CN101786019A - 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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- CN101786019A CN101786019A CN201010115511A CN201010115511A CN101786019A CN 101786019 A CN101786019 A CN 101786019A CN 201010115511 A CN201010115511 A CN 201010115511A CN 201010115511 A CN201010115511 A CN 201010115511A CN 101786019 A CN101786019 A CN 101786019A
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- cyclopentadienyl
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a transition metal catalyst containing cyclopentadienyl and preparation and application thereof. The catalyst is formed by that an organic ligand containing cyclopentadienyl and a metallocene compound containing a phosphoric organic ligand are loaded on a silica carrier; the structural general formula of the metallocene compound is ((R1Cp)2C1R2C2R3(P(R4)2)) MX, wherein Cp is a ligand group containing a cyclopentadiene skeleton, two adjacent substituent groups on R1Cp can be mutually connected to form a more than binary condensed ring; M is selected from titanium, zirconium or hafnium, X is selected from halogen, C1-C24 alkyl, alkoxy, silica or alkaryl; C1R2 and C2R3 can be connected by double bonds or single bond; R1-R4 are selected from hydrogen, alkyl or alkenyl or aryl; P (R4)2 is a phosphoric substituent group; and the polymeric activity of the catalyst is 3100g PE/ gcat.h, polymer grains are sphaeroid, and bulk density is 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; 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 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; The central atom mol ratio of aluminium and transistion metal compound is 10～3000; Polymerization temperature is-78 ℃～200 ℃, and pressure is 0.1～10Mpa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958566A (en) * | 2011-11-25 | 2014-07-30 | 巴斯夫欧洲公司 | Increase of molar mass of polyalkylene polyamines by homogeneously catalyzed alcohol amination |
| CN104059177A (en) * | 2013-03-21 | 2014-09-24 | 中国石油化工股份有限公司 | Supported single metallocene catalyst used for ethylene polymerization |
| CN106832119A (en) * | 2017-02-17 | 2017-06-13 | 宁波工程学院 | Norborneol alkenes, tetrafluoroethene and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
| CN111229329A (en) * | 2018-11-29 | 2020-06-05 | 万华化学集团股份有限公司 | Silica gel supported monophosphine ligand, ethylene oligomerization catalyst composition comprising same and ethylene oligomerization method |
| CN116693729A (en) * | 2023-08-02 | 2023-09-05 | 研峰科技(北京)有限公司 | Method for synthesizing cyclopentadienyl titanium trichloride as metallocene catalyst |
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| CN1910207A (en) * | 2004-09-03 | 2007-02-07 | Lg化学株式会社 | Supported metallocene catalyst, method of preparing the catalyst and method of preparing polyolefin using the catalyst |
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2010
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| EP1033371A1 (en) * | 1999-03-02 | 2000-09-06 | TARGOR GmbH | Transition metal compound, catalyst system, process for the preparation thereof and its use for the polymerization of olefins |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958566A (en) * | 2011-11-25 | 2014-07-30 | 巴斯夫欧洲公司 | Increase of molar mass of polyalkylene polyamines by homogeneously catalyzed alcohol amination |
| CN104059177A (en) * | 2013-03-21 | 2014-09-24 | 中国石油化工股份有限公司 | Supported single metallocene catalyst used for ethylene polymerization |
| CN104059177B (en) * | 2013-03-21 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of load single metallocene catalyst for vinyl polymerization |
| CN106832119A (en) * | 2017-02-17 | 2017-06-13 | 宁波工程学院 | Norborneol alkenes, tetrafluoroethene and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
| CN106832119B (en) * | 2017-02-17 | 2019-03-29 | 宁波工程学院 | Norborneol alkenes, tetrafluoroethene and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
| CN111229329A (en) * | 2018-11-29 | 2020-06-05 | 万华化学集团股份有限公司 | Silica gel supported monophosphine ligand, ethylene oligomerization catalyst composition comprising same and ethylene oligomerization method |
| CN111229329B (en) * | 2018-11-29 | 2022-08-05 | 万华化学集团股份有限公司 | Silica gel supported monophosphine ligand, ethylene oligomerization catalyst composition comprising same and ethylene oligomerization method |
| CN116693729A (en) * | 2023-08-02 | 2023-09-05 | 研峰科技(北京)有限公司 | Method for synthesizing cyclopentadienyl titanium trichloride as metallocene catalyst |
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