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CN101905173A - Supported metallocene catalyst and preparation and application thereof - Google Patents

Supported metallocene catalyst and preparation and application thereof Download PDF

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Publication number
CN101905173A
CN101905173A CN2010102315192A CN201010231519A CN101905173A CN 101905173 A CN101905173 A CN 101905173A CN 2010102315192 A CN2010102315192 A CN 2010102315192A CN 201010231519 A CN201010231519 A CN 201010231519A CN 101905173 A CN101905173 A CN 101905173A
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catalyst
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CN101905173B (en
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陈商涛
毛静
义建军
王莉
王仪森
朱百春
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Petrochina Co Ltd
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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
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    • 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 load type metallocene catalyst and a preparation method and an application thereof; activated SiO2Reacting with halosilane containing double bond to obtain functionalized SiO2A solid; the unsaturated double-bonded halosilane is added in an amount according to the activation of SiO2The surface hydroxyl content of is calculated, halosilane and SiO2The molar ratio of the surface hydroxyl groups is (10000: 1) - (1: 10000); functionalized SiO2With an aluminum-containing organometallic compound; then adding the solution of the metallocene compound into a reaction system for reaction, removing the solvent after the reaction is finished, washing, and carrying out decompression and pumping-out treatment to obtain a solid catalyst; the central atom Ti, Zr or Hf of the metallocene compound accounts for 0.01-50% of the weight of the carrier in percentage by weight; the catalyst is suitable for gas phase process, solution process, slurry process and bulk polymerization process, and has high stability and no adhesion to the reactor during synthesizing polyethylene homopolymer and copolymer.

Description

A kind of carried metallocene catalyst and preparation thereof and application
Technical field
The present invention relates to a kind of carried metallocene catalyst and preparation thereof and application.
Background technology
The metallocene catalysis agent carrierization is exactly that metallocene catalyst is passed through physics or chemical method, loads on SiO 2, MgCl 2, molecular sieve, clay, Al 2O 3On inorganic carrier, perhaps load on the organic carriers such as styrene polymer.At present, most widely used and industrialized supported metallocene catalyst is exactly SiO 2Carrier metallocene catalyst.SiO 2The carrying method of carrier metallocene catalyst has three kinds: first kind of carrying method is that metallocene compound is directly loaded on SiO 2Go up (WKaminsky, Makromol.Chem.Rapid Commun., 1993,14:239, WO9632423), but because ligand of metallocene can make part come off with the hydroxyl reaction on the carrier, cause the complicated of the reduction of catalyst activity and reaction; Second kind of carrying method is that metallocene compound loads on SiO indirectly by MAO or alkyl aluminum 2Go up (US6153551, US5240894, US4937217, US4912075, US4935937 etc.), the advantage of this class catalyst is active high, the character of carrier is less to the influence of metallocene, carrier does not generally have regulating and controlling effect to the microstructure of polymer, and can reduce the consumption of MAO when polymerization, be carrying method comparatively commonly used; The third method is the synthetic metallocene complex of original position on carrier, and the preparation of metallocene and load are carried out simultaneously, the zirconium chloride (ZrCl that makes gasification earlier that typical patent such as EP708116 describe 4) under 160～450 ℃ of temperature, contact and load again that load is good ZrCl with carrier 4With the lithium salts reaction of part, the last cooperation with co-catalyst is used for polymerization, and this load process requires high temperature, high vacuum not to be suitable for industrial production.
In addition, when adopting second method to prepare carried metallocene catalyst, also can handle the carrier of modification again with MAO, then load metallocene earlier with other compound-modified carrier.Main purpose with other compound-modified carrier is for the hydroxy radical content on the adjusting carrier earlier, further weakens the adverse effect of carrier to catalyst simultaneously, thereby improves the activity of supported metallocene catalyst.Can be commonly used to dressing agent with the compound that surface hydroxyl reacts as carrier, reported have a chlorosilane (K Soga, Makromol.Chem., 1993,194:3499), siloxanes (EP727443), carbonic ester (WO9534584), bisphenol-A (EP685494), ammonium fluoride (JP0848715) etc.
Summary of the invention
The purpose of this invention is to provide a kind of effective SiO 2The functional modification method, as the preparing carriers carried metallocene catalyst, the gained catalyst can be used in the homopolymerization and combined polymerization of ethene, propylene, other alpha-olefins and alkadienes, the feature that has advantages of high catalytic activity and do not glue still.
Carried metallocene catalyst of the present invention: major catalyst is a metallocene compound, central atom is IVB group 4 transition metal element (Ti, Zr, Hf), part comprises cyclopentadiene and derivative thereof, or indenyl and derivative thereof, or fluorenyl and derivative thereof, or the cyclopentadiene of bridging and derivative thereof, or the indenyl of bridging and derivative thereof, or the fluorenyl of bridging and derivative thereof; Catalyst-supporting support is modified SiO 2, co-catalyst is a kind of or mixture in alkyl aluminum or the alkylaluminoxane.
Concrete preparation process is as follows:
1. the functional modification of silica
Earlier with the SiO that activates 2Be dispersed in the dry solvent, stirring condition adds the halosilanes that contains unsaturated double-bond down and begins reaction, the control reaction temperature is at-40 ℃～150 ℃, be preferably-5 ℃～100 ℃, reaction time is 0.5～200h, is preferably 1～100h, and reaction finishes after desolventize, washing, post processings such as decompressing and extracting obtain the SiO of functionalization 2Solid.
Described activation SiO 2Time be 0.5～200h, be preferably 1～100h, activation temperature is 100～1000 ℃, preferred 200～800 ℃, through overactivation SiO 2The surface have hydroxyl.
The described addition that contains the unsaturated double-bond halosilanes is according to activation SiO 2The adsorbed hydroxyl content calculate halosilanes and SiO 2The mol ratio of surface hydroxyl is (10000: 1)～(1: 10000), wherein preferred (100: 1)～(1: 100).
Described dry solvent is organic solvents such as toluene, oxolane, dimethylbenzene, hexane, carrene, heptane, preferred toluene, hexane, and the solvent adding amount of 1g activated silica gel is 1g: 0.00001～100000mL.
The described halosilanes that contains unsaturated double-bond is the compound that meets following formula:
Figure BSA00000197839000031
Wherein X is a halogen atom; A is terminal double bond containing aryl or double bond containing alkyl; R 1And R 2Can be H atom, alkyl, aryl, halogen atom, preferred alkyl.
2. functionalization SiO 2The preparation of load metallocene compound catalyst
To go up the functionalization 1g SiO of step preparation earlier 2Be dispersed in the solvent of 0.00001～100000mL drying, the following adding of stirring condition 0.00001mol～1000000mol contains the aluminium organo-metallic compound and reacts, the control reaction temperature is at-40 ℃～150 ℃, be preferably-5 ℃～100 ℃, reaction time is 0.5～200h, is preferably 1～100h.Solution with metallocene compound is added in the reaction system then, continues reaction, and the control reaction temperature is preferably-5 ℃～100 ℃ at-40 ℃～150 ℃, and the reaction time is 0.5～200h, is preferably 1～100h.Reaction finishes after desolventize, washing, and post processings such as decompressing and extracting obtain solid catalyst.
Described functionalization SiO 2Metallocene compound central atom Ti, Zr or Hf account for 0.01～50% of vehicle weight by weight percentage in the load metallocene compound catalyst.
The described aluminium organo-metallic compound that contains is alkyl aluminum or alkylaluminoxane, the preferable methyl aikyiaiurnirsoxan beta.
Described organic metallocene compound can be any symmetrical structure or the unsymmetric structure that adopts general synthetic method to prepare, and the metallocene compound of bridging or non-bridging also can be one or more metallocene compounds.
The solvent that described metallocene compound solution adopts is identical with the dry solvent described in the step 1.
The concentration of described metallocene compound solution is 0.0001%～99.99%, preferred 0.1%～99%.
3. olefinic polyreaction
The present invention also provides a kind of method of carrying out ethylene polymerization, is with support type functionalization SiO of the present invention 2Metallocene compound is the catalyst of polymerisation, in polymerisation, also can add second monomer and carry out copolymerization.
Also need add co-catalyst in the described catalyst, described co-catalyst is one or more in alkylaluminoxane, the alkyl aluminum compound.Common alkylaluminoxane is MAO, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide etc.; Alkyl aluminum is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or tri-n-hexyl aluminum etc.
Described second monomer is propylene, C 4～C 20Alpha-olefin, cycloolefin, alkadienes in any one or two kinds, preferred hexene, hot rare.
In the described polymerisation, promoter metal aluminium (Al) is 10～3000 with the mol ratio Al/M of catalyst center metal (M); Polymerization temperature is-78 ℃～200 ℃, and preferable polymerization temperature is 20～100 ℃; Polymerization pressure is 0.1～10Mpa, and preferred polymeric pressure is 0.1～5Mpa.
The carried metallocene catalyst of the present invention's preparation is applicable to vapor phase method, solwution method, slurry process and bulk technique.This catalyst is used for ethene, propylene, C 4～C 20Alpha-olefin, cycloolefin, the homopolymerization or the copolymerization of two or more mixture arbitrarily in them of alkadienes.
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited thereto.
Specific implementation method
Embodiment 1:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl vinyl chlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip 0.02mL dimethyl vinyl chlorosilane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 75 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. preparation ethyl bridge dichloro two indenes close the zirconium loaded catalyst
The functionalization SiO that the last step was obtained 2Be dispersed in uniformly in the toluene solution of 50mL drying, add the MAO solution of 0.041mol, stir 10h under the room temperature.Then 0.35g ethyl bridge dichloro two indenes are closed in the toluene that zirconium is dissolved in the 100mL drying, be added in the reaction system, 60 ℃ down behind the reaction 8h, leave standstill, upper toluene solution is drained, used dry hexane wash more repeatedly, obtain ruddy solid catalyst after the drying.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
The 2L stainless steel cauldron, after nitrogen is fully replaced, the hexane solution and the 2mL triethyl aluminum (concentration 1.8mol/L) that add the 1L drying carry out removal of impurities, add last loaded ethyl bridge dichloro two indenes that make that go on foot of 5mL MAO (concentration 2.1mol/L) and 0.1g then and close Zr catalyst, continue to feed ethylene gas, keeping the pressure in the still is 1Mpa, is warming up to 75 ℃, polymerisation 1h under this temperature, reaction temperature remains on 75 ℃ in the course of reaction.After reaction finished, logical cooling water to room temperature, stopped the still temperature drop to stir, and gets rid of unreacting gas, and drying obtains the product white polymer.The parameter and the catalytic result of polymerization process see Table 2.
The 2L stainless steel cauldron, after nitrogen is fully replaced, the hexane solution, 10mL hexene and the 2mL triethyl aluminum (concentration 1.8mol/L) that add the 1L drying carry out removal of impurities, add last loaded ethyl bridge dichloro two indenes that make that go on foot of 5mL MAO (concentration 2.1mol/L) and 0.1g then and close Zr catalyst, continue to feed ethylene gas, keeping the pressure in the still is 1Mpa, is warming up to 75 ℃, polymerisation 1h under this temperature, reaction temperature remains on 75 ℃ in the course of reaction.After reaction finished, logical cooling water to room temperature, stopped the still temperature drop to stir, and gets rid of unreacting gas, and drying gets white polymer.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 2:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl-allyl chlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip 0.02mL dimethyl-allyl chlorosilane under the room temperature, begin heating after dropwising, react 24h down, stop to stir at 50 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 3:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the methyl phenyl vinyl chlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip 0.26mL methyl phenyl vinyl chlorosilane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 75 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 4:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the hydride modified SiO of dimethyl vinyl bromide 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip 0.20mL dimethyl vinyl bromide silane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 80 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 5:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the methacrylic dichlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip 0.30mL methacrylic dichlorosilane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 80 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 6:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. vinyl trichlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip the 0.10mL vinyl trichlorosilane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 50 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 7:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the trivinyl chlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip 0.50mL trivinyl chlorosilane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 50 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 8:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. vinyl chlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip the 0.10mL vinyl chlorosilane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 50 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 9:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. dimethyl styrene base chlorosilane is modified SiO 2
Silica gel is activated 6h down at 600 ℃.1g SiO with activation 2Be dispersed in uniformly in the toluene solution of 50mL drying, drip 0.10mL dimethyl styrene base chlorosilane under the room temperature, begin heating after dropwising, react 8h down, stop to stir at 90 ℃.Leave standstill upper toluene solution is drained, use dry hexane wash more repeatedly, obtain white SiO after the drying 2Solid particle.Adopt titration method to measure SiO 2The adsorbed hydroxyl content, SiO 2The conversion ratio of surface hydroxyl sees Table 1.
2. ethyl bridge dichloro two indenes close the zirconium loaded catalyst
Test procedure is with embodiment 1.With arsenazo III spectrophotometry loaded ethyl bridge dichloro two indenes close Zr catalyst the zirconium amount of carrying its results are shown in Table 2.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 10:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl vinyl chlorosilane is modified SiO 2
Test procedure is with embodiment 1.
2. prepare two (cyclopentadienyl group) zirconium dichloride loaded catalysts
The functionalization SiO that the last step was obtained 2Be dispersed in uniformly in the toluene solution of 50mL drying, add the MAO solution of 0.041mol, stir 10h under the room temperature.Then two (cyclopentadienyl group) zirconium dichlorides of 0.20g are dissolved in the toluene of 100mL drying, are added in the reaction system, behind 70 ℃ of following reaction 10h, leave standstill, upper toluene solution is drained, used dry hexane wash more repeatedly, obtain ruddy solid catalyst after the drying.Carrying the zirconium amount it the results are shown in Table 2 with two (cyclopentadienyl group) zirconium dichloride catalyst of arsenazo III spectrophotometry support type.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 11:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl vinyl chlorosilane is modified SiO 2
Test procedure is with embodiment 1.
2. prepare two (cyclopentadienyl group) titanium chloride loaded catalysts
The functionalization SiO that the last step was obtained 2Be dispersed in uniformly in the toluene solution of 50mL drying, add the MAO solution of 0.041mol, stir 10h under the room temperature.Then two (cyclopentadienyl group) titanium chloride of 0.20g are dissolved in the toluene of 100mL drying, are added in the reaction system, behind 70 ℃ of following reaction 10h, leave standstill, upper toluene solution is drained, used dry hexane wash more repeatedly, obtain ruddy solid catalyst after the drying.Carrying the titanium amount it the results are shown in Table 2 with two (cyclopentadienyl group) titanium chloride catalyst of arsenazo III spectrophotometry support type.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 12:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl vinyl chlorosilane is modified SiO 2
Test procedure is with embodiment 1.
2. prepare two (ethyl cyclopentadiene) hafnium dichloride loaded catalysts
The functionalization SiO that the last step was obtained 2Be dispersed in uniformly in the toluene solution of 50mL drying, add the MAO solution of 0.041mol, stir 10h under the room temperature.Then two (ethyl cyclopentadiene) hafnium dichloride of 0.80g are dissolved in the toluene of 100mL drying, are added in the reaction system, behind 70 ℃ of following reaction 10h, leave standstill, upper toluene solution is drained, used dry hexane wash more repeatedly, obtain ruddy solid catalyst after the drying.Carrying the hafnium amount it the results are shown in Table 2 with two (ethyl cyclopentadiene) the hafnium dichloride catalyst of arsenazo III spectrophotometry support type.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 13:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl vinyl chlorosilane is modified SiO 2
Test procedure is with embodiment 1.
2. prepare dichloro two fluorenes zirconium loaded catalysts
The functionalization SiO that the last step was obtained 2Be dispersed in uniformly in the toluene solution of 50mL drying, add the MAO solution of 0.041mol, stir 10h under the room temperature.Then 0.40g dichloro two fluorenes zirconiums are dissolved in the toluene of 100mL drying, are added in the reaction system, behind 70 ℃ of following reaction 10h, leave standstill, upper toluene solution is drained, use dry hexane wash more repeatedly, obtain ruddy solid catalyst after the drying.It the results are shown in Table 2 with the zirconium amount of carrying of arsenazo III spectrophotometry support type dichloro two fluorenes Zr catalysts.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 14:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl vinyl chlorosilane is modified SiO 2
Test procedure is with embodiment 1.
2. prepare dimethyl-silicon bridged indene zirconium dichloride loaded catalyst
The functionalization SiO that the last step was obtained 2Be dispersed in uniformly in the toluene solution of 50mL drying, add the MAO solution of 0.041mol, stir 10h under the room temperature.Then 0.20g dimethyl-silicon bridged indene zirconium dichloride is dissolved in the toluene of 100mL drying, is added in the reaction system, behind 70 ℃ of following reaction 10h, leave standstill, upper toluene solution is drained, used dry hexane wash more repeatedly, obtain lurid solid catalyst after the drying.It the results are shown in Table 2 with the titanium amount of carrying of arsenazo III spectrophotometry support type dimethyl-silicon bridged indene zirconium dichloride catalyst.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Embodiment 15:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
1. the dimethyl vinyl chlorosilane is modified SiO 2
Test procedure is with embodiment 1.
2. prepare dimethyl-silicon bridging (tetramethyl-ring pentadiene) (tert-butyl group amido) titanium chloride loaded catalyst
The functionalization SiO that the last step was obtained 2Be dispersed in uniformly in the toluene solution of 50mL drying, add the MAO solution of 0.041mol, stir 10h under the room temperature.Then 0.20g dimethyl-silicon bridging (tetramethyl-ring pentadiene) (tert-butyl group amido) titanium chloride is dissolved in the toluene of 100mL drying, be added in the reaction system, after reacting 10h under 70 ℃, leave standstill, upper toluene solution is drained, use dry hexane wash more repeatedly, obtain the solid catalyst of good fluidity after the drying.It the results are shown in Table 2 with the titanium amount of carrying of arsenazo III spectrophotometry support type dimethyl-silicon bridging (tetramethyl-ring pentadiene) (tert-butyl group amido) titanium chloride catalyst.
3. the polymerization evaluation of ethene
Test procedure is with embodiment 1.The parameter and the catalytic result of polymerization process see Table 2.
Comparative Examples 1:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
The 2L stainless steel cauldron, after nitrogen is fully replaced, the hexane solution and the 2mL triethyl aluminum (concentration 1.8mol/L) that add the 1L drying carry out removal of impurities, add 5mL MAO (concentration 2.1mol/L) then and 0.1g ethyl bridge dichloro two indenes close Zr catalyst, continue to feed ethylene gas, keeping the pressure in the still is 1Mpa, is warming up to 75 ℃, polymerisation 1h under this temperature, reaction temperature remains on 75 ℃ in the course of reaction.After reaction finished, logical cooling water to room temperature, stopped the still temperature drop to stir, and gets rid of unreacting gas, and drying obtains white polymer.The parameter and the catalytic result of polymerization process see Table 2.
Comparative Examples 2:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
Test procedure is with Comparative Examples 1, and catalyst replaces with two (cyclopentadienyl group) zirconium dichlorides, and the parameter and the catalytic result of polymerization process see Table 2.
Comparative Examples 3:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
Test procedure is with Comparative Examples 1, and catalyst replaces with two (cyclopentadienyl group) titanium chloride, and the parameter and the catalytic result of polymerization process see Table 2.
Comparative Examples 4:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
Test procedure is with Comparative Examples 1, and catalyst replaces with two (ethyl cyclopentadiene) hafnium dichloride, and the parameter and the catalytic result of polymerization process see Table 2.
Comparative Examples 5:
All operations all carries out under the anhydrous and oxygen-free condition, and solvent for use all needs dehydration and deoxidation to handle.
Test procedure is with Comparative Examples 1, and catalyst replaces with dichloro two fluorenes zirconiums, and the parameter and the catalytic result of polymerization process see Table 2.
Table 1 SiO 2The variation of The adsorbed hydroxyl content
Hydroxyl conversion ratio (%)
Embodiment 1 21
Embodiment 2 12
Embodiment 3 6
Embodiment 4 21
Embodiment 5 33
Embodiment 6 9
Embodiment 7 15
Embodiment 8 6
Embodiment 9 27
Polymerizing condition among table 2 embodiment and aggregated data
Figure BSA00000197839000171

Claims (7)

1. the preparation method of a carried metallocene catalyst is characterized in that:
(1) SiO 2Functional modification
SiO 2Activation temperature be 100～1000 ℃, soak time is 0.5～200h, through the SiO of activation processing 2The surface has hydroxyl;
SiO with activation 2Be dispersed in the dry solvent, stirring condition adds the halosilanes reaction that contains unsaturated double-bond down, and the control reaction temperature is at-40 ℃～150 ℃, reaction time is 0.5～200h, reaction finishes after desolventize, washing, and the decompressing and extracting post processing obtains the SiO of functionalization 2Solid; SiO 2With ratio of solvent be 1g: 0.00001～100000mL; The addition of unsaturated double-bond halosilanes is according to activation SiO 2The The adsorbed hydroxyl content meter, halosilanes and SiO 2The mol ratio of surface hydroxyl is (10000: 1)～(1: 10000);
(2) functionalization SiO 2The preparation of load metallocene compound catalyst
1g functionalization SiO 2Be dispersed in the solvent of 0.00001～100000mL drying, the following adding of stirring condition 0.00001mol～1000000mol contains the aluminium organo-metallic compound and reacts, and the control reaction temperature is at-40 ℃～150 ℃, and the reaction time is 0.5～200h; Solution with metallocene compound is added in the reaction system then, continues reaction, and the control reaction temperature is at-40 ℃～150 ℃, and the reaction time is 0.5～200h, and reaction finishes after desolventize, washing, and decompressing and extracting is handled and is obtained solid catalyst;
Central atom Ti, Zr or the Hf of metallocene compound are 0.01～50% of vehicle weight by weight percentage.
2. according to the preparation method of right 1 described carried metallocene catalyst, it is characterized in that: the organic ligand of metallocene compound is cyclopentadienyl group and derivative thereof, or indenyl and derivative thereof, or fluorenyl and derivative thereof, or the cyclopentadienyl group of bridging and derivative thereof, or the indenyl of bridging and derivative thereof, or the fluorenyl of bridging and derivative thereof.
3. according to the preparation method of right 1 described carried metallocene catalyst, it is characterized in that: contain the halosilanes of unsaturated double-bond, its structural formula as shown
Wherein X is a halogen atom; A is terminal double bond containing aryl or double bond containing alkyl; R 1And R 2Be H atom, alkyl, aryl or halogen atom.
4. according to the preparation method of right 1 described carried metallocene catalyst, it is characterized in that: contain the aluminium organo-metallic compound and be one or more of alkyl aluminum and derivative or alkylaluminoxane and derivative thereof.
5. according to the preparation method of right 1 described carried metallocene catalyst, it is characterized in that: dry solvent be toluene, oxolane, dimethylbenzene, hexane, carrene, heptane one or more.
6. right 1 a described carried metallocene catalyst is characterized in that: be the carried metallocene catalyst by right 1 described method preparation.
7. the application of right 1 a described carried metallocene catalyst, it is characterized in that: this catalyst is used for ethene, propylene, C 4～C 20Alpha-olefin, cycloolefin, the homopolymerization or the copolymerization of two or more mixture arbitrarily in them of alkadienes; Co-catalyst is a kind of or mixture of alkyl aluminum or alkylaluminoxane; The mol ratio of the central atom of aluminium and metallocene compound is 10～3000; Polymerization temperature is-78 ℃～200 ℃, and pressure is 0.1～10Mpa.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6369253B1 (en) * 1999-03-25 2002-04-09 Sri International Metallocene compounds from amino alcohol-derived ligands
CN1344282A (en) * 1998-12-30 2002-04-10 英国石油化学品有限公司 Process for preparing supported polymerization catalyst using reduced amounts of solvent and polymerization process
US6861487B2 (en) * 2003-04-15 2005-03-01 Saudi Basic Industries Corporation Catalyst precursor for the polymerization of olefins and polymerization process using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1344282A (en) * 1998-12-30 2002-04-10 英国石油化学品有限公司 Process for preparing supported polymerization catalyst using reduced amounts of solvent and polymerization process
US6369253B1 (en) * 1999-03-25 2002-04-09 Sri International Metallocene compounds from amino alcohol-derived ligands
US6861487B2 (en) * 2003-04-15 2005-03-01 Saudi Basic Industries Corporation Catalyst precursor for the polymerization of olefins and polymerization process using the same

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