CN116854740A - Chromium tri (tetrahydrofuran) trichloride and polymerization system applied to ethylene selective tetramerization - Google Patents
Chromium tri (tetrahydrofuran) trichloride and polymerization system applied to ethylene selective tetramerization Download PDFInfo
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- CN116854740A CN116854740A CN202310821679.XA CN202310821679A CN116854740A CN 116854740 A CN116854740 A CN 116854740A CN 202310821679 A CN202310821679 A CN 202310821679A CN 116854740 A CN116854740 A CN 116854740A
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- trichloride
- chromium
- tetrahydrofuran
- phenyl
- ethylene
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000005977 Ethylene Substances 0.000 title claims abstract description 30
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims abstract description 7
- 229960000359 chromic chloride Drugs 0.000 claims abstract description 7
- 238000005102 attenuated total reflection Methods 0.000 claims abstract description 4
- 238000001228 spectrum Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 82
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 11
- 239000012024 dehydrating agents Substances 0.000 claims description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- 230000037048 polymerization activity Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a chromium tri (tetrahydrofuran) trichloride and a polymerization system applied to ethylene selective tetramerization. The following conditions are satisfied for chromium tri (tetrahydrofuran) trichloride: a is more than or equal to 2.0 3500‑3200 /A 1600‑1500 Not more than 12.0, wherein A 3500‑3200 And A 1600‑1500 3500-3200cm of chromium trichloride in Fourier transform attenuated total reflection infrared (ATR-FTIR) spectrum ‑1 Area and 1600-1500cm ‑1 Peak area of the region. The chromium tri (tetrahydrofuran) trichloride provided by the invention can improve the stability and polymerization activity of the catalyst, and has potential industrial application prospect and economic benefit.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to chromium tri (tetrahydrofuran) trichloride and a polymerization system applied to ethylene selective tetramerization.
Background
The linear alpha-olefin is an important chemical raw material and can be used in the fields of comonomer of linear low-density polyethylene, alcohol for synthetic plasticizer, surfactant intermediate, synthetic lubricating oil and the like. The linear low-density polyethylene resin produced by taking 1-octene as a comonomer has obviously improved tensile strength, impact strength, tearing strength, puncture resistance, environmental stress cracking resistance and the like, and is widely applied to packaging films, agricultural covering films such as greenhouses, sheds and the like.
Organometallic or coordination chemistry of chromium has been widely studied in academia and industry, wherein CrCl 3 (THF) 3 As an important class of chromium compounds, it can catalyze the selective tetramerization of ethylene to prepare 1-octene after reacting with a diphosphine ligand.
Classical CrCl 3 (THF) 3 There are two routes of preparation: firstly, chromium oxide and carbon tetrachloride are used as raw materials, anhydrous chromium trichloride is generated at high temperature, and the anhydrous chromium trichloride reacts with tetrahydrofuran under the action of zinc powder to generate CrCl 3 (THF) 3 (J.org.chem. 1958,23,1404 and Inorganic Synthesis,1966,8,150), this synthesis is relatively harsh, with phosgene production, resulting in anhydrous CrCl 3 Is high in selling price. In the second route, the hexahydrate chromium trichloride reacts with a dehydrating agent (thionyl chloride) to generate anhydrous CrCl 3 Then reacts with tetrahydrofuran to generate CrCl 3 (THF) 3 Or chromium trichloride hexahydrate and trimethylchlorosilane react directly to generate CrCl 3 (THF) 3 (Inorg. Chem.1990,29,1592), crCl prepared by this route 3 (THF) 3 There are cases of non-THF coordination.
Disclosure of Invention
In order to solve the technical problems, the invention provides a chromium tri (tetrahydrofuran) trichloride and a polymerization system applied to ethylene selective tetramerization. The chromium (III) trichloride in the invention satisfies A which is more than or equal to 2.0 3500-3200 /A 1600-1500 Not more than 12.0, wherein A 3500-3200 And A 1600-1500 Fourier transform of chromium trichloride tris (tetrahydrofuran) separately3500-3200cm in attenuated total reflectance infrared (ATR-FTIR) spectrum -1 Area and 1600-1500cm -1 Peak area of the region. The chromium tri (tetrahydrofuran) trichloride can improve the stability and polymerization activity of the catalyst, and has potential industrial application prospect and economic benefit.
In one aspect, the present invention provides a chromium tri (tetrahydrofuran) trichloride useful in the selective tetramerization of ethylene, wherein said chromium tri (tetrahydrofuran) trichloride satisfies formula i:
2.0≤A 3500-3200 /A 1600-1500 less than or equal to 12.0 of formula I
Wherein A is 3500-3200 And A 1600-1500 3500-3200cm of chromium trichloride in Fourier transform attenuated total reflection infrared (ATR-FTIR) spectrum -1 Area and 1600-1500cm -1 Peak area of the region;
in the invention, A 3500-3200 Satisfies A of 10.0 ∈0 3500-3200 ≤24.0；
In the invention, A 1600-1500 Satisfies the requirement of A being less than or equal to 2.0 1600-1500 ≤5.0。
In another aspect, the present invention also provides a procatalyst for use in the selective tetramerization of ethylene, the procatalyst comprising: chromium (tri) trichloride and ligands;
in the present invention, the ligand is selected from compounds of the P-N-P and P-c=c-P backbone structure, preferably:
(phenyl) 2 PN (isopropyl) P (phenyl) 2 ；
(phenyl) 2 PN (tertiary butyl) P (phenyl) 2 ；
(phenyl) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 ；
(phenyl) 2 P (tert-butyl) c=chp (phenyl) 2 ；
(phenyl) 2 P (isopropyl) c=chp (phenyl) 2 ；
(phenyl) 2 P (cyclohexyl) c=chp (phenyl) 2 One or more of the following.
In the invention, the mole ratio of the tri (tetrahydrofuran) chromium trichloride to the ligand is 1:1.0 to 1.2.
In the invention, the preparation method of the tri (tetrahydrofuran) chromium trichloride comprises the following steps: keeping the temperature of the chromium trichloride hexahydrate, then placing the chromium trichloride in a tetrahydrofuran solution, and dripping a dehydrating agent into the tetrahydrofuran solution containing the metallic chromium for reaction to prepare CrCl 3 (THF) 3 。
In the invention, the temperature of the heat preservation is 100-150 ℃, preferably 100-120 ℃, and the heat preservation time is 5-12 h, preferably 5-6 h; in the present invention, the dehydrating agent is selected from trimethylchlorosilane and thionyl chloride.
In the invention, the dosage of the dehydrating agent is that 12-20 eq of the dehydrating agent is dripped into every 100-200 ml of tetrahydrofuran solution containing metal chromium.
In yet another aspect, the present invention also provides a method for preparing a catalyst for the selective tetramerization of ethylene, comprising the steps of: mixing and stirring the chromium tri (tetrahydrofuran) trichloride and the ligand in a solvent, filtering and leaching to obtain the main catalyst.
In the invention, the solvent is selected from one or two of dichloromethane and toluene; and/or the mixing and stirring time is 1-6 hours, preferably 2-4 hours, and the temperature of the mixing and stirring is 20-90 ℃, preferably 40-80 ℃; and/or the solvent which is leached after filtration is selected from n-hexane and tetrahydrofuran.
In another aspect, the present invention provides a polymerization system comprising 30 to 530g/h ethylene, 200 to 300ml/h solvent, 4.0 to 20.0ml/h procatalyst and 0.5 to 10.0ml/h cocatalyst.
In the present invention, the solvent is selected from C5-20 hydrocarbons or mixed hydrocarbons, preferably one or more of pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, isopar E.
In the present invention, the cocatalyst is selected from at least one of MAO, MMAO-3a, EAO and IBAO.
In the reaction, a cocatalyst: the molar ratio of the main catalyst is 500-2000:1, and the concentration of the main catalyst in the reaction kettle is 2.0-10.0 mu mol (calculated by chromium).
Finally, the present invention provides a process for the selective tetramerisation of ethylene, said process comprising the steps of:
(1) Heating the reaction kettle, vacuumizing, replacing by inert gas, and replacing by ethylene after cooling to normal temperature; (2) Adding a solvent, adding a cocatalyst and a main catalyst into a reaction kettle, heating to 50-80 ℃, introducing ethylene of 1-10 MPa, and reacting for 30-120 min.
In the invention, the heating temperature of the reaction kettle in the step (1) is 120-150 ℃, preferably 120-130 ℃; the vacuumizing time is 1-3 hours, preferably 1.5-2 hours; the inert gas is selected from nitrogen.
In the present invention, the number of ethylene substitutions in the step (1) is 3 to 5, preferably 3 to 4.
In the invention, the reaction pressure in the step (2) is 1-10 MPa, preferably 4-5 MPa; the reaction temperature is 50-80 ℃, preferably 50-55 ℃; the reaction time is 30 to 120min, preferably 30 to 60min.
The invention has the beneficial effects that:
the infrared spectrogram of the chromium tri (tetrahydrofuran) trichloride provided by the invention is 3500-3200cm -1 Peak area of the region and 1600-1500cm -1 The peak area ratio of the region is 2.0-12.0 and 3500-3200cm -1 The peak area of the region is 10.0-24.0, 1600-1500cm -1 The peak area of the area is 2.0-5.0, and the chromium tri (tetrahydrofuran) trichloride can improve the stability and polymerization activity of the catalyst in ethylene selective tetramerization, reduce the selectivity of the polymer, and has potential industrial application prospect and economic benefit.
Drawings
FIG. 1CrCl 3 (THF) 3 -1ATR-FTIR spectra
FIG. 2CrCl 3 (THF) 3 -2ATR-FTIR spectra
FIG. 3CrCl 3 (THF) 3 -3ATR-FTIR spectra
FIG. 4CrCl 3 (THF) 3 -4ATR-FTIR spectra
FIG. 5CrCl 3 (THF) 3 -5ATR-FTIR spectrogram
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
The starting materials used in the examples were all conventional in the art and the purity specifications used were analytically or chemically pure.
The main raw material source information in the following examples:
methylcyclohexane: 99.0%, shanghai Ala Biochemical technologies Co., ltd;
MMAO-3a:7% wtAl in methylcyclohexane, noron chemical Co., ltd;
toluene: 99.5%, shanghai microphone Lin Biochemical technology Co., ltd;
dichloromethane: 99.8%, shanghai Ala Biochemical technologies Co., ltd;
n-hexane: 99.0%, beijing enokic science and technology Co., ltd;
(phenyl) 2 PN (isopropyl) P (phenyl) 2 :99.0%, peak grinding technology;
(phenyl) 2 P (tert-butyl) c=chp (phenyl) 2 :98.5%, peak grinding technology;
2. the following test methods are adopted in each example of the invention:
the liquid phase products are characterized by liquid phase chromatography, so that the quality of each liquid phase product is obtained, and the solid products are separated, dried and weighed;
analysis conditions of liquid chromatography: the temperature of the sample injection product is 250 ℃; the temperature of the column box is 35 ℃;
heating program: firstly, keeping at 35 ℃ for 10 minutes, then raising the temperature to 250 ℃ at the speed of 10 ℃/min, then keeping at 250 ℃ for 10 minutes, and then starting to cool until the temperature reaches the room temperature;
detector temperature: 250 ℃; and (3) a carrier: 1.0Mpa; air: 0.03Mpa; hydrogen gas: 0.03Mpa;
characterization of the product was characterized with nonane as internal standard, calculated as follows:
wherein m1 represents the mass of a certain substance, m is the mass of nonane, a1 is the peak area of the substance measured in GC, and a is the peak area of nonane measured in GC. k is a correction coefficient.
Chromium tri (tetrahydrofuran) trichloride was characterized by fourier transform infrared spectroscopy:
parameters: resolution of 4cm -1 ATR accessory, wave number range 4000-400 cm -1 32 scans.
CrCl 3 (THF) 3 Preparation:
preparation example 1: chromium trichloride hexahydrate is placed at 100 ℃ for 5 hours, then placed in tetrahydrofuran solution, and 12eq of dehydrating agent (trimethylchlorosilane) is added dropwise into 100ml of tetrahydrofuran solution containing metallic chromium for reaction to prepare CrCl 3 (THF) 3 -1；
Preparation example 2: chromium trichloride hexahydrate is placed at 120 ℃ for 6 hours, then placed in tetrahydrofuran solution, and 24eq of dehydrating agent (trimethylchlorosilane) is added dropwise into 200ml of tetrahydrofuran solution containing metallic chromium for reaction to prepare CrCl 3 (THF) 3 -2；
Preparation example 3: chromium trichloride hexahydrate is placed at 110 ℃ for 5.5 hours, then placed in tetrahydrofuran solution, 18eq of dehydrating agent (trimethylchlorosilane) is added dropwise into 150ml of tetrahydrofuran solution containing metallic chromium for reaction to prepare CrCl 3 (THF) 3 -3；
Preparation example 4: crCl is prepared by the method of literature (Inorganic Synthesis.1966,8, 150) 3 (THF) 3 -4；
Preparation example 5: crCl is prepared by the method of literature (Inorg. Chem.1990,29,1592) 3 (THF) 3 -5；
Preparation example 6: crCl was prepared by the method of example 1 of patent CN 115073524A 3 (THF) 3 -6。
Example 1
Under nitrogen, 90.51mg (0.2 mmol) of phenyl was taken 2 P (tert-butyl) c=chp (phenyl) 2 And 74.94mg (0.2 mmol) CrCl 3 (THF) 3 -1 placing in a glass bottle, adding 5.0ml of dichloromethane, stirring for 2 hours, removing the solvent after the solution turns from purple to blue, and washing the solid product with n-hexane for 3 times to obtain the main catalyst Cat1.
Example 2
Under nitrogen, 99.56mg (0.22 mmol) of phenyl group was taken 2 P (isopropyl) c=chp (phenyl) 2 And 74.94mg (0.2 mmol) CrCl 3 (THF) 3 -2 placing in a glass bottle, adding 5.0ml of dichloromethane, stirring for 3 hours, removing the solvent after the solution turns from purple to blue, and washing the solid product with n-hexane for 4 times to obtain the main catalyst Cat2.
Example 3
108.61mg (0.24 mmol) of phenyl are taken under nitrogen atmosphere 2 P (cyclohexyl) c=chp (phenyl) 2 And 74.94mg (0.2 mmol) CrCl 3 (THF) 3 -3 placing in a glass bottle, adding 5.0ml of dichloromethane, stirring for 4 hours, removing the solvent after the solution turns from purple to blue, and washing the solid product with n-hexane for 5 times to obtain the main catalyst Cat3.
Comparative example 1
Under nitrogen, 85.50mg (0.2 mmol) of phenyl was taken 2 PN (isopropyl) P (phenyl) 2 And 74.94mg (0.2 mmol) CrCl 3 (THF) 3 -4 placing the mixture in a glass bottle, adding 6.0ml of toluene, heating to 80 ℃ and stirring for 6 hours, removing the solvent after the solution turns from purple to blue, and washing the solid product with n-hexane for 3 times to obtain the main catalyst Cat4.
Comparative example 2
94.05mg (0.22 mmol) of phenyl are taken under nitrogen 2 PN (tertiary butyl) P (phenyl) 2 And 74.94mg (0.2 mmol) CrCl 3 (THF) 3 And (5) placing the mixture in a glass bottle, adding 8.0ml of toluene, heating to 90 ℃ and stirring for 8 hours, removing the solvent after the solution turns from purple to blue, and washing the solid product with n-hexane for 5 times to obtain the main catalyst Cat5.
Comparative example 3
Under nitrogen, 104.35mg (0.24 mmol) of phenyl group was taken 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 And 74.94mg (0.2 mmol) CrCl 3 (THF) 3 And (6) placing the mixture in a glass bottle, adding 8.0ml of toluene, heating to 85 ℃ and stirring for 7 hours, removing the solvent after the solution turns from purple to blue, and washing the solid product with n-hexane for 5 times to obtain the main catalyst Cat5.
The complexes Cat1 to 5 prepared in examples 1 to 3 and comparative examples 1 to 3 were dissolved in 500ml of toluene to prepare a solution having a molar concentration of Cr of 1. Mu. Mol/ml.
An ethylene oligomerization reaction was carried out using a 500ml autoclave, the temperature of the autoclave was heated to 120℃and evacuated for 3 hours, after which nitrogen was substituted several times, and then ethylene was charged and cooled to room temperature, 200ml methylcyclohexane, 1.15ml cocatalyst (Al/Cr=500) and 5ml main catalyst were sequentially added to the autoclave, and ethylene oligomerization reaction was carried out for 60 minutes at 50℃and 5.0MPa, and the experimental results were recorded in Table 1.
After the procatalyst having a concentration of 1. Mu. Mol/ml was allowed to stand for one week in examples 1 to 5, polymerization was again conducted under the above polymerization conditions, and the experimental results are shown in Table 1.
TABLE 1 oligomerization product distribution and catalyst Activity
The experimental data show that 3500-3200cm of infrared spectrogram in chromium tri (tetrahydrofuran) trichloride -1 Peak area of the region and 1600-1500cm -1 The peak area ratio of the region is 2.0-12.0 and 3500-3200cm -1 The peak area of the region is 10.0-24.0, 1600-1500cm -1 When the peak area of the region is 2.0-5.0, the chromium tri (tetrahydrofuran) trichloride can improve the catalyst stability and polymerization activity in ethylene selective tetramerization, and simultaneously reduce the polymer selectivity.
Claims (10)
1. A tris (tetrahydrofuran) chromium trichloride suitable for use in ethylene selective tetramerization, said tris (tetrahydrofuran) chromium trichloride satisfying formula i:
2.0≤A 3500-3200 /A 1600-1500 less than or equal to 12.0 of formula I
Wherein A is 3500-3200 And A 1600-1500 3500-3200cm of chromium trichloride in Fourier transform attenuated total reflection infrared (ATR-FTIR) spectrum -1 Area and 1600-1500cm -1 Peak area of the region.
2. The chromium tri (tetrahydrofuran) trichloride useful for the selective tetramerization of ethylene of claim 1, wherein A 3500-3200 Satisfies A of 10.0 ∈0 3500-3200 ≤24.0；
A 1600-1500 Satisfies the requirement of A being less than or equal to 2.0 1600-1500 ≤5.0。
3. Process for the preparation of chromium tri (tetrahydrofuran) trichloride suitable for the selective tetramerization of ethylene according to claim 1 or 2, characterized by the fact of comprising the following steps: keeping the temperature of the chromium trichloride hexahydrate, then placing the chromium trichloride in a tetrahydrofuran solution, and then adding a dehydrating agent for reaction to prepare CrCl 3 (THF) 3 。
4. A process according to claim 3, wherein the incubation is at a temperature of 100 to 150 ℃, preferably 100 to 120 ℃, for a time of 5 to 12 hours, preferably 5 to 6 hours; and/or the dehydrating agent is selected from one or two of trimethylchlorosilane and thionyl chloride.
5. A procatalyst for use in the selective tetramerization of ethylene, said procatalyst comprising: a chromium tris (tetrahydrofuran) trichloride, a ligand selected from the group consisting of a chromium tris (tetrahydrofuran) trichloride according to any one of claims 1-2 or a chromium tris (tetrahydrofuran) trichloride prepared by the method of any one of claims 3-4, preferably the molar ratio of the chromium tris (tetrahydrofuran) trichloride, ligand is 1:1.0 to 1.2.
6. Procatalyst for use in ethylene selective tetramerisation according to claim 5, characterized in that the ligand is selected from compounds having a P-N-P and P-c=c-P backbone structure, preferably:
(phenyl) 2 PN (isopropyl) P (phenyl) 2 ；
(phenyl) 2 PN (tertiary butyl) P (phenyl) 2 ；
(phenyl) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 ；
(phenyl) 2 P (tert-butyl) c=chp (phenyl) 2 ；
(phenyl) 2 P (isopropyl) c=chp (phenyl) 2 ；
(phenyl) 2 P (cyclohexyl) c=chp (phenyl) 2 One or more of the following.
7. The method for preparing a procatalyst for use in selective tetramerization of ethylene according to claim 5 or 6, wherein the method comprises the steps of: mixing and stirring the chromium tri (tetrahydrofuran) trichloride and the ligand in a solvent, filtering and leaching to obtain the main catalyst.
8. The method according to claim 7, wherein the solvent is one or both of methylene chloride and toluene; and/or the mixing and stirring time is 1-6 hours, preferably 2-4 hours, and the temperature of the mixing and stirring is 20-90 ℃, preferably 40-80 ℃; and/or the solvent which is leached after filtration is selected from n-hexane and tetrahydrofuran.
9. An ethylene polymerization system is characterized by comprising 30-530 g/h of ethylene, 200-300 ml/h of solvent, 4.0-20.0 ml/h of main catalyst and 0.5-10.0 ml/h of cocatalyst; preferably, the solvent is selected from C5-C20 hydrocarbons or mixed hydrocarbons, preferably one or more of pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, isopar E; and/or, preferably, the cocatalyst is selected from at least one of methylaluminoxane MAO, modified methylaluminoxane MMAO-3a, ethylaluminoxane EAO and isobutylaluminoxane IBAO; preferably, the cocatalyst is in the reaction: the molar ratio of the main catalyst is 500-2000:1, and the concentration of the main catalyst in the reaction kettle is 2.0-10.0 mu mol (calculated by chromium).
10. A process for the selective tetramerisation of ethylene, the process comprising the steps of:
(1) Heating the reaction kettle, vacuumizing, replacing by inert gas, and replacing by ethylene after cooling to normal temperature; preferably, the heating temperature of the reaction kettle in the step (1) is 120-150 ℃, more preferably 120-130 ℃; preferably, the time of the vacuumizing is 1-3 hours, more preferably 1.5-2 hours;
(2) Adding a solvent into a reaction kettle, adding a cocatalyst, adding a main catalyst, heating, and introducing ethylene to start reaction;
preferably, the reaction pressure in the step (2) is 1-10 MPa, more preferably 4-5 MPa; preferably, the reaction temperature is 50 to 80 ℃, more preferably 50 to 55 ℃; preferably, the reaction time is 30 to 120min, more preferably 30 to 60min.
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