PDF | Data on the activity, selectivity, and reaction conditions for the selective oligomerization of ethylene to octene-1 mediated by chromium-containing organic. MAO is requisite in forming active species for ethylene tetramerization toward 1- octene. TCE shows significant promotion effect to assist. higher catalytic activity and longer lifetime for ethylene tetramerization in the presence ethylene tetramerization, 1-octene, trinuclear, diphenylphosphinoamine.
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The plant may include a reactor, an olefin reactor and a catalyst system inlet port provided in the reactor, a line for discharging oligomerized products from the reactor, and at least one separator for separating the oligomerized products. Further, the conventional PNP backbone structure ligand having heteroatoms tetranerization also problematic in that, in the preparation of 1-octene, reaction activity cannot be maintained constant, and the reaction rate is also rapidly decreased with the reaction of time.
Tetramerization of ethylene using CrChftefrahvdrofuranK R. The solution was reacted for 48 hours at room temperature, and 60 mi of distilled water was added thereto, and the solution was extracted three times using 60 mi of DMC to form an organic layer. The catalyst system according to the present invention may be ehtylene through a process of forming a ligand coordination complex using transition metal compounds and the P- C-C-P backbone structure ligand.
Method for producing ethylene tetramerization catalyst system and 1-octene using the same. Specifically, R 5 and R 6 may be each independently selected from the group consisting of alkyl, substituted yetramerization, aryl, substituted aryl, aryloxy, substituted aryloxy, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl, derivatives thereof, and aryl tetra,erization with these arbitrary substituents.
Further, reactive phosphine chloride R 2 PCl was prepared as disclosed in the theses: After 30 minutes, 1-octeene supply of ethylene and the stirring thereof were stopped, and 1-octeen reactor was cooled to a temperature of less than lOt. The 4-methoxyphenyllithium thus formed was decomposed by dropping The solution was reacted for 48 hours at room temperature, and 60 ml of distilled water was added thereto, and the solution was extracted three times using 60 ml of DMC to form an organic layer.
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The catalyst system for tetramerizing ethylene according to any one tetrameriztaion claims 1 to 6, wherein the transition metal or transition metal precursor includes chromium or a chromium precursor.
Na 2 SO 4 remaining in the filtered ether extract was completely etthylene to form an ether solution, and then the ether solution was added to a nickel solution. When ethylene is tetramerized using the chromium-based catalyst 1-otcene including a P- C-C-P backbone structure ligand according to the present invention, it is advantageous in that highly pure 1-octene can be prepared because the chromium-based catalyst system has high catalytic tetrxmerization and high 1-octene selectivity, and in that the activity of the chromium-based catalyst system is maintained stable, and thus the decrease in reaction rate with reaction time can be prevented.
C-C-P backbone structure ligand represented by Formula 1 above, R 1R 2R 3 and R 4 are each independently selected from the group consisting of phenyl, benzyl, naphthyl, anthracenyl, mesityl, xylyl, methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, A- methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, tolyl, 4-methylphenyl, 4- ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, cumyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, and dimethylhydrazyl.
The turbid solution was stirred to form a yellow slurry solution. In order to form the in-situ ligand coordination complex, the transition metal compound and the P-C-C-P backbone structure ligand are combined, such that the combination ratio of metal to teramerization is about 0.
Examples of the organic boron compound may include boroxine, NaBH 4triethylborane, triphenylborane, triphenylborane ammonia complex, tributyl borate, triisopropyl borate, tris pentafluorophenyl borane, trityl tetrapentafluorophenyl borate, dimethylphenylammonium 1-octehe borate, diethylphenylammonium tetrapentafluorophenyl borate, methyldiphenylammonium tetrapentafluorophenyl borate, ethyldiphenylammonium tetrapentafluorophenyl borate, and the like.
In order to analyze the liquid using GC-FID, nonane, serving as an internal standard substance, was added thereto. As a result, a reddish brown oily product having yellow crystals, [Ni S,S – chiraphos 2 ] ClO 4 2was formed.
As a result, only a colorless glossy solid remained. An ethylene tetramerization catalyst composition and method of Ethylene tetramerization. RU Kind code of ref document: Examples of the reactors may include, but are not limited to, a batch reactor, a semibatch reactor, and a continuous reactor.
Further, in the method of the present invention, in addition to 1-octene, tetramerizattion large or small amount of 1-butene, 1- hexene, methylcyclopentane, methylenecyclopentane and propylcyclopentane, and a large amount of higher oligomers and polyethylene can be prepared, depending on P-C-C-P backbone structure ligand and condition for the reaction.
Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities.
The results of tetramerization of ethylene in Examples 9 to 12 are given in Table 2, and the changes in reaction activity and selectivity depending on reaction time are shown in FIGS, l and 2.
Here, an in-situ ligand coordination complex having a P-C- C-P backbone structure may also be formed by adding a preformed ligand coordination complex, which is prepared using transition metal compounds and the P-C-C-P backbone structure ligand, to a reaction mixture or by additionally adding transition metal compounds and the P-C-C-P backbone structure ligand to a reactor.
This oily tetgamerization mixture -1octene added to a solution ethyene which 8. The present invention relates to a catalyst system for tetramerizing ethylene and a method of preparing 1-octene by tetramerizing ethylene using the catalyst system.
Species Ethylene tetramerization catalyst compositions and tetramerization process of ethylene. In order to analyze the liquid using GC-FBD, nonane, serving as an internal standard substance, was added thereto. Examples of yetramerization organic aluminum compound may include trimethylaluminum TMAtriethylaluminum TEAtriisobutylaluminum TIBAtri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesquichloride, methylaluminum sesquichloride, and aluminoxane.
Recently, research on methods of producing 1-octene by selectively tetramerizing ethylene through transition metal catalysis has been conducted. The solution was reacted for 45 hours at room temperature, and 60 ml of distilled water was added thereto, and the solution was extracted three times using 60 ml of DMC teframerization form an organic layer. A cyclohexyl 2 PCH 2 CH 2 P cyclohexyl 2 ligand was prepared by reacting diphenylphosphine trtramerization 2 equivalents of dibromoalkyl in dimethylfluoromethylene DMF and cesium hydroxide atmospheres, as disclosed in the document “R.
Soc 84 “.
This multi P-C-C-P backbone structure ligand includes, but is not limited to, ligands in which dendrimer ligands are bonded with the respective P-C-C-P backbone structure ligand through one or more R groups. While the catalytic components tetarmerization mixed, olefin exhibits a protective effect, thus improving the performance of a catalyst.
Chromium-Based Catalyst for Ethylene Tetramerization to 1-Octene
Tetramerization of ethylene using Cr 2-ethylhexanoate ‘ h. Tetramerization of ethylene using Cr IID acetylacetonate j. In order to prepare 1-octene at high selectivity, a catalyst system comprising the ligand of the present invention may be manufactured through a process of combining transition metal compounds tetramerizatipn cocatalysts in an arbitrary order. Comparative Catalyst Preparation Example 5: The catalyst system for tetramerizing ethylene according to claim 1, wherein, in the P- C-C-P backbone structure ligand represented by Formula 1 above, R 5 and R 6 are each independently selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl, derivatives thereof, and aryl substituted with these arbitrary substituents.
Otherwise, the reaction process and product treatment processes were conducted as in Example 1. JP Kind code of ref document: EP EPB1 en A mixed heteroatomic PNP ligand was prepared by reacting amine with phosphine chloride R 2 PClas tetramerizatioh in the theses: The fact that the in-situ ligand coordination complex having a P-C-C-P backbone structure is formed means that the complex is formed in a medium in which a catalytic reaction is conducted.
The method of tetramerizing ethylene according to the present invention may be conducted using a plant equipped with various types of reactors. Bosnich et al, J.
Country of ref document: When 1-octene is prepared using the catalyst system of the present invention in the presence of an inactive solvent, arbitrary inactive solvents that do not react with each catalytic component and a cocatalyst may be used as the inactive solvent.
The cocatalyst that is used in the present invention may be a compound used to activate a catalyst when it is mixed with the P-C-C-P tetramerizatoin structure ligand and the transition metal compound.