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    • 专利摘要:
    The invention relates to a process for preparing a low viscosity oil comprising more than 50% by weight of 9-methyl-11-octyl-henicosane. This method uses a particular metallocene catalyst and makes it possible to prepare a polyalphaolefin oil (PAO) whose kinematic viscosity at 100 ° C., measured according to the ASTM D445 standard, ranges from 3 to 4 mm 2 s -1. This oil can be used as a high-performance lubricant for lubrication in the fields of engines, gears, brakes, hydraulic fluids, refrigerants, greases.
    公开号:FR3021665A1
    申请号:FR1454926
    申请日:2014-05-30
    公开日:2015-12-04
    发明作者:Marion Courtiade；Julien Sanson；Alexandre Welle；Martine Slawinski；Jeroen Wassenaar
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    [0001] This invention relates to a process for the preparation of a low viscosity oil comprising more than 50% by weight of 9-methyl-11-octyl-henicosane. This process uses a particular metallocene catalyst and makes it possible to prepare a polyalphaolefin (PAO) oil whose kinematic viscosity at 100 ° C., measured according to the ASTM D445 standard, ranges from 3 to 4 mm 2 s -1. This oil can be used as a high-performance lubricant for lubrication in the fields of engines, gears, brakes, hydraulic fluids, refrigerants, greases. In the API classification of base oils, polyalphaolefins (PAO) are referenced as Group IV base oils. Thanks to a good compromise between the viscosity, the volatility and the cold properties, these PAO are more and more used in the high performance lubricating formulas. In particular, this better compromise is very advantageous compared to Group III mineral bases. In general, PAOs are synthesized from different olefinic monomers, in particular from C 6 -C 14 monomers, by acid catalysis or in the presence of a metallocene catalyst. In general, to prepare low viscosity products whose grades range from 2 to 10, acid catalysts are used. Processes for the preparation of PAO by metallocene catalysis are known, generally making it possible to produce high viscosity products whose kinematic viscosity at 100 ° C., measured according to the ASTM D445 standard, ranges from 40 to 150 mm 2 .s-1 (40 grades). at 150). In addition, the need for high performance lubricants is increasing. In particular, because of conditions of use whose severity increases, for example because of very high temperatures or mechanical stresses. The spacing of the oil changes and the reduction in the size of the lubrication systems also increase the need for high performance lubricants. Energy efficiency and in particular the improvement of the Fuel Eco (FE) lubricants or the reduction of the fuel consumption of the engines, in particular the engines of 3021665 2 vehicle, are objectives more and more important and lead to the increasing use of high performance lubricants. High performance lubricants must therefore have improved properties, particularly with regard to kinematic viscosity, viscosity index, volatility, dynamic viscosity or cold pour point. Thermal stability and oxidation resistance are also properties to be improved for high performance lubricants. Reduced toxicity and good miscibility with other lubricants or other materials are also properties to look for high performance lubricants. Furthermore, improved PAO preparation methods must also be developed, in particular to improve the yield or selectivity of these processes. The improvement of the catalytic activity must also be aimed at.
    [0002] The processes for preparing PAO should also make it possible to recycle all or part of the secondary products resulting from the oligomerization reactions. PAO preparation processes should also be able to control the molecular weight as well as the polydispersity index and the distribution of PAOs formed. The improvement of the characterization techniques of the different products formed during the synthesis of PAO is also to be sought, in particular during the qualitative or quantitative analysis of the products formed. WO-2013/055480 discloses the preparation of PAOs useful as vehicle engine lubricants. This document describes a lubricating composition comprising such an oil associated with another base oil and a viscosity index improving additive. However, this patent application does not disclose 9-methylene-11-octyl-henicosane or its particular properties. WO-2007/01973 describes the catalytic preparation of PAO. This patent application describes the use of non-bridged metallocene catalysts. This document does not describe the preparation of 9-methyl-11-octyl-henicosane, nor its particular properties. WO-2007/011459 discloses PAOs obtained from the polymerization of C5-C24olefins. This patent application does not disclose 9-methyl-11-octyl-henicosane or its particular properties.
    [0003] WO 02/14384 discloses a metallocene catalyzed olefin polymerization process. The process described uses only fluoro-cyclopentadienyl catalysts. This document does not describe the preparation of 9-methyl-11-octyl-henicosane.
    [0004] There is therefore a need to prepare high performance lubricants to provide a solution to some or all of the lubricant problems or prior art lubricant preparation processes. Thus, the invention provides a process for the preparation of an oil of kinematic viscosity at 100 ° C., measured according to ASTM D445, ranging from 3 to 4 mm 2 s -1, comprising more than 50% by weight of trimer of 1-decene of formula (I), (I) comprising 15 ^ oligomerization of 1-decene in the presence of hydrogen (H2), a metallocene catalyst and an activator compound or in the presence of hydrogen (H2 ), a metallocene catalyst, an activator compound and a coactivator compound; catalytic hydrogenation of the oligomerization products in the presence of hydrogen (H2) and a hydrogenation catalyst; the separation by distillation at reduced pressure of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I). Preferably, the process according to the invention comprises the oligomerization of 1-decene in the presence of hydrogen (H2), a metallocene catalyst, an activator compound and a coactivator compound; catalytic hydrogenation of the oligomerization products in the presence of hydrogen (H2) and a catalyst selected from a hydrogenation catalyst and a hydrogenation catalyst comprising palladium; Separation by distillation at reduced pressure of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I). (I) Preferably, the oligomerization of 1-decene is carried out in the presence of a metallocene catalyst which is a racemic compound of formula (II) L (Q1) (Q2) MR1R2 (II) wherein o M represents a transition metal selected from titanium, zirconium, hafnium, and vanadium or represents zirconium; Q1 and Q2, substituted or unsubstituted, independently represent a cyclic group tetrahydroindenyl or Q1 and Q2 independently represent a cyclic group tetrahydroindenyl and are bonded to form a polycyclic structure; L represents a bridging divalent Cl-C20-alkyl group Q1 and Q2 where L represents a group selected from methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH (CH3) -), 1 -methyl-ethylene (-CH (CH3) -CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH (CH3) -CH2-), 3-methylpropylene (-CH2 -CH 2 -CH (CH 3) -), n-butylene (-CH 2 -CH 2 -CH 2 -CH 2 -), 2-methylbutylene (-CH 2 -CH (CH 3) -CH 2 -CH 2 -), 4-methylbutylene (-CH 2 -CH2-CH2-CH (CH3) -), pentylene and its isomers, hexylene and isomers thereof, heptylene and isomers thereof, octylene and isomers thereof, nonylene and isomers thereof, decylene and isomers thereof, undecylene and isomers thereof, dodecylene and its isomers; R 1 and R 2, substituted or unsubstituted, independently represent an atom or a group selected from hydrogen, halo (such as Cl and l), alkyl (such as Me, Et, nPr, iPr), alkenyl, alkynyl, haloalkyl haloalkenyl, haloalkynyl, silylalkyl, silylalkenyls, silylalkynyls, germylalkyl, germylalkenyl, germylalkynyl; or R1 and R2 form with M 30 a metallocycle comprising from 3 to 20 carbon atoms. More preferably, the metallocene catalyst is a racemic compound of formula (II) wherein M is zirconium; O1 and Q2, substituted or unsubstituted, independently represent a tetrahydroindenyl cyclic group; L represents a group selected from methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH (CH3) -), 1-methyl-ethylene (-CH (CH3) -CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH (CH3) -CH2-), 3-methylpropylene (-CH2-CH2-CH (CH3) -), nbutylene (-CH2- CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH (CH3) -CH2-CH2-), 4-methylbutylene (-CH2-CH2-CH2-CH (CH3) -), pentylene and isomers thereof, hexylene and its isomers, heptylene and isomers thereof, octylene and isomers thereof, nonylene and isomers thereof, decylene and isomers thereof, undecylene and isomers thereof, dodecylene and isomers thereof; R 1 and R 2, substituted or unsubstituted, independently represent a halogen atom, such as Cl and I, or an alkyl group, such as Me, Et, nPr, iPr. Even more preferably, the metallocene catalyst is selected from rac-ethylene bis (tetrahydroindenyl) zirconium dimethyl and rac-ethylene bis (tetrahydroindenyl) zirconium dichloride, in particular rac-ethylene bis (tetrahydroindenyl) zirconium dimethyl.
    [0005] For the process according to the invention, the catalyst is used in an activated form for the oligomerization of 1-decene. Thus, the process according to the invention uses an activator compound during the oligomerization of 1-decene. Advantageously, the activator compound is chosen from an alumoxane, an ionic activator and their mixtures.
    [0006] Preferably for the process according to the invention, the alumoxane is an oligomeric compound comprising residues of the formula -Al (R) -O- in which R is independently a cyclic or linear Cl-C20 alkyl group. Preferably, the alumoxane is chosen from methylalumoxane, modified methylalumoxane, ethylalumoxane, isobutylalumoxane and mixtures thereof.
    [0007] Also preferably, the alumoxane is employed in an alumoxane / catalyst molar ratio ranging from 1 to 10,000, preferably from 10 to 3,000 and more preferably from 100 to 1,500. Preferably, for the process according to the invention, the activator compound is an ionic activator. The ionic activator may be selected from dimethylanilinium tetrakis- (perfluorophenyl) borate (DMAB), triphenylcarbonium tetrakis (perfluorophenyl) borate, dimethylanilinium tetrakis- (perfluorophenyl) aluminate and mixtures thereof. More preferably, the ionic activator is dimethylanilinium tetrakis- (perfluorophenyl) borate (DMAB). Also preferably, the ionic activator is used in an ionic activator / catalyst molar ratio of from 0.5 to 4, preferably from 0.8 to 1.2. During the oligomerization of 1-decene, the process according to the invention uses an activator compound. It may also be advantageous to use a coactivator compound, in particular when using an ionic activator.
    [0008] Preferably, the coactivator compound is a trialkylaluminum derivative. More preferably, the co-activator compound is selected from tri-ethyl aluminum (TEAL), tri-iso-butyl aluminum (TIBAL), tri-methyl aluminum (TMA), methyl-methyl-ethyl aluminum (MMEAL) and tri n-octyl aluminum. Advantageously, tri-iso-butyl aluminum (TIBAL) is used in the form of a dispersion ranging from 10 to 60% by weight. Also preferably, the coactivator compound is used in a co-activator / catalyst compound molar ratio ranging from 10 to 1,000, preferably from 20 to 200.
    [0009] In general, the metallocene catalyst is activated by combining the metallocene catalyst and the activator compound, simultaneously or sequentially, at predetermined time intervals. The combination of the metallocene catalyst and the activator compound can be carried out in the presence or absence of 1-decene and hydrogen (H2). During oligomerization of 1-decene, the coactivator compound may be introduced with the activator compound. Preferably, the activated catalyst is prepared in advance and then introduced into the oligomerization reactor with 1-decene and hydrogen (H2). Advantageously, the metallocene catalyst and the activator compound, optionally in the presence of a coactivator compound, are contacted at a pressure of 1 bar and a temperature of 20 ° C. Advantageously, the oligomerization of 1-decene is carried out in a time ranging from 2 to 300 min. Preferably, the duration of the oligomerization is from 5 to 180 min, in particular from 30 to 140 min.
    [0010] Also advantageously, the oligomerization of 1-decene is carried out in the presence of hydrogen (H 2) at a partial pressure of from 0.1 to 20 bar. Preferably, the hydrogen partial pressure (H2) ranges from 1 to 6 bar. Also advantageously, the oligomerization is carried out at a hydrogen to 1-decene mass ratio of greater than 100 ppm or less than 600 ppm. Preferably, this ratio is between 100 and 600 ppm. Also advantageously, the oligomerization of 1-decene is carried out at a temperature ranging from 50 to 200 ° C, preferably from 70 to 160 ° C. More preferably, the temperature upon oligomerization of 1-decene is from 80 to 150 ° C and even more preferably from 90 to 140 ° C or from 100 to 130 ° C. The oligomerization of 1-decene can be carried out in 1-decene, which then serves as a support for the reaction. The reaction is then advantageously carried out in the absence of a solvent. The oligomerization of 1-decene can also be carried out in a solvent. Preferably, the solvent may be chosen from a linear or branched hydrocarbon, a cyclic or non-cyclic hydrocarbon, an alkyl aromatic compound and mixtures thereof. As preferred solvents for the oligomerization of 1-decene, it is preferred to use a solvent selected from butanes, pentanes, hexanes, heptanes, octanes, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, methylcycloheptane, toluene, xylene and mixtures thereof. After the oligomerization of 1-decene, the process according to the invention implements the catalytic hydrogenation of the oligomerization products. The catalytic hydrogenation of the oligomerization products is carried out in the presence of hydrogen (H2) and a hydrogenation catalyst. Preferably, the hydrogenation catalyst is chosen from a palladium derivative, a supported palladium derivative, a palladium derivative supported on alumina (for example on gamma-alumina), a nickel derivative or a supported nickel derivative. , a nickel derivative supported on kieselguhr, a platinum derivative, a supported platinum derivative, a cobalt-molybdenum derivative, a supported cobalt-molybdenum derivative.
    [0011] More preferably, the hydrogenation catalyst comprises palladium. A particularly preferred hydrogenation catalyst comprises palladium supported on alumina (for example on gamma-alumina).
    [0012] Also preferably, the hydrogen pressure (H2) during the catalytic hydrogenation of the oligomerization products is from 5 to 50 bar, more preferably from 10 to 40 bar, in particular from 15 to 25 bar. After the oligomerization of 1-decene and the catalytic hydrogenation of the oligomerization products, the process according to the invention comprises the separation by distillation at reduced pressure of the fraction of trimers comprising more than 50% by weight of trimer of 1 -ecene of formula (I). The separation by distillation is carried out under reduced pressure. Advantageously, the distillation separation is carried out according to ASTM D2892 or ASTM D5236. More advantageously, the separation is carried out in two stages, by distillation according to ASTM D2892 and then by distillation according to ASTM D5236. Preferably, during the separation by distillation according to ASTM D2892, the initial boiling point (IBP) is less than 370 ° C, preferably less than 375 ° C. The partial pressure is advantageously less than 0.5 mmHg. Distillation according to ASTM D2892 makes it possible to separate products whose boiling point is below these temperatures. Preferably, during the separation by distillation according to ASTM D5236, the initial boiling point (IBP) is between 360 and 485 ° C, preferably between 370 and 480 ° C or between 370 ° C and 370 ° C. and 470 ° C. More preferably, the initial boiling point is between 375 and 465 ° C when carrying out the distillation separation according to ASTM D5236. The partial pressure is advantageously less than 0.5 mmHg. In a preferred manner, the separation by distillation according to ASTM D5236 makes it possible to separate the fraction of trimers comprising more than 50% by weight of 1-decene trimer of formula (I). Thus, separation by distillation at reduced pressure makes it possible to separate the fraction of trimers resulting from the oligomerization of 1-decene and then from the hydrogenation of the oligomerization products. This trimeric fraction comprises more than 50% by weight of 1-decene trimer of formula (I).
    [0013] In addition to the oligomerization steps of 1-decene, catalytic hydrogenation of the oligomerization products and separation by distillation at reduced pressure of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of the formula (I), the method according to the invention may advantageously comprise other steps. Thus, the process according to the invention can also combine all or part of the following steps: the prior preparation of 1-decene by catalytic oligomerization of ethylene; deactivation of the catalyst after the oligomerization of 1-decene or after the catalytic hydrogenation of the oligomerization products; Recycling the dimeric fraction of 1-decene (for example 9-methyl-nonadecane), separated by distillation at reduced pressure and oligomerization of this dimer fraction of 1-decene recycled with 1-decene, in the presence of hydrogen (H2), a metallocene catalyst and an activator compound or in the presence of hydrogen (H2), a metallocene catalyst, an activator compound and a co-activator compound ; a final step of hydrogenation of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I) in the presence of hydrogen (H 2) and of a catalyst chosen from a hydrogenation catalyst and a hydrogenation catalyst comprising palladium.
    [0014] The prior preparation of 1-decene by catalytic oligomerization of ethylene is known as such. It can be particularly advantageous in combination with the other steps of the process according to the invention. This prior preparation of 1-decene by catalytic oligomerization of ethylene makes it possible in particular to use more abundant sources of starting substrate. Furthermore, and preferably, once the oligomerization of 1-decene has been carried out, the process according to the invention may comprise the deactivation of the catalyst. The deactivation of the oligomerization catalyst can be carried out after the oligomerization of 1-decene or after the catalytic hydrogenation of the oligomerization products. Preferably, the deactivation of the oligomerization catalyst is carried out after the oligomerization of 1-decene and before the catalytic hydrogenation of the oligomerization products. Advantageously, the deactivation of the catalyst is effected by the action of air or water or by means of at least one alcohol or a deactivating agent solution. Preferably, the catalyst is deactivated by means of at least one alcohol, for example isopropanol. Particularly advantageously, the process according to the invention may also comprise the recycling of the dimer fraction of 1-decene which is separated by distillation under reduced pressure and then the oligomerization of this dimer fraction of the recycled 1decene with 1-decene. decene. Preferably, this dimer fraction of the recycled 1decene comprises 9-methyl-nonadecane. The oligomerization of this dimeric fraction of the recycled 1-decene can then be carried out in the presence of hydrogen (H 2), a metallocene catalyst and an activator compound or in the presence of hydrogen (H 2), a metallocene catalyst, an activator compound and a coactivator compound. The oligomerization of this dimeric fraction of the recycled 1-decene can be carried out in the oligomerization reactor of 1-decene or in one or more separate reactors. Preferably, it is carried out in the oligomerization reactor of 1-decene and under the same conditions as this oligomerization of 1-decene. Particularly advantageously, the recycling and then the oligomerization of this fraction of dimers of 1-decene recycled with 1-decene makes it possible to improve the overall yield of the preparation process according to the invention and thus to produce a larger quantity. of oil according to the invention comprising more than 50% by weight of 9-methyl-11-octyl-hen icosane. Also advantageously, the process according to the invention may comprise a final stage of hydrogenation of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I). This final hydrogenation is carried out in the presence of hydrogen (H2) and a hydrogenation catalyst. Preferably, the hydrogenation catalyst is chosen from a palladium derivative, a supported palladium derivative, a palladium derivative supported on alumina (for example on gamma-alumina), a nickel derivative, a supported nickel derivative, a kieselguhr supported nickel derivative, a platinum derivative, a supported platinum derivative, a cobalt-molybdenum derivative, a supported cobalt-molybdenum derivative. More preferably, the hydrogenation catalyst comprises palladium. A particularly preferred catalyst comprises palladium supported on alumina (for example on gamma-alumina).
    [0015] The hydrogenation catalyst is advantageously identical to the hydrogenation catalyst used during the hydrogenation of the oligomerization products of 1-decene. Advantageously, during the final hydrogenation, the hydrogen pressure (H 2) is 5 to 50 bar or 10 to 40 bar, preferably 15 to 25 bar. Also advantageously, during the final hydrogenation, the duration of the hydrogenation is between 2 and 600 min, preferably between 30 and 300 min. Advantageously, during the final hydrogenation, the temperature ranges from 50 to 200 ° C or from 60 to 150 ° C. Preferably, the temperature is 70 to 140 ° C or 80 to 120 ° C.
    [0016] Preferably, the process according to the invention is a process for which the oligomerization of 1-decene is carried out in a time ranging from 2 to 300 min or from 5 to 180 min or from 30 to 140 min; or - the oligomerization of 1-decene is carried out in the presence of hydrogen (H2) at a partial pressure ranging from 0.1 to 20 bar or from 1 to 6 bar; or the oligomerization is carried out in the presence of hydrogen (H 2) in a mass ratio hydrogen / 1-decene greater than 100 ppm or less than 600 ppm or between 100 and 600 ppm; or - the oligomerization of 1-decene is carried out at a temperature ranging from 50 to 200 ° C or from 70 to 160 ° C or from 80 to 150 ° C or from 90 to 140 ° C or from 100 to 130 ° C ; or - the metallocene catalyst is a racemic compound of formula (II) L (Q1) (Q2) MR1R2 (II) in which o M represents a transition metal selected from titanium, zirconium, hafnium, and vanadium or represents zirconium; and Q 2, O c), substituted or unsubstituted, independently represent a tetrahydroindenyl ring group or Q1 and Q2 independently represent a tetrahydroindenyl ring group and are bonded to form a polycyclic structure; L represents a Cl-C20-divalent bridging alkyl group Q1 and Q2 where L represents a group selected from methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH (CH3) -), 1- methylethylene (-CH (CH3) -CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH (CH3) -CH2-), 3-methylpropylene ( -CH2-CH2-CH (CH3) -), n-butylene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH (CH3) -CH2-CH2-), 4-methylbutylene (- CH2-CH2-CH2-CH (CH3) -), pentylene and its isomers, hexylene and isomers thereof, heptylene and isomers thereof, octylene and isomers thereof, nonylene and isomers thereof, decylene and its isomers, undecylene and isomers, dodecylene and its isomers; R 1 and R 2, substituted or unsubstituted, independently represent an atom or a group selected from hydrogen, halogen (such as Cl and I), alkyl (such as Me, Et, nPr, iPr), alkenyl, alkynyl, haloalkyl haloalkenyl, haloalkynyl, silylalkyl, silylalkenyls, silylalkynyls, germylalkyl, germylalkenyl, germylalkynyl; or R1 and R2 together with M form a metallocycle comprising from 3 to 20 carbon atoms; or the metallocene catalyst is selected from rac-ethylene bis (tetrahydroindenyl) zirconium dimethyl and rac-ethylene bis (tetrahydroindenyl) zirconium dichloride; or the oligomerization of 1-decene is carried out in a solvent selected from a linear or branched hydrocarbon, a cyclic or non-cyclic hydrocarbon, an alkylated aromatic compound and mixtures thereof or in a solvent selected from butanes, pentanes, hexanes, heptanes, octanes, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, methylcycloheptane, toluene, xylene and their mixtures; or the activator compound is selected from an ionic activator and an oligomeric compound comprising residues of the formula -Al (R) -O- wherein R 25 independently represents a cyclic or linear Cl-C20 alkyl group; or the activator compound is selected from methylalumoxane, modified methylalumoxane, ethylalumoxane, isobutylalumoxane and mixtures thereof; or the activator compound is selected from dimethylanilinium tetrakis (perfluorophenyl) borate (DMAB), triphenylcarbonium tetrakis (perfluorophenyl) borate, dimethylanilinium tetrakis (perfluorophenyl) aluminate, and mixtures thereof; or the coactivator compound is a trialkylaluminum derivative or a compound selected from triethyl aluminum (TEAL), triisobutyl aluminum (TIBAL), tri-methyl aluminum (TMA), methyl methyl ethyl aluminum (MMEAL) ) and tri-n-octyl aluminum; or deactivation of the catalyst is effected by the action of air or water or by means of at least one alcohol or a deactivating agent solution; or the hydrogen pressure (H2) during the catalytic hydrogenation of the oligomerization products is 5 to 50 bar or 10 to 40 bar or 15 to 25 bar; or the hydrogenation catalyst is selected from a palladium derivative, a supported palladium derivative, a palladium derivative supported on alumina (for example on gamma-alumina), a nickel derivative, a supported nickel derivative, a a nickel derivative supported on kieselguhr, a platinum derivative, a supported platinum derivative, a cobalt-molybdenum derivative, a supported cobalt-molybdenum derivative; or 10 ^ the pressure of hydrogen (H2) during the final hydrogenation of the major fraction by weight of 1-decene trimer of formula (I) ranges from 5 to 50 bar or from 10 to 40 bar or from 15 to 25 bar; or the duration of the hydrogenation during the final hydrogenation is between 2 and 600 min or between 30 and 300 min; or the final hydrogenation is carried out at a temperature of 50 to 200 ° C or 60 to 150 ° C or 70 to 140 ° C or 80 to 120 ° C; the hydrogenation catalyst, during the final hydrogenation of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I), is chosen from a palladium derivative, a palladium derivative, supported, a palladium derivative supported on alumina (eg on gamma-alumina), a nickel derivative, a supported nickel derivative, a kieselguhr supported nickel derivative, a platinum derivative, a supported platinum derivative, a cobalt-molybdenum derivative, a supported cobalt-molybdenum derivative. More preferably, the process according to the invention is a process combining all these characteristics. Even more preferably, the process according to the invention is a process for which the oligomerization of 1-decene is carried out in a time ranging from 30 to 140 min; the oligomerization of 1-decene is carried out in the presence of hydrogen (H2) at a partial pressure ranging from 1 to 6 bar; The oligomerization of 1-decene is carried out in a hydrogen / 1-decene mass ratio of between 100 and 600 ppm; the oligomerization of 1-decene is carried out at a temperature ranging from 100 to 130 ° C; the metallocene catalyst is selected from rac-ethylene bis (tetrahydroindenyl) zirconium dimethyl and rac-ethylene bis (tetrahydroindenyl) zirconium dichloride; The oligomerization of 1-decene is carried out in a solvent chosen from butanes, pentanes, hexanes, heptanes, octanes, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, methylcycloheptane, toluene, xylene and their mixtures; The activator compound is selected from an ionic activator selected from dimethylanilinium tetrakis (perfluorophenyl) borate, triphenylcarbonium tetrakis (perfluorophenyl) borate, dimethylanilinium tetrakis (perfluorophenyl) aluminate, and mixtures thereof; the co-activating compound is a compound chosen from triethyl aluminum (TEAL), tri-iso-butyl aluminum (TIBAL), tri-methyl aluminum (TMA), methyl-methyl-ethyl aluminum (MMEAL) and tri-ethyl aluminum; n-octyl aluminum; deactivation of the catalyst is carried out by means of at least one alcohol; the hydrogen pressure (H2) during the catalytic hydrogenation of the oligomerization products is from 15 to 25 bar; The hydrogenation catalyst is a palladium derivative supported on alumina (for example on gamma-alumina); the hydrogen pressure (H2) during the final hydrogenation of the major fraction by weight of 1-decene trimer of formula (I) ranges from 15 to 25 bar; the duration of the hydrogenation during the final hydrogenation is between 30 and 300 min; the final hydrogenation is carried out at a temperature ranging from 80 to 120 ° C; the hydrogenation catalyst, during the final hydrogenation of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I), is a palladium derivative supported on alumina (for example on gamma Alumina). In a particularly advantageous manner, the process according to the invention may also comprise all or at least one of the following additional steps: the prior preparation of 1-decene by catalytic oligomerization of ethylene; Deactivation of the catalyst after oligomerization of 1-decene and before catalytic hydrogenation of the oligomerization products; recycling of the dimer fraction of 1-decene (for example 9-methylnonadecane), separated by distillation at reduced pressure and oligomerization of this dimer fraction of 1-decene recycled with 1-decene, in the presence of 3021665 Hydrogen (H2), a metallocene catalyst, an activator compound and a coactivator compound; a final step of hydrogenation of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I) in the presence of hydrogen (H 2) and a catalyst selected from a catalyst of hydrogenation and a hydrogenation catalyst comprising palladium supported on alumina (for example on gamma-alumina). For the process according to the invention, the oligomerization can be carried out in sequence. The reactants and the catalyst system are then introduced into a reactor to react to a certain total or partial conversion level. Then, generally, the catalyst is deactivated. An example of a sequence method according to the invention may in particular comprise the introduction of 1-decene, alone or in a solvent, into a stirred reactor. The reactor 15 is then heated to the desired temperature and a determined amount of hydrogen (H2) is introduced into the reactor. Once the reaction conditions are established, the metallocene catalyst is introduced into the reactor. The oligomerization rate is controlled by adjusting the concentration of catalyst and 1-decene in the reactor. After a particular reaction time, the catalyst is deactivated.
    [0017] Oligomerization can also be performed in a semi-continuous mode. The reactants and the catalytic system are then introduced into the reactor simultaneously and continuously in order to keep the ratio of the amounts of 1-decene constant with respect to the catalytic system. The reaction takes place up to a pre-established conversion level. Then the catalyst is generally deactivated.
    [0018] The oligomerization can also be carried out in a continuous mode. The reactants and the catalytic system are then introduced into the reactor simultaneously and continuously in order to keep the ratio of the amounts of 1-decene constant with respect to the catalytic system. The reaction products are continuously separated from the reactor, for example a continuous stirred tank reactor (CSTR). After oligomerization, the oligomerization products are hydrogenated in the presence of hydrogen (H2) and a hydrogenation catalyst. The process according to the invention makes it possible to prepare an oil whose kinematic viscosity is particularly advantageous and ranges from 3 to 4 mm 2 s -1. More advantageously, the kinematic viscosity of this oil ranges from 3.2 to 3.8 mm.sup.-2. Preferably, the 2.sup.1.5, 3.5 mm.sup.2, kinematic viscosity of the oil is 3.4 mm or 3.6 mm2.s-1. Also advantageously, the process according to the invention makes it possible to prepare an oil whose viscosity index is greater than 120 or between 120 and 140 or between 125 and 135. Preferably, the viscosity number of this oil is greater than or equal to 130. According to the invention, the viscosity index is generally calculated according to ASTM D2270.
    [0019] Also advantageously, the process according to the invention makes it possible to prepare an oil whose volatility measured according to the ASTM D6375 standard is less than 10.8% by weight. Preferably, the volatility of this oil is less than 10.5% by weight. Also advantageously, the process according to the invention makes it possible to prepare an oil whose dynamic viscosity (CCS) at -35 ° C., measured according to ASTM D5293, is less than 900 mPa.s. Also advantageously, the dynamic viscosity of this oil is less than 800 mPa.s. According to the invention, the dynamic viscosity of the oil is measured on a rotary dynamic viscometer (CCS cold cranking simulator).
    [0020] Also advantageously, the process according to the invention makes it possible to prepare an oil with an average molecular weight of from 300 to 1000 g / mol, preferably from 350 to 450 g / mol. According to the invention, the average molecular weight is generally calculated according to ASTM D2502.
    [0021] Also advantageously, the process according to the invention makes it possible to prepare an oil whose pour point is less than or equal to -50 ° C., preferably less than or equal to -55 or -57 ° C. According to the invention, the pour point is generally measured according to EN ISO 3016.
    [0022] Advantageously, the invention provides a process for preparing an oil which combines (a) a kinematic viscosity at 100 ° C, measured in accordance with ASTM D445 ranging from 3.2 to 3.8 mm 2 s -1; (B) a viscosity number greater than 120; (C) a volatility measured according to ASTM D6375 less than 10.8% by weight; and (d) a dynamic viscosity (CCS) at -35 ° C, measured according to ASTM D5293 below 900 mPa.s.
    [0023] Also advantageously, the process according to the invention makes it possible to prepare an oil combining these properties (a) and (b); (a) and (c); (a) and (d); (b) and (c); (b) and (d); (c) and (d); (a), (b) and (c); (a), (b) and (d); (a), (c) and (d); (b), (c) and (d). Preferably, the process according to the invention makes it possible to prepare an oil combining 10 (a) a kinematic viscosity at 100 ° C., measured according to the ASTM D445 standard of 3.4 mm 2 s -1, of 3.5 mm 2. s-1 or 3.6 mm2.s-1; (b) a viscosity index greater than or equal to 130; (c) a volatility measured according to ASTM D6375 less than 10.5% by weight; and (d) a dynamic viscosity (CCS) at -35 ° C, measured according to ASTM D5293 below 900 mPa.s. Also preferably, the invention makes it possible to prepare an oil combining these properties (a) and (b); (a) and (c); (a) and (d); (b) and (c); (b) and (d); (c) and (d); (a), (b) and (c); (a), (b) and (d); (a), (c) and (d); (b), (c) and (d).
    [0024] Advantageously, the process according to the invention makes it possible to prepare an oil comprising at least 65% by weight of 1-decene trimer of formula (I) or at least 70% by weight of 1-decene trimer of formula ( I). More advantageously, the oil prepared according to the invention comprises at least 80% by weight of 1-decene trimer of formula (I) or at least 90% by weight of 1-decene trimer of formula (I) . Preferably, the process according to the invention makes it possible to prepare an oil comprising from 50 to 99% by weight of 1-decene trimer of formula (I). More preferably, the oil prepared according to the invention comprises from 60 to 90% by weight of 1-decene trimer of formula (I). Even more preferably, the oil prepared according to the invention comprises from 70 to 90% by weight of 1-decene trimer of formula (I). Also preferably, the process according to the invention makes it possible to prepare an oil comprising from 60 to 95% by weight, from 60 to 80% by weight, from 70 to 95% by weight, from 70 to 80% by weight, of 75 to 95% by weight or 75 to 80% by weight of 1-decene trimer of formula (I).
    [0025] In addition to the 1-decene trimer of formula (I), the oil prepared according to the invention may comprise other oligomers derived from the oligomerization of 1-decene. Thus, this oil may comprise at least one other saturated oligomer of 1-decene. Preferably, this other saturated oligomer of 1-decene may be chosen from the other 5 saturated trimers of 1-decene. It may also be selected from a broader group of saturated oligomers including 1-decene dimers, other 1decene trimers, 1-decene tetramers, 1-decene pentamers. Preferably, the oil prepared according to the invention may also comprise at least one other saturated oligomer of 1-decene selected from 9-methyl-nonadecane and 9-methyl-11,13-dioctyl-tricosane. In addition, the oil prepared according to the invention may also comprise other oligomers of 1-decene of larger sizes. Particularly advantageously, the process according to the invention makes it possible to prepare an oil comprising from 51 to 99.9% by weight, preferably from 70 to 90% by weight, of 1 decene trimer of formula (I) and from 0.1 to 49% by weight, preferably from 10 to 30% by weight, of at least one other saturated trimer of 1-decene.
    [0026] Also advantageously, the process according to the invention makes it possible to prepare an oil comprising from 51 to 99.6% by weight of 1-decene trimer of formula (I); from 0.1 to 1% by weight of at least one saturated dimer of 1-decene, for example 9-methyl-nonadecane; From 0.1 to 25% by weight of at least one other saturated trimer of 1-decene; from 0.1 to 20% by weight of at least one saturated tetramer of 1-decene, for example 9-methyl-11,13-dioctyl-tricosane; from 0.1 to 1.5% by weight of at least one pentamer saturated with 1-decene.
    [0027] The process according to the invention makes it possible to prepare an oil which can be used as a base oil or as a lubricating base oil. This use therefore relates to a low viscosity oil comprising more than 50% by weight of 9-methyl-11-octylenesaccane prepared according to the method of the invention. The process according to the invention makes it possible to prepare an oil which can also be used to improve the Fuel Eco (FE) of a lubricant, to reduce the fuel consumption of an engine or to reduce fuel consumption. of a vehicle engine. The process according to the invention makes it possible to prepare an oil which can be incorporated into a lubricating composition. This lubricating composition therefore comprises an oil of low viscosity comprising more than 50% by weight of 9-methyl-11-octyl-henicosane prepared according to the process of the invention. Advantageously, this lubricating composition may comprise at least 10% by weight or at least 20% by weight of an oil prepared according to the invention Also advantageously, this lubricating composition may comprise at least 30% by weight 40, 50 or 60% by weight of an oil prepared according to the invention Also advantageously, this lubricating composition may comprise an oil prepared according to the invention and at least one other base oil, It may also comprise an oil prepared according to the invention and at least one additive or an oil prepared according to the invention, at least one other base oil and at least one additive, As another base oil combined with the oil prepared according to the invention, this lubricating composition may comprise an oil selected from a Group III oil, a Group IV oil The lubricating composition is particularly advantageous for use as a high-performance lubricant. performance for lubrication in the fields of motors, gears, braking, hydraulic fluids, refrigerants, greases. This lubricant composition can also improve the fuel Eco (FE) of a lubricant, reduce the fuel consumption of an engine or reduce the fuel consumption of a vehicle engine.
    [0028] The various aspects of the invention will be the subject of the following examples, which are provided by way of illustration. EXAMPLES An autoclave reactor equipped with an agitator, a temperature control system and inlets for introducing nitrogen, hydrogen and 1-decene was used. 1-decene (product of the company ICI or the company Acros) is used at a purity higher than 94%. It is purified on 3 A and 13 X molecular sieves (Sigma-Aldrich company). Before use, the molecular sieves used are pre-dried at 200 ° C. for 16 hours.
    [0029] The products are characterized by 1 H NMR and two-dimensional gas phase chromatography (GCxGC). For NMR, the PAO samples were diluted in deuterated chloroform and the NMR spectra were made at 300 K on Bruker 400 MHz spectrometers: H, 130, HMQC (heteronuclear multiple quantum coherence) and HMBC (multiple heteronuclear). bond coherence). Two-dimensional chromatography is carried out in continuous mode by means of two apolar and polar columns. The entire effluent from the first column is separated in the second dimension. The separation of the compounds is governed by the volatility on the first column and by specific interactions (rr-rr type, dipolar interactions, etc.) on the second dimension. Depending on their viscosity, the samples are usually diluted twice in heptane. The chromatographic conditions were optimized to elute the PAOs prepared according to the invention. The samples were analyzed by GCxGC with cryogenic modulation (liquid nitrogen), programming of the first oven from 45 ° C (5 min) to 320 ° C (20 min) with a ramp of 3 ° C / min, a secondary furnace programming of 60 ° C (5 min) up to 330 ° C (20 min) with a ramp of 3 ° C / min of the columns used according to the following operating conditions: 20 0 1st dimension: HP1, 25 m, ID 0.32 mm, film thickness: 0.17 μm; o 2nd dimension: BPX-50, 1.5 m, ID 0.1 mm, film thickness: 0.1 μm; o injector: split 100: 1, volume injected: 0.1 pl; o detector: FID, 320 ° C; o temperature of the hot jet: 320 ° C; Cold programming of the 80 to 5 (3/0) modulation period: 4.8 sec Example 1 An 8L autoclave reactor was used. a flow of nitrogen for one hour and then cooled to 110 ° C. Then, it is filled with 3500 ml of 1-decene under a stream of nitrogen, the temperature of the reactor is maintained at 110 ° C. and hydrogen (It) is introduced at a m / m H2 / 1-decene ratio of 414 ppm The catalyst is rac-ethylene bis (tetrahydroindenyl) zirconium dimethyl activated with dimethylanilinium tetrakis (perfluorophenyl) borate (DMAB) in a molar ratio B / Zr of 3021665 21 1.75 Triisobutyl aluminum (TiBAI) is used as a co-activating compound in a molar ratio Al / Zr of 200. It makes it possible to trap impurities present in the reactor. the introduction of the activated catalyst in a concentration of 17 μM with respect to the oligomerization solution.
    [0030] After 120 min, 5 mL of isopropanol was introduced to deactivate the catalyst. The hydrogenation of the reaction products is then carried out using a palladium catalyst supported on alumina (5 g of palladium on gamma-alumina at 5% w / w relative to the alumina - Alfa Aesar product) and the hydrogen (H2) at 20 bar, at a temperature of 100 ° C, for 240 min.
    [0031] The oligomerization products and the trimeric fraction comprising more than 50% by weight of 9-methyl-11-octyl-henicosane are then separated by distillation at reduced pressure (0.5 mmHg) in two steps according to ASTM D2892. then according to ASTM D5236: (1) by means of a column with 15 theoretical plates whose maximum temperature is 375 ° C. and then (2) by means of a column with 2 theoretical plates whose vapor temperature in column head goes from 375 to 445 ° C. Distillation according to ASTM D2892 makes it possible to separate products whose boiling point is below 375 ° C. Distillation according to ASTM D5236 is used to isolate products with a boiling point of 375 to 445 ° C. The oil according to the invention obtained has a content of 9-methyl-11-octyl-henicosane equal to 71.4%. This oil according to the invention comprising more than 50% by weight of 9-methyl-11-octylenesicane has a kinematic viscosity at 100 ° C., measured according to the ASTM D445 standard, of 3.448 mm 2 s -1. The viscosity number of this oil is 130. Its volatility measured according to ASTM D6375 is 10.3% by weight and its dynamic viscosity (CCS) at -35 ° C., measured according to ASTM D5293, is of 780 mPa.s. Its average molecular weight is 372 g / mol. The characteristics of the oil according to the invention make it possible to obtain excellent lubricating, rheological and oxidation resistance properties as well as Fuel Eco. Example 2 The procedure is identical to Example 1 for the oligomerization of 1-decene. The oligomerization products and the trimeric fraction comprising more than 50% by weight of 9-methyl-11-octyl-henicosane are then separated by distillation at reduced pressure (0.5 mm Hg) in two stages according to standard ASTM D2892 then according to ASTM D5236: (1) by means of a column with 15 theoretical plates whose maximum temperature is 375 ° C then (2) by means of a column with 2 theoretical plates whose temperature of the vapors at the top of the column is from 445 to 465 ° C.
    [0032] Distillation according to ASTM D2892 allows the separation of products whose boiling point is below 375 ° C. Distillation according to ASTM D5236 is used to isolate products with a boiling point of 445 to 465 ° C. The oil according to the invention obtained has a content of 9-methyl-11-octyl-henicosane equal to 65.7%.
    [0033] This oil according to the invention comprising more than 50% by weight of 9-methyl-11-octylhenicosane has a kinematic viscosity at 100 ° C, measured according to ASTM D445, of 3,640 mm 2 s -1. The viscosity number of this oil is 132. Its volatility measured according to the ASTM D6375 standard is 9.1% by weight and its dynamic viscosity (CCS) at -35 ° C., measured according to the ASTM D5293 standard, is of 890 mPa.s. Its average molecular weight is 383 g / mol. Again, the characteristics of this oil according to the invention make it possible to obtain excellent lubricating, rheological and oxidation resistance properties as well as Fuel Eco. Example 3 The procedure is identical to Example 1 to prepare a first oil fraction according to the invention. The procedure is identical to Example 2 to prepare a second oil fraction according to the invention. The two fractions are then pooled. Then, the final hydrogenation is carried out using a palladium catalyst (0.5 (3/0 m / m with respect to H 2) supported on alumina (5 g of 5% palladium on gamma-alumina). Alumina (Alfa Aesar product) and hydrogen (H2) at 20 bar, at a temperature of 90 ° C., for 240 minutes The oil according to the invention obtained has a content of 9-methyl-11-octyl-henicosane equal to 74.7% This oil according to the invention comprising more than 50% by weight of 9-methyl-11-octyl-henicosane has a kinematic viscosity at 100 ° C., measured according to ASTM standard 3021665 23 D445, of 3.569 mm2.s-1, the viscosity index of this oil is 130. Its volatility measured according to the ASTM D6375 standard is 10.3% by weight and its dynamic viscosity (CCS ) at -35 ° C, measured according to ASTM D5293, is 720 mPa.s. Its average molecular weight is 378 g / mol.
    [0034] Again, the characteristics of the oil according to the invention make it possible to obtain excellent lubricating, rheological and oxidation resistance properties as well as Fuel Eco.
    [0035] Comparative Example 1 Identical measurements and characterizations were made from a commercial reference oil. It is a PAO oil (ExxonMobil Spectrasyn Plus 3.6 product) prepared from olefins by acid catalysis. This reference PAO oil has a kinematic viscosity at 100 ° C, measured according to ASTM D445, of 3,671 mm 2 s -1. Its viscosity index is 118. Its volatility measured according to the ASTM D6375 standard is 14.3% by weight and its dynamic viscosity (CCS) at -35 ° C., measured according to the ASTM D5293 standard, is 1100 mPa.s. . Its average molecular weight is 374 g / mol. In addition, the specifications of this commercial oil are as follows: kinematic viscosity at 100 ° C., measured according to ASTM D445, from 3.5 to 3.9 mm 2 s -1; volatility measured according to ASTM D5800 below 17% by weight. The process according to the invention thus makes it possible to prepare an oil whose properties are equivalent to or better than commercial PAO oils, in particular the viscosity index or the dynamic viscosity, which are much better for the oils according to the invention.
    权利要求:
    Claims (18)
    [0001]
    REVENDICATIONS1. Process for the preparation of an oil with kinematic viscosity at 100 ° C., measured according to ASTM D445, ranging from 3 to 4 mm.sup.2.sup.-1, comprising more than 50% by weight of 1-decene trimer of formula (I ), (I) comprising oligomerizing 1-decene in the presence of hydrogen (H2), a metallocene catalyst and an activator compound or in the presence of hydrogen (H2), a metallocene catalyst, an activator compound and a coactivator compound; catalytic hydrogenation of the oligomerization products in the presence of hydrogen (H2) and a hydrogenation catalyst; the separation by distillation at reduced pressure of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I).
    [0002]
    2. Method according to claim 1 comprising a final step of hydrogenation of the trimeric fraction comprising more than 50% by weight of 1-decene trimer of formula (I), in the presence of hydrogen (H2) and a hydrogenation catalyst.
    [0003]
    3. Process according to claims 1 or 2 comprising the recycling of the dimer fraction of 1-decene (for example 9-methyl-nonadecane), separated by distillation at reduced pressure and the oligomerization of this fraction of dimers of 1-decene. decene recycled with 1-decene, in the presence of hydrogen (H2), a metallocene catalyst and an activator compound or in the presence of hydrogen (H2), a metallocene catalyst, an activator compound and of a coactivator compound.
    [0004]
    4. Process according to claims 1 to 3 comprising the deactivation of the catalyst after the oligomerization of 1-decene or after the catalytic hydrogenation of the oligomerization products. 3021665 25
    [0005]
    5. Process according to claims 1 to 4 comprising the prior preparation of 1-decene by catalytic oligomerization of ethylene. 5
    [0006]
    6. Process according to claims 1 to 5 wherein the oligomerization of 1-decene is carried out in the presence of hydrogen (H2), a metallocene catalyst, an activator compound and a coactivator compound.
    [0007]
    7. A process according to claims 1 to 6 wherein the metallocene catalyst is a racemic compound of formula (II) L (Q1) (Q2) MR1R2 (II) wherein o M represents a transition metal selected from titanium, zirconium, Hafnium, and vanadium or represents zirconium; Q1 and Q2, substituted or unsubstituted, independently represent a cyclic group tetrahydroindenyl or Q1 and Q2 independently represent a cyclic group tetrahydroindenyl and are bonded to form a polycyclic structure; L represents a bridging divalent Cl-C20-alkyl group Q1 and Q2 where L represents a group selected from methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH (CH3) -), 1 -methyl-ethylene (-CH (CH3) -CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH (CH3) -CH2-), 3-methylpropylene (-CH2 -CH2-CH (CH3) -), n-butylene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH (CH3) -CH2-CH2-), 4-methylbutylene (-CH2 -CH2-CH2-CH (CH3) -), pentylene and its isomers, hexylene and isomers thereof, heptylene and isomers thereof, octylene and isomers thereof, nonylene and isomers thereof, decylene and isomers thereof, undecylene and isomers thereof, dodecylene and its isomers; R 1 and R 2, substituted or unsubstituted, independently represent an atom or a group selected from hydrogen, halogens such as Cl and I, alkyl such as Me, Et, nPr and iPr, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl; , silylalkyl, silylalkenyls, silylalkynyls, germylalkyl, germylalkenyl, germylalkynyl; or R1 and R2 together with M form a metallocycle comprising from 3 to 20 carbon atoms. 3021665 26
    [0008]
    8. Process according to claims 1 to 7 wherein the metallocene catalyst is selected from rac-ethylene bis (tetrahydroindenyl) zirconium dimethyl and rac-ethylene bis (tetrahydroindenyl) zirconium dichloride. 5
    [0009]
    9. Process according to claims 1 to 8 wherein the oligomerization of 1-decene is carried out in a period ranging from 2 to 300 min or 5 to 180 min or 30 to 140 min; or in the presence of hydrogen (H2) at a partial pressure of 0.1 to 20 bar or 1 to 6 bar; or 10 ^ in a mass ratio hydrogen / 1-decene greater than 100 ppm or less than 600 ppm or between 100 and 600 ppm; or at a temperature of 50 to 200 ° C or 70 to 160 ° C or 80 to 150 ° C or 90 to 140 ° C or 100 to 130 ° C; or in a solvent selected from a linear or branched hydrocarbon, a cyclic or non-cyclic hydrocarbon, an alkyl aromatic compound and mixtures thereof or in a solvent selected from butanes, pentanes, hexanes, heptanes, octanes, cyclopentane, cyclohexane, methylcyclopentane methylcyclohexane, methylcycloheptane, toluene, xylene and mixtures thereof. 20
    [0010]
    10. Process according to claims 1 to 9 for which the activator compound is chosen from an ionic activator and an oligomeric compound comprising residues of formula -Al (R) -O- in which R independently represents a Cl-C20 alkyl group, cyclic or linear; or the activator compound is selected from methylalumoxane, modified methylalumoxane, ethylalumoxane, isobutylalumoxane and mixtures thereof; or the activator compound is selected from dimethylanilinium tetrakis (perfluorophenyl) borate (DMAB), triphenylcarbonium tetrakis (perfluorophenyl) borate, dimethylanilinium tetrakis (perfluorophenyl) aluminate, and mixtures thereof.
    [0011]
    The process of claims 1 to 10 wherein the activator compound is an ionic activator and the coactivator compound is a trialkylaluminum derivative; or the activator compound is an ionic activator and the co-activator compound is a compound selected from tri-ethyl aluminum (TEAL), tri-iso-butyl aluminum (TIBAL), tri-methyl aluminum (TMA), methyl- methyl-ethyl aluminum (MMEAL) and tri-n-octyl aluminum. 5
    [0012]
    12. The method of claims 1 to 11 comprising deactivating the catalyst is carried out by the action of air or by the action of water or by means of at least one alcohol or a solution of deactivating agent. 10
    [0013]
    13. Process according to claims 1 to 12, in which, during the catalytic hydrogenation of the oligomerization products, the hydrogen pressure (H 2) ranges from 5 to 50 bar or from 10 to 40 bar or from 15 to 25 bar. bar; or the hydrogenation catalyst is selected from a palladium derivative, a supported palladium derivative, a palladium derivative supported on alumina (eg, gamma-alumina), a nickel derivative, a supported nickel derivative, a derivative nickel supported on kieselguhr, a platinum derivative, a supported platinum derivative, a cobalt-molybdenum derivative, a supported cobalt-molybdenum derivative. 20
    [0014]
    14. Process according to claims 1 to 13, comprising the final hydrogenation of the major fraction by weight of 1-decene trimer of formula (I) carried out at a hydrogen pressure (H 2) ranging from 5 to 50 bar or from 10 to 40 bar or 15 to 25 bar; or 25 in a period of between 2 and 600 min or between 30 and 300 min; or at a temperature of 50 to 200 ° C or 60 to 150 ° C or 70 to 140 ° C or 80 to 120 ° C; or in the presence of a hydrogenation catalyst selected from a palladium derivative, a supported palladium derivative, a palladium derivative supported on alumina (eg gamma-alumina), a nickel derivative, a supported nickel derivative , a nickel derivative supported on kieselguhr, a platinum derivative, a supported platinum derivative, a cobalt-molybdenum derivative, a supported cobalt-molybdenum derivative. 35
    [0015]
    15. A process according to claims 1 to 14 for the preparation of an oil comprising 60 to 90% by weight of 1-decene trimer of formula (I) or 70 to 90% by weight of 1-decene trimer of formula (I), or at least 65% by weight of 1-decene trimer of formula (I) or at least 70% by weight of 1-decene trimer of formula (I) or at least minus 80% by weight of 1-decene trimer of formula (I) or at least 90% by weight of 1-decene trimer of formula (I).
    [0016]
    16. The process according to claims 1 to 15 for the preparation of an oil also comprising at least one other saturated 1-decene oligomer selected from the other 1-decene trimers; or the dimers of 1-decene, the other trimers of 1-decene, the tetramers of 1-decene, the pentamers of 1-decene; or 9-methyl-nonadecane and 9-methyl-11,13-dioctyl-tricosane. 15
    [0017]
    17. A process according to claims 1 to 16 for the preparation of an oil comprising from 51 to 99.9% by weight of 1-decene trimer of formula (I) and from 0.1 to 49% by weight of at least one other saturated trimer of 1-decene; or 70 to 90% by weight of 1-decene trimer of formula (I) and 10 to 30% by weight of at least one other saturated trimer of 1-decene; or 20% from 51 to 99.6% by weight of 1-decene trimer of formula (I); from 0.1 to 1% by weight of at least one saturated dimer of 1-decene (e.g. 9-methyl-nonadecane); from 0.1 to 25% by weight of at least one other saturated trimer of 1-decene; from 0.1 to 20% by weight of at least one saturated tetramer of 1-decene (e.g., 9-methyl-11,13-dioctyl-tricosane); from 0.1 to 1.5% by weight of at least one pentamer saturated with 1-decene.
    [0018]
    18. Process according to claims 1 to 17 for the preparation of an oil comprising more than 50% by weight of 9-methyl-11-octyl-henicosane including (a) kinematic viscosity at 100 ° C, measured according to the standard ASTM D445 is from 3.2 to 3.8 mm 2 s -1 or is 3.5 mm 2 s -1; or (b) the viscosity number is greater than 120 or greater than or equal to 130 or is between 120 and 140 or between 125 and 135; or (c) the volatility measured according to ASTM D6375 is less than 10.8% by mass or less than 10.5% by weight, or of which the dynamic viscosity (CCS) at -35 ° C, measured according to ASTM D5293 is less than 900 mPa.s or less than 800 mPa.s.
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    US11180709B2|2018-02-19|2021-11-23|Exxonmobil Chemical Patents Inc.|Functional fluids comprising low-viscosity, low-volatility polyalpha-olefin base stock|
    CA3091510A1|2018-02-19|2019-08-22|Exxonmobil Chemical Patents Inc.|Functional fluids comprising low-viscosity, low-volatility polyalpha-olefin base stock|
    KR102115676B1|2018-12-28|2020-05-27|대림산업 주식회사|Alphaolefin oligomer having a uniform structure and preparation method thereof|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1454926|2014-05-30|
    FR1454926A|FR3021665B1|2014-05-30|2014-05-30|PROCESS FOR THE PREPARATION OF LOW VISCOSITY LUBRICATING POLYOLEFINS|FR1454926A| FR3021665B1|2014-05-30|2014-05-30|PROCESS FOR THE PREPARATION OF LOW VISCOSITY LUBRICATING POLYOLEFINS|
    US15/314,666| US20170226441A1|2014-05-30|2015-05-29|Method for preparing low-viscosity lubricating polyolefins|
    CA2948618A| CA2948618A1|2014-05-30|2015-05-29|Method for preparing low-viscosity lubricating polyolefins|
    EP15725051.5A| EP3149121A1|2014-05-30|2015-05-29|Method for preparing low-viscosity lubricating polyolefins|
    PCT/EP2015/061956| WO2015181355A1|2014-05-30|2015-05-29|Method for preparing low-viscosity lubricating polyolefins|
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