CN106925348A - Catalyst and its application - Google Patents
Catalyst and its application Download PDFInfo
- Publication number
- CN106925348A CN106925348A CN201511021457.1A CN201511021457A CN106925348A CN 106925348 A CN106925348 A CN 106925348A CN 201511021457 A CN201511021457 A CN 201511021457A CN 106925348 A CN106925348 A CN 106925348A
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- Prior art keywords
- catalyst
- aluminium
- reaction
- catalyst according
- phenyls
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000005977 Ethylene Substances 0.000 claims abstract description 32
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 28
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 9
- 239000003426 co-catalyst Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 40
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- -1 isooctyl Chemical group 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 9
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 8
- OZKRURPNXOGYGD-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1 OZKRURPNXOGYGD-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical class ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 5
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical class CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 5
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- 150000004821 1,3-dichlorobenzenes Chemical class 0.000 claims description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical class CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 65
- 239000002904 solvent Substances 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 15
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 57
- 239000001257 hydrogen Substances 0.000 description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 14
- 238000010790 dilution Methods 0.000 description 14
- 239000012895 dilution Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- BUQMVYQMVLAYRU-UHFFFAOYSA-N 1,1,2,3-tetrachloropropane Chemical compound ClCC(Cl)C(Cl)Cl BUQMVYQMVLAYRU-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 0 *C(CC(I*)=N*)=N* Chemical compound *C(CC(I*)=N*)=N* 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DXJLFETWXVDMLH-UHFFFAOYSA-N CCC1=CC(=N)CC(=N)C1 Chemical class CCC1=CC(=N)CC(=N)C1 DXJLFETWXVDMLH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B01J35/19—
-
- 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
- B01J31/0231—Halogen-containing 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
- 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
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
- C07C2523/22—Vanadium
-
- 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
Abstract
The present invention relates to a kind of catalyst and its application, the catalyst is made up of chromium compounds a, the b of compound containing N, electron donor c, co-catalyst d, and four mol ratios of component are 1:2~10:8~100:40~2000；For being catalyzed ethylene oligomerization synthesis decene, carried out in atent solvent, in ethylene oligomerization autoclave, described catalyst components effective dose according to a certain ratio, catalyst preparation in situ is carried out in atent solvent, ethene is constantly passed through immediately, catalyst is fully contacted with ethene, generation oligomerisation reaction, the catalyst decene is selectively more than 50%.
Description
Technical field
The present invention relates to a kind of catalyst and its application, and in particular to synthesize the catalysis of decene for ethylene oligomerization
Agent.
Background technology
Used as a kind of olefin product with high added value, the weight of height is received in the synthesis of decene with application always
Depending on.Current domestic production decene, can only rely on wax destructive distillation method, and the method C10 yields are low, account for product
20% or so, impurity content is high, and starving；Foreign countries use ethylene oligomerization technology, Neng Gousheng
Decene is produced, but selectivity time is low, and highest accounts for 20% of product or so.The present invention is by changing catalyst ligand
And process conditions, can selectively improve decene does not have oligomer into 50%, and product.
A kind of ethylene oligomerisation catalyst composition, including the positive propionyl of chlorination 2- are disclosed in CN 104107723
Base -1,10- phenanthroline contracting amine iron, containing aluminum cocatalyst, the catalyst system and catalyzing is used for ethylene oligomerization, has
Oligomerisation reaction activity very high, overcomes technology prejudice of the art personnel on water, even if low
During aluminium/iron ratio, still with extraordinary activity, alpha-olefin selectivity is high, but C6~C10 alkene is accounted for altogether
51%.
A kind of chromium system catalyst system and catalyzing is reported in EP 0608447A, as the catalyst of ethylene oligomerization, wherein
Comprising one kind containing chromium compound, azole compounds, containing aluminum cocatalyst, halogen contained compound as accelerator,
The catalyst is higher to the selectivity of hexene -1, and can produce 3% decene.
In the ethylene oligomerization technique of W02004/05647, change part, octene content reaches 69%, hexene
Content is 10~20%, and decene content is 4%.
Not having a kind of ethylene oligomerisation catalyst at present can make ethylene selectivity oligomerisation synthesize decene, the present invention
The catalyst for synthesizing decene for ethylene oligomerization as described in claim 1, can be catalyzed ethylene oligomerization Gao Xuan
Selecting property synthesizes decene, and decene is selectively more than 50%.
The content of the invention
The purpose of the present invention be exploitation it is a kind of include a kind of chromium compounds a, the b of compound containing N, electron donor c,
Co-catalyst d is constituted, and the catalyst is used for ethylene oligomerization and synthesizes decene, makes chromium compounds in part and accelerator
In the presence of, unoccupied orbital is formed, be conducive to the coordination of ethylene molecule or alpha-olefin molecule, and β-H occur
Elimination reaction generates decene.The oligomer for not being found by-product in process of the test is produced.
The present invention provides a kind of catalyst, including following component：
Chromium compounds a, the b of compound containing N, electron donor c, co-catalyst d；
The mol ratio of a, b, c and d is 1:2~10:8~100:40~2000, more preferably
1:2~6:8~20:50~200.
Catalyst of the present invention, wherein, the chromium compounds a is preferably isooctyl acid chromium, chromium acetylacetonate
With one or more in 2- pyridine carboxylic acid chromium.
Catalyst of the present invention, wherein, the b of compound containing N, formula is preferably
Catalyst of the present invention, wherein, R1Preferably methyl, ethyl, isopropyl or the tert-butyl group；
R2Preferably phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,4,6- trimethylphenyls, neighbour
Ethylbenzene, an ethylbenzene, to ethylbenzene, 4- tert-butyl-phenyls, 2- isopropyl phenyls, 3- isopropyl phenyls,
Fluoro- 4 aminomethyl phenyl of 4- isopropyl phenyls, 2,6- diisopropyl phenyls, naphthyl, fluorophenyl, 2-, the fluoro- 5- of 2-
The bromo- 4- methyl of aminomethyl phenyl, 3- chlorphenyls, 2,6- dichlorophenyls, 2,4,6- trichlorophenyls, 2- bromophenyls, 2-
The bromo- 5- aminomethyl phenyls of phenyl, 2-, the bromo- 2,6- 3,5-dimethylphenyls of 4-, 4- methoxyphenyls or 2- methyl -4- methoxies
Base phenyl.
Catalyst of the present invention, wherein, the electron donor c is preferably 1,2- dichloro-benzenes, 1,3- bis-
One or more in chlorobenzene, 1,1,2- trichloroethanes, tert-butyl chloride and the chloropropanes of 1,1,2,3- tetra-.
Catalyst of the present invention, wherein, the co-catalyst d be preferably trimethyl aluminium, triethyl aluminum,
One or more in three n-butylaluminums, triisobutyl aluminium and aluminium diethyl monochloride.
The present invention also provides application of the above-mentioned catalyst in ethylene oligomerization synthesis decene.
A and b are added into flask, quantitative inertia is added and is demarcated thing, c and d are added to syringe
In, syringe is put into microwave radiometer has certain hour to take out, and adds into the flask equipped with a and b,
Flask is vacuumized at 40 DEG C, then adds 20mL solvents to dilute to it, and dilution is directly added into hydrogen shield
In reactor, it is passed through ethene and starts oligomerisation reaction.Reaction temperature be usually 40 DEG C~120 DEG C, preferably 65
DEG C~110 DEG C；Reaction pressure is 0.2MPa~4MPa, preferably 1MPa~4MPa；Reaction time is
0.1h~4h, preferably 0.3~1.5h.
Ethylene oligomerization reaction is mainly carried out in atent solvent.Selectable solvent includes alkane, aromatic hydrocarbons, halogen
For hydrocarbon, alkene or ionic liquid；Alkane is n-hexane, hexahydrotoluene, hexamethylene or heptane；Aromatic hydrocarbons
It is benzene,toluene,xylene or isopropylbenzene；Alkene is hexene -1 or octene-1.
Beneficial effects of the present invention：
There is no oligomer to produce in active high, decene selectivity height and accessory substance.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is premised on technical solution of the present invention
Under implemented, give detailed implementation method and process, but protection scope of the present invention be not limited to it is following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Embodiment 1
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add 2- pyridine carboxylic acid chromium 0.03mmol, N, N- di-o-tolyl -2,4- di-imidogen pentanes 0.06mmol；
Take 1,1,2,3- tetra- chloropropane 0.24mmol and triethyl aluminum 0.15mL (1.2mmol) with syringe, make a,
The mol ratio of b, c and d is 1:2:8:40.Syringe is put into microwave radiometer after 10min add it is anti-
Answer in bottle, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization reaction
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL toluene solvants are added under hydrogen shield, hydrogen shield are poured in kettle, 40 DEG C will be risen in reactor,
By in catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 3MPa is kept, at 60 DEG C
Lower reaction 1h.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 2
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add 2- pyridine carboxylic acid chromium 0.03mmol, N, N- di-o-tolyl -2,4- di-imidogen pentanes 0.3mmol；
1,1,2,3- tetra- chloropropane 0.48mmol and aluminium diethyl monochloride 0.4mL (3mmol) are taken with syringe, is made
The mol ratio of a, b, c and d is 1:10:8:100.Syringe is put into microwave radiometer after 10min plus
Enter in reaction bulb, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL toluene solvants are added under hydrogen shield, hydrogen shield are poured in kettle, 40 DEG C will be risen in reactor,
By in catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 3MPa is kept, at 60 DEG C
Lower reaction 1h.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 3
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add 2- pyridine carboxylic acid chromium 0.03mmol, N, N- di-o-tolyl -2,4- di-imidogen pentanes 0.12mmol；
Take 1,1,2,3- tetra- chloropropane 3mmol and aluminium diethyl monochloride 7.5mL (60mmol) with syringe, make a,
The mol ratio of b, c and d is 1:8:100:2000.Syringe is put into microwave radiometer after 10min plus
Enter in reaction bulb, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL toluene solvants are added under hydrogen shield, hydrogen shield are poured in kettle, 40 DEG C will be risen in reactor,
By in catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 3MPa is kept, at 60 DEG C
Lower reaction 1h.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 4
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Isooctyl acid chromium 0.03mmol, N, N- bis- is added to ethylbenzene -3,5- diimines in heptan 0.06mmol；With injection
Device takes 1,2- dichloro-benzenes 0.24mmol and trimethyl aluminium 0.36mL (3mmol), makes rubbing for a, b, c and d
You are than being 1:2:8:100.Syringe is put into microwave radiometer after 10min in adding reaction bulb, 40 DEG C
Under vacuumize, add 20mL hexamethylenes dilution it is standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL n-hexane solvents are added under hydrogen shield, hydrogen shield is poured in kettle, 40 will be risen in reactor
DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 3.5MPa is kept,
1h is reacted at 80 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 5
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add chromium acetylacetonate 0.03mmol, N, N- couple-(4- tert-butyl-phenyls) -3,5- diimines in heptan 0.06mmol；
1,3- dichloro-benzenes 0.3mmol and triethyl aluminum 0.72mL (6mmol) are taken with syringe, makes a, b, c
It is 1 with the mol ratio of d:2:10:200.Syringe is put into and adds reaction in microwave radiometer after 10min
In bottle, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL cyclohexane solvents are added under hydrogen shield, hydrogen shield is poured in kettle, 40 will be risen in reactor
DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 4MPa is kept,
0.5h is reacted at 100 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 6
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Adding isooctyl acid chromium 0.015mmol, chromium acetylacetonate 0.015mmol, N, N- be double-(4- tert-butyl-phenyls)
- 3,5- diimines in heptan 0.3mmol；1,1,2- trichloroethanes 0.24mmol and aluminium diethyl monochloride are taken with syringe
0.72mL (6mmol), the mol ratio for making a, b, c and d is 1:10:8:200.Syringe is put into
Added after 10min in microwave radiometer in reaction bulb, vacuumized at 40 DEG C, add 20mL hexamethylenes dilute
Release standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL cyclohexane solvents are added under hydrogen shield, hydrogen shield is poured in kettle, 40 will be risen in reactor
DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 4MPa is kept,
0.5h is reacted at 100 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 7
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Isooctyl acid chromium 0.03mmol, N, N- pair-(4- tert-butyl-phenyls) -2,6- dimethyl -3 are added, 5- is sub- in heptan two
Amine 0.3mmol；1,1,2- trichloroethanes 1.5mmol and triisobutyl aluminium 0.6mL (3mmol) are taken with syringe,
The mol ratio for making a, b, c and d is 1:10:50:100.Syringe is put into 10min in microwave radiometer
Add afterwards in reaction bulb, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL methyl cyclohexane alkane solvents are added under hydrogen shield, hydrogen shield is poured in kettle, will risen in reactor
To 40 DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, keeps pressure 2.5MPa,
1h is reacted at 110 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 8
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add chromium acetylacetonate 0.03mmol, N, the N- couple-diimine 0.12mmol of (2- isopropyl phenyls) -2,4- penta；
The chloropropane 1.5mmol of 1,2- dichloro-benzenes 1.5mmol, 1,1,2,3- tetra- and aluminium diethyl monochloride are taken with syringe
7.2mL (60mmol), the mol ratio for making a, b, c and d is 1:4:100:2000.Syringe is put into micro-
Added after 10min in wave emitter in reaction bulb, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes
It is standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
The solvent of 200mL hexenes -1 is added under hydrogen shield, hydrogen shield is poured in kettle, 40 will be risen in reactor
DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 2MPa is kept,
2h is reacted at 100 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 9
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add isooctyl acid chromium 0.015mmol, 2- pyridine carboxylic acid chromium 0.015mmol, N, N- pair-(2,6- diisopropyls
Phenyl) -2,6- dimethyl -3,5- diimines in heptan 0.3mmol；1,1,2,2- tetrachloroethanes 1.5mmol is taken with syringe
With three n-butylaluminum 3.6mL (30mmol), the mol ratio for making a, b, c and d is 1:10:50:1000.Will
Syringe is put into microwave radiometer after 10min in adding reaction bulb, is vacuumized at 40 DEG C, adds 20mL
Hexamethylene dilution is standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL octene-1 solvents are added under hydrogen shield, hydrogen shield is poured in kettle, 40 will be risen in reactor
DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 1.5MPa is kept,
2h is reacted at 110 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 10
1. the preparation of catalyst
2mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from through N2,
Add isooctyl acid chromium 0.03mmol, N, N- dinaphthyl -2,2,6,6- tetramethyl -3,5- diimines in heptan 0.3mmol；
The chloropropane 1.5mmol of 1,1,2,3- tetra-, trimethyl aluminium 0.54mL (7.5mmol), triethyl aluminum are taken with syringe
0.9mL (7.5mmol), the mol ratio for making a, b, c and d is 1:4:20:500.Syringe is put into microwave
Added after 10min in radiator in reaction bulb, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby
With.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL heptane solvents are added under hydrogen shield, hydrogen shield are poured in kettle, 40 DEG C will be risen in reactor,
By in catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 3MPa is kept, at 50 DEG C
Lower reaction 3h.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 11
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Isooctyl acid chromium 0.03mmol, N, N- pair-(4- tert-butyl-phenyls) -2,6- dimethyl -3 are added, 5- is sub- in heptan two
Amine 0.15mmol；Tert-butyl chloride 1.2mmol, 1,1,2- trichloroethanes 1.2mmol and three is taken with syringe
Aluminium isobutyl 0.36mL (3mmol), the mol ratio for making a, b, c and d is 1:6:40:100.By syringe
It is put into microwave radiometer after 10min in adding reaction bulb, is vacuumized at 40 DEG C, adds 20mL hexamethylenes
Alkane dilution is standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL methyl cyclohexane alkane solvents are added under hydrogen shield, hydrogen shield is poured in kettle, will risen in reactor
To 40 DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, keeps pressure 2.5MPa,
1h is reacted at 110 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 12
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add chromium acetylacetonate 0.015mmol, 2- pyridine carboxylic acid chromium 0.015mmol, N, N- dinaphthyl -2,2,6,6-
Tetramethyl -3,5- diimines in heptan 0.3mmol；1,2- dichloro-benzenes 1mmol, 1,1,2- trichloroethanes is taken with syringe
1mmol, 1,1,2,3- tetra- chloropropane 1mmol and three n-butylaluminum 3mL (15mmol), make a, b, c and d
Mol ratio be 1:10:100:500.Syringe is put into microwave radiometer and adds reaction bulb after 10min
In, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL heptane solvents are added under hydrogen shield, hydrogen shield are poured in kettle, 40 DEG C will be risen in reactor,
By in catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 3MPa is kept, at 50 DEG C
Lower reaction 3h.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 13
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Add chromium acetylacetonate 0.01mmol, 2- pyridine carboxylic acid chromium 0.02mmol, N, N- pair-(2- cumenes
Base) the diimine 0.12mmol of -2,4- penta；Tert-butyl chloride 3mmol, triethyl aluminum are taken with syringe
0.9mL (7.5mmol) and aluminium diethyl monochloride 0.54mL (4.5mmol), makes the mol ratio of a, b, c and d
It is 1:4:10:400.Syringe is put into microwave radiometer after 10min in adding reaction bulb, at 40 DEG C
Vacuumize, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
The solvent of 200mL hexenes -1 is added under hydrogen shield, hydrogen shield is poured in kettle, 40 will be risen in reactor
DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 2MPa is kept,
2h is reacted at 100 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Embodiment 14
1. the preparation of catalyst
Through N22mL ethylbenzene is added as internal standard in the 100mL reaction bulbs of the band stirring being sufficiently displaced from,
Adding isooctyl acid chromium 0.015mmol, chromium acetylacetonate 0.015mmol, N, N- be double-(4- tert-butyl-phenyls)
- 3,5- diimines in heptan 0.3mmol；1,1,2- trichloroethanes 0.24mmol, 1,1,2,3- tetrachloro third is taken with syringe
Alkane 0.24mmol, triethyl aluminum 0.9mL (7.5mmol) and aluminium diethyl monochloride 0.72mL (6mmol),
The mol ratio for making a, b, c and d is 1:10:16:700.Syringe is put into 10min in microwave radiometer
Add afterwards in reaction bulb, vacuumized at 40 DEG C, add the dilution of 20mL hexamethylenes standby.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and
200mL cyclohexane solvents are added under hydrogen shield, hydrogen shield is poured in kettle, 40 will be risen in reactor
DEG C, by catalyst addition kettle under hydrogen shield, ethene is then quickly passed through, pressure 4MPa is kept,
0.5h is reacted at 100 DEG C.
Lowered the temperature with frozen water after reaction, release, with the acidic ethanol terminating reaction of mass fraction 10%.Result is shown in
Subordinate list 1.
Subordinate list 1
It can be seen from Table 1 that：The catalyst chromium compound a, the b of compound containing N, electron donor c,
Co-catalyst d, four components can be catalyzed ethylene oligomerization under certain proportioning, and decene selectively may be used in product
Up to 63%, activity up to 11.8 × 106g/molCr.h。
Claims (10)
1. a kind of catalyst, including following component：
Chromium compounds a, the b of compound containing N, electron donor c, co-catalyst d；
The mol ratio of a, b, c and d is 1:2~10:8~100:40~2000.
2. catalyst according to claim 1, it is characterised in that the chromium compounds a be isooctyl acid chromium,
One or more in chromium acetylacetonate and 2- pyridine carboxylic acid chromium.
3. catalyst according to claim 1 and 2, it is characterised in that the b of compound containing N,
Formula is
4. catalyst according to claim 3, it is characterised in that R1It is methyl, ethyl, isopropyl
Or the tert-butyl group；
R2It is phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,4,6- trimethylphenyls, adjacent ethylbenzene
Base, an ethylbenzene, to ethylbenzene, 4- tert-butyl-phenyls, 2- isopropyl phenyls, 3- isopropyl phenyls, 4-
Fluoro- 4 aminomethyl phenyl of isopropyl phenyl, 2,6- diisopropyl phenyls, naphthyl, fluorophenyl, 2-, the fluoro- 5- first of 2-
The bromo- 4- methylbenzenes of base phenyl, 3- chlorphenyls, 2,6- dichlorophenyls, 2,4,6- trichlorophenyls, 2- bromophenyls, 2-
The bromo- 5- aminomethyl phenyls of base, 2-, the bromo- 2,6- 3,5-dimethylphenyls of 4-, 4- methoxyphenyls or 2- methyl -4- methoxyl groups
Phenyl.
5. the catalyst according to claim 1 or 2 or 4, it is characterised in that the electron donor c,
For in 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,1,2- trichloroethanes, tert-butyl chloride and the chloropropanes of 1,1,2,3- tetra-
One or more.
6. catalyst according to claim 3, it is characterised in that the electron donor c is 1,2- bis-
One kind in chlorobenzene, 1,3- dichloro-benzenes, 1,1,2- trichloroethanes, tert-butyl chloride and the chloropropanes of 1,1,2,3- tetra-
Or it is several.
7. the catalyst according to claim 1 or 2 or 4 or 6, it is characterised in that the co-catalysis
Agent d is in trimethyl aluminium, triethyl aluminum, three n-butylaluminums, triisobutyl aluminium and aluminium diethyl monochloride
Plant or several.
8. catalyst according to claim 3, it is characterised in that the co-catalyst d is trimethyl
One or more in aluminium, triethyl aluminum, three n-butylaluminums, triisobutyl aluminium and aluminium diethyl monochloride.
9. catalyst according to claim 5, it is characterised in that the co-catalyst d is trimethyl
One or more in aluminium, triethyl aluminum, three n-butylaluminums, triisobutyl aluminium and aluminium diethyl monochloride.
10. application of the catalyst described in claim 1~9 any one in ethylene oligomerization synthesis decene.
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| US20040147389A1 (en) * | 2001-05-17 | 2004-07-29 | Green Simon Michael | Polymerisation catalyst |
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| CN102443082A (en) * | 2010-10-15 | 2012-05-09 | 中国科学院上海有机化学研究所 | Novel chromium catalyst and application thereof in catalysis of olefin oligomerization and polymerization |
| CN103044181A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Method for preparing octylene-1 by ethylene tetramerization reaction |
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| US20040147389A1 (en) * | 2001-05-17 | 2004-07-29 | Green Simon Michael | Polymerisation catalyst |
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