CN105562099B - 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 invention discloses a kind of ethylene tetramerization carbon monoxide-olefin polymeric, including：Biphosphine ligand, transistion metal compound shown in Formulas I, containing aluminum cocatalyst, water and organic solvent；R in formula1、R2、R3And R4It is each independently selected from alkyl, cycloalkyl or aromatic group；R5Selected from alkyl, cycloalkyl or aromatic group.The invention also discloses a kind of method that ethylene tetramerization reaction is carried out using above-mentioned carbon monoxide-olefin polymeric simultaneously.
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.
Traditional 1- production of octenes methods are ethylene oligomerization methods, and ethylene oligomerization technology is distributed according to Schulz-Flory, no
1- octene products are only obtained, while also have other alpha-olefins and a small amount of solid superpolymer, and the selection of purpose product 1- octenes
Property is very low, no more than 30%.Such as the SHOP methods (US3676523) that Shell companies use are entered using nickel-metal catalyst system
Row ethylene oligomerization reacts, and can obtain 11% 1- octenes；United States Patent (USP) (US6184428) report uses a kind of nickel compound conduct
Catalyst ethylene oligomerization, the yield of 1- octenes is 19%.Japan Patent JP2002121157 reports to be urged using zirconium metal
Agent carries out ethylene oligomerization reaction, and the content of wherein 1- octenes is about 15%.The ethylene tetramerization three-way catalyst reported recently
System can synthesize 1- octenes with high selectivity, such as patent application CN1741850A (WO2004/056478A1), CN1741849A
(WO2004/056479A1)、CN101032695A、CN101351424A、CN101415494A、CN1651142A、
CN101291734A and patent application US2006/0128910A1 is disclosed using P-N-P parts and chromium coordination catalysis ethene four
Poly-, co-catalyst uses aluminum alkoxide.Aluminum alkoxide (including MAO, modified methylaluminoxane etc.) is used as co-catalysis
Agent, the problem of cost is too high, and dosage is excessive be present, for large-scale application when ethylene tetramerization, it certainly will cause production cost high.
Moreover, in the prior art, it is generally recognized that water is very unfavorable to ethylene tetramerization reaction process, therefore is needed in process of production
It is strict controlled in the environment of anhydrous and oxygen-free and is reacted.This causes all at present known ethylene tetramerizations or oligomerisation reaction pair
The requirement of technique is all very harsh, causes the reaction initiation of polymerization technology and repeatability all excessively poor.
The content of the invention
In view of the application containing Phosphine ligands in ethylene tetramerization, present inventor are entered in ethylene tetramerization with catalyst field
The research gone extensively and profoundly, it has surprisingly been found that ethene including the biphosphine ligand shown in Formulas I, transistion metal compound, containing aluminium
The carbon monoxide-olefin polymeric effect of co-catalyst, water and organic solvent is lower to carry out ethylene tetramerization reaction, has higher polymerization on the contrary
Reactivity, and reaction initiation is rapid, operates steadily, be reproducible, the selectivity of 1- octenes also greatly improves in product；So as to
The technology prejudice of those skilled in the art is overcome, achieves unexpected technique effect.
First embodiment of the present invention is related to a kind of ethylene tetramerization carbon monoxide-olefin polymeric, including double shown in Formulas I
Phosphine ligands, transistion metal compound, containing aluminum cocatalyst, water and organic solvent；
R in formula1、R2、R3And R4It is each independently selected from alkyl, cycloalkyl or aromatic group；R5Selected from alkyl, cycloalkyl or virtue
Perfume base group.
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 5~200ppm；More preferably 30~150ppm, most preferably 50~100ppm.
In a preferred embodiment of the present invention, the alkyl refers to C1~C20Straight or branched saturated alkyl, it is excellent
Select C1~C10Straight or branched saturated alkyl, more preferably C1~C6Straight or branched saturated alkyl.Specifically, the alkyl can be with
Selected from 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 etc.；It is preferred that methyl, ethyl, n-propyl, isopropyl, normal-butyl or
Isobutyl group.
In a preferred embodiment of the present invention, the cycloalkyl refers to C3~C10Cycloalkyl, preferably C3~C6Cycloalkanes
Base.Specifically, the alkyl may be selected from cyclopropyl, cyclopenta or cyclohexyl.
In a preferred embodiment of the present invention, the aromatic group refers to C6~C20Monocyclic or multiring aromatic
Group, and the carbon atom on wherein one or more rings of the optional aromatic group is taken by the hetero atom selected from oxygen, nitrogen and sulphur
Generation；Preferably, the aromatic group is substituted by halogen or C1~C20 alkyl.Specifically, the aromatic group may be selected from phenyl or
Substituted-phenyl, naphthyl or pyridine radicals, preferably phenyl or substituted-phenyl.
In some preferred embodiments of the present invention, the transistion metal compound can be transition commonly used in the art
Metallic compound, such as the compound of chromium, molybdenum, iron, titanium, zirconium or nickel, preferably chromium chloride, chromium acetylacetonate, isooctyl acid chromium or three
(tetrahydrofuran) chromium trichloride etc..
In a preferred embodiment of the invention, the organic solvent be selected from hexahydrotoluene, heptane, hexamethylene, ether,
Tetrahydrofuran, benzene,toluene,xylene and dichloromethane, preferably hexahydrotoluene or heptane.
In certain embodiments of the present invention, it is described to be selected from alkyl aluminum compound and alkoxy calorize containing aluminum cocatalyst
Compound, preferably alkyl aluminum compound.
In further preferred embodiment, the aluminum alkoxide is C1-C4 alkylaluminoxanes, wherein C1-C4 alkyl
For the alkyl of straight or branched；Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethyl alumina
Alkane and isobutyl aluminium alkoxide；More preferably MAO.
The formula of the alkyl aluminum compound is AlWnYm, wherein n is 1~3 integer, and m is 0~2 integer, and m+n
Equal to 3, when multiple W be present, it may be the same or different, and be each independently straight or branched C1-C8Alkyl；When multiple Y be present,
It may be the same or different, and be each independently selected from halogen, preferably chlorine and/or bromine；It is further preferred that described alkyl aluminum chemical combination
Thing is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethyl base
At least one of aluminium and ethylaluminium dichloride, more preferably triethyl aluminum and/or triisobutyl aluminium.
In a preferred embodiment of the invention, in the carbon monoxide-olefin polymeric, using the volume of organic solvent as calculating
Benchmark, the content of the biphosphine ligand is 2~500 μm of ol/L, preferably 5~50 μm of ol/L；The transistion metal compound contains
Measure as 2~500 μm of ol/L, preferably 5~50 μm of ol/L；Preferably, aluminium and transition metal compound in co-catalyst of the present invention
The mol ratio of metal is 30~1000 in thing:1, preferably 100~800:1, more preferably 200~500:1.
Second embodiment of the present invention is related to a kind of ethylene tetramerization technique, is included in above-mentioned carbon monoxide-olefin polymeric
In the presence of, carry out ethylene tetramerization reaction.
In a preferred embodiment of the invention, the reaction temperature of the ethylene tetramerization reaction is 0~200 DEG C, preferably instead
It is 10~100 DEG C to answer temperature, and more preferably reaction temperature is 30~60 DEG C；0.1~20MPa of reaction pressure.In general, with second
Alkene pressure rise polymerization activity raises.
, can be by biphosphine ligand, transition metal in the carbon monoxide-olefin polymeric in the ethylene tetramerization reaction of the present invention
Compound, co-catalyst and water are pre-mixed for any two or three, then again with it is another or two kinds together be added to reactant
In system；Or these four components are added directly into reaction system by biphosphine ligand, transistion metal compound, co-catalyst and water
In；Or by after biphosphine ligand, transistion metal compound, co-catalyst and water these four components premix, directly with mixture shape
Formula is added in reaction system.
In above-mentioned ethylene tetramerization technique, the biphosphine ligand and transition metal can also be formed into metal complex first
(as shown in Formula II), then any two kinds in the metal complex, co-catalyst and water are pre-mixed, then again with separately
One kind is added in reaction system together；Or these three components are added directly into instead by metal complex, co-catalyst and water
Answer in system；Or by after metal complex, co-catalyst and water these three components premix, directly add as a mixture anti-
Answer in system.
In the present invention, the metal complex (Formula II), can be led to by the biphosphine ligand of Formulas I with transistion metal compound
Cross conventional chemical reaction to be prepared, wherein M is transition metal, and X is selected from halogen, and q is 1~3 integer.The halogen is selected from
Fluorine, chlorine, bromine and iodine, particularly preferred fluorine, chlorine and bromine.
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.
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 C6And C8, there is a small amount of C4、C10、C12Deng alpha-olefin；The selection of 1- octenes
Property can reach 73% or so.As a result show, catalyst activity reaches as high as 2 × 108g·mol(Cr)-1·h-1.Polyphosphazene polymer
Compound is few.
According to carbon monoxide-olefin polymeric provided by the invention, ethene is including the biphosphine ligand shown in Formulas I, transition metal compound
Thing, the poly- reaction of the lower progress four of composition effect containing aluminum cocatalyst, water and organic solvent, with the anhydrous catalyst reported
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：Part used is reacted by substitution alkynes and diphenyl phosphine chloride, and then in iodate
It is prepared in the presence of copper.
Nuclear magnetic resonance is detected using Bruker companies of Switzerland AV400MHz nuclear magnetic resonance chemical analysers.
Gas-chromatography is detected using the chromatograph of Hewlett-Packard 5890.
Mass spectrum is detected using U.S.'s Finnigan company's T race DSQ type gas chromatograph-mass spectrometers.
Embodiment 1
Using 300mL stainless steel polymeric kettles.Autoclave is heated to 80 DEG C, after vacuumizing with nitrogen displacement for several times, then
It is filled with ethene displacement once, is down to design temperature.Aqueous hexahydrotoluene is added at 40 DEG C, sequentially adds the double phosphines of 1 μm of ol
Part (wherein R1、R2、R3And R4It is phenyl, R5For methyl), 1 μm of ol chromium trichloride, quantitative co-catalyst triethyl aluminum, mix
The cumulative volume for closing liquid is 100mL, is counted on the basis of the weight of organic solvent, the weight content of water is 5ppm, aluminium and chromium mole
Than for 300.Reaction pressure 4.0MPa is controlled, is passed through ethene, carries out ethylene tetramerization reaction.After reaction 0.5 hour, system is cooled to
Room temperature, gaseous products are collected in aerometer measuring tank, liquid-phase product is collected in conical flask, and gas-chromatography point is carried out after metering
Analysis.
It is as follows to measure reaction result：Catalytic activity is 1.06 × 108g·mol(Cr)-1·h-1, 1- Octenes selectivities are
The selectivity of 70.7%, 1- hexene is 15.6%.
Embodiment 2
With embodiment 1, difference is, the weight content of water is 30ppm.Data are shown in Table 1.
Embodiment 3
With embodiment 1, difference is, the weight content of water is 50ppm.Data are shown in Table 1.
Embodiment 4
With embodiment 1, difference is, the weight content of water is 100ppm.Data are shown in Table 1.
Embodiment 5
With embodiment 1, difference is, the weight content of water is 150ppm.Data are shown in Table 1.
Embodiment 6
With embodiment 1, difference is, the weight content of water is 200ppm.Data are shown in Table 1.
Embodiment 7
With embodiment 1, difference is, the weight content of water is 100ppm and the mol ratio of aluminium and chromium is 200.Data
It is shown in Table 1.
Embodiment 8
With embodiment 1, difference is, the weight content of water is 100ppm and the mol ratio of aluminium and chromium is 500.Data
It is shown in Table 1.
Embodiment 9
With embodiment 1, difference is, the weight content of water is 100ppm and reaction temperature is 30 DEG C.Data are shown in Table
1。
Embodiment 10
With embodiment 1, difference is, the weight content of water is 100ppm and reaction temperature is 60 DEG C.Data are shown in Table
1。
Embodiment 11
With embodiment 1, difference is, the weight content of water is 100ppm and R1、R2、R3And R4It is phenyl, R5For
Cyclohexyl.Data are shown in Table 1.
Embodiment 12
With embodiment 1, difference is, the weight content of water is 100ppm and R1、R2、R3And R4It is phenyl, R5For
Normal-butyl.Data are shown in Table 1.
Embodiment 13
With embodiment 1, difference is, the weight content of water is 100ppm and R1、R2、R3、R4And R5It is phenyl.Number
According to being shown in Table 1.
Embodiment 14
With embodiment 1, difference is, the weight content of water is 100ppm and R1、R2、R3And R4It is phenyl, R5For
Hydrogen.Data are shown in Table 1.
Embodiment 15
With embodiment 1, difference is, the weight content of water is 100ppm and R1、R2、R3、R4And R5It is cyclohexyl.
Data are shown in Table 1.
Embodiment 16
With embodiment 1, difference is, the weight content of water is 100ppm and R1、R2、R3And R4For 2- methoxybenzenes
Base, R5It is cyclohexyl.Data are shown in Table 1.
Embodiment 17
With embodiment 1, difference is, the hexahydrotoluene containing gauge water is added at 40 DEG C, sequentially adds 1 μm of ol
Metal complex (such as Formula II, wherein R1、R2、R3And R4It is phenyl, R5For cyclohexyl, M is chromium, and X is chlorine, n=3), it is quantitative
Co-catalyst triethyl aluminum, the cumulative volume of mixed liquor is 100mL, and the weight content that water is counted on the basis of the weight of organic solvent is
The mol ratio of 5ppm, aluminium and chromium is 300.Data are shown in Table 1.
Comparative example 1
With embodiment 1, difference is, the weight content of water is 0ppm.
Comparative example 2
It is 10 in solvent water content using the positive-negative-positive catalyst for ethylene tetramerization described in prior art (CN1741850A)
During~200ppm, reaction can not be normally carried out.
It can see by the data of table 1, for carbon monoxide-olefin polymeric of the invention under the conditions of having existing for water, catalytic activity is anti-
And increase, and show good catalytic activity and the selectivity of 1- octenes.
Table 1
Claims (34)
1. a kind of ethylene tetramerization carbon monoxide-olefin polymeric, including：Biphosphine ligand, transistion metal compound shown in Formulas I, help containing aluminium
Catalyst, water and organic solvent；
R in formula1、R2、R3And R4It is each independently selected from alkyl, cycloalkyl or aromatic group；R5Selected from alkyl, cycloalkyl or aromatic radical
Group；The weight content of the water is 5~200ppm using the weight of organic solvent as calculating benchmark；The organic solvent is selected from first
At least one of butylcyclohexane, heptane, ether, tetrahydrofuran, benzene,toluene,xylene and dichloromethane；Described helped containing aluminium is urged
Agent is selected from alkyl aluminum compound and alkoxy aluminum compound.
2. composition according to claim 1, it is characterised in that the weight content of the water, with the weight of organic solvent
It is 30~150ppm for calculating benchmark.
3. composition according to claim 2, it is characterised in that the weight content of the water, with the weight of organic solvent
It is 50~100ppm for calculating benchmark.
4. composition according to claim 1, it is characterised in that the alkyl is C1~C20The saturation alkane of straight or branched
Base.
5. composition according to claim 4, it is characterised in that the alkyl is C1~C10The saturation alkane of straight or branched
Base.
6. composition according to claim 4, it is characterised in that the alkyl is C1~C6The saturation alkane of straight or branched
Base.
7. composition according to claim 4, it is characterised in that the alkyl is selected from methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, positive heptan
Base and its isomers.
8. composition according to claim 7, it is characterised in that the alkyl is selected from methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl or isobutyl group.
9. composition according to claim 1, it is characterised in that cycloalkyl C3~C10Cycloalkyl.
10. composition according to claim 9, it is characterised in that cycloalkyl C3~C6Cycloalkyl.
11. composition according to claim 9, it is characterised in that cycloalkyl is cyclopropyl, cyclopenta or cyclohexyl.
12. composition according to claim 1, it is characterised in that the aromatic group is C6~C20It is monocyclic or polycyclic
Aromatic group, and optionally, the carbon atom on wherein one or more rings of the aromatic group is by selected from the miscellaneous of oxygen, nitrogen and sulphur
Atom substitutes.
13. composition according to claim 12, it is characterised in that the aromatic group is by halogen or C1~C20 alkyl
Substitution.
14. composition according to claim 12, it is characterised in that the aromatic group be selected from phenyl or substituted-phenyl,
Naphthyl or pyridine radicals.
15. composition according to claim 14, it is characterised in that the aromatic group is phenyl or substituted-phenyl.
16. according to the composition any one of claim 1-15, it is characterised in that the transistion metal compound is optional
At least one of compound from chromium, molybdenum, iron, titanium, zirconium or nickel.
17. composition according to claim 16, it is characterised in that the transistion metal compound is chromium chloride, acetyl
At least one of acetone chromium, isooctyl acid chromium or three (tetrahydrofuran) chromium trichlorides.
18. according to the composition any one of claim 1-15, it is characterised in that the organic solvent is selected from methyl ring
Hexane or heptane.
19. according to the composition any one of claim 1-15, it is characterised in that described containing aluminum cocatalyst is alkyl
Aluminium compound.
20. composition according to claim 19, it is characterised in that the aluminum alkoxide is C1-C4Alkylaluminoxane, its
Middle C1-C4Alkyl is the alkyl of straight or branched；
The formula of the alkyl aluminum compound is AlWnYm, wherein, n is 1~3 integer, and m is 0~2 integer, and m+n etc.
In 3；When multiple W be present, it may be the same or different, and be each independently straight or branched C1-C8 alkyl；When multiple Y be present, its
It may be the same or different, be each independently selected from halogen.
21. composition according to claim 20, it is characterised in that described aikyiaiurnirsoxan beta is selected from MAO, modification
At least one of MAO, ethylaluminoxane and isobutyl aluminium alkoxide.
22. composition according to claim 20, it is characterised in that described aikyiaiurnirsoxan beta is MAO.
23. composition according to claim 20, it is characterised in that in the formula of the alkyl aluminum compound, Y is selected from chlorine
And/or bromine.
24. composition according to claim 20, it is characterised in that described alkyl aluminum compound be selected from trimethyl aluminium,
Triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride
At least one of.
25. composition according to claim 20, it is characterised in that described alkyl aluminum compound is selected from triethyl aluminum
And/or triisobutyl aluminium.
26. according to the composition any one of claim 1-15, it is characterised in that using the volume of organic solvent as calculating
Benchmark, the content of the biphosphine ligand is 2~500 μm of ol/L；The content of the transistion metal compound is 2~500 μm of ol/L.
27. composition according to claim 26, it is characterised in that described using the volume of organic solvent as calculating benchmark
The content of biphosphine ligand is 5~50 μm of ol/L；The content of the transistion metal compound is 5~50 μm of ol/L.
28. composition according to claim 26, it is characterised in that aluminium and transistion metal compound in the co-catalyst
The mol ratio of middle metal is 30~1000:1.
29. composition according to claim 28, it is characterised in that aluminium and transistion metal compound in the co-catalyst
The mol ratio of middle metal is 100~800:1.
30. composition according to claim 28, it is characterised in that aluminium and transistion metal compound in the co-catalyst
The mol ratio of middle metal is 200~500:1.
31. a kind of method of ethylene tetramerization, it is included in the ethylene tetramerization catalysis according to any one of claim 1-30
In the presence of agent composition, ethylene tetramerization reaction is carried out.
32. according to the method for claim 31, it is characterised in that the reaction temperature of the ethylene tetramerization reaction is 0~200
℃；0.1~20MPa of reaction pressure.
33. according to the method for claim 32, it is characterised in that the reaction temperature of ethylene tetramerization reaction for 10~
100℃。
34. according to the method for claim 32, it is characterised in that the reaction temperature of the ethylene tetramerization reaction is 30~60
℃。
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| CN105566036B (en) * | 2014-10-13 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method of ethylene tetramerization |
| KR102605188B1 (en) * | 2018-02-27 | 2023-11-24 | 에스케이이노베이션 주식회사 | Ligand, Oligomerization Catalyst And Process For Preparing Ethylene Oligomer Using Thereof |
| CN111434667B (en) * | 2019-01-15 | 2021-07-30 | 中国石油化工股份有限公司 | Fluorine-containing compound and application thereof, ethylene oligomerization catalyst composition, ethylene oligomerization method, ethylene trimerization method and ethylene tetramerization method |
| KR20210116515A (en) * | 2019-01-15 | 2021-09-27 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Halogen-containing compounds and uses and catalyst compositions and ethylene oligomerization methods and ethylene trimerization methods and ethylene tetramerization methods |
| CN111434668B (en) * | 2019-01-15 | 2021-08-03 | 中国石油化工股份有限公司 | Halogen-containing compound, application thereof, catalyst composition, ethylene oligomerization method, ethylene trimerization method and ethylene tetramerization method |
| CN111434669B (en) * | 2019-01-15 | 2021-07-30 | 中国石油化工股份有限公司 | Fluorine-containing compound and application thereof, ethylene oligomerization catalyst composition, ethylene oligomerization method, ethylene trimerization method and ethylene tetramerization method |
| CN113583052A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Fluorine-containing metal complex and catalyst for ethylene oligomerization |
| CN112742483B (en) * | 2021-01-21 | 2024-04-02 | 华东理工大学 | Catalyst system for ethylene selective oligomerization and preparation and application thereof |
| CN114160210A (en) * | 2021-11-03 | 2022-03-11 | 华东理工大学 | Catalyst for selective tetramerization of ethylene and preparation method and application thereof |
| CN114160211B (en) * | 2021-12-20 | 2024-01-16 | 天津科技大学 | Catalyst system for selective trimerization and tetramerization of ethylene and application method thereof |
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| CN105562099A (en) | 2016-05-11 |
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