CN104072646A - Ethylene gas-phase polymerization or copolymerization catalyst composition, preparation and application thereof - Google Patents
Ethylene gas-phase polymerization or copolymerization catalyst composition, preparation and application thereof Download PDFInfo
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- CN104072646A CN104072646A CN201310103401.5A CN201310103401A CN104072646A CN 104072646 A CN104072646 A CN 104072646A CN 201310103401 A CN201310103401 A CN 201310103401A CN 104072646 A CN104072646 A CN 104072646A
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- catalyst composition
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- phase polymerization
- tetrahydrofuran
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 21
- 238000012685 gas phase polymerization Methods 0.000 title claims abstract description 15
- 239000005977 Ethylene Substances 0.000 title claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 186
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 127
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 94
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 239000012452 mother liquor Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 14
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 13
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 83
- 229960001866 silicon dioxide Drugs 0.000 claims description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical group CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 40
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 235000012239 silicon dioxide Nutrition 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 238000010926 purge Methods 0.000 claims description 22
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 20
- 230000004913 activation Effects 0.000 claims description 13
- 239000012190 activator Substances 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- 238000005243 fluidization Methods 0.000 claims description 13
- 238000000935 solvent evaporation Methods 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 46
- 238000009826 distribution Methods 0.000 abstract description 27
- 239000000843 powder Substances 0.000 abstract description 21
- 230000002902 bimodal effect Effects 0.000 abstract description 16
- -1 polyethylene Polymers 0.000 abstract description 13
- 239000004698 Polyethylene Substances 0.000 abstract description 12
- 229920000573 polyethylene Polymers 0.000 abstract description 12
- 238000010992 reflux Methods 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 150000002506 iron compounds Chemical class 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000000741 silica gel Substances 0.000 description 35
- 229910002027 silica gel Inorganic materials 0.000 description 35
- 239000002002 slurry Substances 0.000 description 33
- 239000000460 chlorine Substances 0.000 description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000012071 phase Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000001994 activation Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 230000000630 rising effect Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 238000007725 thermal activation Methods 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 229960002089 ferrous chloride Drugs 0.000 description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 150000004698 iron complex Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920013716 polyethylene resin Polymers 0.000 description 7
- 238000009834 vaporization Methods 0.000 description 7
- 230000008016 vaporization Effects 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a catalyst composition for ethylene gas phase polymerization or copolymerization, and a preparation method and application thereof; dissolving a titanium compound, an iron compound and a magnesium compound in tetrahydrofuran to prepare a mother solution; adding the modified silicon dioxide carrier subjected to heat treatment and chemical treatment into the mother liquor, refluxing and stirring for 1 hour, blowing and drying the mother liquor by using high-purity nitrogen to remove excessive tetrahydrofuran, and controlling the residual content of the tetrahydrofuran to be 10-15 wt% of the total weight of the obtained product; suspending the obtained solid in a lower alkane solvent, reducing with one or more alkyl aluminum compounds at room temperature for 30min, and blowing with high-purity nitrogen to dry to obtain a catalyst composition; the catalyst shows higher catalytic activity when used for ethylene polymerization, particularly gas-phase fluidized bed polymerization, can prepare polyethylene products with wider molecular weight distribution or bimodal distribution, and the obtained polyethylene products have high bulk density and less fine powder.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method bimodal or broad peak distribution polyethylene that is applicable to produce in single reaction vessel, be specifically related to a kind of bimetal silica gel carrier catalyst composition and method of making the same that is applicable to vinyl polymerization or copolymerization.
Background technology
Polyvinyl resin is one of four large synthetic resins, and high performance polyvinyl resin will have higher toughness, higher intensity and higher environmental stress cracking resistance.Improving poly molecular weight can make these performances correspondingly improve.But, in the time that the molecular weight of polymkeric substance increases, conventionally can make the processing characteristics of this resin decline.There is polymkeric substance wide or bimodal molecular weight distribution by preparation, not only can keep the characteristic performance of high molecular weight resin, and can also improve the processing characteristics of resin.Therefore the research and development of bimodal molded breadth distribution polyethylene resin are current polyethylene production business's questions of common concern.On this resinoid molecular weight distribution curve, generally have two peak types of lower molecular weight section and high molecular section, low molecular weight part can improve the processing characteristics of resin, and high molecular part can improve the mechanical strength feature of resin.Current existing preparation wide or the method for Bi-modal polyethylene resin, substantially can be divided into following three classes:
(1) resin melting blending method.Resin by different molecular weight mixes under molten state, and this method not only cost is higher, thereby and be difficult to reach resin completely evenly fusion affect the final performance of resin;
(2) carry out stage feeding polymerization by staged reactor, can obtain resin comparatively uniformly, operation adjustment handiness is larger, but has efficiency and the high problem of cost of affecting;
(3) in single reaction vessel, adopt bimetal or many metal active constituents catalyzer, utilize the polymerization behavior that they have nothing in common with each other, the polyethylene of direct production wide molecular weight distribution in single reaction vessel.
In general a kind of the third above-mentioned method-develop many metal active constituents catalyzer is comparatively desirable and feasible method.For example: Chinese patent CN88101779, CN1342716A disclose the poly polymerization process of molecular weight distribution in a kind of production, the method adopts the catalyst system of Ti, V bimetallic active center, and Ti component adopts the TiCl loading on silica gel
4/ MgCl
2/ THF/Al (n-C
6h
13)
3catalyzer, V component adopts and loads on VCl on silica gel
3the catalyzer of/THF/DEAC.Before polyreaction, be Ti, V catalyst system by two kinds of catalyst mix, this system when the vinyl polymerization, activity be 2400～3600 grams of polyethylene/mmoles (V+Ti)/hour/100psi ethene (5～7 myriagrams/gram (V+Ti)), MI
2.16be 0.10～1.90, MFR 40～69.It is generally acknowledged that titanium catalyst produces the resin of narrow molecular weight distributions, and catalytic component based on vanadium produces the resin of wide molecular weight distribution, this invention adopts above two components to form mixed catalyst simultaneously, thus the resin of molecular weight distribution in producing.
Chinese patent CN1058601A, CN1478108A also disclose a kind of reduction vanadium compound and organic oxygen-containing zirconium compounds of adopting and have steeped the catalyst composition being deposited on active carrier material by total immersion, the ethene polymers being made by this catalyzer has wide molecular weight distribution, and especially distributing more is the component that molecular weight is higher.Although the molecular weight distribution of this catalyzer resulting polymers is wider, its catalyst activity is on the low side.
Chinese patent CN101225129A discloses and has adopted the composite catalyst of two kinds of rear transition metal iron, nickel composition for the preparation of bimodal polyethylene, but required promotor is generally methylaluminoxane, causes the production cost of bimodal polyethylene higher.
In the US 20050003950 and US20040186251 of the US 20050054519 of Univation Technologies and CN1678640A, CN1413222A, ExxonMobile, all adopt the compound mode of Ziegler-Natta catalyst and metallocene catalyst in single reaction vessel, to produce the polyvinyl resin of bimodal wide distribution.Can find out from above prior art, use the compound system of Ziegler-Natta catalyst and metallocene can in single reaction vessel, produce bimodal wide distribution polyethylene resin, will find that this catalyst system exists more serious problem but carefully analyze.The basic characteristics of typical bimodal wide distribution polyethylene resin are that low molecular weight part reduced branching degree is to improve Drawing abillity, the high degree of branching of high molecular part to improve the mechanical property of material.But the polymkeric substance that the compound system of Ziegler-Natta catalyst and metallocene catalyst obtains is on the contrary, show as the high degree of branching of polymer low-molecular amount part, high molecular part reduced branching degree, this is because add hydrogen can make the very low of the synthetic molecular weight of polyethylene change of metallocene catalyst in the time of polymerization, and metallocene catalyst is better than the copolymerization performance of Ziegler-Natta catalyst, cause thus comonomer to be copolymerized to one section of lower molecular weight.
Can find out from the disclosed catalyzer of above-mentioned patent, although the dynamics model catalyzer that adopts two or more Ziegler-Natta type catalyst component to form can be prepared wide distribution or bimodal distribution polyvinyl resin, but still exist active problem on the low side, generally all at 10 myriagrams/gram below metal; And for the disclosed Ti/V catalyst system of Chinese patent CN88101779, the molecular weight distribution of gained polyvinyl resin is also narrow, its melt flow ratio (MFR) is 40～70.
One object of the present invention is to overcome the defect that above-mentioned prior art exists, a kind of catalyzer of dynamics model is proposed, this catalyzer comprises Ti component and rear transition metal iron component, when for vinyl polymerization, demonstrate higher catalyst activity, and can prepare compared with the polyvinyl resin of wide molecular weight distribution or bimodal distribution.The present invention chooses and can produce low molecular weight polyethylene and the poor rear transition metal iron catalyst of copolymerization performance, with the compound preparation for bimodal wide distribution polyethylene of existing Ziegler-Natta catalyst, solve the problem that a large amount of side chains appear in low molecular weight part, can in single reactor, realize the typical double-peak poly production of lower molecular weight reduced branching degree, the high cultural degree of high molecular.
Another object of the present invention is to provide the application of a kind of above-mentioned catalyzer in preparation wide molecular weight distribution or the poly polymerization process of bimodal distribution.
Summary of the invention
One of object of the present invention is that Ziegler-Natta type Ti catalyzer and rear transition metal iron catalyst are loaded on magnesium chloride/silicon-dioxide complex carrier simultaneously, adopt the method for dipping to prepare complex catalyst system, this system can be prepared bimodal wide distribution polyethylene resin for vinyl polymerization.
Another object of the present invention is the method that uses complex catalyst system wide distribution polyethylene resin of production typical double-peak in single reactor of Ziegler-Natta type Ti catalyzer/rear transition metal iron catalyst.
The composite catalyst of Ziegler-Natta type Ti catalyzer/rear transition metal iron catalyst of the present invention refers to Ziegler-Natta type Ti catalyzer and rear transition metal iron catalyst title complex is loaded in proportion on magnesium chloride/silicon-dioxide complex carrier and obtain composite catalyst.Above-mentioned composite catalyst forms complex catalyst system together with promotor.
For realizing the object of described invention, the technical solution used in the present invention is: a kind of bimetal ethylene polymerization catalyst composition is provided, this catalyzer is made up of support of the catalyst and the titaniferous, iron-containing catalyst active ingredient and the promotor that load on carrier, described support of the catalyst is through thermal treatment and the chemically treated silicon-dioxide of aluminum alkyls, described silicon-dioxide is spherical or class is spherical, and its median size is 10～100 μ m, specific surface area 250～800m
2/ g; Described titaniferous, iron-containing catalyst active ingredient comprises the back flow reaction product of at least one titanium compound, at least one iron complex, at least one magnesium compound and at least one electron donor, and described promotor is alkylaluminium cpd.
The structure of described late transition metal complex is suc as formula shown in I:
The structure of I iron complex
Wherein: R
1～C
3for alkyl, alkoxyl group, phenoxy group, phenmethyl, halogen etc.; M is Fe.Metal complexes shown in general formula I synthetic standby according to W09827124, W09830612 patent system.
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%.
Described magnesium compound is MgCl
2, MgBr
2, MgI
2or its mixture.
Described titanium compound is Ti (OR)
4-nXn or TiX
3, in formula, R is C
1～C
3aliphatic group, X is one or more of F, Cl, Br, the integer that n is 1～4.
Described electron donor is tetrahydrofuran (THF).
The general formula of described alkylaluminium cpd is AlR
mx
3-m, R is identical or not identical C
1-8alkyl, X is halogen, the integer that m is 1～3.
Described alkylaluminium cpd is AlEt
3, Al (iso-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3, AlEt
2the mixture of one or more in Cl.
Described silicon-dioxide carries out modification as follows:
(1) silicon-dioxide is placed in to gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 200～700 DEG C, constant temperature dehydration 4～10 hours, makes dehydrated silica;
(2) in dehydrated silica, add alkane solvent, the add-on of solvent is 10mL/g SiO
2and add the hydroxyl of alkyl metal cpd treat surface, described alkyl metal cpd is aluminum alkyls, the weight ratio of its consumption is: A1/Si is 0.05～0.1:1, under room temperature, stir 1～4 hour, heating makes alkane solvent evaporation, and the temperature of evaporation is 20～30 DEG C, obtains having the activation silicon-dioxide of mobility;
Another technical scheme of the present invention is to provide the preparation method of described ethylene polymerization catalyst composition, and its step is as follows:
(1) titanium compound, iron complex and magnesium compound are dissolved in tetrahydrofuran (THF), wherein select titanous chloride: iron complex: magnesium chloride: tetrahydrofuran (THF)=1:0.5:3.15:247, temperature rising reflux reaction, make mother liquor, wherein titanium compound, iron complex joined in tetrahydrofuran (THF) or by both and add simultaneously before or after magnesium compound; The weight ratio of magnesium compound and iron cpd is 100:1～1:1; The weight ratio of tetrahydrofuran (THF) and iron cpd is 10000:1～1:1;
(2) described silica supports after modification is joined in mother liquor prepared by (1) step, it is purged dry with high pure nitrogen afterwards, remove excessive tetrahydrofuran (THF), controlling its residue content is 10～16 wt%;
(3) solids step (2) being obtained, be suspended in lower paraffin hydrocarbons solvent, at room temperature reduce processing with one or more alkylaluminium cpds, in reactivation process, the add-on of aluminum alkyls is: n(Al)/n (THF)=0.65, the reduction treatment time is 30min, purge and be dried with high pure nitrogen again, make described catalyst composition.
Described lower paraffin hydrocarbons solvent is iso-pentane, pentane or hexane.
Compared with prior art, beneficial effect of the present invention shows as:
Catalyst system of the present invention has good ethylene homo and copolymerization polymerization activity, and the molecular weight of polyethylene obtaining distributes and is bimodal distribution.The bimodal polyethylene resins that the present invention obtains has the feature of low molecular weight part reduced branching degree, the high degree of branching of high molecular part.In addition, double-metal composite catalyst of the present invention can use a kind of promotor, and this has also solved the problem of required two kinds of promotor phases mutual interference in existing double-metal composite catalyst technology.
Ti/Fe complex catalyst system of the present invention obtains resin for vinyl polymerization and has good particle form, goes for slurry process and vapor phase process polymerization technique.
Embodiment
Vinyl polymerization bimetallic catalyst composition of the present invention is mainly applicable to ethene gas-phase polymerization or copolymerization, and it is made up of support of the catalyst, Ti/Fe bimetal active ingredient and promotor.Wherein, improved silica is support of the catalyst; Bimetal Ti/Fe active ingredient is a kind of back flow reaction product that comprises at least one titanium compound, at least one iron complex, at least one magnesium compound and at least one electron donor; Promotor is aluminum alkyls.
Preferred embodiment of the present invention is that the median size of silicon-dioxide used is l0～100 μ m, is preferably 15～50 μ m, and specific surface area is 280～700m
2, be preferably 400～600m
2/ g, the too small charge capacity that can affect active ingredient of specific surface area.In addition, the present invention adopts the following step to carry out modification to silica supports: silicon-dioxide is placed in gas-phase fluidized-bed activator by (1), blows fluidisation with nitrogen anhydrous, anaerobic, is progressively warming up to 200～700 DEG C, be preferably 500～700 DEG C, constant temperature dehydration 4～10 hours.(2) in dehydrated silica, add alkane solvent, and add alkyl metal cpd treat surface, stir 1～4 hour under room temperature, heating makes alkane solvent evaporation, obtains mobility and activates preferably silicon-dioxide.The alkyl metal cpd preferred alkyl aluminium of activation use, the most handy triethyl aluminum, the weight ratio of its consumption is: A1/Si=0.05～0.1:1.
Another preferred embodiment of the present invention is the method for the described catalyst composition of preparation: described titanium compound, iron complex and magnesium compound are dissolved in electron donor, be prepared into mother liquor, then load on the silica-gel carrier after modification by the method for dipping, the step that comparatively preferred method adopts is as follows:
(1) titanium compound, iron complex and magnesium compound are dissolved in tetrahydrofuran (THF), make mother liquor, wherein titanium compound, iron complex can join in tetrahydrofuran (THF) or both add simultaneously before or after magnesium compound;
(2) described silica-gel carrier after modification is joined in the mother liquor of (1) step, after the back flow reaction regular hour, it is dried, remove excessive tetrahydrofuran (THF), general control residue content is at 10～16wt%;
(3) solids step (2) being obtained, is suspended in lower paraffin hydrocarbons solvent, reduces processing with one or more alkylaluminium cpds, then after being dried, makes final catalyst activity component.Wherein described in step (3), lower paraffin hydrocarbons solvent is C
3～C
9alkane, preferably C
5and C
6alkane, such as iso-pentane, pentane, hexane etc.; The general formula of described alkylaluminium cpd is AlR
mx
3-m, R is identical or not identical C
1-8alkyl, X is halogen, the integer that m is 1～3, preferably AlEt
3, Al (n-C
6h
13)
3, AlEt
2cl etc.
The catalyzer the present invention relates to is applicable to the equal polymerization of various ethene or the copolymerization of ethene and other alpha-olefin, and wherein alpha-olefin can be selected from the one in propylene, butylene, amylene, hexene, octene, 4-methylpentene-1.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation, particularly gas-phase fluidized-bed condensation technology.
Embodiment 1
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and median size is 45 μ m, and specific surface area is 350m to take 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 6 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection, add 100mL iso-pentane, by the AlEt that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL
3hexane solution add, 20～30 DEG C of reactions 1 hour, heating made alkane solvent evaporation, obtained having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 0.64mL TiCl
4, 2,6-two [1-(2,6-dimethyl benzene imines) ethyl] pyridine ferrous chloride 0.0968g, 1.74g MgCl
2with 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of modification in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.94Wt%.
(5) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl and Al (n-C
6h
13)
3reaction product to step (4) gained is carried out prereduction, and the recovery time is 30min, controls AlEt
2the mol ratio of Cl/THF is 0.45:1, Al (n-C
6h
13)
3/ THF is 0.20:1.React rear and purged and be dried with high pure nitrogen, obtained micro-yellow solid powder catalyst component.In its catalyst composition: Ti%=1.26Wt%, Fe%=0.08Wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.75, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 80 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 2
The preparation of bimetallic catalyst composition:
(1) (Grace company of the U.S. produces, and median size is 45 μ m, and specific surface area is 350m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 4 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection, add 100mL iso-pentane, by the AlEt that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL
3hexane solution add, 20～30 DEG C of reactions 1 hour, heating made alkane solvent evaporation, obtained having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 0.64mL TiCl
4, 2,6-two [1-(2,6-dimethyl benzene imines) ethyl] pyridine ferrous chloride 0.1937g, 1.74g MgCl
2with and 174mL tetrahydrofuran (THF), temperature rising reflux stir 5 hours, make catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of chemical treatment in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.80Wt%.
(5) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl and Al (n-C
6h
13)
3reaction product to step (4) gained is carried out prereduction, and the recovery time is 30min, controls AlEt
2the mol ratio of Cl/THF is 0.45:1, Al (n-C
6h
13)
3/ THF is 0.20:1.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.14Wt%, Fe%=0.12wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 80 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 3
The preparation of catalyst composition
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 10 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection, add 100mL iso-pentane, by the AlEt that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL
3hexane solution add, 20～30 DEG C of reactions 1 hour, heating made alkane solvent evaporation, obtained having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgCl
2, 2,6-two [1-(2,6-dimethyl benzene imines) ethyl] pyridine ferrous chloride 0.3874g, 0.64mL TiCl
4and 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of chemical treatment in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 10.98Wt%.
(5) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl and Al (n-C
6h
13)
3reaction product to step (4) gained is carried out prereduction 30min, controls AlEt
2the mol ratio of Cl/THF is 0.45:1, Al (n-C
6h
13)
3/ THF is 0.20:1.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.27Wt%, Fe%=0.24wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 4
The preparation of bimetallic catalyst component:
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 7 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection, add 100mL iso-pentane, by the AlEt that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL
3hexane solution add, 20 DEG C of reactions 1 hour, heating made alkane solvent evaporation, vaporization temperature is 25 DEG C, obtains having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgCl
2, 2,6-two [1-(2,6-dimethyl benzene imines) ethyl] pyridine ferrous chloride 0.1937g and 1.03g TiCl
3and 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of chemical treatment in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.8Wt%.
(5) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl and Al (n-C
6h
13)
3reaction product to step (4) gained is carried out prereduction, and the recovery time is 30min, controls AlEt
2the mol ratio of Cl/THF is 0.45:1, Al (n-C
6h
13)
3/ THF is 0.20:1.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.4Wt%, Fe%=0.12%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 80 DEG C are reacted 2 hours.Catalyzer synthesis condition is in table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 5
The preparation of bimetallic catalyst component:
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 4 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection, add 100mL iso-pentane, by the AlEt that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL
3hexane solution add, 25 DEG C of reactions 4 hours, heating made alkane solvent evaporation, vaporization temperature is 20 DEG C, obtains having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgCl
2, 2,6-two [1-(2,6-diisopropyl benzene imines) ethyl] pyridine ferrous chloride 0.1077g, 0.64mL TiCl
4and 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of chemical treatment in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.3Wt%.
(5) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl and Al (n-C
6h
13)
3reaction product to step (4) gained is carried out prereduction 30min, controls AlEt
2the mol ratio of Cl/THF is 0.45, Al (n-C
6h
13)
3/ THF is 0.20.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.27Wt%, Fe%=0.07wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 6
The preparation of bimetallic catalyst component:
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 10 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection, add 100mL iso-pentane, by the AlEt that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL
3hexane solution add, 30 DEG C of reactions 4 hours, heating made alkane solvent evaporation, vaporization temperature is 30 DEG C, obtains having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgCl
2, 2,6-two [1-(2,6-diisopropyl benzene imines) ethyl] pyridine ferrous chloride 0.2145g, 0.64mLTiCl
4and 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of modification in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.3Wt%.
(6) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl carries out prereduction 30min to the reaction product of step (5) gained, controls AlEt
2the mol ratio of Cl/THF is 0.65:1.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.25Wt%, Fe%=0.11wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 7
The preparation of catalyst component
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 8 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection; add 100mL normal hexane; the hexane solution of the trimethyl aluminium that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL is added; 25 DEG C of reactions 4 hours; heating makes alkane solvent evaporation; vaporization temperature is 25 DEG C, obtains having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgBr
2, 2,6-two [1-(2,6-diisopropyl benzene imines) ethyl] pyridine ferrous chloride 0.4290g, 0.64mL TiCl
4and 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of modification in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.4Wt%.
(6) under room temperature taking iso-pentane as solvent, adopt Al (n-C
6h
13)
3reaction product to step (5) gained is carried out prereduction 30min, controls Al (n-C
6h
13)
3the mol ratio of/THF is 0.65, has reacted the high-purity chlorine purging of rear use and has been dried, and obtains micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.25Wt%, Fe%=0.22wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Embodiment 8
The preparation of bimetallic catalyst component:
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 200 DEG C, constant temperature dehydration 8 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection; add 100mL normal heptane; the hexane solution of the tri-n-hexyl aluminum that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL is added; 25 DEG C of reactions 4 hours; heating makes alkane solvent evaporation; vaporization temperature is 30 DEG C, obtains having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgI
2, 2,6-two [1-(2,6-dimethyl benzene imines) ethyl] pyridine ferrous chloride 0.2145g and 1.03g TiCl
3and 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of chemical treatment in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.1Wt%.
(5) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl and Al (n-C
6h
13)
3reaction product to step (5) gained is carried out prereduction 30min, controls AlEt
2the mol ratio of Cl/THF is 0.45:1, Al (n-C
6h
13)
3/ THF is 0.20:1.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.46Wt%, Fe%=0.11wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Comparative example 1
The preparation of bimetallic catalyst component:
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 200 DEG C, constant temperature dehydration 8 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection; add 100mL normal heptane; the hexane solution of the tri-n-hexyl aluminum that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL is added; 25 DEG C of reactions 4 hours; heating makes alkane solvent evaporation; vaporization temperature is 30 DEG C, obtains having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgCl
2, 0.64mL TiCl
4and 174mL tetrahydrofuran (THF) tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of chemical treatment in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 10.9Wt%.
(5) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl and Al (n-C
6h
13)
3reaction product to step (5) gained is carried out prereduction 30min, controls AlEt
2the mol ratio of Cl/THF is 0.45:1, Al (n-C
6h
13)
3/ THF is 0.20:1.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Ti%=1.20Wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
Comparative example 2
The preparation of bimetallic catalyst component:
(1) (Grace company of the U.S. produces, and median size is 55 μ m, and specific surface area is 278m to take about 20g spherical silica gel
2/ g), silicon-dioxide is placed in to gas-phase fluidized-bed activator, blow fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 600 DEG C, constant temperature dehydration 10 hours, makes dehydrated silica.
(2) in the reaction flask of the belt stirrer under nitrogen protection, add 100mL iso-pentane, by the AlEt that in (1) step, the silica gel 10g after thermal activation treatment and 5.6mL concentration are 1mmol/mL
3hexane solution add, 30 DEG C of reactions 4 hours, heating made alkane solvent evaporation, vaporization temperature is 30 DEG C, obtains having the activation silicon-dioxide of mobility.
(3), in the reaction flask of another belt stirrer, add 1.74g MgCl
2, 2,6-two [1-(2,6-diisopropyl benzene imines) ethyl] pyridine ferrous chloride 0.2145g and 174mL tetrahydrofuran (THF), temperature rising reflux stirs 5 hours, makes catalyzer mother liquor.
(4) mother liquor of preparing with (3) step through the good silica gel of modification in (2) step is mixed, return stirring 1 hour, then purges and is dried with high pure nitrogen, obtains mobility faint yellow solid powder, and wherein the content of tetrahydrofuran (THF) is 11.5Wt%.
(6) under room temperature taking iso-pentane as solvent, adopt AlEt
2cl carries out prereduction 30min to the reaction product of step (5) gained, controls AlEt
2the mol ratio of Cl/THF is 0.65:1.React the high-purity chlorine purging of rear use dry, obtained micro-yellow solid powder catalyst component.In its catalyst component: Fe%=0.11wt%.
Evaluating catalyst:
The slurry polymerization of ethene: carry out the evaluation of ethene slurry polymerization in 2L stainless steel cauldron, the consumption 50mg of catalyzer, H
2/ C
2h
4=0.28/0.45, the AlEt of 1mL
3hexane solution (1mmol/mL), 1L hexane, 85 DEG C are reacted 2 hours.The synthesis condition of catalyzer is in table 1, and slurry polymerization the results are shown in Table 2.
The synthesis condition of table 1 catalyzer
Table 2 slurry lab scale evaluation result
Claims (10)
1. a preparation method for ethene gas-phase polymerization or copolymerization catalyst composition, is characterized in that; Comprise the steps:
(1) titanium compound, iron cpd and magnesium compound are dissolved in tetrahydrofuran (THF), make mother liquor, wherein titanium compound, iron cpd joined in tetrahydrofuran (THF) or by both and add simultaneously before or after magnesium compound; The weight ratio of titanium compound and iron cpd is 1000:1～1:1; The weight ratio of magnesium compound and iron cpd is 100:1～1:1; The weight ratio of tetrahydrofuran (THF) and iron cpd is 10000:1～1:1;
(2) will join in mother liquor prepared by (1) step through Overheating Treatment and chemically treated improved silica carrier, return stirring 1 hour, purge dry with high pure nitrogen to it afterwards, remove excessive tetrahydrofuran (THF), the residue content of controlling tetrahydrofuran (THF) accounts for 10～15wt% of products therefrom gross weight;
(3) solids step (2) being obtained, is suspended in lower paraffin hydrocarbons solvent, at room temperature reduces processing with one or more alkylaluminium cpds, and the reduction treatment time is 30min, then purges dryly with high pure nitrogen, makes described catalyst composition.
2. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, is characterized in that:
Described lower paraffin hydrocarbons solvent is iso-pentane, pentane or hexane.
3. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, is characterized in that:
Through Overheating Treatment with chemically treated silica supports is spherical or class is spherical, its median size is 10～100 μ m, specific surface area 250～800m
2/ g; Silicon-dioxide is processed as follows:
A. silicon-dioxide is placed in to gas-phase fluidized-bed activator, blows fluidisation with nitrogen anhydrous, anaerobic, be progressively warming up to 200～700 DEG C, constant temperature dehydration 4～10 hours, makes dehydrated silica;
B. in dehydrated silica, add alkane solvent, the add-on of solvent is 10mL/g SiO
2and add the hydroxyl of alkyl metal cpd treat surface, described alkyl metal cpd is aluminum alkyls, the weight ratio of its consumption is: A1/Si is 0.05～0.1:1, under room temperature, stir 1～4 hour, heating makes alkane solvent evaporation, and the temperature of evaporation is 20～30 DEG C, obtains having the activation silicon-dioxide of mobility.
4. according to the ethene gas-phase polymerization described in claim l or the preparation method of copolymerization catalyst composition, it is characterized in that: described magnesium compound is MgCl
2, MgBr
2, MgI
2or its mixture.
5. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, is characterized in that: described titanium compound is Ti (OR)
4-nXn or TiX
3, in formula, R is C
1～C
xaliphatic group, X is one or more of F, Cl, Br, the integer that n is 1～4.
6. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, is characterized in that: the structure of wherein said iron containing compounds is suc as formula shown in I:
The structure of I late transition metal complex
Wherein: R
1～R
3for alkyl, alkoxyl group, phenoxy group, phenmethyl, halogen etc.; M is Fe.
7. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, is characterized in that: the general formula of described alkylaluminium cpd is AlR
mx
3-m, R is identical or not identical C
1-8alkyl, X is halogen, the integer that m is 1～3.
8. the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition, is characterized in that: described alkylaluminium cpd is AlEt
3, Al (iso-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3, AlEt
2the mixture of one or more in Cl.
9. ethene gas-phase polymerization or a copolymerization catalyst composition, is characterized in that: it is prepared by the preparation method of ethene gas-phase polymerization according to claim 1 or copolymerization catalyst composition.
10. an application for ethene gas-phase polymerization claimed in claim 9 or copolymerization catalyst composition, is characterized in that: described catalyzer forms together with promotor alkylaluminium cpd that complex catalyst system closes for ethylene homo or the copolymerization catalyst of ethene and other alpha-olefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310103401.5A CN104072646B (en) | 2013-03-28 | 2013-03-28 | Ethylene gas-phase polymerization or copolymerization catalyst composition, preparation and application thereof |
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| WO2016095678A1 (en) * | 2014-12-16 | 2016-06-23 | 华东理工大学 | Supported polymetal olefin polymerization catalyst, preparation method and use thereof |
| CN109400778A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst and olefine polymerizing process for olefinic polymerization |
| CN113583159A (en) * | 2021-09-14 | 2021-11-02 | 无锡玖汇科技有限公司 | Supported polyolefin catalyst and preparation method thereof |
| CN113583160A (en) * | 2021-09-14 | 2021-11-02 | 无锡玖汇科技有限公司 | Preparation method of composite carrier |
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| CN113583160A (en) * | 2021-09-14 | 2021-11-02 | 无锡玖汇科技有限公司 | Preparation method of composite carrier |
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| CN104072646B (en) | 2016-11-02 |
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