CN107282125A - A kind of catalyst for ethylene tetramerization composition and its application - Google Patents
A kind of catalyst for ethylene tetramerization composition and its application Download PDFInfo
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- CN107282125A CN107282125A CN201610195794.0A CN201610195794A CN107282125A CN 107282125 A CN107282125 A CN 107282125A CN 201610195794 A CN201610195794 A CN 201610195794A CN 107282125 A CN107282125 A CN 107282125A
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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)
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- 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
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- 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
Abstract
The invention provides a kind of catalyst for ethylene tetramerization composition, including ligand compound shown in Formulas I, transistion metal compound, containing co-catalyst and TBHP；In formula, R1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy, cycloalkyl and halogen；R5And R6It is identical or different, it is each independently substituted or unsubstituted monocyclic or polyaromatic.Present invention also offers a kind of method that ethylene tetramerization is carried out using the catalyst for ethylene tetramerization composition.The composition provided according to the present invention is used for ethylene tetramerization, on the contrary with four higher poly- reactivities, and 1 Octenes selectivity is high.
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.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 can even 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 the part of the skeleton structure containing P-N-P or P-C-C-P used in above-mentioned technology, its is complicated, prepares step
It is rapid cumbersome, and cost is higher.Co-catalyst aluminum alkoxide that above-mentioned patent is used (including MAO, change
Property MAO etc.) too high, the problem of consumption is excessive that there is cost, large-scale application when ethylene tetramerization,
It certainly will cause production cost high.Moreover, in the prior art, it is generally recognized that water reacts work to ethylene tetramerization
Skill is very unfavorable, therefore needs progress in the environment of being strict controlled in anhydrous and oxygen-free anti-in process of production
Should.This make it that the known requirements of ethylene tetramerization or oligomerisation reaction to technique all at present are all very harsh, causes
The reaction of reaction process triggers 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 to such phosphorus-containing catalyst
Research, it has surprisingly been found that ethene is including the catalyst ligand shown in Formulas I, transistion metal compound, containing aluminium
The lower progress ethylene tetramerization of carbon monoxide-olefin polymeric effect of co-catalyst, TBHP and organic solvent is anti-
Should, on the contrary with higher reactivity, and reaction trigger it is rapid, operate steadily, it is reproducible, in product
The selectivity of 1- octenes is also greatly improved；Wherein, TBHP is promoted as organic peroxide
The progress of reaction, so as to overcome the technology prejudice of those skilled in the art, achieves unexpected technology effect
Really.The carbon monoxide-olefin polymeric can effectively be catalyzed ethylene oligomerization reaction, especially ethylene tetramerization and react.
First embodiment of the present invention is related to a kind of catalyst for ethylene tetramerization composition, including shown in Formulas I
Ligand compound, transistion metal compound, containing co-catalyst and TBHP；
In formula, R1、R2、R3And R4It is identical or different, be each independently selected from hydrogen, alkyl, alkoxy,
Cycloalkyl and halogen；R5And R6It is identical or different, it is each independently substituted or unsubstituted monocyclic or polycyclic
Aryl.
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 content of the TBHP is 25-1500ppm, such as
25-1000ppm.In the scope, more preferable four poly- reactivities can be obtained, higher 1- octenes are selected
Property.In an instantiation, preferably the weight content of TBHP is 150-1000ppm, such as
250-750ppm.In the preferred scope, more preferable effect can be obtained.
In a preferred embodiment of the present invention, the alkyl is C1-C20Straight chain or branched saturated alkyl,
Preferably C1-C10Straight chain or branched saturated alkyl, more preferably C1-C6Straight chain or branched saturated alkyl；Enter one
Preferably, the alkyl is selected from following group to step：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl,
N-heptyl and its isomers；Still more preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl
Base, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, isohesyl etc.；Most preferably
Methyl, 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 alcoxyl
Base, preferably C1-C10Straight chain or branched saturation alkoxy, more preferably C1-C6Straight chain or branched saturation alcoxyl
Base；It is further preferred that the alkoxy is selected from following group：It is methoxyl group, ethyoxyl, positive propoxy, different
It is propoxyl group, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, different
Amoxy, positive hexyloxy, secondary hexyloxy, dissident's epoxide, positive epoxide in heptan and its isomers；Still more preferably
Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tertiary fourth
Epoxide, n-pentyloxy, secondary amoxy, isoamoxy, positive hexyloxy, dissident's epoxide etc.；Most preferably methoxy
Base, ethyoxyl, positive propoxy, isopropoxy, n-butoxy or isobutoxy.
In some preferred embodiments of the present invention, the cycloalkyl is C3-C20Saturated cyclic alkyl, preferably
For C3-C10Saturated cyclic alkyl, more preferably C3-C6Saturated cyclic alkyl；It is further preferred that the ring
Alkyl is selected from following group：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Most preferably cyclopropyl,
Cyclobutyl, cyclopenta or cyclohexyl.
In some preferred embodiments of the present invention, described monocyclic and polyaromatic is related to C6-C20It is monocyclic or many
Cyclic aromatic groups, are preferably directed to C5-C10Monocyclic or polycyclic aromatic group.The substituted monocyclic and polyaromatic
Mean the carbon atom on wherein one or more rings be optionally selected from oxygen, nitrogen and sulphur hetero atom substitution and/
Or the hydrogen atom on described monocyclic and polyaromatic is optionally by halogen or C1-C20Alkyl replaces.Preferably,
R5-R6Selected from phenyl, substituted-phenyl, naphthyl and pyridine radicals, more preferably phenyl or substituted-phenyl.
In the preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, R in the part1、R2、R3、R4It is identical or not
Together, selected from hydrogen, methyl, ethyl, methoxyl group, chlorine or bromine.In the present invention, above-mentioned carbon monoxide-olefin polymeric
Described in transistion metal compound can be transistion metal compound commonly used in the art.In some of the present invention
In preferred embodiment, in compound of the transistion metal compound selected from chromium, molybdenum, iron, titanium, zirconium and nickel
At least one, preferably chromium trichloride, chromium acetylacetonate, isooctyl acid chromium and three (tetrahydrofuran) chromium trichlorides
At least one of.
In above-mentioned carbon monoxide-olefin polymeric, co-catalyst can be organo-aluminum compound commonly used in the art.It is preferred that
Alkyl aluminum compound and/or aluminium alkoxide compound；At least one of more preferably following compound：Trimethyl aluminium,
Triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride,
MAO, ethylaluminoxane or modified methylaluminoxane.
In a preferred embodiment of the present invention, the ligand compound, transistion metal compound and help
The mol ratio of catalyst is 1:(0.1-10):(1-1000), preferably 1:(0.25-2):(10-700), more
Preferably 1:(0.5-2):(100-500).Wherein, further, it is preferable to which transistion metal compound and helping is urged
The mol ratio of agent is preferably 1:(50-500).
In a preferred embodiment of the invention, organic solvent used such as organic solvent commonly used in the art.
Organic solvent includes at least one of arene compounds and aliphatic hydrocarbon compound as described.Aromatic hydrocarbons
Compound includes benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene
At least one of and its derivative.Aliphatic hydrocarbon compound includes linear paraffin, branched paraffin and cycloalkanes
At least one of at least one of hydrocarbon, such as pentane, heptane, hexamethylene and hexane.
Second embodiment of the present invention is related to a kind of method of ethylene tetramerization, is included in above-mentioned catalyst group
In the presence of compound, ethylene tetramerization reaction is carried out.
In a preferred embodiment of above-mentioned ethylene tetramerization method, reaction condition can be commonly used in the art
Reaction condition.The condition of optimization is as follows：The reaction temperature of the ethylene tetramerization reaction is 0-200 DEG C；Reaction pressure
Power 0.1-20.0MPa.
In above-mentioned ethylene tetramerization method, can by catalyst ligand in carbon monoxide-olefin polymeric, transistion metal compound,
It is pre-mixed for any two or three, is then added to again together with other components in peroxide and co-catalyst
In reaction system, or these four components are straight by part, transistion metal compound, peroxide and co-catalyst
Connect to be added in reaction system and carry out fabricated in situ, or by component part, transistion metal compound, peroxidating
After thing and co-catalyst premix, directly add as a mixture in reaction system.The organic solvent can be
Added in any mixed process of above-mentioned hybrid mode.
In above-mentioned ethylene tetramerization method, the preferred 0.5-5.0MPa of pressure；The reaction temperature is preferred
0-100℃.In above-mentioned preferred scope, methods described has more excellent resultant effect.
In above-mentioned ethylene tetramerization method, 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 derivative；Aliphatic hydrocarbon compound includes linear paraffin, branched paraffin or cycloalkane,
Such as pentane, heptane, hexamethylene or hexane.Solvent is to ensure that reactant fully dissolves or disperseed.Above-mentioned
In one preferred embodiment of ethylene tetramerization method, it is characterised in that using the volume of composition as calculating benchmark,
The concentration of the transistion metal compound is 0.05-0.3mmol/L.
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, can effectively be catalyzed ethylene tetramerization reaction, and carbon monoxide-olefin polymeric has the reactivity of superelevation, and
Reaction trigger it is rapid, operate steadily, it is reproducible.
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 include C6 and C8, have the α such as a small amount of C4, C10, C12-
Alkene；The selectivity of 1- octenes can reach more than 70%.As a result show, catalyst activity height and polyphosphazene polymer
Compound is few.
The carbon monoxide-olefin polymeric provided according to the present invention, ethene is including the ligand compound shown in Formulas I, transition
Ethene is carried out in the presence of metallic compound, the carbon monoxide-olefin polymeric containing aluminum cocatalyst and TBHP
Four poly- reactions.The ethylene tetramerization or oligomerisation catalyst systems reported, its reaction condition are often required that in anhydrous nothing
Carried out under the conditions of oxygen, and carbon monoxide-olefin polymeric of the present invention, in organic peroxide-tert-butyl hydroperoxide
In the presence of hydrogen, on the contrary with higher reactivity, and reaction trigger it is rapid, operate steadily, it is reproducible,
Achieve beneficial effect.Catalyst activity highest can be more than 5 × 105g·mol(Cr)-1·h-1, the selectivity of 1- octenes
More than 70%, the features such as with high catalytic activity, high selectivity, with preferable prospects for commercial application and economy
Value.
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, 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,
Room temperature is down to after being then charged with ethene displacement.Then organic solvent toluene is added at 30 DEG C, is added simultaneously
10 μm of ol ligand compounds 1 (such as Formulas I, wherein R1=R2=R3=R4=H, R5=R6=Ph), acetylacetone,2,4-pentanedione
Chromium, co-catalyst triethyl aluminum and TBHP, the cumulative volume of mixed liquor is 100mL, wherein matching somebody with somebody
The mol ratio of body, chromic salts and co-catalyst is 2：1：300；Using the weight of toluene as calculating benchmark, the tert-butyl group
The weight content of hydrogen peroxide is 750ppm；Reaction pressure 2.0MPa is controlled, ethene is passed through, ethene is carried out
Four poly- reactions.
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 ethanol as terminator, terminates ethylene tetramerization reaction.Liquid phase is produced
Product measure laggard promoting the circulation of qi analysis of hplc.Data result is shown in Table 1.
Embodiment 2
Be the same as Example 1, difference is that the weight content of TBHP is 25ppm.Data knot
Fruit is shown in Table 1.
Embodiment 3
Be the same as Example 1, difference is that the weight content of TBHP is 150ppm.Data knot
Fruit is shown in Table 1.
Embodiment 4
Be the same as Example 1, difference is that the weight content of TBHP is 250ppm.Data knot
Fruit is shown in Table 1.
Embodiment 5
Be the same as Example 1, difference is that the weight content of TBHP is 500ppm.Data knot
Fruit is shown in Table 1.
Embodiment 6
Be the same as Example 1, difference is that the weight content of TBHP is 1000ppm.Data
It the results are shown in Table 1.
Embodiment 7
Be the same as Example 1, difference is that the weight content of TBHP is 1500ppm.Data
It the results are shown in Table 1.
Embodiment 8
Be the same as Example 1, difference is triethyl aluminum being changed to MAO.Data result is shown in Table 1.
Embodiment 9
Be the same as Example 1, difference is Al/Cr mol ratios being changed to 50.Data result is shown in Table 1.
Embodiment 10
Be the same as Example 1, difference is Al/Cr mol ratios being changed to 500.Data result is shown in Table 1.
Embodiment 11
Be the same as Example 1, difference is, uses ligand compound 2, wherein in Formulas I, R1=R2=R4=H,
R3=Cl, R5=R6=Ph.Data result is shown in Table 1.
Embodiment 12
Be the same as Example 1, difference is, uses ligand compound 3, wherein in Formulas I, R1=CH3,
R2=R3=R4=H, R5=R6=Ph.Data result is shown in Table 1.
Comparative example 1
Be the same as Example 1, difference is that the weight content of TBHP is 0ppm.Data result
It is shown in Table 1.
Table 1
It can be seen from the data in Table 1 that under the same reaction conditions, the catalyst activity with comparative example 1
Contrast, the catalyst activity for the carbon monoxide-olefin polymeric that the present invention is provided will improve several times.And the present invention is implemented
The selectivity for the 1- octenes that example is obtained 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 catalytic reaction activity in the present invention, makes ethene
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.
Claims (10)
1. a kind of catalyst for ethylene tetramerization composition, including ligand compound, transition metal compound shown in Formulas I
Thing, containing co-catalyst and TBHP；
In formula, R1、R2、R3And R4It is identical or different, be each independently selected from hydrogen, alkyl, alkoxy,
Cycloalkyl and halogen；R5And R6It is identical or different, it is each independently substituted or unsubstituted monocyclic or polycyclic
Aryl.
2. composition according to claim 1, it is characterised in that further included in the composition
Organic solvent, using the weight of organic solvent as calculating benchmark, the weight content of the TBHP is
25-1500ppm；More preferably 150-1000ppm, more preferably 250-750ppm.
3. composition according to claim 1 or 2, it is characterised in that the 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)；Further, transistion metal compound and co-catalysis
The mol ratio of agent is preferably 1:(50-500).
4. the composition according to any one in claim 1-3, it is characterised in that the alkyl is
C1-C20Straight chain or branched saturated alkyl, preferably C1-C10Straight chain or branched saturated alkyl, more preferably C1-
C6Straight chain or branched saturated alkyl；And/or
The alkoxy is C1-C20Straight chain or branched saturation alkoxy, preferably C1-C10Straight chain is branched full
And alkoxy, more preferably C1-C6Straight chain or branched saturation alkoxy；And/or,
The cycloalkyl is C3-C20Saturated cyclic alkyl, preferably C3-C10Saturated cyclic alkyl, more preferably
For C3-C6Saturated cyclic alkyl；And/or
Described monocyclic or polyaromatic is C5-C20Monocyclic or polycyclic aromatic group, preferably C5-C10It is monocyclic or many
Cyclic aromatic groups.
5. the composition according to any one in claim 1-4, it is characterised in that the alkyl is 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 isomers；With/
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 following group：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl and suberyl；With
/ or,
R5And R6It is each independently selected from phenyl, substituted-phenyl, naphthyl and pyridine radicals.
6. the composition according to any one of claim 1-5, it is characterised in that the transition metal
Compound is selected from least one of compound of chromium, molybdenum, iron, titanium, zirconium and nickel, preferably is selected from chromium trichloride, second
At least one of acyl acetone chromium, isooctyl acid chromium and three (tetrahydrofuran) chromium trichlorides.
7. the composition according to any one of claim 1-6, 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.
8. the composition according to any one of claim 2-7, it is characterised in that the organic solvent
Including at least one of arene compounds and aliphatic hydrocarbon compound, preferred aromatic hydrocarbons class compound includes
Benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and its derivative
At least one of；Preferred aliphatic series hydrocarbon compound is included in linear paraffin, branched paraffin and cycloalkane
At least one, more preferably including at least one of 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 0-200 DEG C, preferably 0-100 DEG C；Reaction pressure 0.1-20.0MPa, preferably 0.5-5.0MPa；And/or,
Using the volume of the composition as calculating benchmark, the concentration of the transistion metal compound is
0.05-0.3mmol/L。
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Citations (3)
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|---|---|---|---|---|
| CN102909071A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization and application thereof |
| CN104415790A (en) * | 2013-08-23 | 2015-03-18 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and application thereof |
| WO2015148496A1 (en) * | 2014-03-26 | 2015-10-01 | E. I. Du Pont De Nemours And Company | PROCESS FOR MANUFACTURING LINEAR α-OLEFINS |
-
2016
- 2016-03-31 CN CN201610195794.0A patent/CN107282125B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909071A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization and application thereof |
| CN104415790A (en) * | 2013-08-23 | 2015-03-18 | 中国石油化工股份有限公司 | Ethylene tetramerization catalyst composition and application thereof |
| WO2015148496A1 (en) * | 2014-03-26 | 2015-10-01 | E. I. Du Pont De Nemours And Company | PROCESS FOR MANUFACTURING LINEAR α-OLEFINS |
Non-Patent Citations (2)
| Title |
|---|
| 张丹枫: "《烯烃聚合》", 30 September 2014 * |
| 陈泽森等: "《水性建筑涂料生产技术》", 31 January 2007, 中国纺织出版社 * |
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