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Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene

A technology of mixture and hexene, applied in the field of oligomerization of ethylene oligomerization into a mixture of 1-hexene and 1-octene

Active Publication Date: 2016-01-06
SASOL TECHNOLOGY (PTY) LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Alternatively, they may be useful at higher oligomerization temperatures where polymer co-products remain in solution but catalyst stability and sufficient selection for 1-octene sex is the biggest challenge

Method used

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  • Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene
  • Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene
  • Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene

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preparation example Construction

[0127] In the preparation of the catalyst system used in the present invention, the optimum amount of compound to be used for activation can be easily determined by simple tests, for example, by the preparation of small test samples, which can be used for oligomerization A small amount of ethylene and thus determine the activity of the resulting catalyst. It has generally been found that for aluminum alkyls and aluminoxane-type activators or co-activators, a suitable use level is from 0.5 to 2000 moles of aluminum per mole of chromium.

[0128] Examples of suitable organoboron activator compounds are boronoxane, NaBH 4 , trimethylboron, triethylboron, triphenylboron, dimethylphenylammonium tetrakis (phenyl) borate, trityl tetrakis (phenyl) borate, tetrakis (pentafluorophenyl) boric acid Dimethylphenylammonium, Trityltetrakis(pentafluorophenyl)borate, Tris(pentafluorophenyl)boron, Sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate , Dimethylphenylammonium tetrakis[(bis-3,...

Embodiment 1

[0301] Example 1 utilizes (1-benzofuran-7-yl) at 60°C and 45 bar 2 PN(n-hexyl)P(phenyl) 2 the B ene tetramer

[0302] A 600 ml stainless steel reactor was heated to 120 °C under vacuum for 30 min with N 2 Backfill, then cool to 60°C. The reactor was filled with 2,2,4-trimethylpentane (TMP) (100 ml) and heated to 60°C. Separately, MMAO-3A (2.4mmolAl) was added to Cr(acac) 3 (2.5 μmol) and (1-benzofuran-7-yl) 2 PN(n-hexyl)P(phenyl) 2 (2.5 μmol) in cyclohexane (5 ml). Then, this mixture was transferred to the reactor. The reactor was pressurized with ethylene (45 bar) and stirred with a gas-entraining stirrer (1300 r.p.m.). The temperature in the reactor was raised to 62-65°C, at which point the reactor was cooled with an internal cooling coil to maintain a constant temperature of 60°C throughout the run. The reaction pressure was kept constant throughout the run by supplying ethylene on demand and the consumption of ethylene was monitored via a flow meter. ...

Embodiment 2

[0303] Example 2 using (1-benzofuran-7-yl)(phenyl)PN(n-hexyl)P(phenyl) at 60°C and 45 bar 2 ethylene tetramer

[0304] According to the steps of Example 1, the difference is: use 1.0mmolAl as MMAO-3A, ​​1.0μmolCr(acac) 3 and the ligand (1-benzofuran-7-yl)(phenyl)PN(n-hexyl)P(phenyl) 2 (1.0 μmol), and the reaction was terminated after 17 minutes and 150 g of ethylene input. The results are shown in Table 1.

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Abstract

A process for the otigomerisation of ethylene to predominantly 1-hexene or 1-octene or mixtures of 1-hexene and 1-octene includes contacting ethylene with a catalyst under ethylene oligomerisation conditions. The catalyst comprises a source of chromium, a diphosphine ligating compound, and optionally an activator. The diphosphine ligating compound includes at least one optionally substituted fused cyclic structure including at least two rings, the optionally substituted fused cyclic structure including a 5- to 7- membered aromatic first ring bonded to a phosphorus atom, the aromatic first ring being fused to a 4- to 8-membered heterocyclic second ring, the heterocyclic second ring including a heteroatom which is separated by two ring atoms along the shortest connecting path from the phosphorous atom that is bonded to the first aromatic ring.

Description

technical field [0001] The present invention relates to a process for the oligomerization of ethylene primarily to a mixture of 1-hexene and 1-octene, especially in the presence of activated chromium catalysts with novel diphosphine ligands. Background technique [0002] It is well known that chromium-based catalyst systems with bisphosphine ligands catalyze the selective conversion of ethylene to 1-hexene and / or 1-octene, depending on the choice of reaction conditions and ligand structure. In particular, the nature and position of any substituents attached to the aromatic ring of the phosphine have a crucial impact on the selective separation between 1-hexene and 1-octene. Of particular interest to industry are catalysts for the tetramerization of ethylene because these catalysts are relatively rare. Octene is a valuable comonomer for the production of high performance linear low density polyethylene and elastomers, and there are few purposeful routes for this chemical in ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C2/36C08F10/00C07C11/107C07C11/02
CPCC07C2/36C07C2531/14C07C2531/24C07C2531/34Y02P20/52C07C11/107C07C11/02C08F10/00B01J23/86C07C2/32C07C2531/18
Inventor M·克里斯托弗·莫梅拉M·M·莫格若思M·斯蒂芬·摩卡迪亚纳M·J·欧沃雷特K·布莱恩塞德里克·瓦尔·霍尔茨阿普费尔
Owner SASOL TECHNOLOGY (PTY) LTD
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