Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By addition of entire unsaturated molecules – e.g.,...
Reexamination Certificate
1995-08-30
2003-02-18
Langel, Wayne A. (Department: 1754)
Chemistry of hydrocarbon compounds
Unsaturated compound synthesis
By addition of entire unsaturated molecules, e.g.,...
C585S511000, C585S513000
Reexamination Certificate
active
06521806
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing 1-hexene.
2. Background Information
The following processes have been known as the processes for producing 1-hexene by trimerization of ethylene.
Thus, U.S. Pat. No. 4,668,838 discloses a process in which a chromium compound, a hydrocarbyl aluminum hydrolyzed with about 0.8 to about 1.1 mole of water per mole of an aluminum compound and a donor ligand were used as a catalyst. This process, however, had defects that the catalyst was insufficient in activity and selectivity and that maintenance of the activity of the catalyst was uneasy.
EP 0 537 609 and EP 0 622 347 disclose processes in which a chromium complex and an aluminoxane were used as a catalyst. These processes were also unsatisfactory due to insufficient activity and selectivity of the catalyst.
EP 0 611 743 discloses a process in which a chromium compound, an alkylaluminum compound and an amine or a metal amide were used as a catalyst. The process was also unsatisfactory due to insufficient activity and selectivity of the catalyst.
Further, JP-A-6-157655 discloses a process in which a chromium compound, an aluminum compound and a pyrrole compound were used as a catalyst, and EP 0 608 447 discloses a process in which a chromium compound, an aluminum compound, a pyrrole compound and a halogen compound were used as a catalyst. These processes, however, had defects that an apparatus and an excess energy were required for a separation step of 1-hexene, the desired product, and a solvent, which step was necessary because they used other solvent except 1-hexene.
As a result of an extensive study, conducted by the present inventors, on a process for producing 1-hexene which is not suffered from the above defects, it has been found that 1-hexene can be produced with excellent industrial efficiency, maintaining selectivity of the trimer C6−compound and purity of 1-hexene in the C6-compound at a superior level and without requiring an apparatus and energy for separating the desired 1-hexene and a solvent, by trimerizing ethylene using a catalyst comprising a chromium-containing compound, an aluminum compound, a pyrrole compound and a group 13(IIIB)-halogen compound or a group 14(IVB)-halogen compound and using the desired compound 1-hexene as a solvent. The present invention has been accomplished on the basis of such finding.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a process for producing 1-hexene which comprises trimerizing ethylene in a 1-hexene solvent in the presence of a catalyst system prepared by contacting in a 1-hexene solvent the following components (A), (B), (C) and (D):
(A) a chromium-containing compound represented by the general formula: CrXkYm wherein X in Xk is a residue of a carboxylic acid, a residue of a 1,3-diketone, a halogen atom or an alkoxyl group, k is an integer of 2 to 4, Y in Ym is an amine compound, a phosphine compound, a phosphine oxide compound, a nitrosyl group or an ether compound and m is an integer of 0 to 6, with the proviso that any two Y's may be same or different;
(B)trialkylaluminum or dialkylaluminum hydride;
(C) a pyrrole compound or a ;derivative thereof;
(D) a group 13 (IIIB)-halogen compound represented by the general formula: MTtU3-t or a group 14 (IVB)-halogen compound represented by the general formula: M′Tt′U4-t′ wherein M is an atom from the group 13 (IIIB), M′ is an atom from the group 14(IVB), T is an alkyl group, an aryl group, an allyl group or a hydrogen atom, U is a halogen atom, t is a real number of 0 or more and less than 3 and t′ is a real number of 0 or more and less than 4.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in more detail in the following.
The component (A) of the catalyst used in the present invention is a chromium compound represented by the general formula: CrXkYm.
In the component (A), X. in Xk is a residue of a caarboxylic acid, a residue of a 1,3-diketone, a halogen atom or an alkoxyl group and k is an integer of 2 to 4. Y in Ym is an amine compound, a phosphine compound, a phosphine oxide compound, a nitrosyl group or an ether compound and m is an integer of 0 to 6. It is to be noted that any two Y's may be same or different.
The residue of the carboxylic acid having 1 to 20 carbon atoms is preferred and includes, for example, residues of 2-ethylhexanoic acid, naphthenic acid, acetic acid, hydroxy-2-ethylhexanoic acid, dichloroethylhexanoic acid, butyric acid, neopentanoic acid, lauric acid, stearic acid, oxalic acid and the like, whereby the residues of 2-ethylhexanoic acid and naphthenic acid are preferred.
The residue of the 1,3-diketone having 5 to 20 carbon atoms is preferred and includes, for example, residues of acetylacetone, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1-trifluoroacetylacetone., benzoylacetone and the like.
The halogen atom includes chlorine, bromine, iodine and fluorine, whereby chlorine is preferred.
The alkoxyl group having 1 to 20 carbon atoms is preferred and includes, for example, t-butoxy group, isopropoxy group and the like.
The amine compound includes, for example, ammonia, ethylenediamine, diethylenetriamine, pyridine, pyridine derivatives, isoquinoline, isoquinoline derivatives, aniline and the like.
The pyridine derivatives include 4-dimethylaminopyridine, 4-cyanopyridine, 2-picoline, 3-picoline, 4-picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 4-propylpyridine, 4-isopropylpyridine, 3-butylpyridine, 4-butylpyridine, 4-isobutylpyridine, 4-t-butylpyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, 4-phenylpropylpyridine, 4-(5-nonyl)pyridine, 3-(4-pyridyl)-1,5-diphenylpentane, 2-vinylpyridine, 4-vinylpyridine, 4-butenylpyridine, 4-(1-propenylbutenyl)pyridine, 4-pentenylpyridine, 4-(1-butenylpentenyl)pyridine, 2,6-lutidine, 2,4-lutidine, 2,5-lutidine, 3,4-lutidine, 3,5-lutidine, 2-methyl-4-ethylpyridine, 2-methyl-5-ethylpyridine, 3-methyl-4-ethylpyridine, 3-ethyl-4-methylpyridine, 3,4-diethylpyridine, 3,5-diethylpyridine, 2-methyl-5-butylpyridine, 2,6-dipropylpyridine, 2,6-di-t-butylpyridine, 2,6-diphenylpyridine, 2,3-cyclopentenopyridin e, 2,3-cyclohexenopyridine, 2-methyl-G-vinylpyridine, 5-ethyl-2-vinylpyridine, 2,4,6-collidine, 2,3,5-collidine, 2-methyl-3-ethyl-6-propylpyridine, 2,6-di-t-butyl-4-methylpyridine and the like.
The isoquinoline derivatives include 1-methylisoquinoline, 3-methylisoquinoline, phenanthridine and the like.
The phosphine compound include, for example, tributylphosphine, triphenylphosphine and the like.
The phosphine oxide compound includes tributylphosphine oxide, triphenylphosphine oxide and the like.
The ether compound includes tetrahydrofuran and the like.
Specific examples of the component (A) includes trichlorotris(ethylenediamine) chromium(III) 3.5 hydrate, trichlorotris(4-dimethylaminopyridine) chromium(III), trichlorotripyridine chromium(III), trichlorotri(4-ethylpyridine) chromium(III), trichlorotri(4-isopropylpyridine) chromium(III), trichlorotri-(4-t-butylpyridine) chromium(III), trichlorotri(4-phenylpyridine) chromium(III), trichlorotri(4-phenylpropylpyridine) chromium(III), trichlorotri(4-(5-nonyl)-pyridine) chromium(III), trichlorotri(3,5-lutidine) chromium(III), tribromotripyridine chromium(III), trifluorotripyridine chromium(III), dichlorobis(pyridine) chromium(II), dibromobis(pyridine) chromium(II), trichlorotriisoquinoline chromium(III), trichlorotrianiline chromium(III), trichlorotritetrahydrofuran chromium(III), chromium(III) tris(2-ethylhexanoate), chromium(II) bis(2-ethylhexanoate), chromium(III) tris(naphthenate), chromium(II) bis(naphthenate), chromium(III) tris(acetate), chromium(II) bis(acetate), chromium(III) tris(acethylacetona te), chromium(II) bis(acethylacetonate), chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptadionate), chromium(IV) tetra(t-butoxide), dichlorodinitrosylbis(triphenylphosphineo xide) chromium , dichlorobis(triphenylphosphineoxide) chromium(II), d
Ito Yoshiaki
Iwanaga Kiyoshi
Tamura Mitsuhisa
Uchida Kenshi
Langel Wayne A.
Sughrue & Mion, PLLC
Sumitomo Chemical Company Limited
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