CN105562095B - 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 formula1And R2It is independently selected from alkyl, cycloalkyl or aromatic group；R3、R4、R5And R6Independently select aromatic radical or naphthene group.The invention also discloses a kind of methods 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 fields, 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 linear low density polyethylene (LLDPE) of 1- octenes and ethylene copolymer production can significantly improve the properties of PE, 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 Shell companies use SHOP methods (US3676523) using nickel-metal catalyst system into
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 is reported 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 ligands and chromium coordination catalysis ethylene four
Poly-, co-catalyst uses aluminum alkoxide.Aluminum alkoxide (including methylaluminoxane, modified methylaluminoxane etc.) is as co-catalysis
Agent, dosage excessive the problem of excessively high there are cost, large-scale application certainly will cause production cost high when ethylene tetramerization.
Moreover, in the prior art, it is generally recognized that water is very unfavorable, therefore need in process of production to ethylene tetramerization reaction process
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 reaction pair
The requirement of technique is all very harsh, causes the reaction initiation of polymerization technology and repeatability all excessively poor.
Invention content
In view of the application containing Phosphine ligands in ethylene tetramerization, present inventor ethylene tetramerization catalyst field into
The research gone extensively and profoundly, it has surprisingly been found that ethylene including shown in Formulas I biphosphine ligand, 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, instead with higher polymerization
Reactivity, and reaction initiation is rapid, operates steadily, is 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 formula1And R2It is each independently selected from alkyl, cycloalkyl or aromatic group；R3、R4、R5And R6It selects each independently
From aromatic radical or naphthene group.
In a preferred embodiment of the present invention, using the weight of organic solvent as calculating benchmark, the catalyst group
It is 5~200ppm to close the weight content of water contained in object；More preferably 30~150ppm, most preferably 50~100ppm.
In a preferred embodiment of the present invention, the alkyl refers to C1~C20Linear chain or branch chain saturated alkyl, it is excellent
Select C1~C10Linear chain or branch chain saturated alkyl, more preferable C1~C6Linear chain or branch chain saturated alkyl.Specifically, the alkyl can be with
Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, 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 by halogen or C1~C20Alkyl replaces.Specifically, the aromatic group may be selected from phenyl or
Substituted-phenyl, naphthalene or pyridyl group, 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
Close object, optimizing alkyl aluminium compound.
In further preferred embodiment, the aluminum alkoxide is C1~C4Alkylaluminoxane, wherein C1~C4Alkyl
Alkyl for linear chain or branch chain；Preferably, the aikyiaiurnirsoxan beta is selected from methylaluminoxane, modified methylaluminoxane, ethyl alumina
Alkane and isobutyl aluminium alkoxide；More preferable methylaluminoxane.
The general 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, it there are during multiple W, may be the same or different, be each independently linear chain or branch chain C1~C8Alkyl；There are during multiple Y,
It may be the same or different, and be each independently selected from halogen, preferably chlorine and/or bromine；It is further preferred that the alkyl aluminum chemical combination
Object 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 preferable 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
It measures 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 molar ratio of metal is 30~1000 in object: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 preferable reaction temperature is 30~60 DEG C；0.1~20MPa of reaction pressure.In general, with second
Alkene pressure rise polymerization activity increases.
It, can be by biphosphine ligand, transition metal in the carbon monoxide-olefin polymeric in the ethylene tetramerization reaction of the present invention
Object, co-catalyst and water is closed to be pre-mixed for arbitrary two or three, then again with it is another or two kinds are added to reactant together
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, can also the biphosphine ligand and transition metal be formed into metal complex first
Then arbitrary two kinds in the metal complex, co-catalyst and water are pre-mixed by (as shown in Formula II), 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
It answers in system；Or it by after metal complex, co-catalyst and water these three components premix, directly adds in as a mixture anti-
It answers 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
It crosses 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
It closes object not needing to not only remove the moisture in organic solvent, on the contrary, also needing to add in a certain amount of moisture content in organic solvent
To complete the present invention.According to temperature difference, 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、C12Wait alpha-olefins；The selection of 1- octenes
Property can reach more than 70%.The result shows that catalyst activity reaches as high as 2 × 108g·mol(Cr)-1·h-1.Polyphosphazene polymer
It is few to close object.
According to carbon monoxide-olefin polymeric provided by the invention, ethylene is including biphosphine ligand, the transition metal compound shown in Formulas I
Object acts on the poly- reaction of lower progress four containing aluminum cocatalyst, water and organic solvent composition, with the anhydrous catalyst reported
Composition system is compared, instead the polymerization activity with superelevation, and reaction initiation is rapid, operates steadily, is reproducible.
Specific 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：Ligand used is reacted, and then with diphenyl phosphine chloride in iodate by substitution alkynes
It is prepared under the action of copper.
Nuclear magnetic resonance is detected using Bruker companies of Switzerland AV400MHz nuclear magnetic resonance chemical analysers.
Gas-chromatography is detected using 5890 chromatograph of Hewlett-Packard.
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 primary to be filled with ethylene displacement, is down to set temperature.Aqueous hexahydrotoluene is added at 40 DEG C, sequentially adds 1 μm of bis- phosphine of ol
Ligand (wherein R1For methyl, R2For ethyl, R3、R4、R5And R6Be phenyl), 1 μm of ol chromium trichloride, co-catalyst triethyl group
Aluminium, the total volume of mixed liquor are 100mL, are counted on the basis of the weight of organic solvent, and the weight content of water is 5ppm, aluminium and chromium
Molar ratio is 300.Reaction pressure 4.0MPa is controlled, is passed through ethylene, carries out ethylene tetramerization reaction.After reaction 0.5 hour, system drop
It warms to room temperature, gaseous products is collected in aerometer measuring tank, liquid-phase product is collected in conical flask, measures laggard promoting the circulation of qi phase color
Spectrum analysis.
It is as follows to measure reaction result：Catalytic activity is 1.01 × 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, the difference lies in the weight content of water is 30ppm.Data are shown in Table 1.
Embodiment 3
With embodiment 1, the difference lies in the weight content of water is 50ppm.Data are shown in Table 1.
Embodiment 4
With embodiment 1, the difference lies in the weight content of water is 100ppm.Data are shown in Table 1.
Embodiment 5
With embodiment 1, the difference lies in the weight content of water is 150ppm.Data are shown in Table 1.
Embodiment 6
With embodiment 1, the difference lies in the weight content of water is 200ppm.Data are shown in Table 1.
Embodiment 7
With embodiment 1, the difference lies in the weight content of water is 100ppm and the molar ratio of aluminium and chromium is 200.Data
It is shown in Table 1.
Embodiment 8
With embodiment 1, the difference lies in the weight content of water is 100ppm and the molar ratio of aluminium and chromium is 500.Data
It is shown in Table 1.
Embodiment 9
With embodiment 1, the difference lies in 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, the difference lies in 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, the difference lies in the weight content of water is 100ppm and R1For normal-butyl, R2For cyclohexyl, R3、
R4、R5And R6It is phenyl.Data are shown in Table 1.
Embodiment 12
With embodiment 1, the difference lies in the weight content of water is 100ppm and R1For tertiary butyl, R2For cyclopenta, R3、
R4、R5And R6It is phenyl.Data are shown in Table 1.
Embodiment 13
With embodiment 1, the difference lies in the weight content of water is 100ppm and R1For phenyl, R2For phenyl, R3、R4、R5
And R6It is phenyl.Data are shown in Table 1.
Embodiment 14
With embodiment 1, the difference lies in the weight content of water is 100ppm and R1For cyclopropyl, R2For phenyl, R3、
R4、R5And R6It is phenyl.Data are shown in Table 1.
Embodiment 15
With embodiment 1, the difference lies in the weight content of water is 100ppm and R1For methyl, R2For ethyl, R3、R4、R5
And R6It is cyclohexyl.Data are shown in Table 1.
Embodiment 16
With embodiment 1, the difference lies in add in the hexahydrotoluene containing gauge water at 40 DEG C, sequentially add 1 μm of ol
Metal complex (such as Formula II, wherein R1For methyl, R2For ethyl, R3、R4、R5And R6It is phenyl, M is chromium, and X is chlorine, q=3),
Quantitative co-catalyst triethyl aluminum, the total volume of mixed liquor is 100mL, and the weight of water is counted on the basis of the weight of organic solvent
Content is 100ppm, and the molar ratio of aluminium and chromium is 300.Data are shown in Table 1.
Comparative example 1
With embodiment 1, the weight content the difference lies in water is 0ppm.Data are shown in Table 1.
Comparative example 2
It is 10 in solvent water content using the positive-negative-positive catalyst for ethylene tetramerization described in the prior art (CN1741850A)
During~200ppm, reaction cannot be normally carried out.
Table 1
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, show good catalytic activity and the selectivity of 1- octenes.
Claims (34)
1. a kind of ethylene tetramerization carbon monoxide-olefin polymeric, including shown in Formulas I biphosphine ligand, transistion metal compound, help containing aluminium
Catalyst, water and organic solvent；
R in formula1And R2It is each independently selected from alkyl, cycloalkyl or aromatic group；R3、R4、R5And R6It is each independently selected from virtue
Perfume base or naphthene group；Using the weight of organic solvent as calculating benchmark, the weight of the water contained in the carbon monoxide-olefin polymeric contains
It measures as 5~200ppm；The organic solvent be selected from hexahydrotoluene, heptane, ether, tetrahydrofuran, benzene,toluene,xylene and
At least one of dichloromethane；It is described to be selected from alkyl aluminum and alkoxy aluminum compound containing aluminum cocatalyst.
2. composition according to claim 1, which is characterized 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 30~150ppm.
3. composition according to claim 2, which is characterized 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 50~100ppm.
4. composition according to claim 1, which is characterized in that the alkyl is C1~C20The saturation alkane of linear chain or branch chain
Base.
5. composition according to claim 4, which is characterized in that the alkyl is C1~C10The saturation alkane of linear chain or branch chain
Base.
6. composition according to claim 4, which is characterized in that the alkyl is C1~C6The saturation alkane of linear chain or branch chain
Base.
7. composition according to claim 4, which is characterized in that the alkyl is selected from methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl or just
Heptyl.
8. composition according to claim 7, which is characterized in that the alkyl is selected from methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl or isobutyl group.
9. composition according to claim 1, which is characterized in that the cycloalkyl is C3~C10Cycloalkyl.
10. composition according to claim 9, which is characterized in that the cycloalkyl is C3~C6Cycloalkyl.
11. composition according to claim 9, which is characterized in that the cycloalkyl is selected from cyclopropyl, cyclopenta or hexamethylene
Base.
12. composition according to claim 1, which is characterized 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 replaces.
13. composition according to claim 12, which is characterized in that the aromatic group is by halogen or C1~C20Alkyl takes
Generation.
14. composition according to claim 12, which is characterized in that the aromatic group be selected from phenyl or substituted-phenyl,
Naphthalene or pyridyl group.
15. composition according to claim 14, which is characterized in that the aromatic group is selected from phenyl or substituted-phenyl.
16. according to the composition described in any one of claim 1-15, which is characterized in that the transistion metal compound is selected from
Chromium, molybdenum, iron, titanium, zirconium or nickel at least one of compound.
17. composition according to claim 16, which is characterized in that the transistion metal compound is selected from chromium chloride, second
At least one of acyl acetone chromium, isooctyl acid chromium or three (tetrahydrofuran) chromium trichlorides.
18. according to the composition described in any one of claim 1-15, which is characterized in that the organic solvent is selected from methyl ring
Hexane or heptane.
19. according to the composition described in any one of claim 1-15, which is characterized in that the aluminum cocatalyst that contains is alkyl
Aluminium compound.
20. composition according to claim 1, which is characterized in that the aluminum alkoxide is C1~C4Alkylaluminoxane,
Middle C1~C4Alkyl is the alkyl of linear chain or branch chain；
The general 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；It there are during multiple W, may be the same or different, be each independently linear chain or branch chain C1~C8Alkyl；There are during multiple Y,
It may be the same or different, be each independently selected from halogen.
21. composition according to claim 20, which is characterized in that the aikyiaiurnirsoxan beta is selected from methylaluminoxane, modification
At least one of methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide.
22. composition according to claim 20, which is characterized in that the aikyiaiurnirsoxan beta is methylaluminoxane.
23. composition according to claim 20, which is characterized in that in the general formula of the alkyl aluminum compound, Y is selected from
Chlorine or bromine.
24. composition according to claim 20, which is characterized in that the 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, which is characterized in that the alkyl aluminum compound is selected from triethyl aluminum
And/or triisobutyl aluminium.
26. according to the composition described in any one of claim 1-15, which is characterized 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, which is characterized 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, which is characterized in that aluminium and transistion metal compound in the co-catalyst
The molar ratio of middle metal is 30~1000:1.
29. composition according to claim 26, which is characterized in that aluminium and transistion metal compound in the co-catalyst
The molar ratio of middle metal is 100~800:1.
30. composition according to claim 26, which is characterized in that aluminium and transistion metal compound in the co-catalyst
The molar ratio of middle metal is 200~500:1.
31. a kind of method of ethylene tetramerization is included according to the ethylene tetramerization catalysis described in 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, which is characterized 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, which is characterized in that the reaction temperature of ethylene tetramerization reaction for 10~
100℃。
34. according to the method for claim 32, which is characterized in that the reaction temperature of the ethylene tetramerization reaction is 30~60
℃。
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| CN105566046B (en) * | 2014-10-15 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of method of ethylene tetramerization |
| JP7332700B2 (en) * | 2019-01-15 | 2023-08-23 | 中国石油化工股▲ふん▼有限公司 | Halogen-Containing Compounds and Uses, and Catalyst Compositions and Ethylene Oligomerization, Ethylene Trimerization, and Ethylene Tetramerization Processes |
| 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 |
| 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 |
| 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 |
| 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 |
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| Switchable Ethylene Tri-/Tetramerization with High Activity: Subtle Effect Presented by Backbone-Substituent of Carbon-Bridged Diphosphine Ligands;Jun Zhang et al.;《ACS Catalysis》;20130918;第3卷;第2312页scheme 1和第2313页table 1 * |
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