CN107282116A - Ethylene oligomerization carbon monoxide-olefin polymeric and its application - Google Patents
Ethylene oligomerization carbon monoxide-olefin polymeric and its application Download PDFInfo
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- CN107282116A CN107282116A CN201610196108.1A CN201610196108A CN107282116A CN 107282116 A CN107282116 A CN 107282116A CN 201610196108 A CN201610196108 A CN 201610196108A CN 107282116 A CN107282116 A CN 107282116A
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- Prior art keywords
- carbon monoxide
- olefin polymeric
- ethylene oligomerization
- alkyl
- aluminum
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 27
- 239000005977 Ethylene Substances 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- -1 C1~C6Alkyl Chemical class 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003426 co-catalyst Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001399 aluminium compounds Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims 1
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- KUVXJBSVPBXHEK-UHFFFAOYSA-N octylaluminum Chemical compound CCCCCCCC[Al] KUVXJBSVPBXHEK-UHFFFAOYSA-N 0.000 claims 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical class CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 abstract 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 235000010210 aluminium Nutrition 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- BEHYHCBDZZQSBV-UHFFFAOYSA-N 2,3-dimethyl-1,10-phenanthroline Chemical compound C1=CC=NC2=C(N=C(C(C)=C3)C)C3=CC=C21 BEHYHCBDZZQSBV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of carbon monoxide-olefin polymeric for ethylene oligomerization reaction process; replace 2 propionos 1 including the major catalyst chlorination shown in formula (I); 10 phenanthroline, 2,6 diethylanilines of contracting close iron (II) complex, containing aluminum cocatalyst and TBHP.
Description
Technical field
The present invention relates to ethylene oligomerization field, and in particular to a kind of catalyst group for ethylene oligomerization reaction process
Compound.
Background technology
Linear alpha-alkene is in ethylene comonomer, synthesis of surfactant intermediate, plasticizer alcohol, synthesis profit
The field such as lubricating oil and oil dope has a wide range of applications.In recent years, continuing to develop with polyolefin industry,
To the demand rapid development of alpha-olefin in world wide.The alpha-olefin of the overwhelming majority is by acetate oligomerization system at present
For what is obtained.Catalyst used in ethylene oligomerization method mainly has nickel system, chromium system, zirconium system and aluminium system etc., in recent years,
Brookhart groups (Brookhart, M et al, J.Am.Chem.Soc., 1998,120,7143-7144；
WO99/02472,1999), Gibson groups (Gibson, V.C.et al, Chem.Commun., 1998,
849-850；Chem.Eur.J., 2000,2221-2231) some Fe (II) and Co (II) tridentate pyridine is found respectively
Imine composition can be catalyzed ethylene oligomerization, and not only the catalytic activity of catalyst is very high, and the selectivity of alpha-olefin
Also it is very high.
Today, it is generally accepted that water, oxygen are very unfavorable, CN200810111717.8 to ethylene oligomerization reaction process
A kind of method of ethylene oligomerization is disclosed, progress in the environment of anhydrous and oxygen-free, therefore current second is strict controlled in
Alkene oligomerisation reaction is very harsh to technological requirement, causes the reaction of oligomerisation reaction technique to trigger and repeated all non-
Constant.
The content of the invention
For deficiency of the prior art, inventor has been carried out extensively and profoundly in ethylene oligomerization with catalyst field
Research, it has surprisingly been found that ethene is luxuriant and rich with fragrance including major catalyst chlorination substitution -2- propionos -1,10- shown in formula (I)
Cough up quinoline contracting -2,6- diethylanilines and close iron (II) complex, the catalyst containing aluminum cocatalyst and TBHP
Composition effect is lower to carry out oligomerisation reaction, and on the contrary with higher oligomerisation reaction activity, and oligomerisation reaction triggers fast
Speed, operate steadily, it is reproducible；So as to overcome the technology prejudice of those skilled in the art, expectation is achieved
Less than technique effect.
According to an aspect of the invention, there is provided a kind of ethylene oligomerization carbon monoxide-olefin polymeric, the composition
Iron (II) is closed including the major catalyst substitution -2- propiono -1,10- phenanthroline contracting -2,6- diethylanilines shown in formula (I) to match somebody with somebody
Compound, containing aluminum cocatalyst and TBHP：
In formula (I), R1-R6It is each independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
The carbon monoxide-olefin polymeric provided according to the present invention, adds TBHP, on the contrary with higher second
Alkene oligomerisation reaction activity, the selectivity of alpha-olefin is high.
In the present invention, term " C1-C6Alkyl " refers to saturated straight chain or branched-chain hydrocarbons containing 1-6 carbon atom
Base.It is used as C1-C6Alkyl, it can be mentioned that methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
Sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl；Particularly preferred methyl,
Ethyl, n-propyl and isopropyl.
In the present invention, term " C1-C6Alkoxy " refers to above-mentioned C1-C6Alkyl is connected with an oxygen atom
The group arrived.It is used as C1-C6Alkoxy, it can be mentioned that methoxyl group, ethyoxyl, positive propoxy, isopropoxy,
N-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, positive hexyloxy and
Secondary hexyloxy；Particularly preferred methoxyl group and ethyoxyl.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferred fluorine, chlorine and bromine.
In the present invention, the R1-R6The substituent that can be related to for above-mentioned term of selection in any combination.
Wherein, in a preferred embodiment of the present invention, the R in the major catalyst1-R6Select independently of one another
From hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro；Its
In, R1-R6Selection can certainly be above-mentioned group any combination.One in above-mentioned composition is specific
In embodiment, the R in the major catalyst3And R4For methyl, and R1, R2, R5, R6It is hydrogen.
It is described to be selected from aikyiaiurnirsoxan beta and alkyl containing aluminum cocatalyst in a preferred embodiment in the present invention
At least one of aluminium compound.In the present invention, the formula of the alkyl aluminum compound is AlRnXm, its
Middle R is each independently straight or branched C1-C8Alkyl；X is respectively halogen, preferably chlorine or bromine；N is 1~3
Integer, m be 0~2 integer, and m+n be equal to 3.The instantiation bag of described alkyl aluminum compound
Include but be not limited only at least one of following compounds：It is trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, three different
Butyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, such as triethyl aluminum.
In the present invention, the aikyiaiurnirsoxan beta is C1-C4Alkylaluminoxane, wherein C1-C4Alkyl is straight or branched
Alkyl.The example of the aikyiaiurnirsoxan beta is included but are not limited to：MAO, modified methylaluminoxane, ethyl
At least one of aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide；Such as MAO.
In a preferred embodiment of the present invention, in the aluminium in the co-catalyst and the major catalyst
The mol ratio of iron is 30:1 to 900:1, such as 100:1 to 700:1, and for example 148:1 to 196:1.In combinations thereof
In one specific embodiment of thing, the mol ratio of aluminium and the iron in the major catalyst in the co-catalyst is
196:1 to 500:1.In the relatively low molar ratio range of offer, the ethylene oligomerization in the composition is lived
Property is still higher.
In a preferred embodiment in the present invention, in the carbon monoxide-olefin polymeric, TBHP
Weight content be 5~1750ppm, such as 25~1750ppm, such as 35~1300ppm.In a specific example
In, the weight content of the TBHP is 100-1300ppm.Under the conditions of preferably, the uncle
The weight content of butylhydroperoxide is 250~1000ppm, such as 250-500ppm.Described tert-butyl hydroperoxide
In the range of hydrogen content, the carbon monoxide-olefin polymeric has higher ethylene oligomerization activity.
In a preferred embodiment of the present invention, machine solvent is further includeed in the composition, namely
The composition includes the major catalyst chlorination 2- propiono -1,10- phenanthroline contracting -2,6- diethylbenzenes shown in formula (I)
Amine closes iron (II) complex, containing aluminum cocatalyst, TBHP and organic solvent.In the present invention, institute
Weight of the weight content based on organic solvent of TBHP is stated to be calculated.For example, working as the tert-butyl group
The weight content of hydrogen peroxide is 5~1750ppm, the i.e. organic solvent based on 1g, containing 5~1750 in composition
×10-6G TBHP.The organic solvent is organic solvent conventional in the art, and it is specific real
Example is included but are not limited to：Toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and dichloro
The mixture of at least one of methane, such as toluene, dimethylbenzene or toluene and dimethylbenzene.
In when the composition of the present invention is used to produce, the consumption of the major catalyst and co-catalyst can be according to life
The process conditions during concrete application such as production scale and production equipment are selected.The one of the carbon monoxide-olefin polymeric
In individual specific embodiment, using the volume of the composition comprising organic solvent as calculating benchmark, the major catalyst
Content is 2~500 μm of ol/L (i.e. containing 2~500 × 10 in the composition based on 1L, composition-6Mol's sponsors
Agent), such as 20~100 μm ol/L, such as 50 μm ol/L.
According to another aspect of the present invention, a kind of ethylene oligomerization method is additionally provided.Above-mentioned catalyst combination
Thing can be applied to the oligomerisation of ethene, and it is anti-that the ethene carries out ethylene oligomerization in the presence of above-mentioned carbon monoxide-olefin polymeric
Should.One of specific embodiment may include following steps：(1) dried by high temperature, vacuum displacement etc.
Operation enters line replacement to reaction system, it is ensured that anhydrous and oxygen-free in reaction system；(2) using ethene to reactant
It is, into line replacement, reaction system is in ethene environment；(3) carbon monoxide-olefin polymeric is added in reaction system,
Including major catalyst, co-catalyst and TBHP (and organic solvent), it is sufficiently stirred for；(4)
It is passed through ethene and starts oligomerisation reaction, when carrying out oligomerisation reaction, can be carried out in for example following condition：Keep
Reaction pressure be 0.1 to 30MPa, and reaction temperature be -20 to 150 DEG C at, the reaction time can for 30 to
100min；(5) reaction is stopped after reaction a period of time.Reaction product is taken to carry out (GC) analysis with gas-chromatography.
In the present invention, after the major catalyst and co-catalyst described in step (3) first can be dissolved with organic solvent
Add reaction system.The oligomerisation reaction process, major catalyst and co-catalyst are blended under ethene atmosphere
Carry out.The temperature of the oligomerisation reaction is -20 to 150 DEG C, such as 0~80 DEG C.Under the conditions of preferably, scope
Temperature is -20 to 40 DEG C, such as 5 to 35 DEG C.The pressure of the reaction is 0.1~30MPa, with ethylene pressure
Raise oligomerization activity rise.
Ethylene oligomerization is carried out using carbon monoxide-olefin polymeric of the present invention, the ethylene oligomerization product of acquisition includes
C4、C6、C8、C10、C12、C14、C16、C18、C20、C22Deng；The selectivity of alpha-olefin can reach
More than 96%.After ethylene oligomerization reaction terminates, GC analyses are carried out.As a result show, oligomerization activity is reachable
107g·mol(Fe)-1·h-1More than.In addition, the ethanol that remaining reactant mixture is acidified with 5% watery hydrochloric acid
Solution is neutralized, and does not obtain polymer.
The carbon monoxide-olefin polymeric provided according to the present invention, ethene is including the major catalyst chlorination substitution shown in formula (I)
- 2- propiono -1,10- phenanthroline contracting -2,6- diethylanilines close iron (II) complex, containing aluminum cocatalyst and the tert-butyl group
The composition effect of hydrogen peroxide (and organic solvent) is lower to carry out oligomerisation reaction, on the contrary with higher oligomerisation
Reactivity, the selectivity of alpha-olefin is high, and oligomerisation reaction trigger it is rapid, operate steadily, it is reproducible.Root
According to the present invention, under the conditions of low-down Al/Fe ratios, still with preferable oligomerisation reaction activity.Root
According to the present invention, when the reaction is performed at a lower temperature, still with high oligomerisation reaction activity.According to this hair
It is bright, the technology prejudice of those skilled in the art is overcome, unexpected technique effect is achieved.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated and explanation, but does not constitute to the present invention's
Any limitation.
Embodiment 1
Ethylene oligomerization reacts, and specifically includes following steps：(1) dried by high temperature, the operation pair such as vacuum displacement
Reaction system enters line replacement, it is ensured that anhydrous and oxygen-free in reaction system；(2) reaction system is put using ethene
Change, reaction system is in ethene environment；(3) TBHP and toluene solvant are added in a kettle.,
1.37ml triethyl aluminums toluene solution (concentration is 715 μm of ol/ml) is added, 2ml chlorination -2- propionos -5,6- are added
Dimethyl -1,10- phenanthroline contracting -2,6- diethylanilines close iron (II) complex (i.e. R3And R4For methyl, and R1、
R2、R5And R6Be hydrogen) toluene solution (concentration be 2.5 μm ol/ml) after, it is 100ml to make total composition,
Wherein, the weight using organic solvent (toluene) is calculating benchmark, and the weight content of TBHP is
25ppm, Al/Fe=196, after being sufficiently stirred for, are passed through ethene and start oligomerisation reaction；(4) holding ethylene pressure is
1MPa and reaction temperature are to react 30 minutes at 30 DEG C；(7) stop reaction, take out a small amount of reaction product gas
Phase chromatogram carries out (GC) analysis：Oligomerization activity is 0.94 × 107g·mol(Fe)-1·h-1, oligomer content is respectively
C439.19%, C6~C1045.46%, C6~C1859.37% (wherein containing linear alpha-alkene 96.4%), C20~
C281.44%.The ethanol solution that remaining mixture is acidified with 5% hydrochloric acid is neutralized, and does not obtain polymer.
Analysis result is shown in Table 1.
Embodiment 2
Be the same as Example 1, difference is, the weight content of TBHP is 100ppm.Data are shown in
Table 1.
Embodiment 3
Be the same as Example 1, difference is, the weight content of TBHP is 250ppm.Data are shown in
Table 1.
Embodiment 4
Be the same as Example 1, difference is, the weight content of TBHP is 500ppm.Data are shown in
Table 1.
Embodiment 5
Be the same as Example 1, difference is, the weight content of TBHP is 1000ppm.Data
It is shown in Table 1.
Embodiment 6
Be the same as Example 1, difference is, the weight content of TBHP is 1300ppm.Data
It is shown in Table 1.
Embodiment 7
Be the same as Example 1, difference is, the weight content of TBHP is 1750ppm, data
It is shown in Table 1.
Embodiment 8
Be the same as Example 1, difference is, the weight content of TBHP is 500ppm, reaction temperature
Spend for 0 DEG C.Data are shown in Table 1.
Embodiment 9
Be the same as Example 1, difference is, the weight content of TBHP is 500ppm, reaction temperature
Spend for -10 DEG C.Data are shown in Table 1.
Embodiment 10
Be the same as Example 1, difference is, the weight content of TBHP is 500ppm, reaction temperature
Spend for -20 DEG C.Data are shown in Table 1.
Embodiment 11
Be the same as Example 1, difference is, the weight content of TBHP is 500ppm, reaction temperature
Spend for 40 DEG C.Data are shown in Table 1.
Embodiment 12
Be the same as Example 1, difference is, the weight content of TBHP is 500ppm,
Al/Fe=500.Data are shown in Table 1.
Comparative example 1
Be the same as Example 1, difference is, without TBHP in composition.Data are shown in Table 1.
Table 1
It can be seen from the data in Table 1 that the carbon monoxide-olefin polymeric provided according to the present invention, ethene is including formula (I)
Shown major catalyst chlorination substitution -2- propiono -1,10- phenanthroline contracting -2,6- diethylanilines close iron (II) and coordinated
Thing, the lower progress oligomerisation reaction of composition effect containing aluminum cocatalyst, TBHP and organic solvent,
There is higher oligomerisation reaction activity on the contrary, the selectivity of alpha-olefin is high, and oligomerisation reaction triggers rapid, operation
Steadily, it is reproducible.According to the present invention, under the conditions of low-down Al/Fe ratios, still with preferable
Oligomerisation reaction activity.According to the present invention, when the reaction is performed at a lower temperature, still with high oligomerisation
Reactivity.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and in without departing substantially from scope and spirit of the present invention to the present invention progress
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, on the contrary, to can be extended to other all with identical function by the present invention
Methods and applications.
Claims (10)
1. a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including the major catalyst chlorination substitution -2- propionyl shown in formula (I)
Base -1,10- phenanthroline contracting -2,6- diethylanilines close iron (II) complex, containing aluminum cocatalyst and tert-butyl hydroperoxide
Hydrogen：
In formula, R1~R6It is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the carbon monoxide-olefin polymeric,
The weight content of TBHP is 5~1750ppm, preferably 100~1300ppm, is more preferably
250~1000ppm, most preferably 250~500ppm.
3. carbon monoxide-olefin polymeric according to claim 1 or 2, it is characterised in that in the co-catalyst
The mol ratio of aluminium and iron in major catalyst is 30:1 to 900:1, preferably 100:1 to 700:1, more preferably 196:1
To 500:1.
4. according to any described carbon monoxide-olefin polymeric in claim 1-3, it is characterised in that the main catalytic
R in agent1-R6Be each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine,
Methoxyl group, ethyoxyl and nitro；It is preferred that R3And R4For methyl, and R1、R2、R5And R6It is hydrogen.
5. the carbon monoxide-olefin polymeric according to any one in claim 1-4, it is characterised in that described to contain
Aluminum cocatalyst is selected from least one of aikyiaiurnirsoxan beta and alkyl aluminum compound.
6. the carbon monoxide-olefin polymeric according to claim 5, it is characterised in that the alkyl aluminum compound
Formula be AlRnXm, wherein R is each independently straight or branched C1-C8Alkyl；X is halogen, preferably
Chlorine or bromine；N is 1~3 integer, and m is 0~2 integer, and m+n is equal to 3；Preferably, the alkane
Base aluminium compound is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three
At least one of octyl aluminum, diethylaluminum chloride and ethylaluminium dichloride.
7. the carbon monoxide-olefin polymeric according to claim 5 or 6, it is characterised in that the aikyiaiurnirsoxan beta is
C1-C4Alkylaluminoxane, wherein C1-C4Alkyl is the alkyl of straight or branched；Preferably, the aikyiaiurnirsoxan beta choosing
From at least one of MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide.
8. the carbon monoxide-olefin polymeric according to any one in claim 1-7, it is characterised in that described to have
Machine solvent is in toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and dichloromethane
It is at least one.
9. carbon monoxide-olefin polymeric according to claim 8, it is characterised in that the carbon monoxide-olefin polymeric
In, using the volume of composition as calculating benchmark, the content of the major catalyst is 2~500 μm of ol/L, preferably
20~100 μm of ol/L.
10. a kind of ethylene oligomerization method, ethene carbon monoxide-olefin polymeric described in any one in claim 1-9
Catalytic action under carry out oligomerisation reaction, the temperature of preferably described oligomerisation reaction is -20 to 150 DEG C, preferably -20
To 40 DEG C.
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| CN104447161A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
| WO2015148496A1 (en) * | 2014-03-26 | 2015-10-01 | E. I. Du Pont De Nemours And Company | PROCESS FOR MANUFACTURING LINEAR α-OLEFINS |
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| CN104447161A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
| WO2015148496A1 (en) * | 2014-03-26 | 2015-10-01 | E. I. Du Pont De Nemours And Company | PROCESS FOR MANUFACTURING LINEAR α-OLEFINS |
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