CN105562102A - Ethylene tetramerization catalyst composition and ethylene tetramerization method using the same - Google Patents
Ethylene tetramerization catalyst composition and ethylene tetramerization method using the same Download PDFInfo
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Abstract
The invention relates to an ethylene tetramerization catalyst composition. The ethylene tetramerization catalyst composition comprises a catalyst ligand shown in the formula I, a transition metal compound, an aluminum-containing cocatalyst, water and an organic solvent. In the formula I, R1, R2, R3 and R4 are same or different and respectively represent hydrogen, alkyl, alkyloxy, cycloalkyl or halogen and the two R5 groups are same or different and respectively represent monocyclic or polycyclic aryl. The invention also provides an ethylene tetramerization method. The method comprises an ethylene tetramerization reaction in the presence of the ethylene tetramerization catalyst composition.
Description
Technical field
The present invention relates to ethylene oligomerization field, be specifically related to a kind of carbon monoxide-olefin polymeric for ethylene tetramerization.The invention still further relates to a kind of ethylene tetramerization method.
Background technology
1-octene as important Organic Ingredients and chemical intermediate, mainly for the production of high-quality polyethylene (PE).The LLDPE (LLDPE) produced by 1-octene and ethylene copolymer significantly can improve the properties of PE, particularly poly mechanical performance, optical property and tear strength and impact strength are all significantly increased, be very suitable for packaging film and the agricultural mulch films etc. such as greenhouse, canopy room, 1-octene is also used as the intermediate of plasticizer, aliphatic acid, detergent alcohols and lube oil additive simultaneously.
Although the value of 1-octene is well-known, this area does not produce 1-octene with high selectivity at present as ethylene trimer produces 1-hexene.Traditional 1-production of octenes method is ethylene oligomerization method, ethylene oligomerization technology distributes according to Schulz-Flory, not only obtains 1-octene product, also has other alpha-olefins and a small amount of solid superpolymer simultaneously, and object product 1-octene is selective very low, is no more than 30%.The SHOP method (US3676523) that such as Shell company adopts can obtain the 1-octene of 11%; United States Patent (USP) (US6184428) reports and uses a kind of nickel compound as catalyst, and the yield of 1-octene is only 19%.SHOP technique such as US3676523 uses nickel-metal catalyst system to carry out ethylene oligomerization reaction, and wherein the content of 1-octene only accounts for 11%.Japan Patent JP2002121157 reports and uses zirconium metal catalyzer to carry out ethylene oligomerization reaction, and wherein the content of 1-octene is approximately 15%.The catalyst for ethylene tetramerization system of nearest report can synthesize 1-octene by highly selective, P-N-P part and chromium coordination is used as patent application CN1741850A (WO2004/056478A1), CN1741849A (WO2004/056479A1), CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A and patent application US2006/0128910A1 disclose, catalyzed ethylene four gathers, can produce 1-octene by highly selective, in product, the content of 1-octene even can be greater than 70%.
Patent application CN101605605A discloses and utilizes containing the chromium-based catalysts of P-C-C-P backbone structure ligand for ethylene tetramerization, thus highly selective has prepared 1-octene, is selectively the highlyest greater than 70%.But above-mentioned technology only limitedly discloses the substituent structure containing P-N-P or P-C-C-P backbone structure ligand, and the part containing P-N-P or P-C-C-P skeleton structure used in above-mentioned technology, its complex structure, preparation process is loaded down with trivial details, and cost is higher.There is high cost, the problem that consumption is excessive in the co-catalyst aluminum alkoxide (comprising MAO, modified methylaluminoxane etc.) that above-mentioned patent uses, large-scale application is when ethylene tetramerization, and it certainly will cause production cost high.And, in the prior art, it has been generally acknowledged that water is very disadvantageous to ethylene tetramerization reaction process, react under therefore needing to be strict controlled in the environment of anhydrous and oxygen-free in process of production.This make current all known ethylene tetramerization or oligomerisation reaction all very harsh to the requirement of technique, cause the reaction initiation of polymerization technology and all non-constant of repeatability.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, present inventor conducts in-depth research such phosphorus-containing catalyst, be surprised to find, ethene comprise the catalyst ligand shown in formula I, transistion metal compound, containing the carbon monoxide-olefin polymeric effect of aluminum cocatalyst, water and organic solvent under carry out ethylene tetramerization reaction, there is higher polymerization activity on the contrary, and reaction cause rapidly, operate steadily, reproducible, in product, the selective of 1-octene also significantly improves; Thus overcome the technology prejudice of those skilled in the art, achieve unforeseeable technique effect.
First embodiment of the present invention is to provide a kind of brand-new catalyst for ethylene tetramerization composition, comprise the catalyst ligand shown in formula I, transistion metal compound, containing aluminum cocatalyst, water and organic solvent;
R in formula
1, R
2, R
3and R
4identical or different, be selected from hydrogen, alkyl, alkoxyl, cycloalkyl or halogen independently of one another; 2 R existed
5may be the same or different, be selected from monocycle or polyaromatic independently of one another.
In a preferred embodiment of the present invention, with the weight of organic solvent for Calculation Basis, the weight content of the water contained in described carbon monoxide-olefin polymeric is 5 ~ 300ppm; Be more preferably 30 ~ 200ppm, most preferably be 50 ~ 150ppm.
In a preferred embodiment of the present invention, described alkyl is C
1~ C
20straight chain or branching saturated alkyl, be preferably C
1~ C
10straight chain or branching saturated alkyl, be more preferably C
1~ C
6straight chain or branching saturated alkyl; Further preferably, described alkyl is selected from following compound: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and isomers thereof; Further preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or isohesyl; Most preferable, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group.
In a preferred embodiment of the present invention, described alkoxyl is C
1~ C
20straight chain or the saturated alkoxyl of branching, be preferably C
1~ C
10straight chain or the saturated alkoxyl of branching, be more preferably C
1~ C
6straight chain or the saturated alkoxyl of branching; Further preferably, described alkoxyl is selected from following compound: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, just own oxygen base, secondary own oxygen base, dissident's oxygen base, positive heptan oxygen base and isomers thereof; Further preferred methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, just own oxygen base or dissident's oxygen base; Most preferably methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy or isobutoxy.
In a preferred embodiment of the present invention, described cycloalkyl is C
3~ C
20saturated cyclic alkyl, is preferably C
3~ C
10saturated cyclic alkyl, is more preferably C
3~ C
6saturated cyclic alkyl; Most preferably, described cycloalkyl is selected from following compound: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl; Most preferably cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
In a preferred embodiment of the present invention, described monocycle and polyaromatic are C
6~ C
20monocycle or polycyclic aromatic group, and the carbon atom optionally on wherein one or more rings is selected from hydrogen atom on the hybrid atom MCM-41 of oxygen, nitrogen and sulphur and/or described monocycle and polyaromatic by halogen or C
1-C
20alkyl replaces; Preferably, described monocycle and polyaromatic are selected from phenyl, substituted-phenyl, naphthyl or pyridine radicals, more preferably phenyl or substituted-phenyl.
In the preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, R in described part
1, R
2, R
3identical or different, be selected from hydrogen, C
1-C
10alkyl, C
1-C
10alkoxy or halogen, is preferably selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy or halogen, more preferably hydrogen, methyl, ethyl, methoxyl group, chlorine or bromine; R
4be selected from C
6-C
20aryl, is preferably selected from C
6-C
12aryl, is more preferably selected from C
6-C
10aryl, most preferably phenyl or substituted-phenyl.
In a preferred embodiment of the present invention, described halogen is selected from fluorine, chlorine or bromine.
In the present invention, transistion metal compound described in above-mentioned carbon monoxide-olefin polymeric can be the transistion metal compound that this area is commonly used, as the compound of chromium, molybdenum, iron, titanium, zirconium or nickel, be preferably chromium trichloride, chromium acetylacetonate, isooctyl acid chromium or three (oxolane) chromium trichloride etc.
In above-mentioned carbon monoxide-olefin polymeric, co-catalyst can be the organo-aluminum compound that this area is commonly used, as alkyl aluminum compound and/or aluminium alkoxide compound, one or more in preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane or modified methylaluminoxane, most preferable aikyiaiurnirsoxan beta.
In a preferred embodiment of the present invention, in above-mentioned carbon monoxide-olefin polymeric, the mol ratio of described catalyst ligand, transistion metal compound and co-catalyst is 1:0.1 ~ 10:1 ~ 1000, is preferably 1:0.25 ~ 2:10 ~ 700, is more preferably 1:0.5 ~ 2:100 ~ 500; The mol ratio of the transition metal in transistion metal compound and the metal in co-catalyst is preferably 1:50 ~ 500.
In a preferred embodiment of the invention, organic solvent used comprises arene compounds or aliphatic hydrocarbon compound, and arene compounds comprises benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene or monochlorotoluene and derivative thereof; Aliphatic hydrocarbon compound comprises linear paraffin, branched paraffin or cycloalkane, as pentane, heptane, cyclohexane or hexane etc.
Another embodiment of the invention is to provide a kind of ethylene tetramerization technique, under being included in the existence of described ethylene tetramerization carbon monoxide-olefin polymeric, carries out ethylene tetramerization reaction.
In a preferred embodiment of the present invention, the reaction temperature of described ethylene tetramerization reaction is 0 ~ 100 DEG C, preferably 0 ~ 80 DEG C; Reaction pressure 0.1 ~ 6MPa, preferably 0.5 ~ 5.0MPa.
In a preferred embodiment of the present invention, with the weight of organic solvent for Calculation Basis, the concentration of described transistion metal compound is 0.05 ~ 0.3mmol/L.
In above-mentioned ethylene tetramerization technique, can by part, transistion metal compound and co-catalyst in carbon monoxide-olefin polymeric any two kinds be pre-mixed, and then join together with another kind in reaction system, or these three kinds of components of body, transistion metal compound and co-catalyst are directly joined in reaction system and carries out fabricated in situ, or after component part, transistion metal compound and co-catalyst premix, directly add as a mixture in reaction system.
In above-mentioned ethylene tetramerization technique, the reaction condition that reaction condition can be commonly used for this area.Optimize condition as follows: ethene, organic solvent and described carbon monoxide-olefin polymeric are added in reactor, then ethylene pressure be 0.1 ~ 6Mpa, reaction temperature be 0 ~ 100 DEG C at reaction, catalyst concn is 0.05 ~ 0.3mmolCr/L.After reaction terminates, be cooled to room temperature, get gas, liquid product and carry out chromatography.
In above-mentioned ethylene tetramerization technique, described pressure preferably 0.5 ~ 5.0MPa; Described reaction temperature preferably 0 ~ 80 DEG C.
In above-mentioned ethylene tetramerization method, can by catalyst ligand, transistion metal compound and co-catalyst in carbon monoxide-olefin polymeric any two kinds be pre-mixed, and then join together with another kind in reaction system, or these three kinds of components of body, transistion metal compound and co-catalyst are directly joined in reaction system and carries out fabricated in situ, or after component part, transistion metal compound and co-catalyst premix, directly add as a mixture in reaction system.
Beneficial effect of the present invention:
In the present invention, especially in the pilot scale of ethylene tetramerization and industrial processes, use carbon monoxide-olefin polymeric of the present invention not only not need to remove the moisture in organic solvent, on the contrary, also need 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 carry in organic solvent is different, and moisture about the 220ppm of energy in hexahydrotoluene at such as room temperature 30 DEG C, toluene can contain about 350ppm.
Use carbon monoxide-olefin polymeric of the present invention to carry out ethylene tetramerization, after reaction terminates, carry out gas-chromatography and mass spectral analysis.The polymerizate obtained mainly comprises C6 and C8, has the alpha-olefins such as a small amount of C4, C10, C12; The selective of 1-octene can reach more than 70%.Result shows, catalyst activity is high and high molecular polymer is few.
According to carbon monoxide-olefin polymeric provided by the invention, ethene comprise the catalyst ligand shown in formula I, transistion metal compound, containing the composition effect of aluminum cocatalyst, water and organic solvent under carry out four poly-reactions, compared with the anhydrous catalyst composition system reported, there is the polymerization activity of superelevation on the contrary, and reaction cause rapidly, operate steadily, reproducible.
Detailed description of the invention
The following example only for the present invention is described in detail, but is understood that scope of the present invention is not limited to these embodiments.
In an embodiment of the present invention, gas-chromatography adopts Hewlett-Packard 5890 chromatograph to detect.
Embodiment 1:
Adopt stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, vacuumizes the displacement of rear nitrogen for several times, after being then filled with ethene displacement, be down to room temperature.Then add containing water-toluene at 30 DEG C, add simultaneously 10 μm of ol ligand compounds 1 (such as formula I, wherein R
1=R
2=R
3=R
4=H, R
5=Ph) and chromium acetylacetonate and co-catalyst triethyl aluminum, the cumulative volume of mixed liquor is 100mL, and wherein the mol ratio of ligand compound, chromic salts and co-catalyst is 2:1:300; With the weight of toluene for Calculation Basis, the weight content of the water contained in carbon monoxide-olefin polymeric is 150ppm; Control reaction pressure 2.0MPa, pass into ethene, carry out ethylene tetramerization reaction.
After having reacted, system is cooled to room temperature, and gaseous products be collected in aerometer measuring tank, liquid-phase product is collected in conical flask, adds 1mL ethanol as terminator, stops ethylene tetramerization reaction.The laggard promoting the circulation of qi analysis of hplc of liquid phase gauging of products (chromatograph is Hewlett-Packard 5890).Data result is in table 1.
Embodiment 2
With embodiment 1, difference is that water content is 5ppm.Data result is in table 1.
Embodiment 3
With embodiment 1, difference is that water content is 30ppm.Data result is in table 1.
Embodiment 4
With embodiment 1, difference is that water content is 50ppm.Data result is in table 1.
Embodiment 5
With embodiment 1, difference is that water content is 100ppm.Data result is in table 1.
Embodiment 6
With embodiment 1, difference is that water content is 200ppm.Data result is in table 1.
Embodiment 7
With embodiment 1, difference is that water content is 300ppm.Data result is in table 1.
Embodiment 8
With embodiment 1, difference is to change triethyl aluminum into MAO.Data result is in table 1.
Embodiment 9
With embodiment 1, difference is to change Al/Cr mol ratio into 50.Data result is in table 1.
Embodiment 10
With embodiment 1, difference is to change Al/Cr mol ratio into 500.Data result is in table 1.
Embodiment 11
With embodiment 1, difference is, uses ligand compound 2, R in its Chinese style I
1=R
2=R
4=H, R
3=Cl, R
5=Ph.Data result is in table 1.
Embodiment 12
With embodiment 1, difference is, uses ligand compound 3, R in its Chinese style I
1=CH
3, R
2=R
3=R
4=H, R
5=Ph.Data result is in table 1.
Comparative example 1
With embodiment 1, difference is that water content is 0ppm.Data result is in table 1.
Data as can be seen from table 1, under the same reaction conditions, contrast with the catalyst activity of comparative example 1, the catalyst activity of carbon monoxide-olefin polymeric provided by the invention will improve several times.And in the selective and comparative example 1 of 1-octene that obtains of the embodiment of the present invention compared with want high.
In addition, in the present invention ethylene tetramerization reaction cause rapidly, operate steadily, reproducible.Even if when Al/Cr ratio is low to moderate 50, in the present invention, catalyst still has good oligomerisation reaction catalytic activity, ethylene oligomerization reaction cost is declined to a great extent, and it is practical, and industrial prospect is wide.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.Table 1
Claims (12)
1. a catalyst for ethylene tetramerization composition, comprises the catalyst ligand shown in formula I, transistion metal compound, co-catalyst, water and organic solvent;
R in formula
1, R
2, R
3and R
4identical or different, be selected from hydrogen, alkyl, alkoxyl, cycloalkyl or halogen independently of one another; 2 R existed
5may be the same or different, be selected from monocycle or polyaromatic independently of one another.
2. composition according to claim 1, is characterized in that, with the weight of organic solvent for Calculation Basis, the weight content of the water contained in described carbon monoxide-olefin polymeric is 5 ~ 300ppm; Be more preferably 30 ~ 200ppm, most preferably be 50 ~ 150ppm.
3. composition according to claim 1 and 2, is characterized in that, described alkyl is C
1~ C
20straight chain or branching saturated alkyl, be preferably C
1~ C
10straight chain or branching saturated alkyl, be more preferably C
1~ C
6straight chain or branching saturated alkyl; Further preferably, described alkyl is selected from following compound: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and isomers thereof; Further preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or isohesyl; Most preferable, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group.
4. the composition according to any one of claim 1-3, is characterized in that, described alkoxyl is C
1~ C
20straight chain or the saturated alkoxyl of branching, be preferably C
1~ C
10straight chain or the saturated alkoxyl of branching, be more preferably C
1~ C
6straight chain or the saturated alkoxyl of branching; Further preferably, described alkoxyl is selected from following compound: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, just own oxygen base, secondary own oxygen base, dissident's oxygen base, positive heptan oxygen base and isomers thereof; Further preferred methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, just own oxygen base or dissident's oxygen base; Most preferably methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy or isobutoxy.
5. the composition according to any one of claim 1-4, is characterized in that, described cycloalkyl is C
3~ C
20saturated cyclic alkyl, is preferably C
3~ C
10saturated cyclic alkyl, is more preferably C
3~ C
6saturated cyclic alkyl; Most preferably, described cycloalkyl is selected from following compound: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl; Most preferably cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
6. the composition according to any one of claim 1-5, is characterized in that, described monocycle and polyaromatic are C
6~ C
20monocycle or polycyclic aromatic group, and the carbon atom optionally on wherein one or more rings is selected from hydrogen atom on the hybrid atom MCM-41 of oxygen, nitrogen and sulphur and/or described monocycle and polyaromatic by halogen or C
1-C
20alkyl replaces; Preferably, described monocycle and polyaromatic are selected from phenyl, substituted-phenyl, naphthyl or pyridine radicals, more preferably phenyl or substituted-phenyl.
7. the composition according to any one of claim 1-6, it is characterized in that, described transistion metal compound is selected from least one in the compound of chromium, molybdenum, iron, titanium, zirconium and nickel, at least one preferably in chromium trichloride, chromium acetylacetonate, isooctyl acid chromium and three (oxolane) chromium trichloride.
8. the composition according to any one of claim 1-7, is characterized in that, described co-catalyst is organo-aluminum compound; Preferred alkyl aluminium compound and/or aluminium alkoxide compound; More preferably at least one in following compound: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, MAO, ethylaluminoxane and modified methylaluminoxane; Most preferable aikyiaiurnirsoxan beta.
9. the composition according to any one of claim 1-8, it is characterized in that, the mol ratio of ligand compound, transistion metal compound and co-catalyst is 1:0.1 ~ 10:1 ~ 1000, is preferably 1:0.25 ~ 2:10 ~ 700, is more preferably 1:0.5 ~ 2:100 ~ 500; The mol ratio of the transition metal in transistion metal compound and the metal in co-catalyst is preferably 1:50 ~ 500.
10. a method for ethylene tetramerization, under being included in the existence of the ethylene tetramerization carbon monoxide-olefin polymeric according to any one of claim 1-9, carries out ethylene tetramerization reaction.
11. methods according to claim 10, is characterized in that, the reaction temperature of described ethylene tetramerization reaction is 0 ~ 100 DEG C, preferably 0 ~ 80 DEG C; Reaction pressure 0.1 ~ 6MPa, preferably 0.5 ~ 5.0MPa.
12. methods according to claim 10 or 11, it is characterized in that, with the weight of organic solvent for Calculation Basis, the concentration of described transistion metal compound is 0.05 ~ 0.3mmol/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6825297B1 (en) * | 1999-05-14 | 2004-11-30 | The Dow Chemical Company | Transition metal complexes and olefin polymerization process |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
| CN103566973A (en) * | 2012-08-06 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6825297B1 (en) * | 1999-05-14 | 2004-11-30 | The Dow Chemical Company | Transition metal complexes and olefin polymerization process |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
| CN103566973A (en) * | 2012-08-06 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization |
Non-Patent Citations (1)
| Title |
|---|
| 汪秋安 等: "《有机化学实验室技术手册》", 29 February 2012, 化学工业出版社 * |
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