CN103374084B - Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation and application thereof - Google Patents
Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation and application thereof Download PDFInfo
- Publication number
- CN103374084B CN103374084B CN201210109275.XA CN201210109275A CN103374084B CN 103374084 B CN103374084 B CN 103374084B CN 201210109275 A CN201210109275 A CN 201210109275A CN 103374084 B CN103374084 B CN 103374084B
- Authority
- CN
- China
- Prior art keywords
- transition metal
- tetrahydrofuran
- magnesium chloride
- late transition
- metal catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 48
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910001629 magnesium chloride Inorganic materials 0.000 title claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- -1 tetrahydrofuran compound Chemical class 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011949 solid catalyst Substances 0.000 claims abstract description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000005507 spraying Methods 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 239000012452 mother liquor Substances 0.000 claims description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 8
- FIFKDOUCTJYHLV-UHFFFAOYSA-L [Ni](Br)Br.C1=CC=CC=2C(C3=CC=CC=C3C(C12)=N)=N Chemical compound [Ni](Br)Br.C1=CC=CC=2C(C3=CC=CC=C3C(C12)=N)=N FIFKDOUCTJYHLV-UHFFFAOYSA-L 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- HRGXHRPMGDCKQM-UHFFFAOYSA-L dichlorocobalt;pyridine Chemical compound Cl[Co]Cl.C1=CC=NC=C1 HRGXHRPMGDCKQM-UHFFFAOYSA-L 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002002 slurry Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004711 α-olefin Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 238000012685 gas phase polymerization Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000001694 spray drying Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 238000003756 stirring Methods 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 238000010792 warming Methods 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 13
- 235000011147 magnesium chloride Nutrition 0.000 description 13
- 229960002337 magnesium chloride Drugs 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 230000026030 halogenation Effects 0.000 description 10
- 238000005658 halogenation reaction Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000002815 homogeneous catalyst Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 229940091250 magnesium supplement Drugs 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002681 magnesium compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- ZSGJKBKUYXDVIE-UHFFFAOYSA-N CC(C)C[Mg] Chemical compound CC(C)C[Mg] ZSGJKBKUYXDVIE-UHFFFAOYSA-N 0.000 description 1
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 description 1
- KKUZFMJIXIFTND-UHFFFAOYSA-N CCCCCC[Mg] Chemical compound CCCCCC[Mg] KKUZFMJIXIFTND-UHFFFAOYSA-N 0.000 description 1
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 150000002899 organoaluminium compounds Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation and application thereof; in an electron donor tetrahydrofuran compound, reacting magnesium chloride with a late transition metal complex to prepare a matrix; mixing the obtained matrix with nano-scale silicon dioxide carrier particles to obtain a suspension; and carrying out spray drying on the obtained suspension to obtain a solid catalyst component, wherein the molar ratio of the magnesium chloride to the silicon dioxide to the tetrahydrofuran is as follows: 0.1-1: 0.1-2: 5-20; in the loaded late transition metal catalyst, the weight content of the central metal M is 0.01-5%; the catalyst is used for catalyzing the copolymerization reaction of ethylene and high-grade alpha-olefin, has high copolymerization activity, obtains resin powder with good particle form and high bulk density, and can be suitable for slurry polymerization or gas phase polymerization of ethylene.
Description
Technical field
The present invention relates to a kind of magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst for ethene gas-phase polymerization or copolymerization technology and preparation thereof, and the application of this catalyzer in ethene gas-phase polymerization or copolymerization.
Background technology
Late transition metal catalyst for olefin polymerization refers to the catalyst system that the coordination compound of rear transition metal nickel, palladium, iron, cobalt etc. and alkylaluminium cpd form.Rear transition metal is commonly used by people for the research of olefinic polymerization very early, but is inclined to because rear transition metal has stronger β-H to eliminate, and thus most of late transition metal catalyst is only applicable to dimerization or the oligomerisation of alkene, can not get the olefin polymer of high molecular.People once attempted using rear transition metal catalysis in olefine polymerization, but all do not show activity high as IV and V race catalyst system, so they are mainly used in the oligomerisation of alkene and the polyreaction of diolefin, as the acetate oligomerization system linear alpha-alkene technique (SHOP) of Shell company.
1996, DuPont company have submitted the patent application that portion reaches new type polyolefin catalyzer (nickel, the palladium) technology of 500 pages, causes the extensive concern in olefin coordination polymerization field.The outstanding feature of this diimine-nickel (or palladium) catalyzer is without under comonomer existent condition, directly can prepare the polyvinyl resin of highly-branched degree by catalyzed ethylene polymerization.This is the catalyzer of first case rear transition metal for vinyl polymerization.Within 1998, on the basis of alpha-diimine Ni (II) and Pd (II) catalyzer, DuPont company supports that the Englishize scholar Gibson under lower Americanized scholar Brookhart and the support of BP company has independently found a class Novel iron and cobalt olefin polymerization catalysis separately.This kind of catalyzer has that synthesis is simple, yield is high, production cost is low, catalysis in olefine polymerization active advantages of higher weak to the susceptibility of oxygen and polar monomer, and the polyethylene of preparation has wider relative molecular weight distribution than the polyethylene using metallocene catalyst to prepare.Suitable, even higher with the activity of metallocene to the activity of vinyl polymerization.This kind of Novel iron and cobalt catalyst also have activity to propylene polymerization, and through molecular designing, be specially adapted to acetate oligomerization system linear alpha-alkene, the primary product of oligomerisation is 1-hexene, the long-chain olefins such as 1-octene or 1-decene, the selectivity of alpha-olefin is higher than 99%, and its activity has exceeded current other type catalyst for the production of alpha-olefin.Such catalyzer at low temperatures, also can catalysis alpha-olefin living polymerization.Since the discovery report that Brookhart professor and Gibson teach, attract the extensive concern of various countries researchist immediately, many scientists are also on the basis of two professors research work, synthesize many novel tridentate ligand rear transition metal iron, cobalt complex, and the factor affecting such catalyzer has been conducted in-depth research.The discovery of Brookhart professor is after Kaminsky finds that methylaluminoxane realizes metallocene catalysis olefinic polymerization, at the another new breakthrough of polyolefin field.This shows that new olefin polymerization catalysis need not be confined to traditional IVB race metal.For the polyolefine material that low price production application is wider provides another kind of possible method.
The MAO consumption that will reach needed for high reactivity due to homogeneous phase late transition metal catalyst is large, production cost is high, and the polymkeric substance obtained is amorphous, cannot use on widely used slurry process or gas phase polymerization technique, the effective way overcoming the problems referred to above is exactly supported for solubility late transition metal catalyst process is made the catalyzer of loading type.
At present, in the supported research of late transition metal catalyst, everybody adopts the silica gel with good particle form to be carrier substantially, as Keng-YuShih uses the silica gel activating Fe series catalysts of a kind of load aluminum alkyls in WO01/32723, aluminum alkyls can be used for promotor, there is good catalytic activity.Although for the research report also more (PCTInt.Appl.99/21898 of magnesium chloride compound load single site catalysts; US6455647; J.Mol.Catal.A2002,188,123; PCTInt.Appl.2004/078804), but the cost of carrier preparation and catalyst cupport is high, and carrier particle shape is poor, uncontrollable; Although use spherical magnesium chloride the catalyzer of proof load can have good particle form, containing components such as alcohol, water, alkoxyl groups in carrier, carrier preparation is complicated, and above shortcoming limits the industrial application of magnesium chloride load single site catalysts.Chinese patent 200910078595.1 provides a kind of spray-dired method of employing and prepares magnesium chloride support, then carrier is after the process such as heating, vacuum-drying, loaded late transition metal complex compound again, preparation method's also more complicated of this carrier, is unsuitable for suitability for industrialized production.
Summary of the invention
The object of the invention is to provide a kind of spherical magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst and Synthesis and applications thereof, has good particle form with magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst that this method obtains.Above-mentioned supported late transition metal catalyst is used for vinyl polymerization or copolymerization, with common aluminum alkyls as promotor, high polymerization activity can be had.
The preparation method of a kind of magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst of the present invention, comprises the steps:
(1) preparation of parent: in electron donor compound, carries out reaction by magnesium chloride and late transition metal complex and prepares parent;
(2) preparation of complex carrier: the parent of step (1) gained and the blending of nanometer grade silica carrier particle are obtained suspension;
(3) spray shaping: the suspension that step (2) obtains is carried out spraying dry and obtains ingredient of solid catalyst;
Magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) consumption mol ratio is: 0.1 ~ 1: 0.1 ~ 2: 5 ~ 20.
Described magnesium compound can be halogenated magnesium compound.Type for halogenated magnesium compound of the present invention can comprise with Types Below: magnesium dihalide compound is as magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide; Halogenated alkyl magnesium compound is as methylmagnesiumhalide, ethyl-magnesium-halide, halogenation propyl group magnesium, butyl Grignard reagent, halogenation isobutyl-magnesium, halogenation hexyl magnesium and halogenation amyl group magnesium; Halogenated alkoxy magnesium compound is as halogenation magnesium methylate, halogenation magnesium ethylate, halogenation isopropoxy magnesium, halogenation butoxy magnesium and halogenation octyloxy magnesium; Halogen aryloxy magnesium is as halogenation phenoxy group magnesium and halogenated methyl phenoxy group magnesium.These magnesium compounds can single compound or with two or multiple compounds form of mixtures use.The preferred magnesium dichloride of described magnesium compound.
The structure of described late transition metal complex is such as formula shown in I or II:
The structure of I iron complex
Wherein: R
1~ C
3for alkyl, alkoxyl group, phenoxy group, phenmethyl, halogen etc.; M is Fe, Co.The synthesis of the metal complexes shown in general formula I is standby according to WO9827124, WO9830612 patent system.
The structure of II late transition metal complex
Wherein: R
1~ R
5for alkyl, alkoxyl group, phenoxy group, phenmethyl, halogen etc.; M is nickel, palladium etc.The synthesis of the metal complexes shown in general formula I I is prepared according to the method for patent WO9623010.
In the late transition metal catalyst of load, the weight content of central metal M is generally 0.01 ~ 5%, is preferably 0.1 ~ 1%.
Activator component is organo-aluminium compound, and its general formula is AlR '
nx
3-n, in formula R ' for hydrogen or carbonatoms be the alkyl of 1 ~ 20, X is halogen, and n is the number of 1 < n≤3.Be preferably trimethyl aluminium or triethyl aluminum.
The catalyzer adopting supported late transition metal catalyst method of the present invention to prepare can be used on different polymerization processs, as vapour phase polymerization and slurry polymerization etc.Can be used for all polymerizations or the copolymerization of alkene, be specially adapted to the copolymerization of ethylene homo conjunction or ethene and other alpha-olefin, wherein alpha-olefin adopts propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
The temperature of supported late transition metal catalyst when being polymerized is 0 DEG C ~ 100 DEG C, is preferably 60 DEG C ~ 90 DEG C.Polymerization pressure is 0.1 ~ 10.0MPa, preferably 0.5 ~ 2.0MPa.
The present invention compared with prior art has the following advantages:
(1) loaded late transition metal catalyst preparation method of the present invention is simple, and the granules of catalyst form obtained is good, and catalyst particle size is adjustable.
(2) catalyzer prepared in supported late transition metal catalyst method of the present invention with common aluminum alkyls as promotor, can have very high vinyl polymerization catalytic activity.
(3) catalyzer prepared in supported late transition metal catalyst method of the present invention obtains resin powder for olefinic polymerization and has good particle form, and tap density is high, goes for slurry process and vapor phase process polymerization technique.
(4) catalyzer prepared in supported late transition metal catalyst method of the present invention has good hydrogen response energy and copolymerization performance.
Embodiment
Embodiment 1
1. under the preparation nitrogen protection of two [1-(2,6-dimethyl benzene imines) ethyl] pyridyl iron dichloride of supported catalyst 2,6-; in the reactor of 250mL; add Magnesium Chloride Anhydrous 4.868g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.510g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-dimethyl benzene imines) ethyl] the pyridyl iron dichloride 0.1937g of iron homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spray drying unit after stirring is carried out spraying dry, inlet temperature is set to 182 DEG C, Outlet Temperature value is 98 DEG C, speed of evacuation per-cent is 100%, and pump speed per-cent is 30%, and nozzle cleaning frequency is 7 times/min, obtain supported catalyst 8.6219g, adopting atomic absorption spectrum to record iron level is 0.25%, adopts gas chromatography determination content of tetrahydrofuran to be 27.3%, and the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 16.7 μm.
2. the slurry polymerization of ethene
2L reactor is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Embodiment 2
1. the preparation of two [1-(2, the 6-dimethyl benzene imines) ethyl] pyridyl iron dichloride of supported catalyst 2,6-
Under nitrogen protection, in the reactor of 250mL, add Magnesium Chloride Anhydrous 4.85g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.55g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-dimethyl benzene imines) ethyl] the pyridyl iron dichloride 0.3812g of iron homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spraying dry instrument after stirring is carried out spraying dry, inlet temperature is set to 182 DEG C, temperature out is 98 DEG C, pump speed per-cent is 30%, nozzle cleaning frequency is 7 times/min, obtains supported catalyst 8.7325g, and adopting atomic absorption spectrum to record iron level is 0.47%, adopt gas chromatography determination content of tetrahydrofuran to be 29.5%, the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 15.9 μm.
2. the slurry polymerization of ethene
The reactor of 2L is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Embodiment 3
1. the preparation of two [1-(2, the 6-diisopropyl benzene imines) ethyl] pyridyl iron dichloride of supported catalyst 2,6-
Under nitrogen protection, in the reactor of 250mL, add Magnesium Chloride Anhydrous 4.8703g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.5350g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-diisopropyl benzene imines) ethyl] the pyridyl iron dichloride 0.2145g of iron homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spraying dry instrument after stirring is carried out spraying dry, inlet temperature is set to 182 DEG C, temperature out is 98 DEG C, speed of evacuation per-cent is 100%, and pump speed per-cent is 30%, and nozzle cleaning frequency is 7 times/min, obtain supported catalyst 8.9930g, adopting atomic absorption spectrum to record iron level is 0.22%, adopts gas chromatography determination content of tetrahydrofuran to be 27.35%, and the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 17.1 μm.
2. the slurry polymerization of ethene
The reactor of 2L is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Embodiment 4
1. the preparation of two [1-(2,6-dimethyl benzene imines) ethyl] the pyridine cobalt dichloride of supported catalyst 2,6-
Under nitrogen protection, in the reactor of 250mL, add Magnesium Chloride Anhydrous 4.8189g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.55g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-dimethyl benzene imines) ethyl] the pyridine cobalt dichloride 0.1930g of iron homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spraying dry instrument after stirring is carried out spraying dry, inlet temperature is set to 182 DEG C, temperature out is 98 DEG C, speed of evacuation per-cent is 100%, and pump speed per-cent is 30%, and nozzle cleaning frequency is 7 times/min, obtain supported catalyst 8.8629g, adopting atomic absorption spectrum to record iron level is 0.25%, adopts gas chromatography determination content of tetrahydrofuran to be 28.32%, and the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 18.1 μm.
2. the slurry polymerization of ethene
2L reactor is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Embodiment 5
1. the preparation of two [1-(2,6-dimethyl benzene)] the anthraquinone diimine Nickel Bromide of supported catalyst 2,6-
Under nitrogen protection, in the reactor of 250mL, add Magnesium Chloride Anhydrous 4.8285g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.4990g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-dimethyl benzene)] the anthraquinone diimine Nickel Bromide 0.1891g of nickel homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spraying dry instrument after stirring is carried out spraying dry, inlet temperature currency is set to 192 DEG C, temperature out currency is 97 DEG C, inlet temperature set(ting)value is 190 DEG C, speed of evacuation per-cent is 100%, pump speed per-cent is 25%, nozzle cleaning frequency is 7 times/min, obtain supported catalyst 7.5291g, adopting atomic absorption spectrum to record nickel content is 0.26%, adopt gas chromatography determination content of tetrahydrofuran to be 28.48%, the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 17.6 μm.
2. the slurry polymerization of ethene
The reactor of 2L is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Embodiment 6
1. the preparation of two [1-(2,6-dimethyl benzene)] the anthraquinone diimine Nickel Bromide of supported catalyst 2,6-
Under nitrogen protection, in the reactor of 250mL, add Magnesium Chloride Anhydrous 4.8230g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.5235g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-dimethyl benzene)] the anthraquinone diimine Nickel Bromide 0.4521g of nickel homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spraying dry instrument after stirring is carried out spraying dry, inlet temperature is set to 192 DEG C, temperature out is 97 DEG C, speed of evacuation per-cent is 100%, and pump speed per-cent is 25%, and nozzle cleaning frequency is 7 times/min, obtain supported catalyst 8.22g, adopting atomic absorption spectrum to record nickel content is 0.61%, adopts gas chromatography determination content of tetrahydrofuran to be 27.67%, and the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 18.3 μm.
2. the slurry polymerization of ethene
2L reactor is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Embodiment 7
1. the preparation of two [1-(2,6-diisopropyl benzene)] the anthraquinone diimine Nickel Bromide of supported catalyst 2,6-
Under nitrogen protection, in the reactor of 250mL, add Magnesium Chloride Anhydrous 4.8216g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.51g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-diisopropyl benzene)] the anthraquinone diimine Nickel Bromide 0.2400g of nickel homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spraying dry instrument after stirring is carried out spraying dry, inlet temperature is set to 192 DEG C, temperature out is 97 DEG C, speed of evacuation per-cent is 100%, and pump speed per-cent is 25%, and nozzle cleaning frequency is 7 times/min, obtain supported catalyst 7.88g, adopting atomic absorption spectrum to record nickel content is 0.25%, adopts gas chromatography determination content of tetrahydrofuran to be 28.55%, and the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 18.2 μm.
2. the slurry polymerization of ethene
2L reactor is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Embodiment 8
1. the preparation of two [1-(2,6-dimethyl benzene)] the anthraquinone diimine dibrominated palladium of supported catalyst 2,6-
Under nitrogen protection, in the reactor of 250mL, add Magnesium Chloride Anhydrous 4.8225g, add refining THF130mL, keep 70 DEG C of thermostatically heating to stir 1 hour.In reactor, add the TS-610 silica gel 7.56g through nitrogen replacement, keep temperature 30 DEG C, stir 1 hour.Add two [1-(2,6-dimethyl benzene)] the anthraquinone diimine dibrominated palladium 0.2632g of nickel homogeneous catalyst 2,6-, stir 15 minutes under the condition of 30 DEG C.Mother liquor spraying dry instrument after stirring is carried out spraying dry, inlet temperature is set to 192 DEG C, temperature out is 97 DEG C, speed of evacuation per-cent is 100%, and pump speed per-cent is 25%, and nozzle cleaning frequency is 7 times/min, obtain supported catalyst 7.92g, adopting atomic absorption spectrum to record nickel content is 0.51%, adopts gas chromatography determination content of tetrahydrofuran to be 28.11%, and the particle diameter adopting Malvern laser fineness gage to measure loaded late transition metal catalyst is 17.6 μm.
2. the slurry polymerization of ethene
2L reactor is heated to about 80 DEG C, vacuumizes 1h, replace with drying nitrogen.1L hexane is added in polymeric kettle, add a certain amount of triethyl aluminum and above-mentioned catalyzer 50mg simultaneously, be warming up to 45 DEG C subsequently, add a certain amount of hydrogen, adding ethene after hydrogenation makes still internal pressure reach 1.03MPa, after being warming up to 50 DEG C, reacts after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 2.
Table 1 loaded late transition metal catalyst preparation condition and analytical results
Table 2 vinyl polymerization lab scale evaluation result
Claims (4)
1. a preparation method for magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst, is characterized in that:
(1) preparation of parent: add magnesium chloride in electron donor tetrahydrofuran-compound;
(2) preparation of complex carrier: the parent of step (1) gained and the blending of nanometer grade silica carrier particle are obtained suspension, adds late transition metal complex and obtain mother liquor;
(3) spray shaping: the mother liquor that step (2) obtains is carried out spraying dry and obtains ingredient of solid catalyst;
Magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) consumption mol ratio is: 0.1 ~ 1:0.1 ~ 2:5 ~ 20;
Described late transition metal complex is 2, two [the 1-(2 of 6-, 6-dimethyl benzene imines) ethyl] pyridyl iron dichloride, 2, two [the 1-(2 of 6-, 6-diisopropyl benzene imines) ethyl] pyridyl iron dichloride, 2, two [the 1-(2 of 6-, 6-dimethyl benzene imines) ethyl] pyridine cobalt dichloride, 2, two [the 1-(2 of 6-, 6-dimethyl benzene)] anthraquinone diimine Nickel Bromide, 2, two [the 1-(2 of 6-, 6-diisopropyl benzene)] anthraquinone diimine Nickel Bromide, 2, two [the 1-(2 of 6-, 6-dimethyl benzene)] one in anthraquinone diimine dibrominated palladium.
2. the preparation method of the magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst according to claim l, is characterized in that: the particle diameter of nanosized silica particles is 0.01 ~ 0.1 μm.
3. magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst, is characterized in that: this catalyzer is prepared by method according to claim 1.
4. the application of magnesium chloride/silicon-dioxide/tetrahydrofuran (THF) loaded late transition metal catalyst according to claim 3, it is characterized in that: for all polymerizations or the copolymerization catalyzer of alkene, temperature during polymerization is 0 DEG C ~ 100 DEG C, and polymerization pressure is 0.1 ~ 10.0MPa;
Wherein also add trimethyl aluminium or triethyl aluminum in catalyzer, the mol ratio of aluminium and rear transition metal is 10 ~ 500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210109275.XA CN103374084B (en) | 2012-04-13 | 2012-04-13 | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210109275.XA CN103374084B (en) | 2012-04-13 | 2012-04-13 | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103374084A CN103374084A (en) | 2013-10-30 |
| CN103374084B true CN103374084B (en) | 2016-01-20 |
Family
ID=49459965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210109275.XA Active CN103374084B (en) | 2012-04-13 | 2012-04-13 | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103374084B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804030B (en) * | 2015-04-30 | 2017-06-06 | 天津工业大学 | Support type α diimine compounds and its application in olefin polymerization |
| CN107459594B (en) * | 2016-06-06 | 2020-02-18 | 中国石油化工股份有限公司 | Supported iron catalyst, preparation method thereof and iron catalyst system |
| CN107459597B (en) * | 2016-06-06 | 2020-02-18 | 中国石油化工股份有限公司 | Supported iron catalyst, preparation method thereof and iron catalyst system |
| CN108034014A (en) * | 2017-12-27 | 2018-05-15 | 安徽工业大学 | A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst |
| CN112724004B (en) * | 2021-01-19 | 2022-09-16 | 温州大学 | A kind of synthetic method of aromatic ketone substituted at α or β position |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510055A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Magnesium chloride composite carrier and the ethylene polymerization solid catalyst component prepared therefrom |
| CN101225129A (en) * | 2007-01-19 | 2008-07-23 | 中国石油化工股份有限公司 | Late transition metal double-peak catalyst for ethane polymerization, preparation method and uses thereof |
-
2012
- 2012-04-13 CN CN201210109275.XA patent/CN103374084B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510055A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Magnesium chloride composite carrier and the ethylene polymerization solid catalyst component prepared therefrom |
| CN101225129A (en) * | 2007-01-19 | 2008-07-23 | 中国石油化工股份有限公司 | Late transition metal double-peak catalyst for ethane polymerization, preparation method and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103374084A (en) | 2013-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103374084B (en) | Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation and application thereof | |
| CN102180910A (en) | Asymmetrical alpha-diimine nickel complex catalyst and preparation method and application thereof | |
| CN105289741A (en) | Chromium catalyst for nitrogen and phosphorous ligand framework and application of chromium catalyst in catalyzing ethylene oligomerization | |
| CN105481998B (en) | A kind of olefin polymerization catalysis and its methods for making and using same | |
| CN1315883C (en) | Polymerisation catalyst | |
| CN103087241B (en) | Method for preparing metallocene polyethylene | |
| CN104725533B (en) | A kind of olefin polymerization catalysis and olefine polymerizing process and polyolefin | |
| CN106397259A (en) | Diimine ligand, and diimine-nickel complex and application thereof | |
| CN104059175B (en) | A kind of for the supported late transition metal catalyst of vinyl polymerization, method for making and application | |
| CN106397260A (en) | Diimine ligand compound, and nickel complex and application thereof | |
| CN101423574B (en) | Supported non-metallocene single site catalyst component and preparation method thereof and use | |
| CN102796218A (en) | Metallocene catalyst for producing low gel polyethylene, and preparation method and application thereof | |
| CN105111336A (en) | Electron donor of ethylene polymerization catalyst, ball-like catalyst and preparation method | |
| CN104387424B (en) | The methyl substituted difluorophenyl Branched polyethylene preparation method of two (phenyl) of one kind and vinyl polymerization | |
| CN101817893B (en) | Method for preparing magnesium chloride loaded late transition metal catalyst | |
| CN101817892B (en) | Method for preparing magnesium chloride loaded metallocene catalyst | |
| CN101569865A (en) | Ethylene oligomerization catalysis system | |
| CN102272172A (en) | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst | |
| CN104059180B (en) | A kind of loaded late transition metal catalyst for vinyl polymerization | |
| CN104059173B (en) | A kind of supported late transition metal catalyst for vinyl polymerization | |
| CN106397263A (en) | Ligand compound and preparation thereof, and complex containing ligand compound | |
| CN103012196B (en) | 2- [ (2-hydroxy) -benzylimino ] methylphenol complex and preparation and application thereof | |
| CN102372796B (en) | Silica gel supported composite chromium-based catalyst, its preparation method and its application | |
| CN106397262A (en) | Diimine ligand, and preparation method and application thereof | |
| CN116903772A (en) | Method for preparing polyolefin plastomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |