CN102558107B - Process for preparing tris (tetrahydrofuran)-trihalogenated chromium and application thereof for preparing olefin oligomerization catalyst - Google Patents
Process for preparing tris (tetrahydrofuran)-trihalogenated chromium and application thereof for preparing olefin oligomerization catalyst Download PDFInfo
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Abstract
The invention relates to a process for preparing tris (tetrahydrofuran)-trihalogenated chromium, which comprises the step of reacting trihalogenated chromium with tetrahydrofuran under the condition of microwave radiation. The process for preparing tris (tetrahydrofuran)- trihalogenated chromium has the advantages that the required time is short so that the efficiency is high. The invention also relates to a process for preparing an ethylene trimerization chrome base catalyst including the above process and a process for preparing 1-hexene by ethylene trimerization.
Description
Technical field
The present invention relates to one prepare three (oxolane) three hafnium halide (be also expressed as CrX
3.THF
3or CrX
3. (THF)
3) method, and also relate to the preparation method of the ethylene trimer chromium-based catalysts comprising this preparation method and prepared the method for 1-hexene by ethylene trimer.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry, the small-numerator olefin of cheapness can be changed into have high value-added product, as 1-hexene, 1-octene by oligomerisation reaction.1-hexene is the important comonomer producing LLDPE and HDPE, is also the raw material of some fine chemicals.By the LLDPE resin of 1-hervene copolymer compared with the copolymer by 1-butene, hot strength, impact strength, tear resistance and performance durable in use are all obviously excellent, are specially adapted to packaging film and the agricultural mulch films etc. such as greenhouse, canopy room.John R.Briggs, at J.Chem.Soc., Chem.Commun., in 1989,674-675 page, reports and carry out catalyzed ethylene trimerization selective preparation 1-hexene with homogeneous phase ternary chromium-based catalysts, but the catalyst activity and selectivity obtained is all lower.
EP0608447A1 reports a kind of chromium-based catalysts composition, as the catalyst of ethylene oligomerization and/or copolymerization, wherein uses a kind of compound containing chromium as one of component of carbon monoxide-olefin polymeric; Use azole compounds as the component two of carbon monoxide-olefin polymeric; Have employed a kind of using lewis acid and/or metal alkyl compound for activator is as the component three of this carbon monoxide-olefin polymeric; Also point out simultaneously, also optionally can comprise a kind of halogen source in catalyst system as the component four in this carbon monoxide-olefin polymeric, this halogen source both can be inorganic halides, also can be many eurypalynous organohalogen compounds, selective higher to 1-hexene of this catalyst, but its catalytic activity is not high.
USP5910619 reports employing 1,2,3,4,5,6-hexachlorocyclohexanes as improver, and composition four-way catalyst composition, though the activity of this catalyst increases, can not meet the demands.People wish the performance improving chromium-based catalysts further, to improve the activity and selectivity of catalyst.Be referred in USP5910619 and three (oxolane) chromium trichloride can be adopted as containing chromium compound, but the synthesis of this compound not mentioned.
Three (oxolane) chromium trichloride adopts soxhlet extraction to synthesize usually, namely by the backflow effect of solvent, the solids extracted in sleeve pipe is extracted continuously, finally obtain the mixed solution containing target product, but the reaction time of this building-up process is long, be generally 6-8 hour or longer, thus efficiency is not high.
Therefore, need one to prepare the method for three (oxolane) chromium trichloride easily, the method reaction time is short, and efficiency is high.
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor three (oxolane) three hafnium halide preparation in carried out research extensively and profoundly, found that, when adopting microwave to prepare three (oxolane) three hafnium halide, can Reaction time shorten greatly, reaction efficiency is high.
Therefore, the object of this invention is to provide one and prepare three (oxolane) three method of hafnium halide, this preparation method is compared to traditional soxhlet extraction, and the reaction time of needs is short, and thus efficiency is high.
Another object of the present invention is to provide a kind of method preparing ethylene trimer chromium-based catalysts, and the method comprises the method for preparation three (oxolane) three hafnium halide of the present invention.
Another object of the present invention is to provide a kind of method being prepared 1-hexene by ethylene trimer, and the method comprises the method preparing ethylene trimer chromium-based catalysts of the present invention.
These and other objects of the present invention, feature and advantage will become more clear after reading this description.
One aspect of the present invention provides one and prepares three (oxolane) three hafnium halide CrX
3. (THF)
3method, comprise and three hafnium halides and oxolane are reacted under the condition of microwave, wherein X is identical or different and is selected from fluorine, chlorine, bromine or iodine, be preferably chlorine or bromine, be more preferably chlorine.
The present invention provides a kind of method preparing ethylene trimer chromium-based catalysts on the other hand, and this catalyst comprises following component a-d:
A. as three (oxolane) three hafnium halide of chromium compound;
B. azole derivatives;
C. alkyl aluminum; With
D. as one or more in group under being selected from of improver: 1,1,1-trichloroethanes, 1,1,2-trichloroethanes, 1,1,2,2-tetrachloroethanes, pentachloroethane, carbon trichloride, 1,1,2-trichloropropane, 1,1,2,2-tetra-chloropropane, 1,1,1-tri-chlorobutane, 1,1,2,2-tetra-chlorobutane, 1,1,1-tribromoethane, 1,1,2,2-tetra-chloropentane, 1,1,2,2-tetrabromobutane and 1,1,2,2-tetrabromobutane
Described method comprises the following steps:
1) three (oxolane) three hafnium halide CrX is prepared according to the method for preparation three (oxolane) three hafnium halide of the present invention
3. (THF)
3, wherein X is identical or different and is selected from fluorine, chlorine, bromine or iodine, preferably three (oxolane) chromium trichloride; And
2) chromium compound a, azole derivatives b and improver d are pre-mixed, obtain mixed solution, then under the oligomerisation condition of ethene existence, this mixed solution is contacted with alkyl aluminum c, preferably contact with the solution of alkyl aluminum c in inert organic solvents.
Further aspect of the present invention provides a kind of method being prepared 1-hexene by ethylene trimer, the method comprises the method preparing ethylene trimer chromium-based catalysts according to the present invention and prepares ethylene trimer chromium-based catalysts, and makes ethene contact with the described chromium-based catalysts original position of catalytically effective amount and the trimerization reaction of ethene occurs.
In the method for preparation three (oxolane) three hafnium halide of the present invention, oxolane usually relative to three hafnium halides stoichiometrically or stoichiometric excess use.Advantageously, the mol ratio of three hafnium halides and oxolane is 1: 5-1: 100, preferably 1: 10-1: 50.
In the present invention, in order to make three hafnium halides and oxolane react generation three (oxolane) three hafnium halide, microwave is adopted to carry out irradiation to reactant mixture.The selection of microwave irradiation power should advantageously make, the reactant mixture of every 500ml adopt the power of microwave to be 100-2000W, be preferably 400W-1000W.Under microwave, the reaction of three hafnium halides and oxolane carries out 5 minutes-5 hours usually, preferably 10 minutes-3 hours.Typically, microwave irradiation power is higher, and the time of microwave is shorter; Microwave irradiation power is lower, and the time of microwave is longer; In addition, the gross mass of reactant mixture is larger, and required microwave irradiation power is higher.
Make with microwave before three hafnium halides and oxolane react, advantageously three hafnium halides to be mixed with oxolane, be exposed in microwave more afterwards and react, such as, be placed in microwave reactor and react.After reaction terminates, cooled by reactant mixture, such as, be cooled to 0 DEG C, filter, washing, such as, use anhydrous heptane, final drying, advantageously vacuum drying, obtains three (oxolane) three hafnium halide.
Prepare in the method for ethylene trimer chromium-based catalysts in the present invention, azole derivatives as components b used is the conventional azole derivatives for the preparation of ethylene trimer chromium-based catalysts, such as can adopt in lower group one or more: 2, 4-dimethyl pyrrole, 3, 4-dimethyl pyrrole, 2, 5-dimethyl pyrrole, 2, 5-dimethyl-3-N-ethyl pyrrole N-, pyrroles-2-ketone, 2-methyl-5-N-ethyl pyrrole N-, 1, 2, 5-trimethyl-3-N-ethyl pyrrole N-, 2, 5-dimethyl pyrrole-3-ketone, 1-methylpyrrole, 2-methylpyrrole, 3-methylpyrrole and 2-methylpyrrole-4-ketone.
Prepare in the method for ethylene trimer chromium-based catalysts in the present invention, alkyl aluminum compound as amount of component b used is the conventional alkyl aluminum compound for the preparation of ethylene trimer chromium-based catalysts, such as can adopt in lower group one or more: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, diethylaluminium ethoxide, chloro diethyl aluminum, chloro diisobutyl aluminum, tri-n-hexyl aluminum and dichloro-aluminium ethide, preferred triethyl aluminum.
Prepare in the method for ethylene trimer chromium-based catalysts in the present invention, the improver as component d used be selected from lower group one or more: 1,1,1-trichloroethanes, 1,1,2-trichloroethanes, 1,1,2,2-tetrachloroethanes, pentachloroethane, carbon trichloride, 1,1,2-trichloropropane, 1,1,2,2-tetra-chloropropane, 1,1,1-tri-chlorobutane, 1,1,2,2-tetra-chlorobutane, 1,1,1-tribromoethane, 1,1,2,2-tetra-chloropentane, 1,1,2,2-tetrabromobutane and 1,1,2,2-tetrabromobutane; Preferably 1,1,2,2-tetrachloroethanes, 1,1,1-trichloroethanes, pentachloroethane or carbon trichloride.
In a preferred embodiment of inventive catalyst composition preparation method, the mol ratio of three (oxolane) three hafnium halide a and azole derivatives b, alkyl aluminum c and improver d is generally a: b: c: d=1: 0.5-20: 5-2000: 0.1-50, preferred mol ratio is 1: 1-10: 10-500: 1-40, and preferred mol ratio is 1: 1.5-7: 20-200: 2-30.
In order to prepare carbon monoxide-olefin polymeric of the present invention, chromium compound a, azole derivatives b and improver d being pre-mixed, then contacting with alkyl aluminum c under the oligomerisation condition of ethene existence, preferably contacting with the solution of alkyl aluminum c in inert organic solvents.To this advantageously, chromium compound a, azole derivatives b and improver d are dissolved in inert organic solvents respectively, and then their solution is mixed, thus realize being pre-mixed of chromium compound a, azole derivatives b and improver d.
Inert organic solvents for dissolved constituent a, b, c and d refers to and can make the mutual Homogeneous phase mixing of catalyst components and ethene solubility is high any alkane, cycloalkane, alkene and/or aromatic hydrocarbons wherein, and the oligomerisation of the not chemical participation ethene of this solvent.Inert organic solvents for dissolved constituent a, b, c and d may be the same or different, preferably identical, can use be selected from lower group one or more: n-hexane, cyclohexane, normal heptane, isoheptane, normal octane, isooctane, n-decane, n-dodecane, hexahydrotoluene, benzene, toluene, ortho-xylene, 1-hexene and 1-octene, preferred normal heptane or toluene.
Prepared in the method for 1-hexene by ethylene trimer of the present invention, prepare ethylene trimer chromium-based catalysts according to the method preparing ethylene trimer chromium-based catalysts of the present invention, make ethene contact with the described chromium-based catalysts original position of catalytically effective amount and the trimerization reaction of ethene occurs.Such as, first by three (oxolane) three hafnium halide a be dispersed in inert organic solvents and be pre-mixed with azole derivatives b and improver d solution separately again, then under the reaction condition of ethylene trimer, said mixture and the solution containing alkyl aluminum are separately joined in reactor, and cause ethylene trimer reaction immediately.The reaction temperature of ethylene trimer is generally 20-200 DEG C, is preferably 50-160 DEG C, is more preferably 80-160 DEG C; Reaction pressure is generally 1-20MPa, is preferably 2-10MPa, is more preferably 3-7MPa; Reaction time is generally 0.1-3h, is preferably 0.3-2h, is more preferably 0.5-2h.The solvent that this polymerisation uses is similarly and makes the mutual Homogeneous phase mixing of catalyst components and ethene solubility is high any alkane, cycloalkane, alkene and/or aromatic hydrocarbons wherein, and the oligomerisation of the not chemical participation ethene of this solvent.As an example, n-hexane, cyclohexane, normal heptane, isoheptane, normal octane, isooctane, n-decane can be mentioned, n-dodecane, hexahydrotoluene, benzene, toluene, ortho-xylene, 1-hexene and 1-octene, preferred heptane, toluene or 1-hexene.
Main feature of the present invention:
1) method of microwave is adopted fast, efficiently to prepare three (oxolane) three hafnium halide;
2) by prefabricated to the component a of three in carbon monoxide-olefin polymeric, b and d, be conducive to the coordination in three coordinate bonds of chromium being in right angle of three ethylene molecules, thus be conducive to the autohemagglutination of three ethylene molecules and optionally generate 1-hexene, therefore, catalyst prepared by the method have active high, 1-hexene is selective good, and the feature that by-product polymer is few.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but scope of the present invention is not limited to these embodiments.
Embodiment 1
1. prepare anhyd chromic chloride
Cleaning with churned mechanically 250ml flask in add 50g six hydrated chromium trichloride, then add the thionyl chloride of 150ml through air-distillation process.At room temperature start simultaneously and stir and heating, be heated to backflow, reaction backflow 20h, obtains violet solid, removes unnecessary thionyl chloride, obtain the anhydrous chromium trichloride of product, heavy 27.25g (productive rate 91.5%).
2. prepare three (oxolane) chromium trichloride
In the churned mechanically 1000ml round-bottomed flask of the band of replacing through nitrogen, add the oxolane of 6.0mol, then take anhyd chromic chloride 0.25mol obtained above and add wherein, stir and be placed in microwave reactor in ten minutes, microwave irradiation power 400W.Radiation is after 3 hours, and cooling, suction filtration, drying, obtain mauve solid product, heavy 53.86g (productive rate is 58%).
Elementary analysis instrument is the CE-440 type that Jia Lian Instrument Ltd. of the U.S. produces.
Atomic absorption instrument is the AA-400 type that PerkinElmer company of the U.S. produces.
The elementary analysis of product is: theoretical value (actual value): C:38.78 (38.45), H:5.70 (5.92), O:12.91 (13.28)
The chromium content that product Atomic absorption records is 14.01 % by weight, and theoretical value is 13.99 % by weight, and test value and theoretical value are closely.
Above characterization data shows, gained aubergine solid is three (oxolane) chromium trichloride.
Embodiment 2
Repeat embodiment 1, difference is: microwave irradiation power is 700W, and radiated time is 1 hour.Three (oxolane) chromium trichloride productive rate obtained is 63%.
Embodiment 3
Repeat embodiment 1, difference is: microwave irradiation power is 1000W, and radiated time is 10 minutes.Three (oxolane) chromium trichloride productive rate obtained is 55%.
Embodiment 4
Repeat embodiment 1, difference is: microwave irradiation power is 1000W, and radiated time is 10 minutes, and anhyd chromic chloride consumption is 0.5mol.Three (oxolane) chromium trichloride productive rate obtained is 54%.
Embodiment 5
Repeat embodiment 1, difference is: anhydrous chromium tribromide is replaced anhyd chromic chloride in embodiment 1.Obtain solid product, show the elementary analysis of this product and atomic absorption method Chromium Content Analysis, products therefrom is three (oxolane) chromium tribromide, and productive rate is 52%.
Embodiment 6
Three (oxolane) chromium trichloride 0.001mol (in chromium) obtained in Example 1, be diluted to 100ml with dehydration normal heptane, in solution, chromium concn is 0.01mmol/mL.Same dehydration normal heptane is as solvent, and obtained 100ml concentration is the triethyl aluminium solution of 0.5mmol/mL respectively, and 100ml concentration is 2, the 5-dimethyl pyrrole solution of 0.03mmol/mL, and 100ml concentration is the tetrachloroethanes solution of 0.05mmol/mL, for subsequent use.
Embodiment 7
The stainless steel polymeric kettle of 300ml is adopted to carry out ethylene trimer evaluation test.First carry out pressurize test to this reactor, under determining that reactor seals intact condition, use high pure nitrogen to replace three times, ethene replaces three times.Then, dehydration normal heptane 100ml is added at normal temperatures in polymeric kettle, be warming up to 80 DEG C, add the n-heptane solution 1ml, 2 of three (oxolane) chromium trichloride obtained in embodiment 6 simultaneously, the n-heptane solution 1ml of the n-heptane solution 1ml of 5-dimethyl pyrrole solution and the n-heptane solution of tetrachloroethanes, finally adds the n-heptane solution 2ml of triethyl aluminum.Pass into ethene, open and stir, start ethylene oligomerization reaction, and keep temperature to be 80 DEG C, maintaining reaction pressure in course of reaction is 5MPa.React with ice-water bath cooling, pressure release after 30 minutes, the gas respectively in metering kettle and liquid, with the composition of chromatographic liquid and gas, solid product is weighed after filtration and after at room temperature drying, and oligomerization the results are shown in subordinate list 1.
Definition:
Catalyst activity: the total amount of the ethylene oligomerization product of every gram of crome metal generation per hour, Kg oligomerization product/g Cr. hour.
Embodiment 8
Repeat embodiment 7, difference is: after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 9
Repeat embodiment 7, difference is: after passing into ethene, temperature is risen to 160 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 10
Repeat embodiment 7, difference is: after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C, and to maintain reaction pressure in course of reaction be 3MPa instead of 5MPa.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 11
Repeat embodiment 7, difference is: after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C, and to maintain reaction pressure in course of reaction be 7MPa instead of 5MPa.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 12
Repeat embodiment 7, difference is: after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C, and reacts after 1 hour instead of lower the temperature with ice-water bath after 30 minutes.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 13
Repeat embodiment 7, difference is: after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C, and reacts after 2 hours instead of lower the temperature with ice-water bath after 30 minutes.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 14
Repeat embodiment 7, difference is: the addition of the n-heptane solution of triethyl aluminum is 1ml instead of 2ml, and after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 15
Repeat embodiment 7, difference is: the addition of the n-heptane solution of triethyl aluminum is 3ml instead of 2ml, and after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 16
Repeat embodiment 7, difference is: the addition of the n-heptane solution of three (oxolane) chromium trichloride is 2ml instead of 1ml, the addition of the n-heptane solution of triethyl aluminum is 3ml instead of 2ml, and after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 17
Repeat embodiment 7, difference is: the addition of the n-heptane solution of three (oxolane) chromium trichloride is 2ml instead of 1ml, 2, the addition of the n-heptane solution of 5-dimethyl pyrrole solution is 2ml instead of 1ml, the addition of the n-heptane solution of triethyl aluminum is 3ml instead of 2ml, and after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 18
Repeat embodiment 7, difference is: the 100ml that adds in the polymeric kettle normal heptane that dewaters changes and makes 100ml toluene, and after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Embodiment 19
Repeat embodiment 7, difference is: the 100ml that adds in the polymeric kettle normal heptane that dewaters changes and makes 100ml 1-hexene, and after passing into ethene, temperature is risen to 120 DEG C instead of remain 80 DEG C.Ethylene oligomerization reaction the results are shown in subordinate list 1.
Claims (20)
1. prepare three (oxolane) three hafnium halide CrX for one kind
3. (THF)
3method, three hafnium halides and oxolane are reacted under the condition of microwave, wherein X is identical or different and is selected from chlorine or bromine, and every 500ml reactant mixture adopt the power of microwave to be 100-2000W, microwave irradiation time is 5 minutes-3 hours.
2. method as claimed in claim 1, wherein X is identical and is chlorine or bromine.
3. method as claimed in claim 1, wherein the mol ratio of three hafnium halides and oxolane is 1: 5-1: 100.
4. method as claimed in claim 3, wherein the mol ratio of three hafnium halides and oxolane is 1: 10-1: 50.
5. method as claimed in claim 1, wherein every 500ml reactant mixture adopt the power of microwave to be 400-1000W.
6. method required any one of claim 1-5, wherein microwave irradiation time is 10 minutes-3 hours.
7. prepare a method for ethylene trimer chromium-based catalysts, this catalyst comprises following component a-d:
A. as three (oxolane) three hafnium halide of chromium compound;
B. azole derivatives;
C. alkyl aluminum; With
D. as one or more in group under being selected from of improver: 1,1,1-trichloroethanes, 1,1,2-trichloroethanes, 1,1,2,2-tetrachloroethanes, pentachloroethane, carbon trichloride, 1,1,2-trichloropropane, 1,1,2,2-tetra-chloropropane, 1,1,1-tri-chlorobutane, 1,1,2,2-tetra-chlorobutane, 1,1,1-tribromoethane, 1,1,2,2-tetra-chloropentane, 1,1,2,2-tetrabromobutane and 1,1,2,2-tetrabromobutane
Described method comprises the following steps:
1) three (oxolane) three hafnium halide CrX is prepared according to method according to any one of claim 1-6
3. (THF)
3; And
2) chromium compound a, azole derivatives b and improver d are pre-mixed, obtain mixed solution, then under the oligomerisation condition of ethene existence, this mixed solution is contacted with alkyl aluminum c.
8. method as claimed in claim 7, wherein three (oxolane) three hafnium halide be three (oxolane) chromium trichloride.
9. method, wherein step 2 as claimed in claim 7) described in the contact of mixed solution and alkyl aluminum c be that described mixed solution contacts with the solution of alkyl aluminum c in inert organic solvents.
10. method as claimed in claim 7, wherein the mol ratio of component a, b, c and d is 1: 0.5-20: 5-2000: 0.1-50.
11. methods as claimed, wherein the mol ratio of component a, b, c and d is 1: 1-10: 10-500: 1-40.
12. methods as claimed in claim 11, wherein the mol ratio of component a, b, c and d is 1: 1.5-7: 20-200: 2-30.
13. methods required any one of claim 7-12, are wherein dissolved into chromium compound a, azole derivatives b and improver d in inert organic solvents respectively, and then mix.
14. methods required any one of claim 7-12, wherein azole derivatives be selected from lower group one or more: 2,4-dimethyl pyrrole, 3,4-dimethyl pyrrole, 2,5-dimethyl pyrrole, 2,5-dimethyl-3-N-ethyl pyrrole N-s, pyrroles-2-ketone, 2-methyl-5-N-ethyl pyrrole N-, 1,2,5-trimethyl-3-N-ethyl pyrrole N-, 2,5-dimethyl pyrrole-3-ketone, 1-methylpyrrole, 2-methylpyrrole, 3-methylpyrrole and 2-methylpyrrole-4-ketone; And/or alkyl aluminum be selected from lower group one or more: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, diethylaluminium ethoxide, chloro diethyl aluminum, chloro diisobutyl aluminum, tri-n-hexyl aluminum and dichloro-aluminium ethide.
15. methods as claimed in claim 14, wherein azole derivatives is 2,5-dimethyl pyrrole.
16. methods as claimed in claim 14, wherein alkyl aluminum is triethyl aluminum.
17. methods required any one of claim 7-12, wherein inert organic solvents is identical or different, and one or more for being selected from lower group: n-hexane, cyclohexane, normal heptane, isoheptane, normal octane, isooctane, n-decane, n-dodecane, hexahydrotoluene, benzene, toluene, ortho-xylene, 1-hexene and 1-octene.
18. methods required any one of claim 7-12, wherein inert organic solvents is identical or different, and for being selected from normal heptane or toluene.
The method of 1-hexene is prepared for 19. 1 kinds by ethylene trimer, the method comprised according to any one of claim 7-18 prepares ethylene trimer chromium-based catalysts, and makes ethene contact with the described chromium-based catalysts original position of catalytically effective amount and the trimerization reaction of ethene occurs.
20. methods required by claim 19, the temperature of wherein ethylene trimer reaction is 80-160 DEG C, and reaction pressure is 3-7MPa, and the reaction time is 0.5-2h.
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US10099970B2 (en) | 2014-12-23 | 2018-10-16 | Public Joint Stock Company “SIBUR Holding” | Methods of preparing oligomers of an olefin |
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CN115073524A (en) * | 2022-07-22 | 2022-09-20 | 山东京博石油化工有限公司 | Preparation method of chromium trichloride complex of tetrahydrofuran |
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