CN105562102B - A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method - Google Patents
A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for ethylene tetramerization composition, including catalyst ligand shown in Formulas I, transistion metal compound, containing aluminum cocatalyst, water and organic solvent；R in formula1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy, cycloalkyl or halogen；Existing 2 R5It may be the same or different, be each independently selected from monocyclic or polyaromatic.Present invention also offers a kind of method of ethylene tetramerization, is included in the presence of described ethylene tetramerization carbon monoxide-olefin polymeric, carries out ethylene tetramerization reaction.
Description
Technical field
The present invention relates to ethylene oligomerization field, and in particular to a kind of carbon monoxide-olefin polymeric for ethylene tetramerization.The present invention
Further relate to a kind of ethylene tetramerization method.
Background technology
1- octenes are as important Organic Ingredients and chemical intermediate, mainly for the production of high-quality polyethylene (PE).By
The LLDPE (LLDPE) of 1- octenes and ethylene copolymer production can significantly improve PE properties, particularly pair
Mechanical performance, optical property and the tear strength and impact strength of polyethylene are all significantly increased, and are very suitable for packaging film
With the agricultural mulch films such as greenhouse, canopy room etc., while 1- octenes also serve as plasticizer, aliphatic acid, detergent alcohols and lubricating oil
The intermediate of additive.
Value although 1- octenes be it is well known that this area at present not as ethylene trimer produce 1- hexenes
1- octenes are produced with high selectivity.Traditional 1- production of octenes methods are ethylene oligomerization methods, and ethylene oligomerization technology is according to Schulz-
Flory is distributed, and not only obtains 1- octene products, while also has other alpha-olefins and a small amount of solid superpolymer, and purpose product
The selectivity of 1- octenes is very low, no more than 30%.Such as the SHOP methods (US3676523) available 11% that Shell companies use
1- octenes；United States Patent (USP) (US6184428), which reports, uses a kind of nickel compound to be only as catalyst, the yield of 1- octenes
19%.SHOP techniques such as US3676523 carries out the content of ethylene oligomerization reaction, wherein 1- octenes using nickel-metal catalyst system
Only account for 11%.Japan Patent JP2002121157 reports carries out ethylene oligomerization reaction using zirconium metal catalyzer, and wherein 1- is pungent
The content of alkene is about 15%.The catalyst for ethylene tetramerization system reported recently can synthesize 1- octenes with high selectivity, such as specially
Profit application CN1741850A (WO2004/056478A1), CN1741849A (WO2004/056479A1), CN101032695A,
CN101351424A, CN101415494A, CN1651142A, CN101291734A and patent application US2006/0128910A1 are public
Open and be coordinated using P-N-P parts and chromium, be catalyzed ethylene tetramerization, can produce 1- octenes with high selectivity, 1- octenes in product
Content can even be more than 70%.
Patent application CN101605605A, which is disclosed, utilizes the chromium-based catalysts of the backbone structure ligand containing P-C-C-P to be used for second
Alkene four is poly-, and so as to be prepared for 1- octenes with high selectivity, selective highest can be more than 70%.But above-mentioned technology only limitedly discloses
The substituent structure of the backbone structure ligand containing P-N-P or P-C-C-P, and used in above-mentioned technology contain P-N-P or P-C-C-P
The part of skeleton structure, its is complicated, and preparation process is cumbersome, and cost is higher.The co-catalyst alcoxyl that above-mentioned patent uses
The problem of cost is too high, and dosage is excessive be present in base aluminium (including MAO, modified methylaluminoxane etc.), large-scale application in
During ethylene tetramerization, it certainly will cause production cost high.Moreover, in the prior art, it is generally recognized that water is reacted ethylene tetramerization
Technique is very unfavorable, therefore needs to be strict controlled in process of production and reacted in the environment of anhydrous and oxygen-free.This makes
It is all very harsh to obtain the known requirements of ethylene tetramerization or oligomerisation reaction to technique all at present, causes the anti-of polymerization technology
It should trigger and repeatability is all excessively poor.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, present inventor has carried out deep grind to such phosphorus-containing catalyst
Study carefully, it has surprisingly been found that ethene including the catalyst ligand shown in Formulas I, transistion metal compound, containing aluminum cocatalyst, water and
The carbon monoxide-olefin polymeric effect of organic solvent is lower to carry out ethylene tetramerization reaction, has higher polymerization activity on the contrary, and instead
Should trigger it is rapid, operate steadily, be reproducible, the selectivity of 1- octenes also greatly improves in product；So as to overcome this area
The technology prejudice of technical staff, achieves unexpected technique effect.
First embodiment of the present invention is to provide a kind of brand-new catalyst for ethylene tetramerization composition, including Formulas I
Shown catalyst ligand, transistion metal compound, containing aluminum cocatalyst, water and organic solvent；
R in formula1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy, cycloalkyl or halogen；
Existing 2 R5It may be the same or different, be each independently selected from monocyclic or polyaromatic.
In a preferred embodiment of the present invention, using the weight of organic solvent as calculating benchmark, the catalyst group
The weight content of the water contained in compound is 5~300ppm；More preferably 30~200ppm, most preferably 50~150ppm.
In a preferred embodiment of the present invention, the alkyl is C1~C20Straight chain or branched saturated alkyl, preferably
For C1~C10Straight chain or branched saturated alkyl, more preferably C1~C6Straight chain or branched saturated alkyl；It is it is further preferred that described
Alkyl is selected from following compound：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, positive penta
Base, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and its isomers；Still more preferably methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or dissident
Base；Most preferable, ethyl, n-propyl, isopropyl, normal-butyl or isobutyl group.
In a preferred embodiment of the present invention, the alkoxy is C1~C20Straight chain or branched saturation alkoxy,
Preferably C1~C10Straight chain or branched saturation alkoxy, more preferably C1~C6Straight chain or branched saturation alkoxy；Further preferably
Ground, the alkoxy are selected from following compound：Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl oxygen
Base, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, positive hexyloxy, secondary hexyloxy, dissident's epoxide, just
Heptan epoxide and its isomers；Still more preferably methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl oxygen
Base, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, positive hexyloxy or dissident's epoxide；Most preferably methoxy
Base, ethyoxyl, positive propoxy, isopropoxy, n-butoxy or isobutoxy.
In a preferred embodiment of the present invention, the cycloalkyl is C3~C20Saturated cyclic alkyl, preferably C3
~C10Saturated cyclic alkyl, more preferably C3~C6Saturated cyclic alkyl；Most preferably, the cycloalkyl is selected from following chemical combination
Thing：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Most preferably cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
In a preferred embodiment of the present invention, described monocyclic and polyaromatic is C6~C20Monocyclic or polycyclic aromatic
Group, and the carbon atom optionally on wherein one or more rings is substituted and/or described monocyclic by the hetero atom selected from oxygen, nitrogen and sulphur
And the hydrogen atom on polyaromatic is by halogen or C1-C20Alkyl substitutes；Preferably, described monocyclic and polyaromatic be selected from phenyl,
Substituted-phenyl, naphthyl or pyridine radicals, more preferably phenyl or substituted-phenyl.
In the preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, R in the part1、R2、R3It is identical or different, selected from hydrogen,
C1-C10Alkyl, C1-C10Alkoxy or halogen, it is preferably selected from hydrogen, C1-C6Alkyl, C1-C6Alkoxy or halogen, more preferably hydrogen, first
Base, ethyl, methoxyl group, chlorine or bromine；R4Selected from C6-C20Aryl, it is preferably selected from C6-C12Aryl, it is more preferably selected from C6-C10Aryl,
Most preferably phenyl or substituted-phenyl.
In a preferred embodiment of the present invention, the halogen is selected from fluorine, chlorine or bromine.
In the present invention, the transistion metal compound described in above-mentioned carbon monoxide-olefin polymeric can be commonly used in the art
Transistion metal compound, such as the compound of chromium, molybdenum, iron, titanium, zirconium or nickel, preferably chromium trichloride, chromium acetylacetonate, isooctyl acid
Chromium or three (tetrahydrofuran) chromium trichlorides etc..
In above-mentioned carbon monoxide-olefin polymeric, co-catalyst can be organo-aluminum compound commonly used in the art, such as alkyl aluminum
Compound and/or aluminium alkoxide compound, preferably trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three n-octyls
One kind or several in aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane or modified methylaluminoxane
Kind, most preferable aikyiaiurnirsoxan beta.
In a preferred embodiment of the present invention, in above-mentioned carbon monoxide-olefin polymeric, the catalyst ligand, transition
The mol ratio of metallic compound and co-catalyst is 1：0.1~10：1~1000, preferably 1：0.25~2：10~700, it is more excellent
Elect 1 as：0.5~2：100~500；The mol ratio of the metal in transition metal and co-catalyst in transistion metal compound is excellent
Elect 1 as:50~500.
In a preferred embodiment of the invention, organic solvent used includes arene compounds or aliphatic hydrocarbon chemical combination
Thing, arene compounds include benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and its spread out
Biology；Aliphatic hydrocarbon compound includes linear paraffin, branched paraffin or cycloalkane, such as pentane, heptane, hexamethylene or hexane.
Another embodiment of the invention is to provide a kind of ethylene tetramerization technique, is included in described ethylene tetramerization and uses
In the presence of carbon monoxide-olefin polymeric, ethylene tetramerization reaction is carried out.
In a preferred embodiment of the present invention, the reaction temperature of the ethylene tetramerization reaction is 0~100 DEG C, excellent
Select 0~80 DEG C；0.1~6MPa of reaction pressure, preferably 0.5~5.0MPa.
In a preferred embodiment of the present invention, using the weight of organic solvent as calculating benchmark, the transition metal
The concentration of compound is 0.05~0.3mmol/L.
, can be by part, transistion metal compound and co-catalyst in carbon monoxide-olefin polymeric in above-mentioned ethylene tetramerization technique
In any two kinds be pre-mixed, be then added to again with together with another kind in reaction system, or by body, transistion metal compound
It is added directly into co-catalyst these three components in reaction system and carries out fabricated in situ, or by component part, transition metal
After compound and co-catalyst premix, directly add as a mixture in reaction system.
In above-mentioned ethylene tetramerization technique, reaction condition can be reaction condition commonly used in the art.The condition of optimization is as follows：
Ethene, organic solvent and described carbon monoxide-olefin polymeric are added in reactor, are then 0.1~6Mpa, instead in ethylene pressure
It is to be reacted at 0~100 DEG C to answer temperature, and catalyst concn is 0.05~0.3mmolCr/L.After reaction terminates, room temperature is cooled to, is taken
Gas, liquid product carries out chromatography.
In above-mentioned ethylene tetramerization technique, the pressure preferably 0.5~5.0MPa；Preferably 0~80 DEG C of the reaction temperature.
In above-mentioned ethylene tetramerization method, by catalyst ligand, transistion metal compound in carbon monoxide-olefin polymeric and it can help
Any two kinds are pre-mixed in catalyst, are then added to again with together with another kind in reaction system, or by body, transition metal
Compound and co-catalyst these three components, which are added directly into reaction system, carries out fabricated in situ, or by component part, mistake
After crossing metallic compound and co-catalyst premix, directly add as a mixture in reaction system.
Beneficial effects of the present invention：
In the present invention, especially in the pilot scale and industrial processes of ethylene tetramerization, the catalyst group of the present invention is used
Compound need not only remove the moisture in organic solvent, on the contrary, also needing to add a certain amount of moisture content in organic solvent
To complete the present invention.Different according to temperature, the saturation moisture content that can be carried in organic solvent is different, such as first at 30 DEG C of room temperature
Aqueous 220ppm of energy or so in butylcyclohexane, toluene can contain 350ppm or so.
Ethylene tetramerization is carried out using carbon monoxide-olefin polymeric of the present invention, after reaction terminates, carries out gas-chromatography
And mass spectral analysis.The polymerizate of acquisition mainly includes C6 and C8, there is the alpha-olefins such as a small amount of C4, C10, C12；The choosing of 1- octenes
Selecting property can reach more than 70%.As a result show, catalyst activity is high and high molecular polymer is few.
According to carbon monoxide-olefin polymeric provided by the invention, ethene is including the catalyst ligand shown in Formulas I, transition metal
Compound, the poly- reaction of the lower progress four of composition effect containing aluminum cocatalyst, water and organic solvent, with the anhydrous catalysis reported
Agent composition system is compared, on the contrary the polymerization activity with superelevation, and reaction initiation is rapid, operates steadily, be reproducible.
Embodiment
The following example is only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not limited to
These embodiments.
In an embodiment of the present invention, gas-chromatography is detected using the chromatograph of Hewlett-Packard 5890.
Embodiment 1：
Using stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, after vacuumizing with nitrogen displacement for several times, is then charged with second
Room temperature is down to after alkene displacement.Then added at 30 DEG C and contain water-toluene, while 10 μm of ol ligand compounds 1 of addition (such as Formulas I, its
Middle R1=R2=R3=R4=H, R5=Ph) and chromium acetylacetonate and co-catalyst triethyl aluminum, the cumulative volume of mixed liquor be
100mL, wherein ligand compound, chromic salts and co-catalyst mol ratio are 2：1：300；Using the weight of toluene as calculating benchmark,
The weight content of the water contained in carbon monoxide-olefin polymeric is 150ppm；Reaction pressure 2.0MPa is controlled, is passed through ethene, carries out ethene
Four poly- reactions.
After the completion of reaction, system is cooled to room temperature, and gaseous products are collected in aerometer measuring tank, and liquid-phase product is collected
In conical flask, 1mL ethanol is added as terminator, terminates ethylene tetramerization reaction.Gas-chromatography is carried out after liquid phase gauging of products
Analyze (chromatograph is Hewlett-Packard 5890).Data result is shown in Table 1.
Embodiment 2
With embodiment 1, difference is that water content is 5ppm.Data result is shown in Table 1.
Embodiment 3
With embodiment 1, difference is that water content is 30ppm.Data result is shown in Table 1.
Embodiment 4
With embodiment 1, difference is that water content is 50ppm.Data result is shown in Table 1.
Embodiment 5
With embodiment 1, difference is that water content is 100ppm.Data result is shown in Table 1.
Embodiment 6
With embodiment 1, difference is that water content is 200ppm.Data result is shown in Table 1.
Embodiment 7
With embodiment 1, difference is that water content is 300ppm.Data result is shown in Table 1.
Embodiment 8
With embodiment 1, difference is triethyl aluminum being changed to MAO.Data result is shown in Table 1.
Embodiment 9
With embodiment 1, difference is Al/Cr mol ratios being changed to 50.Data result is shown in Table 1.
Embodiment 10
With embodiment 1, difference is Al/Cr mol ratios being changed to 500.Data result is shown in Table 1.
Embodiment 11
With embodiment 1, difference is, uses ligand compound 2, wherein R in Formulas I1=R2=R4=H, R3=Cl, R5
=Ph.Data result is shown in Table 1.
Embodiment 12
With embodiment 1, difference is, uses ligand compound 3, wherein R in Formulas I1=CH3, R2=R3=R4=H,
R5=Ph.Data result is shown in Table 1.
Comparative example 1
With embodiment 1, difference is that water content is 0ppm.Data result is shown in Table 1.
It can be seen from the data in Table 1 that under the same reaction conditions, contrasted with the catalyst activity of comparative example 1, the present invention
The catalyst activity of the carbon monoxide-olefin polymeric of offer will improve several times.And the obtained selectivity of 1- octenes of the embodiment of the present invention with
Compared to high in comparative example 1.
In addition, ethylene tetramerization reaction initiation is rapid in the present invention, operates steadily, be reproducible.Even in Al/Cr ratios as little as
When 50, catalyst still has preferable oligomerisation reaction catalytic activity in the present invention, ethylene oligomerization reaction cost is declined to a great extent,
Its is practical, and industrial prospect is wide.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Table 1
Claims (37)
1. a kind of catalyst for ethylene tetramerization composition, including catalyst ligand, transistion metal compound, co-catalysis shown in Formulas I
Agent, water and organic solvent；
R in formula1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy, cycloalkyl or halogen；It is existing
2 R5It may be the same or different, be each independently selected from monocyclic or polyaromatic；Using the weight of organic solvent as calculating benchmark, institute
The weight content for stating the water contained in carbon monoxide-olefin polymeric is 5~300ppm；The organic solvent be selected from benzene,toluene,xylene,
Monochlor-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene, pentane, heptane and hexane.
2. composition according to claim 1, it is characterised in that described to urge using the weight of organic solvent as calculating benchmark
The weight content of the water contained in agent composition is 30~200ppm.
3. composition according to claim 2, it is characterised in that described to urge using the weight of organic solvent as calculating benchmark
The weight content of the water contained in agent composition is 50~150ppm.
4. composition according to claim 1, it is characterised in that the alkyl is C1~C20Straight chain or branched saturation alkane
Base.
5. composition according to claim 4, it is characterised in that the alkyl is C1~C10Straight chain or branched saturation alkane
Base.
6. composition according to claim 4, it is characterised in that the alkyl is C1~C6Straight chain or branched saturation alkane
Base.
7. composition according to claim 4, it is characterised in that the alkyl is selected from following compound：Methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl,
Isohesyl, n-heptyl and its isomers.
8. composition according to claim 4, it is characterised in that the alkyl is selected from following compound：Methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or dissident
Base.
9. composition according to claim 4, it is characterised in that the alkyl is selected from following compound：Methyl, ethyl,
N-propyl, isopropyl, normal-butyl or isobutyl group.
10. composition according to claim 1, it is characterised in that the alkoxy is C1~C20Straight chain or branched saturation
Alkoxy.
11. composition according to claim 10, it is characterised in that the alkoxy is C1~C10Straight chain or branched saturation
Alkoxy.
12. composition according to claim 10, it is characterised in that the alkoxy is C1~C6Straight chain or branched saturation
Alkoxy.
13. composition according to claim 10, it is characterised in that the alkoxy is selected from following compound：Methoxyl group,
Ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary penta oxygen
Base, isoamoxy, positive hexyloxy, secondary hexyloxy, dissident's epoxide, positive epoxide in heptan and its isomers.
14. composition according to claim 10, it is characterised in that the alkoxy is selected from following compound：Methoxyl group,
Ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary penta oxygen
Base, isoamoxy, positive hexyloxy or dissident's epoxide.
15. composition according to claim 10, it is characterised in that the alkoxy is selected from following compound：Methoxyl group,
Ethyoxyl, positive propoxy, isopropoxy, n-butoxy or isobutoxy.
16. composition according to claim 1, it is characterised in that the cycloalkyl is C3~C20Saturated cyclic alkyl.
17. composition according to claim 16, it is characterised in that the cycloalkyl is C3~C10Saturated cyclic alkyl.
18. composition according to claim 16, it is characterised in that the cycloalkyl is C3~C6Saturated cyclic alkyl.
19. composition according to claim 16, it is characterised in that the cycloalkyl is selected from following compound：Cyclopropyl,
Cyclobutyl, cyclopenta, cyclohexyl, suberyl.
20. composition according to claim 16, it is characterised in that the cycloalkyl is selected from following compound：Cyclopropyl,
Cyclobutyl, cyclopenta or cyclohexyl.
21. composition according to claim 1, it is characterised in that described monocyclic and polyaromatic is C6~C20It is monocyclic or
Polycyclic aromatic group, and the carbon atom optionally on wherein one or more rings substituted by the hetero atom selected from oxygen, nitrogen and sulphur and/or
Hydrogen atom on described monocyclic and polyaromatic is by halogen or C1-C20Alkyl substitutes.
22. composition according to claim 21, it is characterised in that described monocyclic and polyaromatic is selected from phenyl, substitution
Phenyl, naphthyl or pyridine radicals.
23. composition according to claim 21, it is characterised in that described monocyclic and polyaromatic is selected from phenyl or substitution
Phenyl.
24. composition according to claim 1, it is characterised in that the transistion metal compound be selected from chromium, molybdenum, iron,
At least one of compound of titanium, zirconium and nickel.
25. composition according to claim 1, it is characterised in that the transistion metal compound is selected from chromium trichloride, second
At least one of acyl acetone chromium, isooctyl acid chromium and three (tetrahydrofuran) chromium trichlorides.
26. composition according to claim 1, it is characterised in that the co-catalyst is organo-aluminum compound.
27. composition according to claim 26, it is characterised in that the co-catalyst be alkyl aluminum compound and/or
Aluminium alkoxide compound.
28. composition according to claim 26, it is characterised in that the co-catalyst in following compound extremely
Few one kind：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, two chloroethenes
Base aluminium, MAO, ethylaluminoxane and modified methylaluminoxane.
29. composition according to claim 26, it is characterised in that the co-catalyst is MAO.
30. according to the composition any one of claim 1-29, it is characterised in that ligand compound, transition metal
The mol ratio of compound and co-catalyst is 1：0.1~10：1~1000.
31. composition according to claim 30, it is characterised in that ligand compound, transistion metal compound and helping is urged
The mol ratio of agent is 1：0.25~2：10~700.
32. composition according to claim 30, it is characterised in that ligand compound, transistion metal compound and helping is urged
The mol ratio of agent is 1：0.5~2：100~500.
33. composition according to claim 30, it is characterised in that transition metal in transistion metal compound and helping is urged
The mol ratio of metal in agent is 1:50~500.
34. a kind of method of ethylene tetramerization, it is included in the ethylene tetramerization catalysis according to any one of claim 1-33
In the presence of agent composition, ethylene tetramerization reaction is carried out.
35. according to the method for claim 34, it is characterised in that the reaction temperature of the ethylene tetramerization reaction is 0~100
℃；0.1~6MPa of reaction pressure.
36. according to the method for claim 35, it is characterised in that the reaction temperature of the ethylene tetramerization reaction is 0~80
℃；0.5~5.0MPa of reaction pressure.
37. according to the method any one of claim 34-36, it is characterised in that using the weight of organic solvent as calculating
Benchmark, the concentration of the transistion metal compound is 0.05~0.3mmol/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6825297B1 (en) * | 1999-05-14 | 2004-11-30 | The Dow Chemical Company | Transition metal complexes and olefin polymerization process |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
| CN103566973A (en) * | 2012-08-06 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6825297B1 (en) * | 1999-05-14 | 2004-11-30 | The Dow Chemical Company | Transition metal complexes and olefin polymerization process |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
| CN103566973A (en) * | 2012-08-06 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization |
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