CN107282130A - Catalyst for ethylene tetramerization composition and its application - Google Patents

Catalyst for ethylene tetramerization composition and its application Download PDF

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CN107282130A
CN107282130A CN201610196257.8A CN201610196257A CN107282130A CN 107282130 A CN107282130 A CN 107282130A CN 201610196257 A CN201610196257 A CN 201610196257A CN 107282130 A CN107282130 A CN 107282130A
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compound
catalyst
alkyl
ethylene tetramerization
reaction
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CN107282130B (en
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吴红飞
郑明芳
刘珺
王霄青
韩春卉
栗同林
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a kind of catalyst for ethylene tetramerization composition, including ligand compound, transistion metal compound, co-catalyst and TBHP shown in Formulas I；R in formula1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy, cycloalkyl or halogen；R5And R6It is identical or different, it is each independently selected from monocyclic or polyaromatic.Present invention also offers a kind of method of ethylene tetramerization, be included in the presence of described ethylene tetramerization carbon monoxide-olefin polymeric, carry out ethylene tetramerization reaction, the reactivity with superelevation, and reaction trigger it is rapid, operate steadily, it is reproducible.

Description

Catalyst for ethylene tetramerization composition and its application
Technical field
The present invention relates to ethylene oligomerization field, and in particular to a kind of carbon monoxide-olefin polymeric for ethylene tetramerization.This Invention further relates 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). The LLDPE (LLDPE) produced by 1- octenes and ethylene copolymer can significantly improve PE items Can, particularly have significantly to the mechanical performance of polyethylene, optical property and tear strength and impact strength Improve, be very suitable for agricultural mulch films such as packaging film and greenhouse, canopy room etc., while 1- octenes also serve as plasticizer, The intermediate of aliphatic acid, detergent alcohols and lube oil additive.
Value although 1- octenes be it is well known that this area at present not as ethylene trimer produce 1- hexenes It is the same that 1- octenes are produced with high selectivity.Traditional 1- production of octenes methods are ethylene oligomerization method, ethylene oligomerization skill Art is distributed according to Schulz-Flory, not only obtains 1- octene products, while also having other alpha-olefins and a small amount of solid High polymers, and the selectivity of purpose product 1- octenes is very low, no more than 30%.For example Shell companies adopt The 1- octenes of SHOP methods (US3676523) available 11%；United States Patent (USP) (US6184428), which is reported, to be made With a kind of nickel compound as catalyst, the yield of 1- octenes is only 19%.SHOP techniques such as US3676523 Ethylene oligomerization reaction is carried out using nickel-metal catalyst system, the content of wherein 1- octenes only accounts for 11%.It is Japanese special Sharp JP2002121157 is reported carries out ethylene oligomerization reaction using zirconium metal catalyzer, and wherein 1- octenes contain Amount is about 15%.The catalyst for ethylene tetramerization system reported recently can synthesize 1- octenes with high selectivity, such as Patent application CN1741850A (WO2004/056478A1), CN1741849A (WO2004/056479A1), CN101032695A、CN101351424A、CN101415494A、CN1651142A、CN101291734A Disclose and be coordinated using P-N-P parts with chromium with patent application US2006/0128910A1, be catalyzed ethylene tetramerization, The content of 1- octenes in 1- octenes, product can be produced with high selectivity more than 60%.
Patent application CN101605605A discloses the chromium-based catalysts using the backbone structure ligand containing P-C-C-P For ethylene tetramerization.But above-mentioned technology only limitedly discloses the backbone structure ligand containing P-N-P or P-C-C-P Substituent structure, its is complicated, and preparation process is cumbersome, and cost is higher.The co-catalysis that above-mentioned patent is used Agent aluminum alkoxide (including MAO, modified methylaluminoxane etc.) has that cost is too high, and consumption is excessive Problem, large-scale application is when ethylene tetramerization, and it certainly will cause production cost high.Moreover, in prior art In, it is generally recognized that water and oxygen are very unfavorable to ethylene tetramerization reaction process, therefore are needed in process of production It is strict controlled in the environment of anhydrous and oxygen-free and is reacted.This causes known ethylene tetramerizations all at present or oligomerisation The requirement reacted to technique is all very harsh, causes the reaction of reaction process to trigger and repeated 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 to such phosphorus-containing catalyst Research, it has surprisingly been found that ethene is including the ligand compound shown in Formulas I, transistion metal compound, containing aluminium The carbon monoxide-olefin polymeric effect of co-catalyst and TBHP (and organic solvent) is lower to carry out ethene four Poly- reaction, on the contrary with higher reactivity, and reaction trigger it is rapid, operate steadily, reproducible, production The selectivity of 1- octenes is also greatly improved in thing；So as to overcome the technology prejudice of those skilled in the art, obtain Unexpected technique effect.
An object of the present invention is to provide a kind of brand-new catalyst for ethylene tetramerization composition, including shown in Formulas I Ligand compound, transistion metal compound, co-catalyst and TBHP；
R in formula1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy, ring Alkyl or halogen；R5And R6It is identical or different, it is each independently selected from monocyclic or polyaromatic.
In the prior art, it is generally recognized that oxide is unfavorable to ethylene tetramerization reaction.Those skilled in the art are led to It often may require that four poly- reactions are carried out under the conditions of anhydrous and oxygen-free.And found according to the research of the present invention, in the application In composition effect under, ethylene tetramerization reaction has higher activity on the contrary, and the selectivity of 1- octenes is high, So as to break the preoccupation of thought of people, unexpected technique effect is achieved.
In a preferred embodiment of the present invention, machine solvent is further includeed in the composition.To have The weight of machine solvent is calculating benchmark, and the weight of the TBHP contained in the carbon monoxide-olefin polymeric contains Measure as 25-1500ppm, such as 25-1000ppm.In the scope, more preferable four poly- reactions can be obtained and lived Property, higher 1- Octenes selectivities.In an instantiation, the preferred weight content of TBHP For 150-1000ppm, such as 250-750ppm.In the scope, more preferable effect can be obtained.
In a preferred embodiment of the present invention, the alkyl is C1-C20Straight chain or branched-alkyl, preferably For C1-C10Straight chain or branched-alkyl, more preferably C1-C6Straight chain or branched-alkyl.Further, the alkane Base can be selected from following group：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 isomery Body, still more preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, uncle Butyl, n-pentyl, sec-amyl, isopentyl, n-hexyl or isohesyl；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 alkoxy, Preferably C1-C10Straight chain or branched alkoxy, more preferably C1-C6Straight chain or branched alkoxy.It is further excellent Selection of land, the alkoxy is selected from following group：Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth Epoxide, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, just oneself Epoxide, secondary hexyloxy, dissident's epoxide, positive epoxide in heptan and its isomers；Still more preferably methoxyl group, ethoxy Base, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, positive penta oxygen Base, secondary amoxy, isoamoxy, positive hexyloxy or dissident's epoxide；Most preferably methoxyl group, ethyoxyl, positive third Epoxide, isopropoxy, n-butoxy or isobutoxy.
In a preferred embodiment of the present invention, the cycloalkyl is C3-C20Cycloalkyl, preferably C3-C10 Cycloalkyl, more preferably C3-C6Cycloalkyl.Such as described cycloalkyl is selected from following group：Cyclopropyl, ring fourth Base, cyclopenta, cyclohexyl, suberyl；Most preferably cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
In a preferred embodiment of the present invention, the halogen is selected from fluorine, chlorine or bromine.It is described monocyclic or many Cyclophane base is selected from phenyl and anthryl.
In a preferred embodiment of the present invention, R in the part1-R3It is identical or different, selected from hydrogen, C1-C10Alkyl, C1-C10Alkoxy or halogen, is such as selected from hydrogen, C1-C6Alkyl, C1-C6Alkoxy or halogen, Specific such as hydrogen, methyl, ethyl, methoxyl group, chlorine or bromine.
In the present invention, the transistion metal compound described in above-mentioned carbon monoxide-olefin polymeric can be that this area is normal Transistion metal compound.Such as chromium compound, molybdenum compound, iron compound, titanium compound, zirconium chemical combination At least one of thing and nickel compound, preferably chromium trichloride, chromium acetylacetonate, isooctyl acid chromium and three (tetrahydrochysenes At least one of furans) chromium trichloride etc..
In a preferred embodiment of the present invention, the co-catalyst is organo-aluminum compound.Help as described Catalyst can be conventional in the art alkyl aluminum compound and/or aluminium alkoxide compound.It is specific real at one In example, the co-catalyst preferably at least one of following compound：It is trimethyl aluminium, triethyl aluminum, three different Butyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, Ethylaluminoxane and modified methylaluminoxane.
In above-mentioned carbon monoxide-olefin polymeric, the ligand compound, transistion metal compound and co-catalyst Mol ratio is 1:(0.1-10):(1-1000), preferably 1:(0.25-2):(10-700), such as 1:(0.25-2): (50-700).Under the conditions of preferably, the ligand compound, transistion metal compound and co-catalyst Mol ratio is 1:(0.5-2):(100-500), such as 2:(1-2):(50-500).Within the above range, institute Stating composition has higher active and 1- Octenes selectivities.In a specific example, the part chemical combination The mol ratio of thing, transistion metal compound and co-catalyst is 2：1:(50-500).
In a preferred embodiment of the present invention, the organic solvent is solvent conventional in the art, such as Arene compounds and aliphatic hydrocarbon compound can be selected from.The arene compounds preferably be selected from benzene, toluene, Dimethylbenzene, monochlor-benzene, dichlorobenzene, trichloro-benzene and at least one of monochlorotoluene and its derivative. The aliphatic hydrocarbon compound is selected from least one of linear paraffin, branched paraffin and cycloalkane, more preferably penta At least one of alkane, heptane, hexamethylene and hexane.The consumption of organic solvent causes other components fully to dissolve Or it is scattered.Wherein, the amount of the ligand compound, transistion metal compound and co-catalyst is catalytic amount. In a specific embodiment, using the volume of composition as calculating benchmark, the transistion metal compound it is dense Spend for 0.05-0.3mmol/L.
It is a further object of the present invention to provide a kind of ethylene tetramerization method, it is included in above-mentioned carbon monoxide-olefin polymeric In the presence of, carry out ethylene tetramerization reaction.
In a specific embodiment of the inventive method, the reaction temperature of the ethylene tetramerization reaction is 0-100 DEG C, such as 30-60 DEG C.In the temperature range, methods described has more preferable resultant effect.Wherein, The reaction pressure of the ethylene tetramerization is 0.1-6MPa, and such as 1-5MPa, pressure limit is moderate, with more preferable Resultant effect.In another specific embodiment of the inventive method, using the volume of composition as calculating benchmark, The concentration of the transistion metal compound is 0.05-0.3mmol/L.
, can be by the ligand compound in carbon monoxide-olefin polymeric, transition metal compound in above-mentioned ethylene tetramerization method Any two kinds are pre-mixed in thing, co-catalyst and TBHP, are then added again together with other two These three components are direct into reaction system, or by ligand compound, transistion metal compound and co-catalyst It is added in reaction system and carries out fabricated in situ, or by ligand compound, transistion metal compound, co-catalysis After agent and TBHP premix, directly add as a mixture in reaction system.Described is organic molten Agent can be added in the arbitrary process of any one in above-mentioned hybrid mode.In addition it is also possible to be urged above-mentioned Ligand compound, transistion metal compound and the cocatalyst component of agent are dissolved in organic solvent respectively, then Introduce reactor mixed, or by the ligand compound of above-mentioned catalyst, transistion metal compound, help and urge Agent is dissolved in organic solvent with random order, then adds TBHP, is then added to reactant In system.
In above-mentioned ethylene tetramerization method, reaction condition can be reaction condition commonly used in the art.The condition of optimization It is as follows：Ethene, organic solvent and described carbon monoxide-olefin polymeric are added in reactor, then in ethylene pressure It is reaction at 0-100 DEG C for 0.1-6Mpa, reaction temperature, the concentration of transistion metal compound is 0.05-0.3mmol/L.After reaction terminates, room temperature is cooled to, takes gas, liquid product to carry out chromatography.
In one preferred embodiment of above-mentioned ethylene tetramerization method, the pressure is 0.5-5.0MPa；It is described anti- It is 0-80 DEG C, such as 30-60 DEG C to answer temperature.In above-mentioned preferred scope, methods described has more excellent comprehensive Close effect.
In the present invention, especially in the pilot scale and industrial processes of ethylene tetramerization, the catalysis of the present invention is used Agent composition need not only keep strict oxygen free operation, on the contrary, also needing to add one in organic solvent Quantitative TBHP is to complete the present invention.TBHP is used as organic oxidation in the present invention Thing can significantly improve the performance of catalyst system and catalyzing and the selectivity of target product.
Ethylene tetramerization is carried out using carbon monoxide-olefin polymeric of the present invention, after reaction terminates, gas phase is carried out Chromatogram and mass spectral analysis.The product of acquisition mainly includes C6And C8, there is a small amount of C4、C10、C12Deng α-alkene Hydrocarbon；In product, the selectivity of 1- octenes can be more than more than 70%.As a result show, catalyst activity height and high score Sub- polymer is few.
The carbon monoxide-olefin polymeric provided according to the present invention, ethene is including the ligand compound shown in Formulas I, transition Metallic compound, the poly- reaction of the lower progress four of composition effect containing aluminum cocatalyst, TBHP, with The catalyst composition system for the anhydrous and oxygen-free reported is compared, on the contrary the reactivity with superelevation, and reaction Trigger it is rapid, operate steadily, it is 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 It is limited to these embodiments.
In an embodiment of the present invention, nuclear magnetic resonance uses Bruker companies of Switzerland AV400MHz nuclear magnetic resonance Spectrometer is detected.Gas-chromatography is detected using the chromatograph of Hewlett-Packard 5890.Mass spectrum is using the luxuriant and rich with fragrance Buddhist nun in the U.S. Root company's T race DSQ type gas chromatograph-mass spectrometers are detected.
Embodiment 1
Using stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, after vacuumizing with nitrogen displacement for several times, Room temperature is down to after being then charged with ethene displacement.Then toluene is added at 30 DEG C, matched somebody with somebody while adding 10 μm of ol Body compound 1 (such as Formulas I, wherein R1=R2=R3=R4=H, R5=R6=Ph), chromium acetylacetonate and help Catalyst triethyl aluminum, the cumulative volume of composition is 100mL, and wherein part, chromic salts and co-catalyst rubs You are than being 2：1：300, i.e. Al/Cr mol ratios are 300；Using the gross weight of organic solvent (toluene) as meter The weight content for calculating the TBHP contained in benchmark, carbon monoxide-olefin polymeric is 750ppm；Control is anti- Pressure 2.0MPa is answered, ethene is passed through, ethylene tetramerization reaction is carried out.
After the completion of reaction, system is cooled to room temperature, gaseous products is collected in aerometer measuring tank, liquid phase Product is collected in conical flask, adds 1mL ethanol as terminator, terminates ethylene tetramerization reaction.Gas-liquid The laggard promoting the circulation of qi analysis of hplc of phase gauging of products (chromatograph is Hewlett-Packard 5890).Data result is shown in Table 1.
Embodiment 2
Be the same as Example 1, difference is that TBHP content is 25ppm.Data result is shown in Table 1。
Embodiment 3
Be the same as Example 1, difference is that TBHP content is 250ppm.Data result is shown in Table 1.
Embodiment 4
Be the same as Example 1, difference is that TBHP content is 1000ppm.Data result is shown in Table 1.
Embodiment 5
Be the same as Example 1, difference is triethyl aluminum being changed to MAO.Data result is shown in Table 1.
Embodiment 6
Be the same as Example 1, difference is Al/Cr mol ratios being changed to 50.Data result is shown in Table 1.
Embodiment 7
Be the same as Example 1, difference is Al/Cr mol ratios being changed to 500.Data result is shown in Table 1. Embodiment 8
Be the same as Example 1, difference is, uses ligand compound 2, wherein R in Formulas I1=R2=R4=H, R3=Cl, R5=R6=Ph.Data result is shown in Table 1.
Embodiment 9
Be the same as Example 1, difference is, uses ligand compound 3, wherein R in Formulas I1=CH3, R2=R3=R4=H, R5=R6=Ph.Data result is shown in Table 1.
Embodiment 10
Be the same as Example 1, difference is that reaction temperature is changed to 60 DEG C.Data result is shown in Table 1.
Embodiment 11
Be the same as Example 1, difference is that reaction pressure is changed to 5.0MPa.Data result is shown in Table 1.
Comparative example 1
Be the same as Example 1, difference is that TBHP content is 0ppm.Data result is shown in Table 1.
Although being only exemplified by the data under partial parameters in table 1, invention technician can be from table 1 Middle data can be seen that the catalyst activity contrast with comparative example 1, the catalyst combination that the present invention is provided Under the same conditions, catalyst activity will improve several times to thing.And the obtained 1- octenes of the embodiment of the present invention Selectivity will height compared with comparative example 1.
In addition, in the present invention ethylene tetramerization reaction trigger it is rapid, operate steadily, it is reproducible.Even in During Al/Cr ratios as little as 50, catalyst still has preferable oligomerisation reaction catalytic activity in the present invention, makes Ethylene oligomerization reaction cost declines to a great extent, and 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 constitute to this hair Bright any limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that its In used word be descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation at this The present invention is modified in the range of invention claim, and without departing substantially from the scope of the present invention and essence The present invention is revised in refreshing.Although the present invention described in it is related to specific method, material and reality Example is applied, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention is expansible To other all methods and applications with identical function.
Table 1

Claims (10)

1. a kind of catalyst for ethylene tetramerization composition, including ligand compound, transition metal compound shown in Formulas I Thing, co-catalyst and TBHP；
R in formula1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy, ring Alkyl or halogen；R5And R6It is identical or different, it is each independently selected from monocyclic or polyaromatic.
2. composition according to claim 1, it is characterised in that further included in the composition Organic solvent, preferably using the weight of organic solvent as calculating benchmark, the tertiary fourth contained in the carbon monoxide-olefin polymeric The weight content of base hydrogen peroxide is 25-1500ppm；Preferably 150-1000ppm, be most preferably 250-750ppm。
3. composition according to claim 1 or 2, it is characterised in that the alkyl is C1-C20Directly Chain or branched-alkyl, preferably C1-C10Straight chain or branched-alkyl, more preferably C1-C6Straight chain or branched-alkyl； And/or
The alkoxy is C1-C20Straight chain or branched alkoxy, preferably C1-C10Straight chain or branched alkoxy, More preferably C1-C6Straight chain or branched alkoxy；And/or
The cycloalkyl is C3-C20Cycloalkyl, preferably C3-C10Cycloalkyl, more preferably C3-C6Cycloalkyl.
4. the composition according to any one of claim 1-3, it is characterised in that the alkyl be selected from Lower group：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, just Amyl group, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and its isomers；And/or
The alkoxy is selected from following group：Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth oxygen Base, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, just own oxygen Base, secondary hexyloxy, dissident's epoxide, positive epoxide in heptan and its isomers；And/or
The cycloalkyl is selected from cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl and suberyl；And/or
Described monocyclic or polyaromatic is selected from phenyl and anthryl.
5. the composition according to any one of claim 1-4, it is characterised in that the transition metal Compound is in chromium compound, molybdenum compound, iron compound, titanium compound, zirconium compounds and nickel compound At least one, preferably is selected from chromium trichloride, chromium acetylacetonate, isooctyl acid chromium and three (tetrahydrofuran) chromium trichlorides At least one.
6. the composition according to any one of claim 1-5, it is characterised in that the co-catalyst is Organo-aluminum compound；Preferably alkyl aluminum compound and/or aluminium alkoxide compound；In more preferably following compound It is at least one：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, a chlorine Diethyl aluminum, ethyl aluminum dichloride, MAO, ethylaluminoxane and modified methylaluminoxane.
7. the composition according to any one of claim 1-6, it is characterised in that ligand compound, mistake The mol ratio for crossing metallic compound and co-catalyst is 1:(0.1-10):(1-1000), preferably 1:(0.25-2): (10-700), more preferably 1:(0.5-2):(100-500), more preferably 2:(1-2):(50-500).
8. the composition according to any one of claim 1-7, it is characterised in that enter in the composition One step includes organic solvent；Preferable organic solvent is selected from arene compounds and aliphatic hydrocarbon compound；Wherein, The arene compounds preferably be selected from benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene and At least one of monochlorotoluene and its derivative；Or the aliphatic hydrocarbon compound preferably is selected from linear paraffin, branch At least one of at least one of alkane and cycloalkane, more preferably pentane, heptane, hexamethylene and hexane.
9. a kind of method of ethylene tetramerization, is included in the ethylene tetramerization according to any one of claim 1-8 In the presence of carbon monoxide-olefin polymeric, ethylene tetramerization reaction is carried out.
10. method according to claim 9, it is characterised in that the reaction temperature of the ethylene tetramerization reaction Spend for 0-100 DEG C, preferably 30-60 DEG C；Reaction pressure 0.1-6MPa, preferably 1-3MPa；And/or with composition Volume be calculating benchmark, the concentration of the transistion metal compound is 0.05-0.3mmol/L.
CN201610196257.8A 2016-03-31 2016-03-31 Ethylene tetramerization catalyst composition and application thereof Active CN107282130B (en)

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CN101210061A (en) * 2006-12-27 2008-07-02 华东理工大学 Functional olefin copolymers and its preparing process and application
CN101605605A (en) * 2007-01-18 2009-12-16 Sk能源株式会社 Ethene four gathers catalyst systems and uses this catalyst system to prepare the method for 1-octene
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