CN102875701B - Supported metallocene catalyst and preparation method thereof - Google Patents
Supported metallocene catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a supported metallocene catalyst and a preparation method thereof. The supported metallocene catalyst mainly comprises an inorganic silica silica-gel carrier, a polystyrene azo chlorine compound, a metallocene and a metallocene cocatalyst. The polystyrene azo chlorine compound serving as a sustained release agent is reacted with the metallocene to immobilize the metallocene in a skeleton network, and the metallocene is released in the supporting process and is supported by a carrier activated by alkyl aluminoxane, so that metallocene active centers are distributed uniformly, and a condition that effective active centers are reduced after the metallocene is combined with the cocatalyst because the local concentration of the metallocene active centers is too high is avoided. Therefore, by the method, the utilization efficiency of the metallocene in high price is improved, the production cost of the metallocene catalyst is reduced and the activity of the catalyst is kept.
Description
Technical field
The present invention relates to a kind of metallocene catalyst and preparation method thereof, be specifically related to a kind of supported metallocene catalyst and preparation method thereof.
Technical background
When metallocene catalyst carries out industrial applications, generally metallocene/alkylaluminoxane homogeneous catalyst system need to be carried out to load.At present, about the report of metallocene catalyst is very many.US4,808,561, US5,026,797, US5,763,543, US5,661,098, US6,455,647, CN1174549, CN1356343 report is prepared the metallocene catalyst of load as carrier take inorganics as silicon-dioxide, magnesium chloride, aluminum oxide etc.Although the metallocene catalyst of preparing the load of gained above-mentioned does not need to use a large amount of alkylaluminoxanes as promotor, but because catalyst activity is lower, cause catalyzer residual more in polymkeric substance, cause polymer processing to go wrong and polymer quality is worsened, in gas-phase fluidized-bed, cannot be widely used.Also there is bibliographical information to use silica gel, magnesium chloride compound carrier loaded metallocene, as CN101423575.Although its catalyzer of preparing gained can improve catalyst activity, resulting polymers form is poor, and fine powder is more, cannot be applicable to existing apparatus.World patent WO97/29134 and U.S. Pat 6225251 are improved and are optimized on original metallocene catalyst system, prepare active higher carried metallocene catalyst under applicable metallocene compound and alkylaluminoxane content, load temperature and silica-gel carrier particle diameter condition.Foregoing invention, by the optimization to load process condition, in reducing alkylaluminoxane and metallocene compound consumption, still obtains active higher metallocene catalyst.By reducing expensive alkylaluminoxane and metallocene compound consumption, make metallocene catalyst cost like this.But, experiment is found, metallocene compound and alkylaluminoxane load in the process of carrier, because initial reaction stage metallocene active centre partial concn is too high, in the time that promotor is combined, cause effective active centre to be reduced, cause metallocene compound utilization ratio to reduce, thereby in the time preparing metallocene catalyst, need to use more metallocene compound and expensive alkylaluminoxane promotor.
Summary of the invention
The present invention adds a kind of polystyrene azo chlorine compound with vesicular structure in metallocene catalyst, as the slowly-releasing reagent of metallocene compound, in metallocene catalyst preparation process, this sustained release dosage first carries out combination with metallocene compound, then in loading process, slowly release the silica-gel carrier effect that metallocene compound and promotor were processed, load obtains highly active carried metallocene catalyst, not only can improve the utilising efficiency of metallocene compound, and can reduce the consumption of expensive alkylaluminoxane, thereby reduce the cost of carried metallocene catalyst.
Carried metallocene catalyst of the present invention is mainly made up of inorganic silicon dioxide silica-gel carrier, polystyrene azo chlorine compound, metallocene compound and the metallocene compound promotor with vesicular structure, and preparation method comprises:
Following all operations all carries out under the condition of anhydrous and oxygen-free,
(1) silicon-dioxide silica-gel carrier, through high-temperature activation processing, then reacts 1～120 minute at-40 ℃～120 ℃ with metallocene compound promoter aluminium alkyl oxygen alkane organic solvent;
(2), in organic solvent, the polystyrene azo chlorine compound with vesicular structure is reacted to 0.5-2 hour with metallocene compound;
(3) (2) reaction product is joined in (1), at-40 ℃～60 ℃ temperature, react and within 1～180 minute, carry out load, washing obtains the metallocene catalyst of load after being dried after completion of the reaction.
Wherein (1) and (2) step order can be exchanged, and does not affect effect of the present invention.
In the present invention, the temperature of reaction of silicon-dioxide silica-gel carrier and promoter aluminium alkyl oxygen alkane is-40 ℃～120 ℃, and preferably at-40 ℃～50 ℃, the best is 0 ℃～30 ℃, 1～120 minute reaction times, preferably 15～120 minutes.Promoter aluminium alkyl oxygen alkane (take mole number scale of aluminium Al) is 1 mmole/gram carrier to 12 mmole/gram carrier with the amount ratio of carrier, preferably 5 mmoles/gram carrier to 10 mmole/gram carrier, preferably 5 mmoles/gram carrier to 8 mmole/gram carrier.Obtain after completion of the reaction the carrier slurry that promotor was processed, the end liquid reacting with metallocene compound as next step.Also can washing and filtering obtain the support powder that promotor processed for subsequent use.
In the present invention, metallocene compound stirs after 0.5-2 hour with the polystyrene azo muriate with vesicular structure in organic solvent, and the slurry of the silica supports of processing with above-mentioned promotor is carried out load, prepares metallocene catalyst.Load-reaction temperature is at-40 ℃～60 ℃, and preferably at-40 ℃～40 ℃, the best is-20 ℃～20 ℃, reacts preferably 15～120 minutes 1～180 minute.The mol ratio M of metallocene compound (with mole number scale of atoms metal in compound, with M represent) and alkylaluminoxane promotor (take mole number scale of aluminium Al): Al is as 50～500, and preferably 75～300, the best is 100～200.After completion of the reaction, slurries can be directly used in to polyreaction, or reactant is removed to desolventizing, washs the solid catalyst that obtains good fluidity after being dried.
In the present invention, there is the polystyrene azo chlorine compound of vesicular structure for the polystyrene compound of the azo chlorination containing 1-10% Vinylstyrene (DVB) comonomer, use molecular formula PS-N
2cl represents.The molar content of azo chlorine functional group is 5%～15%, and particle mean pore size is 2-20nm, and median size is 20-50 μ m.In the present invention, the macromolecular compound of this vesicular structure itself is not as the carrier of metallocene catalyst, but first and metallocene compound effect, metallocene compound is fixed in its three-dimensional network skeleton, in loading process, be fixed on metallocene compound on its three-dimensional network skeleton and slowly release again and inorganic silicon dioxide silica-gel carrier load after alkylaluminoxane activation, obtain carried metallocene catalyst.In the present invention, there is the polystyrene azo chlorine compound consumption of vesicular structure and inorganic silicon dioxide carrier amount ratio (weight) 1: 200-1: between 5, the best is 1: 50-1: between 10.
In the present invention because chlorine azo polystyrene compound is not as the carrier of supported catalyst, carry out after Methods for Immobilization of Metallocene Catalysts, can separate, reclaim use to chlorine azo polystyrene compound, also can not separate, the operation such as recovery, and directly obtain the metallocene catalyst of load.
In the present invention, the polystyrene azo chlorine compound with vesicular structure can adopt either method of the prior art to be prepared.
The present invention's carrier used is a kind of inorganic silicon dioxide of solid particulate porous, and its specific surface area is 50-500 meters squared per gram, and preferably 100～400 meters squared per gram, are preferably 250～350 meters squared per gram; Its mean particle size is 5～150 μ m, preferably 20～70 μ m, and the best is 30～50 μ m; Carrier pore volume is 0.5～5.0 ml/g, and preferably 1.5～2.5 mls/g, the best is 1.5～2.0 mls/g.Inorganic silicon dioxide carrier needs through high-temperature activation before using, and under nitrogen atmosphere, removes moisture and most of hydroxyl on silica supports at 200-800 ℃.
Being applicable to metallocene compound general formula of the present invention is CpxMAyBz, and wherein Cp is cyclopentadienyl, indenyl or the fluorenyl that does not replace or replace, and indenyl or fluorenyl ligand also can exist with the form of hydrogenation; M is bridging atom, and A and B are halogen atom, hydrogen atom or alkyl, the integer that x, y, z is 0-3.In superincumbent metallocene compound general formula, bridging atom M is zirconium preferably, and Cp base is cyclopentadienyl, indenyl or the fluorenyl that does not replace or replace, and x is at least 1.Substituting group on cyclopentadienyl is the straight chained alkyl of 1～6 carbon atom preferably.In the time that the x of metallocene general formula equals 2 above, cyclopentadienyl can also pass through polymethylene or dialkyl silane bridge joint, as by-Si (CH
3)
2-,-C (CH
3)
2-,-CH
2-,-CH
2-CH
2-similarly bridge joint.In metallocene compound general formula, A and B substituting group can be halogen atoms above, and y+z is equal to or less than 3, and condition is that x+y+z equals M value.If in metallocene compound general formula, substituent A and B are alkyl above, the straight chain of 1～8 carbon atom that they preferably contain or band branched-chain alkyl, as methyl, ethyl, n-propyl, normal-butyl, isobutyl-or n-pentyl.Suitable metallocene compound comprises two (cyclopentadienyl) metal dihalides, two (cyclopentadienyl) metal monoalkyl monohalide, two (cyclopentadienyl) metal dialkyl compound and two (indenyl) metal dihalides, atoms metal is wherein zirconium or hafnium, halogen is chlorine preferably, and alkyl is the alkyl containing 1～6 carbon atom.Example is below used for explanation, and unrestricted metallocene compound, comprise two (cyclopentadienyl) zirconium dichloride, two (cyclopentadienyl) hafnium dichloride, two (cyclopentadienyl) zirconium dimethyl, two (cyclopentadienyl) dimethyl hafnium, two (n-butyl cyclopentadienyl) zirconium dichloride, two (n-butyl cyclopentadienyl) hafnium dichloride, two (n-butyl cyclopentadienyl) zirconium dimethyl, two (n-butyl cyclopentadienyl) zirconium dichloride, two (dimethyl cyclopentadienyl) zirconium dichloride, two (tetramethyl-ring pentadienyl) zirconium dimethyl, two (tetramethyl-ring pentadienyl) zirconium dichloride, α-olefins, methylene bridge α-olefins and two (4, 5, 6, 7-tetrahydrochysene-1-indenyl) zirconium dichloride.
The alkylaluminoxane compound that is applicable to metallocene compound promotor of the present invention includes but not limited to methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide, butyl aikyiaiurnirsoxan beta, amyl group aikyiaiurnirsoxan beta, decyl aikyiaiurnirsoxan beta, modified methylaluminoxane etc., preferable methyl aikyiaiurnirsoxan beta.
Be applicable to organic solvent of the present invention and comprise aromatic hydrocarbons, halogenated aryl hydrocarbon, ether, cyclic ethers or ester, be wherein preferably toluene.
Supported metallocene catalyst system of the present invention is applicable to gas phase or slurry polymerization, and suitable reaction conditions is 30～120 ℃ of temperature, pressure 0.5～1.5MPa.The applicable solvent of slurry polymerization is the alkane containing 5～10 carbon atoms, and preferred solvent is hexane.
Supported metallocene catalyst system of the present invention can be used for polymerization or the copolyreaction of alkene, be particularly suitable for that ethylene homo closes or the copolymerization of ethene and other alpha-olefin, wherein alpha-olefin adopts propylene, butylene, amylene, hexene, octene, 4-methyl 1-amylene etc.In polymerization, add a small amount of alkylaluminium cpd, as triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, tri-n-hexyl aluminum etc., as polymerization reaction system cleaner.
Metallocene catalyst of the present invention in preparation process owing to having added polystyrene azo chlorine compound as sustained release dosage, metallocene compound is first fixed in the back bone network of polystyrene azo chlorine compound, in loading process, discharge, carry out load with the carrier after alkylaluminoxane activation, make metallocene active center distribution more even, avoid too high because of metallocene active centre partial concn, after being combined with promotor, cause the minimizing at effective active center.Therefore, the inventive method has improved the utilising efficiency of expensive metallocene compound, has reduced metallocene catalyst production cost, and the activity of catalyzer is still maintained simultaneously.
Embodiment
Embodiment 1
The muriatic preparation of polystyrene azo: the following examples all adopt the preparation method identical from embodiment 1 to obtain the polystyrene azo chlorine compound that azo chlorine functional group molar content is different.
In 500ml round-bottomed flask, add 10g to contain the polystyrene resin of 8%DVB, add the salpeter solution of 13ml10%, add 85ml water, be warming up to 45 ℃, react after 3 hours, at room temperature add 3.5g tindichloride and 5ml10% hydrochloric acid, react 3 hours, the solid obtaining after filtration, adds 4.3g Sodium Nitrite and 30ml10% hydrochloric acid solution, at room temperature react 5 hours, filter after completion of the reaction, carry out vacuum-drying and after 12 hours, obtain 10.4g polystyrene azo chlorine compound at 130 ℃, azo chlorine molar content is 13.7%.
By the 21.5 grams of Davison955 of Grace company silica supports, (median size is that 46 μ m) are placed in retort furnace for specific surface area 300 meters squared per gram, 1.58 mls/g of pore volumes, 600 ℃ of roastings 6 hours under nitrogen protection.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the methylaluminoxane (production of chemical research center, PetroChina Company Limited. Lanzhou) of 90ml10% (mass percent), at 20 ℃, stir 1 hour, obtain the SiO 2 slurry liquid that methylaluminoxane was processed.In another 250ml flask, add 0.54 gram (n-BuCp)
2zrCl
2(two n-butyl cyclopentadienyl zirconium dichloride) metallocene compound, 80ml toluene and 1.48 grams of polystyrene azo chlorine compounds (azo chlorine molar content is 13.7%, 8%DVB), stir 1 hour.Then joined in the SiO 2 slurry liquid that methylaluminoxane processed, keeping temperature of reaction kettle is 20 ℃, stirs 0.5 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains faint yellow free flowing powder, is designated as cat1.Aluminium content is 13.1 % by weight, and zirconium content is 0.38 % by weight.
Embodiment 2
The 21.5 grams of Davison955 of Grace company silica supports are placed in to retort furnace, 600 ℃ of roastings 6 hours under nitrogen protection.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, the toluene solution that adds the methylaluminoxane (production of chemical research center, PetroChina Company Limited. Lanzhou) of 90ml10% (mass percent) stirs 1 hour at 20 ℃.In another 250ml flask, add 0.57 gram (n-BuCp)
2zrCl
2(two n-butyl cyclopentadienyl zirconium dichloride) metallocene compound, 80ml toluene and 1.9 grams of polystyrene azo chlorine compounds (azo cl content is 13.7%, 8%DVB), stir 1 hour.Metallocene compound reaction solution is added in the SiO 2 slurry liquid that methylaluminoxane processed, and keeping temperature of reaction kettle is 20 ℃, stirs 0.5 hour, then at-20 ℃, react 3 hours, after reaction, except desolventizing, after being dried, obtain faint yellow free flowing powder, be designated as cat2.Aluminium content is 13.2 % by weight, and zirconium content is 0.41 % by weight.
Embodiment 3
By the 19.5 grams of Davison955 of Grace company silica supports in retort furnace, under nitrogen protection at 600 ℃, roasting 6 hours.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the methylaluminoxane of 103ml10% (mass percent), at 20 ℃, stir 1 hour.In another 250ml flask, add 0.61 gram (n-BuCp)
2zrCl
2(two n-butyl cyclopentadienyl zirconium dichloride) metallocene compound, 80ml toluene and 1.8 grams of polystyrene azo chlorine compounds (azo chlorine molar content is 13.7%, 8%DVB), stir 1 hour.Metallocene compound reaction solution is added in the SiO 2 slurry liquid that methylaluminoxane processed, and keeping temperature of reaction kettle is 20 ℃, stirs after 0.5 hour, then at-20 ℃, react 3 hours, after reaction, except desolventizing, after being dried, obtain faint yellow free flowing powder, be designated as cat3.Aluminium content is 14.3 % by weight, and zirconium content is 0.45 % by weight.
Embodiment 4
By the 22.5 grams of LSG-1 of Petroleum Chemical Engineering Institute of PetroChina Company Limited. silica supports, (median size is that 38 μ m) are placed in retort furnace for specific surface area 300 meters squared per gram, 1.67 mls/g of pore volumes, roasting 6 hours in nitrogen atmosphere at 600 ℃.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the methylaluminoxane of 95ml10% (mass percent), at 20 ℃, stir 1 hour.In another 250ml flask, add 0.56 gram of (CH
2)
2(Ind)
2zrCl
2(ethylidene abutment α-olefins) metallocene compound, 80ml toluene and 1.5 grams of polystyrene azo chlorine compounds (azo chlorine molar content is 8.9%, 5%DVB), stir 1 hour, forms brown solution.Then adding and keeping temperature of reaction kettle is 20 ℃, stirs after 1 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains brown free flowing powder, is designated as cat4.Aluminium content is 13.2 % by weight, and zirconium content is 0.37 % by weight.
Embodiment 5
22.5 gram of 955 silica gel silica supports is placed in retort furnace to roasting 6 hours in nitrogen atmosphere at 600 ℃.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the ethylaluminoxane of 90ml10% (mass percent), at 20 ℃, stir 1 hour.In another 250ml flask, add 0.56 gram of (CH
2)
2(IndH
4)
2zrCl
2[two (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride] metallocene compound, 80ml toluene and 1.1 grams of polystyrene azo chlorine compounds (azo chlorine molar content is 8.9%, 5%DVB), stir 1 hour, forms brown solution.Then adding and keeping temperature of reaction kettle is 20 ℃, stirs after 1 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains brown free flowing powder, is designated as cat5.Aluminium content is 13.5 % by weight, and zirconium content is 0.39 % by weight.
Embodiment 6
The 22.5 grams of LSG-1 of Petroleum Chemical Engineering Institute of PetroChina Company Limited. silica supports are placed in retort furnace to roasting 6 hours in nitrogen atmosphere at 600 ℃.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, the toluene solution (normal-butyl molar content be alkyl content 20%) that adds the normal-butyl modified methylaluminoxane of 95ml10% (mass percent) stirs 1 hour at 20 ℃.In another 250ml flask, add 0.56 gram (n-BuCp)
2zrCl
2(two n-butyl cyclopentadienyl zirconium dichloride) metallocene compound, 80ml toluene and 1.5 grams of polystyrene azo chlorine compounds (azo chlorine molar content is 8.9%, 5%DVB), stir 1 hour, forms brown solution.Then adding and keeping temperature of reaction kettle is 20 ℃, stirs after 1 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains faint yellow free flowing powder, is designated as cat6.Aluminium content is 13.1 % by weight, and zirconium content is 0.41 % by weight.
Embodiment 7
By the 22.5 grams of LSG-1 of Petroleum Chemical Engineering Institute of PetroChina Company Limited. silica supports, (median size is that 38 μ m) are placed in retort furnace for specific surface area 300 meters squared per gram, 1.67 mls/g of pore volumes, roasting 6 hours in nitrogen atmosphere at 600 ℃.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the methylaluminoxane of 90ml10% (mass percent), at 20 ℃, stir 1 hour.In another 250ml flask, add 0.53 gram of [Cp (CH3) 4] 2ZrCl2[bis-(tetramethyl-ring pentadienyl)] zirconium dichloride metallocene compound, (azo chlorine molar content is 4.9% for 80ml toluene and 1.3 grams of polystyrene azo chlorine compounds, 5%DVB), stir 1 hour, form brown solution.Then adding and keeping temperature of reaction kettle is 20 ℃, stirs after 1 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains brown free flowing powder, is designated as cat7.Aluminium content is 13.4 % by weight, and zirconium content is 0.38 % by weight.
Comparative example 1
The 21.3 grams of Davison955 of Grace company silica supports are placed in retort furnace to roasting 6 hours in nitrogen atmosphere at 600 ℃.Silica supports after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the methylaluminoxane of 108ml10% (mass percent), at 20 ℃, stir 1 hour, then add 0.63 gram (n-BuCp)
2zrCl
2(two n-butyl cyclopentadienyl zirconium dichloride) metallocene compound, forms yellow solution.Keeping temperature of reaction kettle is 20 ℃, stirs after 0.5 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains faint yellow free flowing powder, is designated as cat8.Aluminium content is 14.3 % by weight, and zirconium content is 0.47 % by weight.
Comparative example 2
The 19.5 grams of Davison955 of Grace company silica supports are placed in retort furnace to roasting 6 hours in nitrogen atmosphere at 600 ℃.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the methylaluminoxane of 118ml10% (mass percent), at 20 ℃, stir 1 hour, then add 0.76 gram (n-BuCp)
2zrCl
2(two n-butyl cyclopentadienyl zirconium dichloride) metallocene compound, forms yellow solution.Keeping temperature of reaction kettle is 20 ℃, stirs after 0.5 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains faint yellow free flowing powder, is designated as cat9.Aluminium content is 15.7 % by weight, and zirconium content is 0.59 % by weight.
Comparative example 3
The 22.5 grams of LSG-1 of Petroleum Chemical Engineering Institute of PetroChina Company Limited. silica supports are placed in retort furnace to roasting 6 hours in nitrogen atmosphere at 600 ℃.Silicon-dioxide after treatment is added in the reactor that 500ml nitrogen replacement is good, add the toluene solution of the methylaluminoxane of 103ml10% (mass percent), at 20 ℃, stir 1 hour, then add 0.62 gram of (CH
2)
2(Ind)
2zrCl
2(ethylidene abutment α-olefins) metallocene compound, forms brown solution.Keeping temperature of reaction kettle is 20 ℃, stirs after 1 hour, then at-20 ℃, reacts 3 hours, after reaction, except desolventizing, after being dried, obtains brown free flowing powder, is designated as cat10.Aluminium content is 13.7 % by weight, and zirconium content is 0.41 % by weight.
Catalyzer is for vinyl polymerization
In a polymerization reactor, use prepared metallocene catalyst cat 1-10 in embodiment 1-7 and comparative example 1-3 to carry out ethene slurry polymerization, obtain polymerization product, experimental result is in table 1.
2.0 liters of dry hexanes are joined in nitrogen replacement and dried 5 liters of stainless steel autoclaves, then add 5 milliliters of triethyl aluminum TEA (1.6 mol/L), stirring velocity is 450 revs/min, then add 0.2 gram of above-mentioned catalyzer, pass into ethene and make reactor internal pressure remain on 1.0MPa, at 80 ℃, stir under 450 revs/min of conditions polymerization 1 hour, termination reaction, is cooled to room temperature, after being dried, obtains polyethylene product.
Table 1 supported metallocene catalyst system component content and ethene slurry polymerization result table look-up
As can be known from the results of Table 1, when metallocene compound is (n-BuCp)
2zrC1
2time, in the situation that activity is suitable, the aluminium content of embodiment 1,2 supported catalysts is approximately than approximately few 8% in comparative example 1, and zirconium content approximately less 15%.In the situation that aluminium, zirconium content are suitable (embodiment 3, comparative example 1), in embodiment, catalyst activity is than high 20% left and right of comparative example.When metallocene compound is (CH
2)
2(Ind)
2zrCl
2, also can see identical trend.Illustrate in the present invention, add polystyrene azo chlorine compound can effectively reduce promotor and metallocene compound consumption, or can effectively improve load metallocene catalyst activity.
Claims (4)
1. a carried metallocene catalyst, it is characterized in that mainly by inorganic silicon dioxide silica-gel carrier, polystyrene azo chlorine compound, the promotor composition of metallocene compound and metallocene compound, wherein the promotor of metallocene compound is alkylaluminoxane, with mole number scale of aluminium Al, with the amount ratio of carrier be 1 mmole/gram carrier to 12 mmole/gram carrier, metallocene compound, with mole number scale of atoms metal in compound, represent with M, with alkylaluminoxane, take the mol ratio M:Al of mole number scale of aluminium Al as 50～500, polystyrene azo chlorine compound consumption and inorganic silicon dioxide carrier consumption weight ratio are between 1:200-1:5, described polystyrene azo chlorine compound is the polystyrene compound containing the azo chlorination of 1-10% Vinylstyrene comonomer, the molar content of azo chlorine functional group is 5%～15%, particle mean pore size is 2-20nm, median size is 20-50 μ m.
2. carried metallocene catalyst according to claim 1, is characterized in that described inorganic silicon dioxide silica-gel carrier surface-area is 50-500 meters squared per gram, and mean particle size is 5～150 μ m, and pore volume is 0.5～5.0 ml/g.
3. carried metallocene catalyst according to claim 1, is characterized in that described metallocene compound general formula is Cp
xmA
yb
z, wherein Cp is cyclopentadienyl, indenyl or the fluorenyl that does not replace or replace, indenyl or fluorenyl ligand also can exist with the form of hydrogenation; M is bridging atom, and A and B are halogen atom, hydrogen atom or alkyl, the integer that x, y, z is 0-3.
4. carried metallocene catalyst according to claim 1, is characterized in that described promoter aluminium alkyl oxygen alkane comprises methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide, butyl aikyiaiurnirsoxan beta, amyl group aikyiaiurnirsoxan beta, decyl aikyiaiurnirsoxan beta, modified methylaluminoxane.
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| US6090740A (en) * | 1996-02-08 | 2000-07-18 | Exxon Chemical Patents Inc. | Supported metallocene catalyst systems |
| US6225251B1 (en) * | 1996-12-20 | 2001-05-01 | Fina Technology, Inc. | Catalyst efficiency for supported metallocene catalyst |
| CN101423575A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst component and preparation method thereof and use |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090740A (en) * | 1996-02-08 | 2000-07-18 | Exxon Chemical Patents Inc. | Supported metallocene catalyst systems |
| US6225251B1 (en) * | 1996-12-20 | 2001-05-01 | Fina Technology, Inc. | Catalyst efficiency for supported metallocene catalyst |
| CN101423575A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst component and preparation method thereof and use |
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