JP2017519097A5

JP2017519097A5 -

Info

Publication number: JP2017519097A5
Application number: JP2017514972A
Authority: JP
Filing date: 2015-05-29
Publication date: 2018-06-14

Description

本質的特性として、本発明の油は、５０ｗｔ％超の９−メチル−１１−オクチル−ヘンイコサンを含む。好ましくは、５０ｗｔ％超の９−メチル−１１−オクチル−ヘンイコサンを含む本発明の油は、
・水素（Ｈ₂）、メタロセン触媒、及び活性剤化合物の存在下、又は、水素（Ｈ₂）、メタロセン触媒、活性剤化合物及び共活性剤（ｃｏ−ａｃｔｉｖａｔｏｒ）化合物の存在下で、１−デセンをオリゴマー化する工程と、
・水素（Ｈ₂）と、水素化触媒及びパラジウム含有水素化触媒の中から選択される触媒との存在下で、オリゴマー化生成物を接触水素化する工程と、
・５０ｗｔ％超の式（Ｉ）

の１−デセントリマーを含むトリマー留分を、減圧蒸留を通じて分離する工程と
を含む方法に従って調製される。 As an essential characteristic, the oil of the present invention comprises more than 50 wt% 9-methyl-11-octyl-henicosane. Preferably, the oil of the present invention comprising more than 50 wt% 9-methyl-11-octyl-henicosane
1-decene in the presence of hydrogen (H ₂ ), metallocene catalyst and activator compound, or in the presence of hydrogen (H ₂ ), metallocene catalyst, activator compound and co-activator compound An oligomerization step,
Catalytic hydrogenation of the oligomerization product in the presence of hydrogen (H ₂ ) and a catalyst selected from hydrogenation catalysts and palladium-containing hydrogenation catalysts;
-Formula (I) exceeding 50 wt%

The trimer fraction comprising of 1-decene trimer, is therefore prepared in a method comprising the step of separating through distillation under reduced pressure.

Claims

Formula (I) exceeding 50 wt%

An oil having a kinematic viscosity in the range of 3-4 mm ² · s ⁻¹ at 100 ° C., as measured according to standard ASTM D445.

50-99 wt% of 1-decent trimer of formula (I), or 60-90 wt% of 1-decent trimer of formula (I), or 70-90 wt% of 1-decent trimer of formula (I) Item 2. The oil according to Item 1.

65 wt% or more of the 1-decent trimer of the formula (I), or 70 wt% or more of the 1-decent trimer of the formula (I), or 80 wt% or more of the 1-decent trimer of the formula (I), or 90 wt% or more of the formula The oil according to claim 1 or 2, comprising 1-descent trimer of (I).

Selected from other 1-decene trimers, or
Selected from 1-decene dimer, other 1-decene trimer, 1-decene tetramer, 1-decene pentamer,
4. Oil according to any one of claims 1 to 3, which also contains at least one other saturated oligomer of 1-decene.

5. The method according to claim 1, further comprising at least one other saturated oligomer of 1-decene selected from 9-methyl-nonadecane and 9-methyl-11,13-dioctyl-tricosane. Oil as described in

6. The composition according to claim 1, comprising 51-99.9 wt% of 1-decene trimer of formula (I) and 0.1-49 wt% of at least one other 1-decene saturated trimer. Listed oil.

51 to 99.6 wt% of 1-descent trimer of formula (I),
0.1-1 wt% of at least one 1-decene saturated dimer or 9-methyl-nonadecane,
0.1 to 25 wt% of at least one other 1-decene saturated trimer;
0.1-20 wt% of at least one 1-decene saturated tetramer or 9-methyl-11,13-dioctyl-tricosane;
Oil according to any one of claims 1 to 6, comprising 0.1 to 1.5 wt% of at least one 1-decene saturated pentamer.

(A) kinematic viscosity at 100 ° C., as measured according to the standard ASTM D445, is whether or 3.5 mm ² · s ^-1 ranges from 3.2~3.8mm ² · s ^-1, or ( b) a viscosity index greater than 120, or greater than or equal to 130, or 120-140, or 125-135, or (c) a volatility of less than 10.8 mass%, as measured according to standard ASTM D6375, or 10. The cold cranking viscosity (CCS) at -35 ° C is less than 900 mPa · s, or less than 800 mPa · s, as measured according to standard ASTM D5293. The oil according to any one of the above.

(A) kinematic viscosity at 100 ° C. is measured according to standard ASTM D445, is or 3.5 mm ² · s ^-1 ranges from 3.2~3.8mm ² · s ^-1,
(B) the viscosity index is greater than 120, or 130 or greater, or 120-140, or 125-135;
(C) has a volatility of less than 10.8 mass%, or less than 10.5 mass%, as measured according to standard ASTM D6375,
(D) The cold cranking viscosity (CCS) at −35 ° C. is less than 900 mPa · s, or less than 800 mPa · s, as measured according to standard ASTM D5293. oil.

A step of oligomerizing 1-decene 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 co-activator compound. When,
Catalytic hydrogenation of the oligomerization product in the presence of hydrogen (H ₂ ) and a catalyst selected from hydrogenation catalysts and palladium-containing hydrogenation catalysts;
Including a 1-decent trimer of formula (I), prepared using a process comprising separating a trimer fraction comprising greater than 50 wt% of a 1-decent trimer of formula (I) through vacuum distillation The oil according to any one of claims 1 to 9.

Pre-preparing 1-decene through catalytic oligomerization of ethylene, or deactivating the catalyst after oligomerization of 1-decene or after catalytic hydrogenation of the oligomerization product,
Reusing a dimer fraction of 1-decene (for example, 9-methyl-nonadecane) separated by distillation under reduced pressure, and reusing the dimer fraction of 1-decene into hydrogen (H ₂ ), metallocene catalyst And oligomerizing with 1-decene in the presence of active compound or in the presence of hydrogen (H ₂ ), metallocene catalyst, activator compound and co-activator compound, or hydrogen (H ₂ ), Final hydrogenating a trimer fraction comprising greater than 50 wt% of the 1-decene trimer of formula (I) in the presence of a catalyst selected from among hydrogenation catalysts and palladium-containing hydrogenation catalysts; 10. Oil according to any one of claims 1 to 9, comprising a 1-decent trimer of formula (I), prepared according to the method of claim 10.

The oligomerization of 1-decene is carried out over a time period ranging from 2 to 300 minutes or from 5 to 180 minutes or from 30 to 140 minutes, or
The oligomerization of 1-decene is carried out in the presence of partial pressure of hydrogen (H ₂ ) in the range of 0.1-20 bar or 1-6 bar, or
The oligomerization is carried out with a hydrogen / 1-decene mass ratio of more than 100 ppm or less than 600 ppm, or 100-600 ppm, or
The oligomerization of 1-decene is carried out at a temperature in the range 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
The metallocene catalyst is of formula (II)
L (Q ¹ ) (Q ² ) MR ¹ R ²
(II)
A racemic compound of the formula:
M is a transition metal selected from titanium, zirconium, hafnium and vanadium, or zirconium,
Q ¹ and Q ² are independently a substituted or unsubstituted cyclic tetrahydroindenyl group, or Q ¹ and Q ² are independently a cyclic tetrahydroindenyl group, and a polycyclic structure is formed. Combined to form,
L is either a divalent alkyl group of C ₁ -C ₂₀ bridging the Q ¹ and Q ^2, or, L is methylene (-CH ₂ -), ethylene (-CH ₂ -CH ₂ -), methyl Methylene (—CH (CH ₃ ) —), 1-methyl-ethylene (—CH (CH ₃ ) —CH ₂ —), n-propylene (—CH ₂ —CH ₂ —CH ₂ —), 2-methylpropylene ( _{_{-CH 2 -CH (CH 3) -CH}} 2 -), 3- methylpropylene _{_{(-CH 2 -CH 2 -CH (CH}} 3) -), n- butylene (-CH _{_₂} -CH ₂ -CH ₂ -CH ₂ -), 2-methyl-butylene _{_{(-CH 2 -CH (CH 3)}} -CH 2 -CH 2 -), 4- methyl-butylene _{_{_{(-CH 2 -CH 2 -CH 2 -CH}}} (CH 3) -), Pentylene and isomers thereof, hexylene and isomers thereof, heptylene and isomers thereof, octylene A group selected from among len and their isomers, nonylene and their isomers, decylene and their isomers, undecylene and their isomers, dodecylene and their isomers,
R ¹ and R ² are independently substituted or unsubstituted hydrogen, halogen (eg, Cl and I), alkyl (eg, Me, Et, nPr, iPr), alkenyl, alkynyl, haloalkyl, haloalkenyl, An atom or group selected from haloalkynyl, silylalkyl, silylalkenyl, silylalkynyl, germylalkyl, germylalkenyl, germylalkynyl, or 3 to 20 R ¹ and R ² together with M Form a metallacycle having 5 carbon atoms, or
The metallocene catalyst is selected from rac-ethylenebis (tetrahydroindenyl) zirconium dimethyl and rac-ethylenebis (tetrahydroindenyl) zirconium dichloride, or
The oligomerization of 1-decene is a solvent selected from linear or branched hydrocarbons, cyclic or acyclic hydrocarbons, aromatic alkylates and mixtures thereof, or butane, pentane Hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, methylcycloheptane, toluene, xylene and mixtures thereof, or
- activator compound, an ionic activator and the formula -Al (R) -O- (wherein, R is independently a is cyclic or linear C ₁ -C ₂₀ alkyl group) residues Selected from among the oligomeric compounds comprising or selected from methylalumoxane, modified methylalumoxane, ethylalumoxane, isobutylalumoxane and mixtures thereof, or dimethylanilinium tetrakis- (perfluorophenyl) borate ( DMAB), triphenylcarbonium tetrakis- (perfluorophenyl) borate, dimethylanilinium tetrakis- (perfluorophenyl) aluminate, and mixtures thereof, or
Co-activator compounds are trialkylaluminum derivatives or tri-ethylaluminum (TEAL), tri-iso-butylaluminum (TIBAL), tri-methylaluminum (TMA), tri-n-octylaluminum and methyl-methyl-ethyl A compound selected from among aluminum (MMAL), or
The deactivation of the catalyst is obtained by the action of air or water, or using a solution of at least one alcohol or deactivator, or
The pressure of hydrogen (H ₂ ) for the catalytic hydrogenation of the oligomerization product is in the range of 5-50 bar or 10-40 bar or 15-25 bar, or
-Hydrogenation catalyst is palladium derivative, supported palladium derivative, derivative of palladium supported on alumina (for example, on gamma alumina), nickel derivative, derivative of supported nickel, derivative of nickel supported on diatomaceous earth, platinum derivative, derivative of supported platinum, cobalt- Selected from molybdenum derivatives, supported cobalt-molybdenum derivatives, or
The pressure of hydrogen (H ₂ ) for the final hydrogenation of 1-decent trimer of the formula (I) in a majority proportion by mass is in the range from 5 to 50 bar or from 10 to 40 bar or from 15 to 25 bar, or ,
The hydrogenation time for the final hydrogenation is 2 to 600 minutes or 30 to 300 minutes, or
The end of the final hydrogenation is carried out at a temperature in the range of 50 to 200 ° C. or 60 to 150 ° C. or 70 to 140 ° C. or 80 to 120 ° C., or
The hydrogenation catalyst for the final hydrogenation of the trimer fraction containing more than 50 wt% of the 1-decene trimer of formula (I) is a palladium derivative, a derivative of supported palladium, a derivative of palladium on alumina (eg on gamma alumina ), Nickel derivatives, supported nickel derivatives, diatomaceous earth supported nickel derivatives, platinum derivatives, supported platinum derivatives, cobalt-molybdenum derivatives, supported cobalt-molybdenum derivatives. 10. An oil according to any one of claims 1 to 9, comprising a 1-descent trimer of formula (I), prepared as described above.

The oligomerization of 1-decene is carried out over a period in the range of 2 to 300 minutes or 5 to 180 minutes or 30 to 140 minutes;
The oligomerization of 1-decene is carried out in the presence of hydrogen (H ₂ ) at a partial pressure in the range of 0.1-20 bar or 1-6 bar;
The oligomerization of 1-decene is carried out in a mass ratio of hydrogen / 1-decene greater than 100 ppm or less than 600 ppm, or 100-600 ppm, or the oligomerization of 1-decene is 50-200 ° C. or 70- Performed at a temperature in the range of 160 ° C or 80-150 ° C or 90-140 ° C or 100-130 ° C,
The metallocene catalyst is of formula (II)
L (Q ¹ ) (Q ² ) MR ¹ R ²
(II)
A racemic compound of the formula:
M is a transition metal selected from titanium, zirconium, hafnium and vanadium, or zirconium,
Q ¹ and Q ² are independently a substituted or unsubstituted cyclic tetrahydroindenyl group, or Q ¹ and Q ² are independently a cyclic tetrahydroindenyl group, and a polycyclic structure is formed. Combined to form,
L is either a divalent alkyl group of C ₁ -C ₂₀ bridging the Q ¹ and Q ^2, or, L is methylene (-CH ₂ -), ethylene (-CH ₂ -CH ₂ -), methyl Methylene (—CH (CH ₃ ) —), 1-methyl-ethylene (—CH (CH ₃ ) —CH ₂ —), n-propylene (—CH ₂ —CH ₂ —CH ₂ —), 2-methylpropylene ( _{_{-CH 2 -CH (CH 3) -CH}} 2 -), 3- methylpropylene _{_{(-CH 2 -CH 2 -CH (CH}} 3) -), n- butylene (-CH _{_₂} -CH ₂ -CH ₂ -CH ₂ -), 2-methyl-butylene _{_{(-CH 2 -CH (CH 3)}} -CH 2 -CH 2 -), 4- methyl-butylene _{_{_{(-CH 2 -CH 2 -CH 2 -CH}}} (CH 3) -), Pentylene and isomers thereof, hexylene and isomers thereof, heptylene and isomers thereof, octylene A group selected from among len and their isomers, nonylene and their isomers, decylene and their isomers, undecylene and their isomers, dodecylene and their isomers,
R ¹ and R ² are independently substituted or unsubstituted hydrogen, halogen (eg, Cl and I), alkyl (eg, Me, Et, nPr, iPr), alkenyl, alkynyl, haloalkyl, haloalkenyl, An atom or group selected from haloalkynyl, silylalkyl, silylalkenyl, silylalkynyl, germylalkyl, germylalkenyl, germylalkynyl, or 3 to 20 R ¹ and R ² together with M Form a metallacycle having 5 carbon atoms, or
The metallocene catalyst is selected from rac-ethylenebis (tetrahydroindenyl) zirconium dimethyl and rac-ethylenebis (tetrahydroindenyl) zirconium dichloride;
The oligomerization of 1-decene is a solvent selected from linear or branched hydrocarbons, cyclic or acyclic hydrocarbons, aromatic alkylates and mixtures thereof, or butane, pentane , Hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, methylcycloheptane, toluene, xylene and mixtures thereof,
- activator compound, an ionic activator and the formula -Al (R) -O- (wherein, R is independently a is cyclic or linear C ₁ -C ₂₀ alkyl group) residues Selected from oligomeric compounds comprising, or selected from methylalumoxane, modified methylalumoxane, ethylalumoxane, isobutylalumoxane and mixtures thereof, or dimethylanilinium tetrakis- (perfluorophenyl) borate, Selected from triphenylcarbonium tetrakis- (perfluorophenyl) borate, dimethylanilinium tetrakis- (perfluorophenyl) aluminate, and mixtures thereof;
Co-activator compounds are trialkylaluminum derivatives or tri-ethylaluminum (TEAL), tri-iso-butylaluminum (TIBAL), tri-methylaluminum (TMA), tri-n-octylaluminum and methyl-methyl-ethyl A compound selected from aluminum (MMAL),
The deactivation of the catalyst is obtained by the action of air or water or using a solution of at least one alcohol or deactivator, or hydrogen for the catalytic hydrogenation of the oligomerization product ( pressure H ₂₎ is in the range of 5~50bar or 10~40bar or 15～25Bar,
-Hydrogenation catalyst is palladium derivative, derivative of supported palladium, derivative of palladium supported on alumina (for example, on gamma alumina), nickel derivative, derivative of supported nickel, derivative of nickel supported on diatomaceous earth, platinum derivative, derivative of supported platinum, cobalt -Selected from molybdenum derivatives, supported cobalt-molybdenum derivatives,
The pressure of hydrogen (H ₂ ) for the final hydrogenation of 1-decent trimer of the formula (I) in a majority proportion by mass is in the range from 5 to 50 bar or from 10 to 40 bar or from 15 to 25 bar;
-The hydrogenation time for the final hydrogenation is 2 to 600 minutes or 30 to 300 minutes,
The final hydrogenation is carried out at a temperature in the range of 50-200 ° C or 60-150 ° C or 70-140 ° C or 80-120 ° C;
The hydrogenation catalyst for the final hydrogenation of the trimer fraction containing more than 50 wt% of the 1-decene trimer of formula (I) is a palladium derivative, a derivative of supported palladium, a derivative of palladium on alumina (eg on gamma alumina ), Nickel derivatives, supported nickel derivatives, diatomaceous earth supported nickel derivatives, platinum derivatives, supported platinum derivatives, cobalt-molybdenum derivatives, supported cobalt-molybdenum derivatives. 10. An oil according to any one of the preceding claims comprising a 1-decent trimer of formula (I), prepared using the method.

Use of the oil according to any one of claims 1 to 13 as a base oil or as a lubricating base oil.

14. To improve fuel economy (FE) of a lubricant, to reduce fuel consumption of an engine, or to reduce fuel consumption of a vehicular engine. Use of the oil described in 1.

At least one base oil selected from among the oils according to any one of claims 1 to 13, or selected from among the oils according to any one of claims 1 to 13. At least one base oil and at least one other base oil, or at least one base oil selected from the oils of any one of claims 1 to 13 and at least one addition A lubricant composition comprising at least one base oil selected from the oils according to any one of claims 1 to 13, at least one other base oil, and at least one additive. object.

14 wt% or more, 30 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, or 60 wt% or more of at least one selected from the oils according to any one of claims 1-13. The lubricating composition of claim 16 comprising a base oil.

18. Use of a lubricating composition according to claim 16 or 17 to improve fuel economy (FE) of a lubricant, to reduce engine fuel consumption, or to reduce fuel consumption of a vehicle engine.