JP2004256415A - Method for producing olefin oligomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an olefin oligomer, by which the ≥30C olefin oligomer can efficiently be obtained in high selectivity without giving a large environmental load and without corroding a reactor. <P>SOLUTION: This method for producing the olefin oligomer is characterized by polymerizing a 4 to 14C olefin or its mixture in the presence of a Bronsted acid catalyst containing a non-coordinating counter-anion represented by general formula (1): [H(OCH<SB>2</SB>CH<SB>3</SB>)<SB>2</SB>]<SP>+</SP>A<SP>-</SP>(1) (A<SP>-</SP>is a non-coordinating anion species). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an efficient method for producing an olefin oligomer useful as a lubricating oil such as an automobile engine oil, an automatic transmission oil, a gas turbine oil, an aircraft operating oil, and an electric insulating oil.
[0002]
[Prior art]
Currently, olefins, especially olefin oligomers obtained by polymerizing α-olefins having 6 to 14 carbon atoms, are used as base materials for lubricating oils such as automobile engine oils, automatic transmission oils, gas turbine oils, aircraft operating oils, and electric insulating oils. Widely used as such. Above all, in application fields such as automobile engine oils used as lubricating oils, it is necessary to remove fractions having less than 30 carbon atoms in order to suppress evaporation loss, and to efficiently produce olefin oligomers It is important to improve the selectivity to an olefin oligomer having 30 or more carbon atoms.
[0003]
As a method for producing an olefin oligomer used for such a lubricating oil base material, a method using a Lewis acid such as aluminum chloride or boron trifluoride as a catalyst has been known so far. Uses boron trifluoride having high selectivity to an olefin oligomer having 30 or more carbon atoms, which is more preferable in the properties of the product.
[0004]
However, boron trifluoride is harmful to the human body, and the polymerization reaction of olefins using boron trifluoride as a catalyst requires separation of the catalyst, washing of the product, decomposition of the separated catalyst, and disposal after the reaction is completed. And other steps are required. In addition, disposal of the catalyst causes a problem of causing environmental pollution. Furthermore, since these catalysts are highly corrosive, the production of olefin oligomers requires the use of equipment made of high-grade corrosion-resistant materials.
[0005]
In order to solve such problems, production methods using various solid acid catalysts have been conventionally studied.However, any of the known solid acid catalysts has low activity or low selectivity. If severe polymerization conditions are adopted to improve the production method using these, the isomerization reaction proceeds in addition to the polymerization reaction. The method has not yet been put to practical use.
[0006]
[Non-patent document 1]
Chem. Rev .. 91, p613 (1991)
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation in the related art. That is, an object of the present invention is to provide an oligomerization reaction of an olefin having 4 to 14 carbon atoms, which is excellent in the selectivity of an olefin oligomer having 30 or more carbon atoms, has no great environmental load, and corrodes the reaction apparatus. Accordingly, it is an object of the present invention to provide an industrially suitable method for producing an olefin oligomer which efficiently produces a useful olefin oligomer.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, using a specific Bronsted acid having a non-coordinating counter anion having low reactivity in the oligomerization reaction of α-olefin as a catalyst. The present inventors have found that olefin oligomers having 30 or more carbon atoms can be obtained with high selectivity, and have completed the present invention.
That is, the method for producing an olefin oligomer of the present invention comprises the general formula (1)
^{_{[H (OCH 2 CH 3)}} 2] + A - (1)
(Wherein, A ⁻ represents a non-coordinating anion species). A olefin having 4 to 14 carbon atoms or a mixture thereof is polymerized in the presence of a Bronsted acid catalyst containing a non-coordinating counter anion represented by the following formula: It is characterized by reacting. The starting olefin is preferably an α-olefin, and among them, 1-decene is preferably used.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The non-coordinating counter anion-containing Bronsted acid used as a catalyst in the present invention is represented by the following general formula (1) and is a known document [eg, Organometallics, 19, 1442 (2000)]. Can be easily produced by the method described in, for example.
^{_{[H (OCH 2 CH 3)}} 2] + A - (1)
In the general formula (1), A ⁻ represents a non-coordinating anion species. Note that CH ₂ CH ₃ in the formula is an ethyl group, and is hereinafter referred to as “Et”.
[0010]
A ⁻ in the general formula (1) may be any non-coordinating anionic species, and specific examples thereof include tetraphenylborate anion, tetrakis (4-fluorophenyl) borate anion, Examples include tetrakis (pentafluorophenyl) borate anion, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anion, 1-carbadodecaborate anion, and perchlorate anion.
[0011]
Specific examples of the Bronsted acid catalyst used in the present invention include [H (OEt ₂ ) ₂ ] ⁺ [B (4-FC ₆ H ₄ ) ₄ ] ⁻ , [H (OEt ₂ ) ₂ ] ⁺ [ ^{_{B (C 6 F 5) 4}} ] -, [H (OEt 2) 2] + [B (3,5- (CF 3) 2 C 6 H 3] -, [H (OEt 2) 2] + [CB _{^{11 H 12] -, [H}} (OEt 2) 2] + [ClO 4] - , and the like.
[0012]
The olefin used as the polymerization raw material is an olefin having 4 to 20 carbon atoms, preferably an olefin having 6 to 14 carbon atoms, among which α-olefins, internal olefins, and mixtures thereof are used. 6 to 14 α-olefins are preferred, and specifically, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene And the like, and it is particularly preferable to use 1-decene.
[0013]
When an olefin is polymerized using the above Bronsted acid catalyst, an olefin oligomer having 30 or more carbon atoms, preferably 30 to 70 carbon atoms, can be selectively obtained. Further, the method for producing an olefin oligomer of the present invention has excellent advantages such as low environmental pollution and no need to use a reactor for expensive corrosion-resistant materials.
[0014]
The amount of the Brönsted acid used in the reaction of the present invention is a so-called catalytic amount, which is 0.01 to 200 mol%, preferably 0.05 to 100 mol%, more preferably 0.1 to 10 mol% based on the starting olefin. is there.
The polymerization reaction temperature can be usually in the range of −50 to 200 ° C., but preferably 0 to 120 ° C. for easy operation. The reaction time is usually from 10 minutes to 20 hours. Although a solvent is not particularly required for this reaction, a chain saturated hydrocarbon, an alicyclic hydrocarbon, a halogenated hydrocarbon, or the like may be used as a solvent, if desired.
[0015]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Example 1
The 1-decene _{593mg (4.23mmol) [H (OEt} 2) 2] + [B (C 6 F 5) 4] - 17mg (0.020mmol, 0.48mol%) after stirring the mixture for 10 minutes, The polymerization reaction was performed while stirring at 100 ° C. for 18 hours. Thereafter, the resulting reaction mixture was cooled to room temperature, the precipitated catalyst was separated, and the low-boiling products were removed under reduced pressure. When 308 mg (yield 52%) of the obtained product was analyzed by the FD-MS method, the formation ratio of each oligomer was 3% for the dimer, 21% for the trimer, 71% for the tetramer and 71% for the 5 5%, and the tetramer was the main component.
[0016]
Example 2
The 1-decene _{701mg (5.0mmol) [H (OEt} 2) 2] + [B (C 6 F 5) 4] - 41mg80.050mmol, After stirring 1.0 mol%) was added for 10 minutes, 120 ° C. The polymerization reaction was carried out with stirring for 14 hours. Thereafter, the resulting reaction mixture was cooled to room temperature, the precipitated catalyst was separated, and the low-boiling products were removed under reduced pressure. When the obtained product (477 mg, yield 68%) was analyzed by the FD-MS method, the formation ratio of each oligomer was 3% for trimer, 13% for tetramer, 36% for pentamer, and 6% for 6-mer. 30% of the isomer and 17% of the heptamer were present, and the pentamer to pentamer were the main components.
[0017]
Example 3
The 1-decene _{701mg (5.0mmol) [H (OEt} 2) 2] + [B (C 6 F 5) 4] - 41mg (0.050mmol, 1.0mol%) was stirred for addition 10 minutes, The polymerization reaction was carried out while stirring at 100 ° C. for 14 hours. Thereafter, the resulting reaction mixture was cooled to room temperature, the precipitated catalyst was separated, and the low-boiling products were removed under reduced pressure. When 490 mg (yield 70%) of the obtained product was analyzed by the FD-MS method, the formation ratio of each oligomer was 4% for trimers, 13% for tetramers, 32% for pentamers, and 32% for 6-mers. 30% of the isomer and 21% of the heptamer, and the pentamer to pentamer were the main components.
[0018]
Example 4
The 1-decene _{701mg (5.0mmol) [H (OEt} 2) 2] + [B (C 6 F 5) 4] - 41mg (0.050mmol, 1.0mol%) was stirred for addition 10 minutes, The polymerization reaction was performed while stirring at 100 ° C. for 4 hours. Thereafter, the resulting reaction mixture was cooled to room temperature, the precipitated catalyst was separated, and the low-boiling products were removed under reduced pressure. When 498 mg (yield 71%) of the obtained product was analyzed by the FD-MS method, the formation ratio of each oligomer was 9% for trimer, 37% for tetramer, 31% for pentamer, 31% for 6 17% of the isomer and 6% of the heptamer were present, with the tetramer to hexamer being the main components.
[0019]
【The invention's effect】
Since the present invention uses a specific Bronsted acid catalyst for the polymerization of olefins, it can reduce environmental pollution and can obtain olefin oligomers having 30 or more carbon atoms at a high selectivity without corrosive reaction equipment. Which is useful for industrial production.

Claims (3)

General formula (1)
^{_{[H (OCH 2 CH 3)}} 2] + A - (1)
(Wherein, A ⁻ represents a non-coordinating anion species). A olefin having 4 to 14 carbon atoms or a mixture thereof is polymerized in the presence of a Bronsted acid catalyst containing a non-coordinating counter anion represented by the following formula: A method for producing an olefin oligomer, which comprises reacting. The method for producing an olefin oligomer according to claim 1, wherein the olefin having 4 to 14 carbon atoms is an α-olefin having 6 to 14 carbon atoms. The method for producing an olefin oligomer according to claim 1 or 2, wherein the α-olefin is 1-decene.