to 10,000 kPa and in particular in the range from 100 to 4000 kPa.
- the oligomerization can therefore be carried out using the low-pressure, medium-pressure and high-pressure processes.
- the amount of catalyst used is not critical.
- oligomers with molecular weights Mw (weight average) of preferably 100 to 20,000, particularly preferably 100 to 10,000, in particular 100 to 5,000, which have a high content of terminal vinylidene double bonds.
- the degree of polymerization of the olefin oligomers is generally in the range from 2 to 200, preferably in the range from 2 to 100.
- the molecular weight distribution Mw / Mn (weight average / number average), measured with the method of gel permeation chromatography (GPC) at 35 ° C. with polystyrene as column material and THF as solvent against a polystyrene standard, the 5 olefin oligomers thus obtained is 1. 0 to 2.4, preferably 1.8 to 2.2 and in particular 1.8 to 2.0.
- the GPC diagram advantageously shows only a relative maximum for the molecular weight distribution, i.e. there is a monomodal molecular weight distribution.
- the olefin oligomers obtained in this way can be further processed with the customary chemical reactions, such as hydoformylation or hydroamination or a combination of both methods, to functionalized oligo-olefins which are suitable, for example, as lubricants or fuel or oil additives are. Because of their double bond content, the olefin oligomers obtained can also be used as macromonomers.
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96900602A EP0807096A1 (fr) | 1995-02-01 | 1996-01-20 | Procede de preparation d'oligomeres d'olefine |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19503089.3 | 1995-02-01 | ||
DE19503089 | 1995-02-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996023751A1 true WO1996023751A1 (fr) | 1996-08-08 |
Family
ID=7752799
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/000235 WO1996023751A1 (fr) | 1995-02-01 | 1996-01-20 | Procede de preparation d'oligomeres d'olefine |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0807096A1 (fr) |
WO (1) | WO1996023751A1 (fr) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998052888A1 (fr) * | 1997-05-23 | 1998-11-26 | Sasol Technology (Proprietary) Limited | Production d'oligomeres |
WO1999067347A2 (fr) * | 1998-06-19 | 1999-12-29 | Basf Aktiengesellschaft | Oligodecenes produits par catalyse au metallocene, leur production et leur utilisation comme composants dans des lubrifiants |
US6706828B2 (en) | 2002-06-04 | 2004-03-16 | Crompton Corporation | Process for the oligomerization of α-olefins having low unsaturation |
WO2007011973A1 (fr) * | 2005-07-19 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Procede pour produire des polyalphaolefines de faible viscosite |
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 |
WO2012166571A1 (fr) | 2011-05-27 | 2012-12-06 | Exxonmobil Research And Engineering Company | Procédé pour la production d'une composition de lubrifiant à deux phases |
WO2012166999A1 (fr) | 2011-06-01 | 2012-12-06 | Exxonmbil Research And Engineering Company | Composition lubrifiante à haute efficacité |
WO2012166575A1 (fr) | 2011-05-27 | 2012-12-06 | Exxonmobil Research And Engineering Company | Compositions d'huile dans de l'huile et leurs procédés de fabrication |
US8357829B2 (en) | 2008-05-07 | 2013-01-22 | Basf Se | α-olefin/isobutene diblock copolymers |
US8569216B2 (en) | 2011-06-16 | 2013-10-29 | Exxonmobil Research And Engineering Company | Lubricant formulation with high oxidation performance |
US8834705B2 (en) | 2006-06-06 | 2014-09-16 | Exxonmobil Research And Engineering Company | Gear oil compositions |
US8865959B2 (en) | 2008-03-18 | 2014-10-21 | Exxonmobil Chemical Patents Inc. | Process for synthetic lubricant production |
US8921291B2 (en) | 2005-07-19 | 2014-12-30 | Exxonmobil Chemical Patents Inc. | Lubricants from mixed alpha-olefin feeds |
US8921290B2 (en) | 2006-06-06 | 2014-12-30 | Exxonmobil Research And Engineering Company | Gear oil compositions |
US8957159B2 (en) | 2002-10-15 | 2015-02-17 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US9365663B2 (en) | 2008-03-31 | 2016-06-14 | Exxonmobil Chemical Patents Inc. | Production of shear-stable high viscosity PAO |
US9422385B2 (en) | 2013-01-30 | 2016-08-23 | Exxonmobil Chemical Patents Inc. | Polyethylene copolymers with vinyl terminated macromonomers as comonomers |
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 |
US9815915B2 (en) | 2010-09-03 | 2017-11-14 | Exxonmobil Chemical Patents Inc. | Production of liquid polyolefins |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0268214A1 (fr) * | 1986-11-13 | 1988-05-25 | Idemitsu Kosan Company Limited | Procédé pour l'oligomérisation de propylène |
DE4030399A1 (de) * | 1990-09-26 | 1992-04-02 | Basf Ag | Makromolekuele des propylens mit einem funktionellen kettenende |
EP0519237A2 (fr) * | 1991-06-18 | 1992-12-23 | BASF Aktiengesellschaft | Systèmes catalytiques solubles pour préparation de poly-1-alcènes de haut poids moléculaire |
EP0540108A1 (fr) * | 1991-10-28 | 1993-05-05 | Shell Internationale Researchmaatschappij B.V. | Composition de catalyseur |
EP0545140A1 (fr) * | 1991-11-29 | 1993-06-09 | BASF Aktiengesellschaft | Copolymères d'éthylène de faible densité |
-
1996
- 1996-01-20 EP EP96900602A patent/EP0807096A1/fr not_active Ceased
- 1996-01-20 WO PCT/EP1996/000235 patent/WO1996023751A1/fr not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0268214A1 (fr) * | 1986-11-13 | 1988-05-25 | Idemitsu Kosan Company Limited | Procédé pour l'oligomérisation de propylène |
DE4030399A1 (de) * | 1990-09-26 | 1992-04-02 | Basf Ag | Makromolekuele des propylens mit einem funktionellen kettenende |
EP0519237A2 (fr) * | 1991-06-18 | 1992-12-23 | BASF Aktiengesellschaft | Systèmes catalytiques solubles pour préparation de poly-1-alcènes de haut poids moléculaire |
EP0540108A1 (fr) * | 1991-10-28 | 1993-05-05 | Shell Internationale Researchmaatschappij B.V. | Composition de catalyseur |
EP0545140A1 (fr) * | 1991-11-29 | 1993-06-09 | BASF Aktiengesellschaft | Copolymères d'éthylène de faible densité |
Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998052888A1 (fr) * | 1997-05-23 | 1998-11-26 | Sasol Technology (Proprietary) Limited | Production d'oligomeres |
WO1999067347A2 (fr) * | 1998-06-19 | 1999-12-29 | Basf Aktiengesellschaft | Oligodecenes produits par catalyse au metallocene, leur production et leur utilisation comme composants dans des lubrifiants |
WO1999067347A3 (fr) * | 1998-06-19 | 2000-02-17 | Basf Ag | Oligodecenes produits par catalyse au metallocene, leur production et leur utilisation comme composants dans des lubrifiants |
US6706828B2 (en) | 2002-06-04 | 2004-03-16 | Crompton Corporation | Process for the oligomerization of α-olefins having low unsaturation |
US7129306B2 (en) | 2002-06-04 | 2006-10-31 | Crompton Corporation | Process for the oligomerization of α-olefins having low unsaturation |
US8957159B2 (en) | 2002-10-15 | 2015-02-17 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US9593288B2 (en) | 2005-07-19 | 2017-03-14 | Exxonmobil Chemical Patents Inc. | Lubricants from mixed alpha-olefin feeds |
JP2009501836A (ja) * | 2005-07-19 | 2009-01-22 | エクソンモービル・ケミカル・パテンツ・インク | ポリαオレフィン組成物およびこれを生成するためのプロセス |
AU2006270436B2 (en) * | 2005-07-19 | 2011-12-15 | Exxonmobil Chemical Patents Inc. | Polyalpha-olefin compositions and processes to produce the same |
US9409834B2 (en) | 2005-07-19 | 2016-08-09 | Exxonmobil Chemical Patents Inc. | Low viscosity poly-alpha-olefins |
WO2007011459A1 (fr) | 2005-07-19 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Nouvelles compositions polyalphaolefiniques et procedes de realisation afferents |
WO2007011973A1 (fr) * | 2005-07-19 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Procede pour produire des polyalphaolefines de faible viscosite |
US8921291B2 (en) | 2005-07-19 | 2014-12-30 | Exxonmobil Chemical Patents Inc. | Lubricants from mixed alpha-olefin feeds |
US8834705B2 (en) | 2006-06-06 | 2014-09-16 | Exxonmobil Research And Engineering Company | Gear oil compositions |
US8921290B2 (en) | 2006-06-06 | 2014-12-30 | 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 |
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 |
US8865959B2 (en) | 2008-03-18 | 2014-10-21 | Exxonmobil Chemical Patents Inc. | Process for synthetic lubricant production |
US9365663B2 (en) | 2008-03-31 | 2016-06-14 | Exxonmobil Chemical Patents Inc. | Production of shear-stable high viscosity PAO |
US8357829B2 (en) | 2008-05-07 | 2013-01-22 | Basf Se | α-olefin/isobutene diblock copolymers |
US9701595B2 (en) | 2009-12-24 | 2017-07-11 | Exxonmobil Chemical Patents Inc. | Process for producing novel synthetic basestocks |
WO2011079042A2 (fr) | 2009-12-24 | 2011-06-30 | Exxonmobil Chemical Patents Inc. | Procédé de production d'huiles de base synthétiques inédites |
US8557902B2 (en) | 2010-08-25 | 2013-10-15 | Exxonmobil Chemical Patents Inc. | Functionalizable synthetic hydrocarbon fluids and integrated method for production thereof |
WO2012027139A2 (fr) | 2010-08-25 | 2012-03-01 | Exxonmobil Chemical Patents Inc. | Hydrocarbures synthétiques fluides pouvant être fonctionnalisés et leur procédé intégré de production |
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 |
WO2012166575A1 (fr) | 2011-05-27 | 2012-12-06 | Exxonmobil Research And Engineering Company | Compositions d'huile dans de l'huile et leurs procédés de fabrication |
WO2012166571A1 (fr) | 2011-05-27 | 2012-12-06 | Exxonmobil Research And Engineering Company | Procédé pour la production d'une composition de lubrifiant à deux phases |
US8623796B2 (en) | 2011-05-27 | 2014-01-07 | Exxonmobil Research And Engineering Company | Oil-in-oil compositions and methods of making |
US9127231B2 (en) | 2011-06-01 | 2015-09-08 | Exxonmobil Research And Engineering Company | High efficiency lubricating composition |
WO2012166999A1 (fr) | 2011-06-01 | 2012-12-06 | Exxonmbil Research And Engineering Company | Composition lubrifiante à haute efficacité |
US8569216B2 (en) | 2011-06-16 | 2013-10-29 | Exxonmobil Research And Engineering Company | Lubricant formulation with high oxidation performance |
US9422385B2 (en) | 2013-01-30 | 2016-08-23 | Exxonmobil Chemical Patents Inc. | Polyethylene copolymers with vinyl terminated macromonomers as comonomers |
Also Published As
Publication number | Publication date |
---|---|
EP0807096A1 (fr) | 1997-11-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0807096A1 (fr) | Procede de preparation d'oligomeres d'olefine | |
EP0687693B1 (fr) | Systèmes catalytiques amidinato pour la polymérisation d'oléfines | |
EP0603232B1 (fr) | Procede pour la fabrication de polypropylene sous haute pression | |
DE69702978T3 (de) | Polymerisationsverfahren unter erhöhtem druck mit spätübergangsmetallkatalysatorsystemen | |
EP0069951B1 (fr) | Procédé de préparation de polyoléfines | |
DE69922536T2 (de) | Verbrückte hafnocenen für die copolymerisation von olefinen | |
EP0582195B1 (fr) | Procédé de préparation de polymères utilisant des métallocènes spécifiques | |
EP0781783B1 (fr) | Systèmes catalytiques à base de métallocène comportant une base de Lewis présentant un encombrement stérique | |
DE3124223A1 (de) | "verfahren zur herstellung eines polyolefins und katalysator hierfuer" | |
EP0459185A2 (fr) | Procédé de préparation d'une polyoléfine | |
DE112011100520T5 (de) | Katalysator zur stereoselektiven Olefinpolymerisation und Verfahren zur Herstellung von stereoselektivem Polyolefin | |
DE2110209A1 (de) | Verfahren zur Herstellung einer Zubereitung eines Ubergangsmetalls fur das Polymerisieren von Olefinen | |
DE4205932A1 (de) | Verfahren zur herstellung von propenoligomeren | |
DE69917932T2 (de) | Katalysatorsystem für olefinpolymerisation | |
EP0384263A1 (fr) | Procédé de préparation d'un copolymère statistique de propylène | |
DE19516803A1 (de) | Organometallverbindung | |
DE2027302B2 (de) | Verfahren zur Herstellung von Äthylenpolymerisaten | |
DE19719517A1 (de) | Katalysatorlösung zur Polymerisation von alpha-Olefinen | |
EP1095069B1 (fr) | Procede permettant de preparer un systeme de catalyseur supporte | |
EP0068256B1 (fr) | Procédé de préparation d'un polymère d'oléfine et d'un catalyseur approprié | |
EP0608707B1 (fr) | Co-oligomère d'alpha-oléfines et de faible quantité d'éthylène | |
DE69835373T2 (de) | Olefin-polymerisationskatalysatorzusammensetzung, die übergangsmetallverbindungen in niedriger oxidationsstufe enthält | |
EP0707010B1 (fr) | Métallocènes | |
DE3336761A1 (de) | Verfahren zur herstellung eines aethylen-copolymeren | |
EP0007061A1 (fr) | Procédé pour la polymérisation des 1-oléfines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1996900602 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref country code: US Ref document number: 1997 875415 Date of ref document: 19970728 Kind code of ref document: A Format of ref document f/p: F |
|
WWP | Wipo information: published in national office |
Ref document number: 1996900602 Country of ref document: EP |
|
WWR | Wipo information: refused in national office |
Ref document number: 1996900602 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1996900602 Country of ref document: EP |