CN101786019B - Transition metal catalyst containing cyclopentadienyl and preparation and application thereof - Google Patents
Transition metal catalyst containing cyclopentadienyl and preparation and application thereof Download PDFInfo
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- CN101786019B CN101786019B CN201010115511XA CN201010115511A CN101786019B CN 101786019 B CN101786019 B CN 101786019B CN 201010115511X A CN201010115511X A CN 201010115511XA CN 201010115511 A CN201010115511 A CN 201010115511A CN 101786019 B CN101786019 B CN 101786019B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052735 hafnium Chemical group 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- -1 C1~C24Alkyl Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims abstract description 3
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- KKDBZWZRJNRBGA-UHFFFAOYSA-L Cl[Ti]Cl.[CH]1C=CC=C1 Chemical compound Cl[Ti]Cl.[CH]1C=CC=C1 KKDBZWZRJNRBGA-UHFFFAOYSA-L 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000007725 thermal activation Methods 0.000 claims description 3
- ZCSQKFUQLUJERT-UHFFFAOYSA-K cyclopenta-1,3-diene titanium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3].C1C=CC=C1 ZCSQKFUQLUJERT-UHFFFAOYSA-K 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 150000001925 cycloalkenes Chemical class 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 230000037048 polymerization activity Effects 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract 2
- 239000011574 phosphorus Substances 0.000 abstract 2
- 125000001424 substituent group Chemical group 0.000 abstract 2
- 150000002367 halogens Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000004698 Polyethylene Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- DQQNMIPXXNPGCV-UHFFFAOYSA-N 3-hexyne Chemical group CCC#CCC DQQNMIPXXNPGCV-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical compound [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UDEISTCPVNLKRJ-UHFFFAOYSA-N oct-3-yne Chemical group CCCCC#CCC UDEISTCPVNLKRJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 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)
Abstract
The invention relates to a transition metal catalyst containing cyclopentadienyl and a preparation method thereofAnd applications; the composition is formed by that a metallocene compound containing cyclopentadienyl organic ligand and phosphorus-containing organic ligand is loaded on a silicon dioxide carrier, and the structural general formula of the metallocene compound is ((R)1Cp)2C1R2C2R3(P(R4)2) MX): wherein Cp is a ligand group containing a cyclopentadiene skeleton, R1Two adjacent substituents on Cp can be connected with each other to form a fused ring with more than two elements; m is selected from titanium, zirconium or hafnium, X is selected from halogen, C1～C24Alkyl, alkoxy, siloxy or alkaryl of ; c1R2And C2R3May be connected by a double or single bond; r1-R4Selected from hydrogen, alkyl or alkenyl or aryl; p 4)2Is a phosphorus-containing substituent; the polymerization activity of the catalyst was 3100g PE/gcat.h, the polymer particles were in the form of spheres and the bulk density was 0.32 g/ml.
Description
Technical field
The present invention relates to a kind of titanium, zirconium or hafnium transient metal complex that contains cyclopentadienyl group and be carried on catalyst and preparation and application on the silica supports.
Background technology
Metallocene catalyst has high activity and high copolymerization performance, and the polymer of preparation has the characteristics of narrow molecular weight distribution.The homogeneous phase metallocene catalyst system exists in product form difference and the polymerization process promoter aluminium alkyl oxygen alkane consumption to cross problems such as height in polymerization process.By homogeneous catalyst being carried on the carrier with definite shape and intensity, in polymerization process, polymer obtains high fluidity, the polymeric articles of high-bulk-density by the form of replicating vector.Not only help polymerization process mass transport and packing, and can effectively reduce needed co-catalyst consumption in the polymerization process, thereby reduce cost, reduce content of ashes in the polymer, make metallocene catalyst can be applicable to slurry process and vapor phase method manufacture of polyolefins device.
Porous material such as silica gel, aluminium oxide, zeolite, clay etc. are often used as load metallocene and back transition catalyst.For example, European patent EP 0206794, EP0323716, US5332706, the silica gel effect of US5626015 by metallocene and MAO were handled can effectively improve polymer and glue still, the problem of polymer morphology difference.But the catalytic activity of carried catalyst is lower, is unfavorable for the large-scale industrialization application
Summary of the invention
The purpose of this invention is to provide a kind of being carried on the silica supports with titanium, zirconium or the hafnium transient metal complex that contains cyclopentadienyl group is major catalyst, aluminum contained compound is polyolefin catalyst and the preparation and the application of co-catalyst, and the gained catalyst can be used for the equal polymerization and the combined polymerization of catalyzed ethylene, propylene and other alpha-olefins.Carried catalyst preparation method of the present invention is simple, easy operating, and good reproducibility, the olefinic polymerization of gained catalyst has advantages of high catalytic activity.
Its composition is to be carried on the silica supports with the metallocene compound that contains cyclopentadienyl group organic ligand and phosphorous organic ligand to constitute, and the general structure of metallocene compound is ((R
1Cp)
2C
1R
2C
2R
3(P (R
4)
2)) MX: wherein Cp is the ligand groups that contains cyclopentadienyl skeleton, R
1Two adjacent substituting groups on the Cp can be connected with each other and form the above condensed ring of binary; M is selected from titanium, zirconium or hafnium, and X is selected from halogen, C
1～C
24Alkyl, alkoxyl, siloxy or alkaryl; C
1R
2And C
2R
3Between can connect by two keys or singly-bound; R
1-R
4Be selected from hydrogen, alkyl or alkenyl or aryl; P (R
4)
2Be phosphorous substituting group.
Contain the transition metal compound loaded on spherical silica of cyclopentadienyl group organic ligand, wherein organic ligand comprises that all contain the compound of cyclopentadienyl group, comprise cyclopentadienyl group and derivative thereof, part can be bridging also can be non-bridging, what participate in coordination can be a cyclopentadienyl group and derivative thereof, also can be two cyclopentadienyl groups and derivative thereof.
Being prepared as follows of a kind of transition-metal catalyst that contains cyclopentadienyl group of the present invention:
Preparation process is as follows:
(1) thermal activation of carrier and finishing
Spherical silica is placed Muffle furnace, heat-treat from 25 ℃-800 ℃ and to slough surface water and most surfaces hydroxyl, after being cooled to room temperature, get 1 gram silica, add 10 milliliters of toluene, drip the dimethyldichlorosilane of 2-5 mM, reacted 1-5 hour down at 50 ℃-150 ℃, vacuum is removed toluene and excessive dichlorosilane, with solid dispersed in oxolane, in-50 ℃-30 ℃ adding 1.0 mM cyclopentadienyl group lithiums, reacted 1-5 hour ,-50 ℃-30 ℃ are continued to add 1.0 mM n-butyllithium solutions reaction 1-5 hour, add 1.0 mM cyclopentadiene tri-chlorination zirconiums then, cyclopentadiene titanium trichloride or cyclopentadiene tri-chlorination hafnium, reacted 1-3 hour, with oxolane washing 4 times, drying is removed to desolvate and is obtained bis cyclopentadienyl zirconium dichloride, the silica supports that cyclopentadienyl titanium dichloride or dichloro hafnocene are modified.
(2) preparation of carried catalyst
Under the high pure nitrogen protection;-50 ℃-30 ℃ to containing zirconium; the bis cyclopentadienyl zirconium dichloride of titanium or hafnium 1 mM; adding n-butyllithium solution 2 mMs in the silica supports that cyclopentadienyl titanium dichloride or dichloro hafnocene are modified kept 1-2 hour; the N that adds 2 mMs then; N-dimethyl-4-methylamino pyridine; at room temperature reacted 1-2 hour; add 3-hexin 1 mM and continue to stir 1-3h; add diphenyl phosphorus chloride 1 mM again and stir 1-3h, with the oxolane washing, filter under the room temperature in this temperature; repeated washing filters; dry removing desolvated, with zirconium in the carrier; the mole of titanium or hafnium is a benchmark, adds the toluene solution of MAO; the mol ratio of aluminium and zirconium/titanium/hafnium metal is 50-5000; stirred 1-3 hour under the room temperature, vacuum is removed toluene, uses hexane wash; filter, drying obtains supported catalysts.
(3) the polymerization evaluation of carried catalyst
Two liters of stainless steel autoclave dryings vacuumize nitrogen replacement.Add 1 liter of anhydrous and oxygen-free hexane successively, 1 milliliter of triethyl aluminum (0.5 mole every liter) removal of impurities, 0.1 gram supported catalysts, 70 ℃ fed the 1.0MPa ethylene polymerization 1 hour, calculated polymerization activity.
The polymerization activity of catalyst is 3100g PE/gcat.h, and polymer particle is ball-type, and bulk density is 0.32 grams per milliliter.
The specific embodiment:
Embodiment 1: two (cyclopentadienyl groups) (1,2-diphenyl-2-diphenylphosphine-vinyl) zirconium chloride loaded catalyst
(1) thermal activation of carrier and finishing
Get 50 gram spherical silicas (Grace 955), in Muffle furnace, in 2 hours, be warmed up to 400 ℃, 400 ℃ of following constant temperature 4 hours from room temperature; In 30 minutes, be warmed up to 600 ℃ from 400 ℃ then, cooled to 200 ℃ then naturally in 2 hours, from Muffle furnace, take out fast and transfer in three mouthfuls of reaction bulbs, vacuumize nitrogen replacement at 600 ℃ of following constant temperature.Get 1 gram silica gel and disperse in hexane, with the Lithium Aluminium Hydride reaction, measure the gas flow that produces, calculating the silica surface hydroxy radical content is the every grams of 1.2 mM hydroxyls.Get the silica after 5 grams activate, add 50 milliliters of toluene, drip 3 gram dimethyldichlorosilanes, reacted 5 hours down at 100 ℃.Vacuum is removed organic solvent and excessive dichlorosilane, uses hexane wash three times, and each 50 milliliters, solvent removed in vacuo.The gained solid dispersed is in 50 milliliters of oxolanes, and 0 ℃ adds cyclopentadienyl group lithium (by cyclopentadiene and butyl lithium 0 ℃ of prepared in reaction) 6 mMs and reacted 2 hours under this temperature.0 ℃ is continued to add n-butyllithium solution 6 mMs reaction 3 hours, adds cyclopentadiene tri-chlorination zirconium (CpZrCl then
3) 6 mMs, reacted 3 hours, with oxolane washing 4 times, the dry silica supports that obtains the bis cyclopentadienyl zirconium dichloride modification except that desolvating.It is 4.5wt% (the every gram silica of about 0.5 mM) that AAS records zirconium content.
(2) preparation of carried catalyst
Under protecting 0 ℃, high pure nitrogen in the silica supports (containing zirconium 2.5 mMs) that 5 gram bis cyclopentadienyl zirconium dichlorides are modified, adds n-butyllithium solution 5 mMs reaction 2 hours.The N that adds 2.5 mMs then, N-dimethyl-4-methylamino pyridine at room temperature reacted 2 hours, added dibenzenyl 2.5 mMs and continued to stir 3 hours, added diphenyl phosphorus chloride 2.5 mMs again and stirred 3h in this temperature.With the oxolane washing, filter under the room temperature, repeated washing filters, and dry removing desolvated.5.4 milliliters of 10% toluene solutions (aluminium is 3000 with zirconium/titanium/hafnium metal ratio) that add MAO stirred 3 hours under the room temperature, and vacuum is removed toluene, used hexane wash 5 times, and each 50 milliliters, to filter, drying obtains supported catalysts.
(3) the polymerization evaluation of carried catalyst
Two liters of stainless steel autoclave dryings vacuumize nitrogen replacement.Add 1 liter of anhydrous and oxygen-free hexane successively, 1 milliliter of triethyl aluminum (1.0 moles every liter) removal of impurities, 0.1 gram supported catalysts, 70 ℃ fed the 1.0MPa ethylene polymerization 1 hour, obtained polymer 360 grams, and polymerization activity is 3600g PE/gcat.h.
Embodiment 2: two (cyclopentadienyl groups) (1,2-diethyl-2-diphenylphosphine-vinyl) zirconium chloride loaded catalyst
Replace dibenzenyl with diethylacetylene, preparation method and polymerization evaluation are with embodiment 1, and polymerization activity is 3400g PE/gcat.h.
Embodiment 3: two (cyclopentadienyl groups) (1-ethyl-2-butyl-2-diphenylphosphine-vinyl) zirconium chloride loaded catalyst
Replace dibenzenyl with 1-ethyl-2-butyl-acetylene, preparation method and polymerization evaluation are with embodiment 1, and polymerization activity is 3200g PE/gcat.h.
Embodiment 4: two (cyclopentadienyl groups) (1,2-diphenyl-2-diphenylphosphine-vinyl) titanium chloride loaded catalyst
Replace bis cyclopentadienyl zirconium dichloride with cyclopentadienyl titanium dichloride, preparation method and polymerization evaluation are with embodiment 1, and the carried catalyst polymerization activity is 2100g PE/gcat.h.
Embodiment 5: two (cyclopentadienyl groups) (1,2-diphenyl-2-diphenylphosphine-vinyl) hafnium chloride loaded catalyst
Replace bis cyclopentadienyl zirconium dichloride with the dichloro hafnocene, preparation method and polymerization evaluation are with embodiment 1, and the carried catalyst polymerization activity is 1800g PE/gcat.h.
Embodiment 6: ethene and 1-hervene copolymer close reaction
Method for preparing catalyst is with embodiment 1.Two liters of stainless steel autoclave dryings vacuumize nitrogen replacement.Add 1 liter of anhydrous and oxygen-free hexane successively, 10 mM 1-hexenes, 1 milliliter of triethyl aluminum (0.5 mole every liter) removal of impurities, 0.1 gram supported catalysts, 70 ℃ fed the 1.0MPa ethylene polymerization 1 hour, obtained polymer 380 grams, and polymerization activity is 3800g PE/gcat.h.
Embodiment 7: ethene and dicyclopentadiene copolymerization
Method for preparing catalyst is with embodiment 1.Two liters of stainless steel autoclave dryings vacuumize nitrogen replacement.Add 1 liter of anhydrous and oxygen-free hexane successively, 10 mM dicyclopentadienes, 1 milliliter of triethyl aluminum (0.5 mole every liter) removal of impurities, 0.1 gram supported catalysts, 70 ℃ fed the 1.0MPa ethylene polymerization 1 hour, obtained polymer 170 grams, and polymerization activity is 1700g PE/gcat.h.
Claims (4)
1. transition-metal catalyst that contains cyclopentadienyl group, it is characterized in that: its composition is to be carried on the silica supports with the metallocene compound that contains cyclopentadienyl group organic ligand and phosphorous organic ligand to constitute, and the general structure of metallocene compound is
((R
1Cp)
2C
1R
2C
2R
3(P (R
4)
2)) MX: wherein Cp is the ligand groups that contains cyclopentadienyl skeleton, R
1Two adjacent substituting groups on the Cp can be connected with each other and form the above condensed ring of binary; M is selected from titanium, zirconium or hafnium, and X is selected from halogen, C
1～C
24Alkyl, alkoxyl, siloxy or alkaryl; C
1R
2And C
2R
3Between can connect by two keys or singly-bound; R
1-R
4Be selected from hydrogen, alkyl or alkenyl or aryl; P (R
4)
2Be phosphorous substituting group.
2. described preparation method who contains the transition-metal catalyst of cyclopentadienyl group of claim 1 is characterized in that:
Preparation process is as follows:
(1) thermal activation of carrier and finishing
Spherical silica is placed Muffle furnace, heat-treat from 25 ℃-800 ℃ and to slough surface water and most surfaces hydroxyl, after being cooled to room temperature, get 1 gram silica, add 10 milliliters of toluene, drip the dimethyldichlorosilane of 2-5 mM, reacted 1-5 hour down at 50 ℃-150 ℃, vacuum is removed toluene and excessive dichlorosilane, with solid dispersed in oxolane, in-50 ℃-30 ℃ adding 1.0 mM cyclopentadienyl group lithiums, reacted 1-5 hour ,-50 ℃-30 ℃ are continued to add 1.0 mM n-butyllithium solutions reaction 1-5 hour, add 1.0 mM cyclopentadiene tri-chlorination zirconiums then, cyclopentadiene titanium trichloride or cyclopentadiene tri-chlorination hafnium, reacted 1-3 hour, with oxolane washing 4 times, drying is removed to desolvate and is obtained bis cyclopentadienyl zirconium dichloride, the silica supports that cyclopentadienyl titanium dichloride or dichloro hafnocene are modified;
(2) preparation of carried catalyst
Under the high pure nitrogen protection;-50 ℃-30 ℃ to containing zirconium; the bis cyclopentadienyl zirconium dichloride of titanium or hafnium 1 mM; adding n-butyllithium solution 2 mMs in the silica supports that cyclopentadienyl titanium dichloride or dichloro hafnocene are modified kept 1-2 hour; the N that adds 2 mMs then; N-dimethyl-4-methylamino pyridine; at room temperature reacted 1-2 hour; add 3-hexin 1 mM and continue to stir 1-3h; add diphenyl phosphorus chloride 1 mM again and stir 1-3h, with the oxolane washing, filter under the room temperature in this temperature; repeated washing filters; dry removing desolvated, with zirconium in the carrier; the mole of titanium or hafnium is a benchmark, adds the toluene solution of MAO; aluminium and zirconium; the mol ratio of titanium or hafnium metal is 50-5000; stirred 1-3 hour under the room temperature, vacuum is removed toluene, uses hexane wash; filter, drying obtains supported catalysts.
3. the preparation method who contains the transition-metal catalyst of cyclopentadienyl group according to claim 2 is characterized in that: titanium, zirconium or hafnium account for the 0.01-30% of total catalyst weight by weight percentage.
4. according to the right 1 described application that contains the transition-metal catalyst of cyclopentadienyl group, it is characterized in that: this catalyst is used for ethene, C
3～C
20Alpha-olefin, cycloolefin, alkadienes or their two or more mixture homopolymerization or copolymerization arbitrarily; Co-catalyst is alkyl aluminum, haloalkyl aluminium or alkylaluminoxane; Aluminium and M mol ratio are 10～3000; Polymerization temperature is-78 ℃～200 ℃, and pressure is 0.1～10Mpa.
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