CN102731688B - Supported metallocene catalyst and its preparation method - Google Patents
Supported metallocene catalyst and its preparation method Download PDFInfo
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- CN102731688B CN102731688B CN201110080422.0A CN201110080422A CN102731688B CN 102731688 B CN102731688 B CN 102731688B CN 201110080422 A CN201110080422 A CN 201110080422A CN 102731688 B CN102731688 B CN 102731688B
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Abstract
The invention discloses a supported metallocene catalyst and its preparation method, and is characterized in that the catalyst comprises a carrier and a metallocene compound and alkyl aluminoxane which are loaded on the carrier. The carrier is spherical mesoporous silicon dioxide. The average particle diameter of the carrier is 1-10 micrometers, its specific surface area is 1000-2000 square meter/gram, its pore volume is 0.3-1.5 ml/g, and its most probable pore size is 4-20 nanometers. The metallocene compound has a structure as shown in the formula 1 defined in the specification, in which M is one of titanium, zirconium and hafnium and X is halogen. When the supported metallocene catalyst provided by the invention is used to catalyze alkene polymerization, the catalytic efficiency can reach 1605g PE/gcath.
Description
Technical field
The present invention relates to a kind of carried metallocene catalyst and preparation method thereof.
Background technology
The Application and Development of metallocene catalyst is after traditional Ziegler-Natta catalyst, the another important breakthrough in olefin polymerization catalysis field.Due to catalyzed by homogeneous metallocene catalyst, to reach the required methylaluminoxane of high reactivity (MAO) consumption large, and production cost is high, and the polymkeric substance obtaining is without particle shape, cannot in widely used slurry process or gas phase polymerization technique, use.And the activity of metallocene catalyst is very high, in polymerization process, is easy to occur local polymerization velocity very fast, and then causes implode.
The effective way addressing the above problem is carried out load processing solubility metallocene catalyst exactly.At present, relevant Methods for Immobilization of Metallocene Catalysts is studied in report with SiO
2for example, for the report most study of carrier: CN1174848A, CN1174849A, CN1356343A, US4,808,561, US5,026,797, US5,763,543 and US5,661,098 all disclose with SiO
2carried metallocene catalyst for carrier.Yet, for furtheing investigate new support/catalyst/co-catalyst system, be necessary to attempt different carriers, to promote further developing of loaded catalyst and polyolefin industry.
Molecular sieve is to have evenly regular one dimension or the material of solid netted sieve aperture, and surfactivity is higher, absorption property good, have obvious molecule shape selectivity energy, and it allows the monomer of certain size and the polymkeric substance of formation thereof to insert in the duct of molecular sieve.And because molecular sieve has nano pore, in polymerization process, the inserted mode of monomer is different from freeboard with propagation process, the chance that double-basis stops has been reduced in limited space to a certain extent, makes polyreaction show the feature of " living polymerization ".
Olefin polymerization catalysis is carried on to molecular sieve, and tool has the following advantages:
(1) molecular sieve of synthetic does not contain the impurity that easily makes polymer degradation, will improve the ageing resistance of polyolefine material;
(2) molecular sieve nano pore has the dual-use function of carrier and reactor, and catalyst cupport efficiency is high, and polymerization process is easily controlled, and can in the skeleton of polymerization reactor, key in active centre, accelerates reaction process, improves productive rate;
(3) monomer is inserted with polyreaction and has three-dimensional selection effect, can improve polyolefinic molecular weight and fusing point.
As can be seen here, the olefin coordination polymerization that appears as of molecular sieve carried olefin polymerization catalysis has been opened up a new field.
Compare with industrial silica gel, ordered mesoporous molecular sieve (molecular sieve that aperture is 2-50nm), has larger specific surface area and relatively large aperture, can process larger molecule or group, can make catalyzer bring into play well its due catalytic activity.
CN1718596A discloses a kind of carried metallocene catalyst, and this catalyzer is by by Cp
2zrCl
2load on the bar-shaped SBA-15 that processes through MAO upper and obtain.But the catalytic activity of the disclosed carried metallocene catalyst of CN1718596A needs further to improve.
CN1923862A discloses a kind of olefin polymerization catalysis of mesoporous molecular sieve carried, and this catalyzer is that the bar-shaped SBA-15 processing through MAO is upper to be obtained by the semi-sandwich alum metallic compound shown in following formula is loaded on,
But the catalytic activity of the disclosed catalyzer of CN1923862A is the highest also only has 10
6g PE/ (molZrh).
In addition, compare with SBA-15 club shaped structure, the geometric shape of mesoporous material if be spherical, by being beneficial to the reunion that reduces powder, increases its mobility, is more of value to industrial application.Mostly conventional spherical mesoporous material is to be prepared from as silicon source with traditional silicon ester (tetraethoxy or methyl silicate) at present, compares synthetic cost higher with industrial silica gel.Though industrial silica gel cost is low, but be highly susceptible to fragmentation in metallocene loading process, make polyethylene product pattern variation, be unfavorable for industrial application.Therefore, if obtain a kind of with low cost, Stability Analysis of Structures, carried metallocene catalyst that catalytic activity is high remains a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome the problem that catalytic activity is low, cost is higher and the physical strength of mesoporous material is lower of the carried metallocene catalyst of prior art, a kind of with low cost, Stability Analysis of Structures, carried metallocene catalyst that catalytic activity is high are provided.
The present inventor finds, it is spherical by mesoporous material is made, can be by the large pore volume of mesoporous material, aperture large and narrowly distributing and the feature of bigger serface and the advantage that microballoon can reduce powder reuniting, mobility combine, and spherical mesoporous material and cheap silicon source water glass is compound, can form cheap, Stability Analysis of Structures, matrix material that catalytic activity is high, can solve thus that catalyst activity is low, structural instability and the high problem of price.
The invention provides a kind of carried metallocene catalyst, it is characterized in that, this catalyzer comprises carrier and loads on alkylaluminoxane and the metallocene compound on described carrier, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, and the specific surface area of carrier is 1000-2000 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1:
Formula 1
Wherein, M is a kind of in titanium, zirconium and hafnium, and X is halogen.
The present invention also provides a kind of method of preparing described carried metallocene catalyst, and the method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
According to carried metallocene catalyst of the present invention, described metallocene compound has sandwich structure, loaded on the mesoporous silicon oxide of spherical aperture large and narrowly distributing and bigger serface, can access a Stability Analysis of Structures, the carried metallocene catalyst that catalytic activity is high, therefore has high catalytic activity.
Particularly, carried metallocene catalyst according to the present invention is when for catalysis in olefine polymerization, catalytic efficiency can reach 1605g PE/ (gcath), and in the situation that other conditions are identical, the catalytic efficiency during metallocene compound of two (1-indenyl) zirconium dichlorides of industrial 955 silica gel load rac-ethene is only 660g PE/ (gcath).
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern (a) of sphericity mesoporous silicon dioxide carrier vector JKQ, X-coordinate unit be 2 θ (
0), ordinate zou is intensity;
Fig. 2 is the x-ray diffraction pattern (b) of carried metallocene catalyst JKQ-YIN, X-coordinate unit be 2 θ (
0), ordinate zou is intensity;
Fig. 3 is the N of sphericity mesoporous silicon dioxide carrier JKQ and carried metallocene catalyst JKQ-YIN
2adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0, ordinate zou is pore volume absorption, unit is cm
3/ gSTP;
Fig. 4 is the graph of pore diameter distribution of sphericity mesoporous silicon dioxide carrier JKQ and carried metallocene catalyst JKQ-YIN, and wherein, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g;
A in Fig. 5
1and a
2for the stereoscan photograph of sphericity mesoporous silicon dioxide carrier JKQ, b
1and b
2stereoscan photograph for carried metallocene catalyst JKQ-YIN.
In Fig. 6, a is the transmission electron microscope photo of sphericity mesoporous silicon dioxide carrier JKQ, and b is the transmission electron microscope photo of carried metallocene catalyst JKQ-YIN.
Embodiment
The invention provides a kind of carried metallocene catalyst, it is characterized in that, this catalyzer comprises carrier and loads on metallocene compound and the alkylaluminoxane on described carrier, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, and the specific surface area of carrier is 1000-2000 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1,
Formula 1
Wherein, M is a kind of in titanium, zirconium and hafnium, and X is halogen.
According to carried metallocene catalyst of the present invention, what the M in formula 1 can be in titanium, zirconium and hafnium is a kind of.Preferably, M is zirconium.
According to carried metallocene catalyst of the present invention, the X in formula 1 is halogen.What particularly, the X in formula 1 can be in fluorine, chlorine, bromine and iodine is a kind of.Preferably, the X in formula 1 is chlorine or bromine.More preferably, the X in formula 1 is chlorine.
The present inventor finds in research process, and the M in formula 1 is zirconium, and when X is chlorine, described carried metallocene catalyst during for the polyreaction of catalyzed alkene, demonstrates excellent especially catalytic activity.
According to the present invention, the specific surface area of described carried metallocene catalyst can be 600-1200 meters squared per gram, is preferably 700-1000 meters squared per gram, more preferably 874 meters squared per gram; Pore volume can be 0.1-1 ml/g, is preferably 0.2-0.8 ml/g, more preferably 0.4 ml/g; Most probable aperture can be 1-3 nanometer, is preferably 1.2-2.5 nanometer, more preferably 1.6 nanometers.
According to carried metallocene catalyst of the present invention, loading on metallocene compound on described carrier and the amount of alkylaluminoxane can change within a large range.The present inventor finds, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 10-60 % by weight, when the content of described carrier is 40-90 % by weight, not only can obtain gratifying catalytic effect, but also can reduce costs.More preferably, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 15-55 % by weight, and the content of described carrier is 45-85 % by weight.Further under preferable case, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 20-80 % by weight, and the content of described carrier is 20-80 % by weight.Further under preferable case, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 25-40 % by weight, and the content of described carrier is 60-75 % by weight.
According to loaded catalyst of the present invention, the ratio between described alkylaluminoxane and metallocene compound can be for the technician of field of olefin polymerisation known content.Particularly, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound can be 50-500: 1, be preferably 60-400: and 1,70-300 more preferably: 1, be further preferably 80-200: 1, be preferably 139: 1.
According to carried metallocene catalyst of the present invention, described alkylaluminoxane can be the conventional various alkylaluminoxanes in metallocene catalyst field.Usually, the alkyl in described alkylaluminoxane is C
1-C
5alkyl.Preferably, described alkylaluminoxane is methylaluminoxane.
According to carried metallocene catalyst of the present invention, loading on metallocene compound on described carrier and the amount of alkylaluminoxane can change within a large range.The present inventor finds, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 10-60 % by weight, when the content of described carrier is 40-90 % by weight, not only can obtain gratifying catalytic effect, but also can reduce costs.More preferably, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 15-55 % by weight, and the content of described carrier is 45-85 % by weight.Further under preferable case, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 20-80 % by weight, and the content of described carrier is 80-20 % by weight.Further under preferable case, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 25-40 % by weight, and the content of described carrier is 60-75 % by weight.
According to carried metallocene catalyst of the present invention, the ratio between described alkylaluminoxane and metallocene compound can be for the technician of field of olefin polymerisation known content.Particularly, the mol ratio of the zirconium in the aluminium in described alkylaluminoxane and described metallocene compound can be 50-500: 1, be preferably 60-400: and 1,70-300 more preferably: 1, be further preferably 80-200: 1, most preferably be 139: 1.
According to carried metallocene catalyst of the present invention, wherein, the average particle diameter of described carrier is 1-10 micron, and specific surface area is 1000-2000 meters squared per gram, and pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Under preferable case, the average particle diameter of described carrier is 2-8 micron, and specific surface area is 1100-1800 meters squared per gram, and pore volume is 0.4-0.8 ml/g, and most probable aperture is 4-12 nanometer; More preferably in situation, the average particle diameter of described carrier is 2-8 micron, and specific surface area is 1345 meters squared per gram, and pore volume is 0.6 ml/g, and most probable aperture is 5 nanometers.
According to the present invention, described carrier is sphericity mesoporous silicon dioxide, and described sphericity mesoporous silicon dioxide can prepare by the method comprising the following steps:
(1) cetyl trimethylammonium bromide (CTAB), Triton X-100 (triton x-100) and hydrochloric acid are stirred to dissolving at 25-60 ℃ of temperature;
(2) step (1) gained solution and water glass are stirred to 10-60 minute to dissolving at 25-60 ℃ of temperature;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) by the heating of step (3) gained crystallization product, removed template method;
Described template is cetyl trimethylammonium bromide and Triton X-100.
Described crystallization condition comprises: crystallization temperature can be 25-60 ℃, is preferably 30-50 ℃; Crystallization time can be 10-40 hour, is preferably 15-30 hour; The condition of described removed template method comprises that temperature can be 250-800 ℃, is preferably 300-600 ℃; Time can be 10-40 hour, is preferably 15-35 hour.
According to the present invention, count in molar ratio, water glass: Triton X-100: cetyl trimethylammonium bromide (CTAB): hydrogenchloride: water=1: 0.01-0.5: 0.1-0.6: 5-50: 100-500, be preferably 1: 0.01-0.3: 0.1-0.4: 5-20: 100-300, is particularly preferably 1: 0.03: 0.11: 7.97: 111.Wherein, the mole number of Triton X-100 calculates according to the molecular-weight average of Triton X-100.
Described Triton X-100 can be the various Triton X-100s that can be used as template, for example triton x-100.
Kind and the content of described carrier, alkylaluminoxane and metallocene compound are described above, do not repeat them here.
Aforesaid method adopts water glass as silicon source, be equipped with cetyl trimethylammonium bromide (CTAB) and Triton X-100 (triton x-100) as mixed templates, make it possible to obtain the sphericity mesoporous silicon dioxide of micron order high-ratio surface.
The present invention also provides a kind of method of preparing described carried metallocene catalyst, and the method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
The method according to this invention is included under protection of inert gas, successively load alkylaluminoxane and metallocene compound on carrier.Can adopt the method for well known to a person skilled in the art that alkylaluminoxane and metallocene compound are loaded on described carrier.Preferably, successively on carrier, the method for load alkylaluminoxane and metallocene compound comprises: under protection of inert gas, described carrier is contacted with the first solution, described the first solution contains described alkylaluminoxane and the first solvent; The carrier that has removed the first solvent is contacted with the second solution, and described the second solution contains described metallocene compound and the second solvent, and removes the second solvent.Described the first solvent and the second solvent can be identical or different, are preferably toluene.
The present invention is for described carrier being contacted with the first solution and the carrier that has removed described the first solvent being not particularly limited with the method that the second solution contacts, the whole bag of tricks that can be known to the skilled person, for example: dipping, spraying.The method of employing dipping can be so that solution enters in the duct on carrier more fully, and therefore, the present invention is preferably flooded.
Carrier is not particularly limited with the condition that the second solution contacts with the first solution, for example: carrier can comprise with the condition that described the first solution contacts: the time is 1-10 hour, and temperature is 25-80 ℃; The described carrier that has removed the first solvent can be comprised with the condition that described the second solution contacts: the time is 0.3-2 hour, and temperature is 25-80 ℃.
According to the present invention, toluene preferably adopts the method that well known to a person skilled in the art to refine before use, for example: can within 24-48 hour, refine by toluene is refluxed on sodium, with except impurity such as water in desolventizing.
The method according to this invention can also be included in described in load before alkylaluminoxane and described metallocene compound; under protection of inert gas; described carrier is heated to 7-10 hour at the temperature of 300-900 ℃, for example, (: water) to remove the volatile matter that contains in the hydroxyl of carrier surface and carrier.
According to the present invention, can there is not chemically interactive various gas with carrier, alkylaluminoxane, metallocene compound for various in described rare gas element.For example, described rare gas element can be nitrogen, argon gas.
According to the present invention, it is benchmark that described alkylaluminoxane and the metallocene compound charge capacity on described carrier makes to take the total amount of described carried metallocene catalyst, the total amount of described metallocene compound and alkylaluminoxane is 10-60 % by weight, when the content of described carrier is 40-90 % by weight, not only can obtain gratifying catalytic effect, but also can reduce costs.More preferably, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 15-55 % by weight, and the content of described carrier is 45-85 % by weight.Further under preferable case, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 20-80 % by weight, and the content of described carrier is 80-20 % by weight.Further under preferable case, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 25-40 % by weight, and the content of described carrier is 60-75 % by weight; The mol ratio of the zirconium in the aluminium in described alkylaluminoxane and described metallocene compound can be 50-500: 1, be preferably 60-400: and 1,70-300 more preferably: 1, be further preferably 80-200: 1, most preferably be 139: 1.
The 1st step, by Triton X-100 (triton x-100) and cetyl trimethylammonium bromide (CTAB), joins in aqueous hydrochloric acid, presses molar feed ratio,
Water glass: Triton X-100 (triton x-100): cetyl trimethylammonium bromide (CTAB): hydrogenchloride: water=1: 0.01-0.5: 0.1-0.6: 5-50: 100-500, be preferably 1: 0.01-0.3: 0.1-0.4: 5-20: 100-300, be particularly preferably 1: 0.03: 0.11: 7.97: 111
At 25-60 ℃ of temperature, be stirred to dissolving;
The 2nd step adds water glass in previous step gained solution, stirs 10-60 minute to dissolving at 25-60 ℃ of temperature;
The 3rd step, by previous step products therefrom crystallization 10-40 hour at 25-60 ℃ of temperature, filters crystallization after product, wash, be dried, and obtains the former powder of spherical mesoporous material;
The 4th step, by the former powder of previous step gained spherical mesoporous material in retort furnace at 250-800 ℃ of temperature lower calcination 10-40 hour, removed template method, obtains the spherical mesoporous material of removed template method;
The 5th step, under nitrogen protection, in 300-900 ℃ of calcining thermal activation in 7-10 hour, obtains the spherical mesoporous material after thermal activation by previous step gained spherical mesoporous material;
The 6th step, spherical mesoporous material after the thermal activation of previous step gained is transferred in the reactor after nitrogen is fully replaced, add toluene and alkylaluminoxane, count in molar ratio, spherical mesoporous material (take silicon-dioxide): toluene: the amount ratio of alkylaluminoxane is 1: 10-100: 0.1-2, be preferably 1: 20-90: 0.3-1.5, more preferably 1: 38.02: 1.036, in 25-80 ℃, stir 1-10 hour again, after, with hexane washing 2 times, afterwards solid is dried up with nitrogen again, obtain the spherical mesoporous material of load methylaluminoxane;
The 7th step, under nitrogen protection, joins the spherical mesoporous material of previous step gained load methylaluminoxane in reactor, adds stirring solvent to make slurries; In the container of crossing with nitrogen replacement in advance, metallocene compound is dissolved and makes solution, under 30 ℃ of agitation conditions, slowly metallocene compound solution is added drop-wise in reactor, meter in molar ratio, spherical mesoporous material (take silicon-dioxide): toluene: the amount ratio of two (1-indenyl) zirconium dichlorides of metallocene compound rac-ethene is 1: 10-150: 2 * 10
-3-15 * 10
-3, be preferably 1: 10-100: 3 * 10
-3-12 * 10
-3, more preferably 1: 38.02: 10.53 * 10
-3, stirring reaction 0.3-2 hour, after reaction finishes, standing, leach liquid, with toluene and hexane washing, with nitrogen, dry up, obtain described carried metallocene catalyst.Wherein the molecular weight of alkylaluminoxane is in RAlO, and wherein R is alkyl, and for example the molecular weight of methylaluminoxane is with CH
3alO meter is 58.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, described Triton X-100 (triton x-100) is purchased from ACROS company of Belgian reagent company; Methylaluminoxane is purchased from U.S. Albemarle Corporation; Two (1-indenyl) zirconium dichlorides of rac-ethene are purchased from Alfa Aesar; Described cetyl trimethylammonium bromide (CTAB) is purchased from J & KChemical LTD company, CAS 57-09-0.
In following examples, X-ray diffraction analysis instrument is purchased from the German Bruker AXS model D8Advance of company; Transmission electron microscope is purchased from the Dutch model Tecnai of FEI Co. 20; Scanning electronic microscope is purchased from the model XL-30 of U.S. FEI Co.; Elemental analyser is purchased from the model 7500CX of U.S. An Jielun company.
Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption instrument, sample is degassed 4 hours at 200 ℃.
Preparation example 1
This preparation example is for illustrating according to carried metallocene catalyst of the present invention and preparation method thereof.
By 1.5 grams of cetyl trimethylammonium bromides (CTAB), be 1.07g/ml with 1.5ml density, in the hydrochloric acid soln that the concentrated hydrochloric acid that it is 37 % by weight that the Triton X-100 of concentration weight 5% (triton x-100) joins by 29.6 grams of concentration and 75 grams of water form, at 40 ℃, be stirred to CTAB and triton x-100 dissolves completely; 4.6 grams of industrial water glass are joined in above-mentioned solution at 40 ℃ again and stir 15 minutes, water glass dissolves completely, then 40 ℃ of crystallization 24 hours, through filtering, washing, obtain former powder mesoporous material after dry; By former powder mesoporous material in retort furnace 600 ℃ calcining 24 hours, removed template method, obtains sphericity mesoporous silicon dioxide material (called after JKQ).
By above-mentioned sphericity mesoporous silicon dioxide material JKQ under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the sphericity mesoporous silicon dioxide material through thermal activation.
0.3 gram of sphericity mesoporous silicon dioxide material through thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 20 milliliters of refining toluene, 0.3 gram of methylaluminoxane to stir 4 hours in 50 ℃.After, then with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen, obtaining load has the JKQ carrier of methylaluminoxane (called after MAO/JKQ).
Under nitrogen protection, the MAO/JKQ obtaining is all joined in 250 milliliters of glass reactors, add 20 milliliters of refining toluene, at 30 ℃, slowly drip two (1-indenyl) zirconium dichlorides of rac-ethene of 22 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, after layering, leach liquid, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after JKQ-YIN).With XRD, the experiment of nitrogen adsorption-desorption, scanning electron microscope, X-ray energy spectrometer and ICP ultimate analysis, this carried metallocene catalyst is characterized.
Fig. 1 is the little angle x-ray diffraction pattern of sphericity mesoporous silicon dioxide carrier JKQ, and Fig. 2 is the little angle x-ray diffraction pattern of carried metallocene catalyst JKQ-YIN, X-coordinate unit be 2 θ (
0), ordinate zou is intensity.From XRD spectra, can obviously find out, all in little angular region, there are 3 diffraction peaks in sphericity mesoporous silicon dioxide carrier JKQ and carried metallocene catalyst JKQ-YIN, illustrate that spherical mesoporous silicon-dioxide JKQ and carried metallocene catalyst JKQ-YIN have good mesoporous phase structure, the mesoporous material XRD spectra of this and bibliographical information is consistent, owing to also having two small peaks except main peak, illustrate that meso-hole structure is very good.
Fig. 3 is the N of sphericity mesoporous silicon dioxide carrier JKQ (a) and carried metallocene catalyst JKQ-YIN (b)
2adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0, ordinate zou is pore volume absorption, unit is cm
3/ gSTP.In Fig. 3, nitrogen adsorption-desorption thermoisopleth shows that sphericity mesoporous silicon dioxide carrier JKQ and carried metallocene catalyst JKQ-YIN are the IV class adsorption-desorption thermoisopleths of typical IUPAC definition, proved that sphericity mesoporous silicon dioxide carrier JKQ and carried metallocene catalyst JKQ-YIN have the meso-hole structure (XueleiPang of distinctive cube of cage structure of bibliographical information, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1～6; Chengzhong Yu, Bozhi Tian, Jie Fan, Galen D.Stucky, Dongyuan Zhao, J.Am.Chem.Soc.2002,124,4556-4557).
Fig. 4 is the graph of pore diameter distribution (b) of sphericity mesoporous silicon dioxide carrier JKQ (a) and carried metallocene catalyst JKQ-YIN, and wherein, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g.Sphericity mesoporous silicon dioxide carrier JKQ has narrow pore size distribution as can be seen from Figure 4, and duct is very even, and carried metallocene catalyst JKQ-YIN keeps narrow pore size distribution and even duct.
A in Fig. 5
1and a
2for the stereoscan photograph of sphericity mesoporous silicon dioxide carrier JKQ, b
1and b
2stereoscan photograph for carried metallocene catalyst JKQ-YIN.As can be seen from Figure 5, the microscopic appearance figure of sphericity mesoporous silicon dioxide carrier JKQ and carried metallocene catalyst JKQ-YIN is spherical, size is micron level, and after load-reaction, the microscopic appearance of Mesoporous Spheres remains unchanged substantially, still keeps spherical preferably.
In Fig. 6, a is the transmission electron microscope photo of sphericity mesoporous silicon dioxide carrier JKQ, and b is the transmission electron microscope photo of carried metallocene catalyst JKQ-YIN.From Fig. 6, can know and see that sample high-specific surface area spherical mesoporous silica supports JKQ and carried metallocene catalyst JKQ-YIN have more regular pore size distribution, the conclusion that this point and XRD diffracting spectrum obtain is consistent.
Table 1 is sphericity mesoporous silicon dioxide carrier JKQ and carried metallocene catalyst JKQ-YIN pore structure parameter.
Table 1 pore structure parameter
| Sample | Specific surface area (m 2/g) | Pore volume (ml/g) | Most probable aperture (nm) |
| JKQ | 1345 | 0.6 | 5 |
| JKQ-YIN | 874 | 0.4 | 1.6 |
Ultimate analysis ICP result shows, load the sphericity mesoporous silicon dioxide carrier of two (1-indenyl) zirconium dichlorides of promotor methylaluminoxane (MAO) and metallocene compound rac-ethene be that the content of the aluminium element of carried metallocene catalyst JKQ-YIN is 14.4%, the content of Zr is that the mol ratio of 0.35%, Al/Zr is 139: 1.Through converting, learn, the total amount of described carried metallocene catalyst of take is benchmark, and the total content of methylaluminoxane (MAO) and metallocene compound is 32.56 % by weight, and the content of carrier is 67.44 % by weight.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of carried metallocene catalyst of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, then add 800 milliliters of hexanes, along with adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol/L, then the carried metallocene catalyst JKQ-YIN that adds 62.3 milligrams of above-described embodiments 1 to make, passed into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 100 grams of polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.300g/ml, melting index MI
2.16=0.005g/10min.Determine as calculated, the efficiency of catalyzer is 1605g PE/ (gcath) (that is, 4.2 * 10
7gPE/ (mol Zrh)).
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of carried metallocene catalyst of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 70 ℃, add again 800 milliliters of hexanes, along with adding of hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of 1 mol/L, then the carried metallocene catalyst JKQ-YIN that adds above-described embodiment 1 of 64.4 milligrams to make, pass into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 47 grams of polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.290g/ml, melting index MI
2.16=0.200g/10min.Determine as calculated, the efficiency of catalyzer is 730g PE/ (gcath) (that is, 1.9 * 10
7g PE/ (molZrh)).
Comparative example 1
This comparative example is used for illustrating the preparation of two (1-indenyl) zirconium dichlorides of silica gel (ES955) load metallocene catalyst rac-ethene.
The 1st step, by the 400 ℃ of calcinings 10 hours (thermal activation) under nitrogen protection of ES955 silica gel, removes hydroxyl and remaining moisture, obtains the ES955 silica gel after thermal activation;
The 2nd step: under nitrogen protection, 0.44 gram of ES955 silica gel is joined in reactor, add 0.45 gram of MAO and 10ml toluene solution, under 50 ℃ of conditions, stirring reaction, after 4 hours, is used toluene wash 3 times, after, with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen again, obtain alkylaluminoxane/ES955 silica gel complex compound carrier (MAO/ES955);
The 3rd step: under nitrogen protection; alkylaluminoxane/ES955 silica gel complex compound carrier is joined in reactor; add 20 milliliters of refining toluene; slurries are made in stirring; at 30 ℃; slowly drip two (1-indenyl) zirconium dichlorides of metallocene catalyst precursors rac-ethene of 20.7 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen.By the supported catalyst called after ES955-YIN of gained.
Results of elemental analyses demonstration, the aluminium content in ES955-YIN is 16.1 % by weight, and the content of Zr is 0.4 % by weight, and the mol ratio of Al/Zr is 136: 1.
Experiment comparative example 1
The catalytic activity of the carried metallocene catalyst that this experiment comparative example is used for illustrating that comparative example 1 makes.
Adopt the method identical with EXPERIMENTAL EXAMPLE 1 to carry out the homopolymerization of ethene, different, the catalyzer of employing is the ES955-YIN of comparative example 1 preparation.The carried metallocene catalyst ES955-YIN that adds 109.4 milligrams of above-mentioned comparative examples 1 to make, result obtains 72g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.316g/mL, melting index MI
2.16=0.006g/10min.Determine as calculated, the efficiency of catalyzer is 660g PE/ (gcath) (that is, 1.5 * 10
7g PE/ (mol Zrh)).
Experiment comparative example 2
The catalytic activity of the carried metallocene catalyst that this experiment comparative example is used for illustrating that comparative example 1 makes.
Adopt the method identical with EXPERIMENTAL EXAMPLE 2 that ethene and hexene are carried out to copolymerization, different, the catalyzer of employing is the ES955-YIN of comparative example 1 preparation.The carried metallocene catalyst ES955-YIN that adds 120.5 milligrams of above-mentioned comparative examples 1 to make, result obtains 43 grams of polymkeric substance, and the bulk density of this polymkeric substance (BD) is 0.263g/mL, and melting index is MI
2.16=0.031/10min.Determine as calculated, the efficiency of catalyzer is 357g PE/ (gcath) (that is, 0.8 * 10
7g PE/ (molZrh)).
Comparative example 2
This comparative example is the carried metallocene catalyst of bicyclic pentadiene zirconium dichloride for the preparation of metallocene compound.
Adopt the method identical with embodiment 1 to prepare carried metallocene catalyst, different, adopt bicyclic pentadiene zirconium dichloride CpZrCl
2as metallocene compound, obtain carried metallocene catalyst (called after JKQ-Cp).Results of elemental analyses demonstration, in JKQ-Cp, the content of aluminium element is 24 % by weight, and the content of Zr element is 1 % by weight, and the mol ratio of Al/Zr is 81: 1.
Experiment comparative example 3
The catalytic activity of the carried metallocene catalyst that this experiment comparative example is used for illustrating that comparative example 2 makes.
Adopt the method identical with EXPERIMENTAL EXAMPLE 1 to carry out the homopolymerization of ethene, different, the catalyzer of employing is the JKQ-Cp of comparative example 2 preparations.The carried metallocene catalyst JKQ-Cp that adds 93.75 milligrams of above-mentioned comparative examples 2 to make, result obtains 36g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.30g/ml, melting index: MI
2.16=0.011g/10min.Determine as calculated, the efficiency of catalyzer is 384g PE/gcath (that is, 3.5 * 10
6g PE/ (mol Zrh)).
Experiment comparative example 4
The catalytic activity of the carried metallocene catalyst that this experiment comparative example is used for illustrating that comparative example 2 makes.
Adopt the method identical with EXPERIMENTAL EXAMPLE 2 that ethene and hexene are carried out to copolymerization, different, the catalyzer of employing is the JKQ-Cp of comparative example 2 preparations.The carried metallocene catalyst JKQ-Cp that adds 98.17 milligrams of above-mentioned comparative examples 2 to make, result obtains the multipolymer of 43 grams of ethene and hexene, and the bulk density of the multipolymer of this ethene and hexene (BD) is 0.304g/ml, and melting index is MI
2.16=0.077/10min.Determine as calculated, the efficiency of catalyzer is 438g PE/gcath (that is, 4.0 * 10
6gPE/ (mol Zrh)).
Claims (12)
1. a carried metallocene catalyst, it is characterized in that, this catalyzer comprises carrier and loads on metallocene compound and the alkylaluminoxane on described carrier, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, and specific surface area is 1000-2000 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1,
Wherein, M is a kind of in titanium, zirconium and hafnium, and X is halogen.
2. carried metallocene catalyst according to claim 1, wherein, the total amount of described carried metallocene catalyst of take is benchmark, and the total content of described metallocene compound and alkylaluminoxane is 10-60 % by weight, and the content of described carrier is 40-90 % by weight; The mol ratio of M in aluminium in described alkylaluminoxane and described metallocene compound is 50-500:1.
3. carried metallocene catalyst according to claim 2, wherein, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound is 139:1.
4. according to the carried metallocene catalyst described in claim 1,2 or 3, wherein, M is zirconium, and X is chlorine.
5. according to the carried metallocene catalyst described in claim 1,2 or 3, wherein, the alkyl in described alkylaluminoxane is C
1-C
5alkyl.
6. carried metallocene catalyst according to claim 5, wherein, described alkylaluminoxane is methylaluminoxane.
7. carried metallocene catalyst according to claim 1, wherein, the average particle diameter of described carrier is 2-8 micron, and specific surface area is 1100-1800 meters squared per gram, and pore volume is 0.4-0.8 ml/g, and most probable aperture is 4-12 nanometer.
8. according to the carried metallocene catalyst described in any one in claim 1-3, wherein, described carrier is made by the method comprising the following steps:
(1), at 25-60 ℃, template is dissolved in hydrochloric acid;
(2), at 25-60 ℃, water glass is dissolved in step (1) gained solution;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) by the heating of step (3) gained crystallization product, removed template method;
Described template is cetyl trimethylammonium bromide and Triton X-100.
9. carried metallocene catalyst according to claim 8, wherein, described crystallization condition comprises: crystallization temperature is 25-60 ℃, crystallization time is 10-40 hour; The condition of described removed template method comprises that temperature is 250-800 ℃, and the time is 10-40 hour.
10. carried metallocene catalyst according to claim 8, wherein, counts water glass: Triton X-100: cetyl trimethylammonium bromide: hydrogenchloride: water=1:0.01-0.5:0.1-0.6:5-50:100-500 in molar ratio.
11. 1 kinds of methods of preparing the carried metallocene catalyst described in any one in claim 1-10, is characterized in that, the method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
12. methods according to claim 11 wherein, before the method is also included in load alkylaluminoxane, under protection of inert gas, heat 7-10 hour by described carrier at 300-900 ℃ of temperature.
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| Jian Liu，et al.Morphological and Structural Evolution of Mesoporous Silicas in a Mild Buffer Solution and Lysozyme Adsorption.《Langmuir》.2007,第257卷(第1期),7255-7262. * |
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