CN102558107A - 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 a kind of preparation three (THF) three hafnium halides and (also be expressed as CrX
3.THF
3Or CrX
3. (THF)
3) method, and also relate to the ethylene trimer that comprises this preparation method prepares the 1-hexene with the preparation method of chromium-based catalysts with by ethylene trimer method.
Background technology
Ethylene oligomerization is one of most important reaction in the olefinic polymerization industry, can the small-numerator olefin of cheapness be changed into through oligomerisation reaction to have high value-added product, like 1-hexene, 1-octene.The 1-hexene is an important comonomer of producing LLDPE and HDPE, also is the raw material of some fine chemicals.By the LLDPE resin of 1-hervene copolymer with compare by the multipolymer of 1-butylene copolymerization, tensile strength, resistance to impact shock, tear strength and performance durable in use are all obviously excellent, are specially adapted to agricultural mulch films such as packing film and greenhouse, canopy chamber etc.John R.Briggs is at J.Chem.Soc., Chem.Commun., and 1989, in the 674-675 page or leaf, reported with homogeneous phase ternary chromium-based catalysts and come catalyzed ethylene trimerization selectivity to prepare the 1-hexene, but resulting catalyst activity and selectivity are all lower.
EP0608447A1 has reported a kind of chromium-based catalysts compsn, as the catalyzer of ethylene oligomerization and/or copolymerization, wherein uses a kind of compound that contains chromium as one of component of catalyst composition; Use azole cpds as two of the component of catalyst composition; Having adopted a kind of is acvator as three of the component of this catalyst composition with Lewis acid and/or metal alkyl compound; Also point out simultaneously; Also can choose wantonly in the catalyst system and comprise a kind of halogen source as four of the component in this catalyst composition, this halogen source both can be inorganic halides, also can be the Organohalogen compounds of numerous types; This catalyzer is higher to the selectivity of 1-hexene, but its catalytic activity is not high.
USP5910619 has reported and has adopted 1,2,3,4,5 that the 6-HEXACHLOROBUTADIENE is formed the four-way catalyst compsn as improving agent, though this activity of such catalysts increases, can not meet the demands.People hope further to improve the performance of chromium-based catalysts, to improve activity of such catalysts and selectivity.Mentioned among the USP5910619 and can adopt the conduct of three (THF) chromium trichloride to contain chromium cpd, but not mentioned this compound is synthetic.
Three (THF) chromium trichloride adopts soxhlet extraction to synthesize usually; Promptly pass through the backflow effect of solvent; Solids to extracting in the sleeve pipe extracts continuously, finally obtains containing the mixing solutions of title product, but the long reaction time of this building-up process; Be generally 6-8 hour or longer, thereby efficient is not high.
Therefore, need a kind of method for preparing three (THF) chromium trichloride easily, this method reaction times is short, and efficient is high.
Summary of the invention
Situation in view of above-mentioned prior art; Contriver of the present invention is carrying out research extensively and profoundly aspect the preparation of three (THFs), three hafnium halides, the result finds, when adopting microwave radiation to prepare three (THFs), three hafnium halides; Can shorten the reaction times greatly, reaction efficiency is high.
Therefore, the purpose of this invention is to provide a kind of method of preparation three (THFs) three hafnium halides, this preparation method is than traditional soxhlet extraction, and the reaction times that needs is short, thereby efficient is high.
Another object of the present invention provides a kind of method for preparing ethylene trimer with chromium-based catalysts, and this method comprises the method for preparation three of the present invention (THF) three hafnium halides.
A purpose more of the present invention provides and a kind ofly prepares the method for 1-hexene by ethylene trimer, and this method comprises the method for preparing ethylene trimer with chromium-based catalysts of the present invention.
Of the present invention these will become more clear with other purposes, characteristic and advantage after reading this specification sheets.
One aspect of the present invention provides a kind of preparation three (THF) three hafnium halide CrX
3. (THF)
3Method, comprise three hafnium halides and THF are reacted that wherein X is identical or different and is selected from fluorine, chlorine, bromine or iodine, is preferably chlorine or bromine, more preferably chlorine under the condition of microwave radiation.
The present invention provides a kind of method for preparing ethylene trimer with chromium-based catalysts on the other hand, and this catalyzer comprises following component a-d:
A. as three (THFs), three hafnium halides of chromium cpd;
B. pyrrole derivative;
C. aluminum alkyls; With
D. as under being selected from of improving agent the group in one or more: 1, vinyl trichloride, sym.-tetrachloroethane, pentaline, Sesquichloratum, 1; 1,2-trichloropropane, 1,1,2,2-tetrachloro propane, 1,1,1-three chlorobutanes, 1,1; 2,2-tetrachloro butane, 1,1,1-tribromoethane, 1,1,2,2-tetrachloro pentane, 1; 1,2,2-tetrabromobutane and 1,1,2,2-tetrabromobutane
Said method comprises the following steps:
1) method according to preparation three of the present invention (THF) three hafnium halides prepares three (THF) three hafnium halide CrX
3. (THF)
3, wherein X is identical or different and is selected from fluorine, chlorine, bromine or iodine, preferred three (THF) chromium trichloride; And
2) chromium cpd a, pyrrole derivative b and improving agent d are pre-mixed, obtain mixing solutions, under the oligomerisation condition that ethene exists, this mixing solutions is contacted with aluminum alkyls c then, preferably contact with the solution of aluminum alkyls c in inert organic solvents.
Further aspect of the present invention provides a kind of method that is prepared the 1-hexene by ethylene trimer; This method comprises that the ethylene trimer for preparing according to the present invention prepares ethylene trimer with the method for chromium-based catalysts and uses chromium-based catalysts, and makes the ethene and the said chromium-based catalysts original position of catalytically effective amount contact and take place the trimerization reaction of ethene.
In the method for preparation three of the present invention (THF) three hafnium halides, THF usually with respect to three hafnium halides with stoichiometry or the excessive use of stoichiometry.Advantageously, the mol ratio of three hafnium halides and THF is 1: 5-1: 100, preferred 1: 10-1: 50.
In the present invention, generate three (THFs), three hafnium halides, adopt microwave that reaction mixture is carried out irradiation in order to make the reaction of three hafnium halides and THF.The selection of microwave irradiation power should make advantageously that the power of the microwave radiation that reaction mixture adopts of every 500ml is 100-2000W, is preferably 400W-1000W.Under microwave radiation, the reaction of three hafnium halides and THF was carried out 5 minutes-5 hours usually, preferred 10 minutes-3 hours.Usually, microwave irradiation power is high more, and the time of microwave radiation is short more; Microwave irradiation power is low more, and the time of microwave radiation is long more; In addition, the total mass of reaction mixture is big more, and required microwave irradiation power is high more.
Make the reaction of three hafnium halides and THF with microwave radiation before, advantageously three hafnium halides and THF are mixed, be exposed in the microwave radiation more afterwards and react, for example place microwave reactor to react.After reaction finishes, with the reaction mixture cooling, for example be cooled to 0 ℃, filter, anhydrous heptane wash is for example used in washing, final drying, and advantageously vacuum-drying obtains three (THFs), three hafnium halides.
Prepare in the method for ethylene trimer with chromium-based catalysts in the present invention; The used pyrrole derivative as components b is used to prepare the pyrrole derivative of ethylene trimer with chromium-based catalysts for conventional, for example can adopt down in the group one or more: 2, and 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-trimethylammonium-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 with chromium-based catalysts in the present invention; The used alkylaluminium cpd as amount of component b is used to prepare the alkylaluminium cpd of ethylene trimer with chromium-based catalysts for routine; For example can adopt down in the group one or more: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, oxyethyl group diethyl aluminum, chloro diethyl aluminum, chloro diisobutyl aluminum, tri-n-hexyl aluminum and dichloro-aluminium triethyl, preferred triethyl aluminum.
Prepare in the method for ethylene trimer with chromium-based catalysts in the present invention, used improving agent as component d be selected from down the group in one or more: 1, vinyl trichloride, 1,1,2; 2-tetrachloroethane, pentaline, Sesquichloratum, 1,1,2-trichloropropane, 1,1,2,2-tetrachloro propane, 1,1,1-three chlorobutanes, 1; 1,2,2-tetrachloro butane, 1,1,1-tribromoethane, 1,1,2; 2-tetrachloro pentane, 1,1,2,2-tetrabromobutane and 1,1,2,2-tetrabromobutane; Preferred sym.-tetrachloroethane, 1, pentaline or Sesquichloratum.
In a catalyst composition preparing method's of the present invention preferred embodiment; The mol ratio of three (THF) three hafnium halide a and pyrrole derivative b, aluminum alkyls c and improving agent 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, preferred mol ratio is 1: 1.5-7: 20-200: 2-30.
In order to prepare catalyst composition of the present invention, chromium cpd a, pyrrole derivative b and improving agent d are pre-mixed, under the oligomerisation condition that ethene exists, contact then with aluminum alkyls c, preferably contact with the solution of aluminum alkyls c in inert organic solvents.To this advantageously, chromium cpd a, pyrrole derivative b and improving agent d are dissolved in the inert organic solvents respectively, and then their solution is mixed, thereby realize being pre-mixed of chromium cpd a, pyrrole derivative b and improving agent d.
The inert organic solvents that is used for dissolved constituent a, b, c and d is meant and can makes mutual uniform mixing of each composition of catalyzer and ethene high any alkane, naphthenic hydrocarbon, alkene and/or the aromatic hydrocarbons of solubleness therein, and the oligomerisation of the not chemical participation ethene of this solvent.The inert organic solvents that is used for dissolved constituent a, b, c and d can be identical or different; Preferably identical; Can use be selected from down the group in one or more: normal hexane, hexanaphthene, normal heptane, isoheptane, octane, octane-iso, n-decane; N-dodecane, methylcyclohexane, benzene, toluene, o-Xylol, 1-hexene and 1-octene, preferred normal heptane or toluene.
In the method for preparing the 1-hexene by ethylene trimer of the present invention; Prepare ethylene trimer with the method for chromium-based catalysts and use chromium-based catalysts according to the ethylene trimer for preparing of the present invention, make the ethene and the said chromium-based catalysts original position of catalytically effective amount contact and take place the trimerization reaction of ethene.For example; At first three (THF) three hafnium halide a are dispersed in the inert organic solvents and are pre-mixed with pyrrole derivative b and improving agent d solution separately again; Under the reaction conditions of ethylene trimer, said mixture and the solution that contains aluminum alkyls are separately joined in the reactor drum then, and cause the ethylene trimer reaction immediately.The temperature of reaction of ethylene trimer is generally 20-200 ℃, is preferably 50-160 ℃, more preferably 80-160 ℃; Reaction pressure is generally 1-20MPa, is preferably 2-10MPa, more preferably 3-7MPa; Reaction time is generally 0.1-3h, is preferably 0.3-2h, more preferably 0.5-2h.The employed solvent of this polyreaction is similarly and makes mutual uniform mixing of each composition of catalyzer and ethene high any alkane, naphthenic hydrocarbon, alkene and/or the aromatic hydrocarbons of solubleness therein, and the oligomerisation of the not chemical participation ethene of this solvent.As an example, can mention normal hexane, hexanaphthene, normal heptane, isoheptane, octane, octane-iso, n-decane, n-dodecane, methylcyclohexane, benzene, toluene, o-Xylol, 1-hexene and 1-octene, preferred heptane, toluene or 1-hexene.
Principal feature of the present invention:
1) quick, efficient production three (THF) three hafnium halides of the method for employing microwave radiation;
2) three component a, b and d in the catalyst composition are prefabricated; Help the coordination on three co-ordination bonds of mutual rectangular chromium of three ethylene molecules; Thereby help the autohemagglutination of three ethylene molecules and optionally generate the 1-hexene; Therefore, the catalyzer of this method preparation has active height, 1-hexene selectivity is good, and the few characteristics of by-product polymer.
Embodiment
The present invention is described further below in conjunction with concrete embodiment, but scope of the present invention is not limited to these embodiment.
Embodiment 1
1. preparation anhyd chromic chloride
Add 50g six hydrated chromium trichlorides in having of cleaning in the churned mechanically 250ml flask, add the thionyl chloride that 150ml handled through the normal pressure distillation again.At room temperature start simultaneously and stir and heating, be heated to backflow, reaction backflow 20h obtains the purple solid, removes unnecessary thionyl chloride, obtains the anhydrous chromium trichloride of product, heavy 27.25g (productive rate 91.5%).
2. prepare three (THF) chromium trichloride
Through nitrogen replacement with churned mechanically 1000ml round-bottomed flask in add the THF of 6.0mol, take by weighing the above-mentioned anhyd chromic chloride 0.25mol that obtains again and add wherein, stir and be placed in the microwave reactor microwave irradiation power 400W in ten minutes.After the radiation 3 hours, cooling, suction filtration, drying promptly get mauve solid product, heavy 53.86g (productive rate is 58%).
The ultimate analysis instrument is the CE-440 type that U.S. Jia Lian Instr Ltd. produces.
The atomic absorption instrument is the AA-400 type that U.S. PerkinElmer company produces.
The ultimate 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 uses atomic absorption to record is 14.01 weight %, and theoretical value is 13.99 weight %, and test value and theoretical value are very approaching.
Above characterization data shows that gained red-purple solid is three (THF) chromium trichloride.
Embodiment 2
Repeat embodiment 1, difference is: microwave irradiation power is 700W, and radiated time is 1 hour.Three (THF) chromium trichloride productive rate that obtains is 63%.
Embodiment 3
Repeat embodiment 1, difference is: microwave irradiation power is 1000W, and radiated time is 10 minutes.Three (THF) chromium trichloride productive rate that obtains is 55%.
Embodiment 4
Repeat embodiment 1, difference is: microwave irradiation power is 1000W, and radiated time is 10 minutes, and the anhyd chromic chloride consumption is 0.5mol.Three (THF) chromium trichloride productive rate that obtains is 54%.
Embodiment 5
Repeat embodiment 1, difference is: anhydrous chromium tribromide is replaced anhyd chromic chloride among the embodiment 1.Obtain solid product, the ultimate analysis and the atomic absorption method chromium content analysis of this product shown that products therefrom is three (THF) chromium tribromide, productive rate is 52%.
Embodiment 6
Get three (THF) the chromium trichloride 0.001mol (in chromium) that makes among the embodiment 1, be diluted to 100ml with the dehydration normal heptane, chromium concn is 0.01mmol/mL in the solution.Same with the dehydration normal heptane as solvent, make the triethyl aluminium solution that 100ml concentration is 0.5mmol/mL respectively, 100ml concentration is 2 of 0.03mmol/mL, 5-dimethyl pyrrole solution, and 100ml concentration is the tetrachloroethane solution of 0.05mmol/mL is subsequent use.
Embodiment 7
Adopt the stainless steel polymeric kettle of 300ml to carry out the ethylene trimer evaluation test.At first this reaction kettle is carried out the pressurize test, confirming to use high pure nitrogen displacement three times, ethene displacement three times under the intact condition of reaction kettle sealing.Then; In polymeric kettle, add dehydration normal heptane 100ml at normal temperatures; Be warming up to 80 ℃; The n-heptane solution 1ml, 2 that adds three (THF) chromium trichloride that makes among the 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 tetrachloroethane adds the n-heptane solution 2ml of triethyl aluminum at last.Feed ethene, open and stir, beginning ethylene oligomerization reaction, and to keep temperature be 80 ℃ keeps that reaction pressure is 5MPa in the reaction process.React after 30 minutes with ice-water bath cooling, pressure release, measure gas and liquid in the still respectively, analyze the composition of liquid and gas with gas chromatograph, solid product is through filtering and at room temperature weighing after the drying, and the oligomerization result sees attached list 1.
Definition:
Catalyst activity: the total amount of the ethylene oligomerization product that every gram chromium metal per hour generates, Kg oligomerization product/g Cr. hour.
Embodiment 8
Repeat embodiment 7, difference is: feed after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 9
Repeat embodiment 7, difference is: feed after the ethene temperature is risen to 160 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 10
Repeat embodiment 7, difference is: feed after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃, and keep that reaction pressure is 3MPa rather than 5MPa in the reaction process.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 11
Repeat embodiment 7, difference is: feed after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃, and keep that reaction pressure is 7MPa rather than 5MPa in the reaction process.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 12
Repeat embodiment 7, difference is: feed after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃, and react after 1 hour rather than lower the temperature with ice-water bath after 30 minutes.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 13
Repeat embodiment 7, difference is: feed after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃, and react after 2 hours rather than lower the temperature with ice-water bath after 30 minutes.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 14
Repeat embodiment 7, difference is: the addition of the n-heptane solution of triethyl aluminum is 1ml rather than 2ml, and feeds after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 15
Repeat embodiment 7, difference is: the addition of the n-heptane solution of triethyl aluminum is 3ml rather than 2ml, and feeds after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 16
Repeat embodiment 7; Difference is: the addition of the n-heptane solution of three (THF) chromium trichloride is 2ml rather than 1ml; The addition of the n-heptane solution of triethyl aluminum is 3ml rather than 2ml, and feeds after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 17
Repeat embodiment 7; Difference is: the addition of the n-heptane solution of three (THF) chromium trichloride is 2ml rather than 1ml; 2; The addition of the n-heptane solution of 5-dimethyl pyrrole solution is 2ml rather than 1ml, and the addition of the n-heptane solution of triethyl aluminum is 3ml rather than 2ml, and feeds after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 18
Repeat embodiment 7, difference is: the 100ml dehydration normal heptane that in polymeric kettle, adds changes makes 100ml toluene, and feeds after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Embodiment 19
Repeat embodiment 7, difference is: the 100ml dehydration normal heptane that in polymeric kettle, adds changes makes 100ml 1-hexene, and feeds after the ethene temperature is risen to 120 ℃ rather than remain 80 ℃.Ethylene oligomerization reaction result sees attached list 1.
Claims (11)
1. one kind prepares three (THF) three hafnium halide CrX
3. (THF)
3Method, comprise three hafnium halides and THF are reacted that wherein X is identical or different and is selected from fluorine, chlorine, bromine or iodine, is preferably chlorine or bromine, more preferably chlorine under the condition of microwave radiation.
2. like the desired method of claim 1, wherein the mol ratio of chromium trichloride and THF is 1: 5-1: 100, preferred 1: 10-1: 50.
3. like claim 1 or 2 desired methods, the power of wherein every 500ml microwave radiation that reaction mixture adopts is 100-2000W, is preferably 400-1000W.
4. like each desired method among the claim 1-3, wherein microwave irradiation time is 5 minutes-5 hours, is preferably 10 minutes-3 hours.
5. method for preparing ethylene trimer with chromium-based catalysts, this catalyzer comprises following component a-d:
A. as three (THFs), three hafnium halides of chromium cpd;
B. pyrrole derivative;
C. aluminum alkyls; With
D. as under being selected from of improving agent the group in one or more: 1, vinyl trichloride, sym.-tetrachloroethane, pentaline, Sesquichloratum, 1; 1,2-trichloropropane, 1,1,2,2-tetrachloro propane, 1,1,1-three chlorobutanes, 1,1; 2,2-tetrachloro butane, 1,1,1-tribromoethane, 1,1,2,2-tetrachloro pentane, 1; 1,2,2-tetrabromobutane and 1,1,2,2-tetrabromobutane
Said method comprises the following steps:
1) according to each said method preparation three (THF) three hafnium halide CrX among the claim 1-4
3. (THF)
3, wherein X is identical or different and is selected from fluorine, chlorine, bromine or iodine, preferred three (THF) chromium trichloride; And
2) chromium cpd a, pyrrole derivative b and improving agent d are pre-mixed, obtain mixing solutions, under the oligomerisation condition that ethene exists, this mixing solutions is contacted with aluminum alkyls c then, preferably contact with the solution of aluminum alkyls c in inert organic solvents.
6. like the desired method of claim 5, wherein the mol ratio of component a, b, c and d is 1: 0.5-20: 5-2000: 0.1-50, preferred 1: 1-10: 10-500: 1-40, more preferably 1: 1.5-7: 20-200: 2-30.
7. like claim 5 or 6 desired methods, wherein chromium cpd a, pyrrole derivative b and improving agent d are dissolved in the inert organic solvents respectively, and then mix.
8. like each desired method among the claim 5-7, wherein pyrrole derivative is to be selected from down in the group one or more: 2, and 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-trimethylammonium-3-N-ethyl pyrrole N-, 2,5-dimethyl pyrrole-3-ketone, 1-methylpyrrole, 2-methylpyrrole, 3-methylpyrrole and 2-methylpyrrole-4-ketone; Preferred 2, the 5-dimethyl pyrrole; And/or aluminum alkyls is to be selected from down in the group one or more: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, oxyethyl group diethyl aluminum, chloro diethyl aluminum, chloro diisobutyl aluminum, tri-n-hexyl aluminum and dichloro-aluminium triethyl, preferred triethyl aluminum.
9. like each desired method among the claim 5-8; Wherein inert organic solvents is identical or different; And for being selected from down in the group one or more: normal hexane, hexanaphthene, normal heptane, isoheptane, octane, octane-iso, n-decane, n-dodecane, methylcyclohexane, benzene, toluene, o-Xylol, 1-hexene and 1-octene, preferably normal heptane or toluene.
10. method for preparing the 1-hexene by ethylene trimer; Comprise that preparing ethylene trimer according to each described method among the claim 5-9 uses chromium-based catalysts, and make the ethene and the said chromium-based catalysts original position of catalytically effective amount contact and take place the trimerization reaction of ethene.
11. according to the desired method of claim 10, the temperature of therein ethylene trimerization reaction is 80-160 ℃, reaction pressure is that 3-7MPa and reaction times are 0.5-2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016105228A1 (en) | 2014-12-23 | 2016-06-30 | Public Joint Stock Company "Sibur Holding" | Methods of preparing oligomers of an olefin |
| CN113600244A (en) * | 2021-08-06 | 2021-11-05 | 山东京博石油化工有限公司 | Catalyst for synthesizing 1-octene and application thereof |
| 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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| 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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