CN102718896B - Loaded metallocene catalyst and preparation method thereof - Google Patents
Loaded metallocene catalyst and preparation method thereof Download PDFInfo
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- CN102718896B CN102718896B CN201110080343.XA CN201110080343A CN102718896B CN 102718896 B CN102718896 B CN 102718896B CN 201110080343 A CN201110080343 A CN 201110080343A CN 102718896 B CN102718896 B CN 102718896B
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Abstract
The invention provides a loaded metallocene catalyst and a preparation method thereof. The catalyst comprises a carrier and a metallocene compound and alkyl aluminoxane which are loaded on the carrier, wherein the carrier is rodlike macroporous silica, the average particle diameter of the carrier is 20-80 micrometers, the specific surface area is 400-700 m<2>/g, the pore volume is 0.3-1.5 ml/g, the most probable aperture is 3-20 nanometers; the metallocene compound has the structure shown in formula 1, wherein M is one of titanium, zirconium and hafnium, and X is halogen. When the loaded metallocene catalyst is used for catalyzing olefin to polymerize, the catalytic efficiency can reach 2409 g PE/gcat-h.
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 research report is very many, wherein with SiO
2for example, for the report most study of carrier: CN1174848A, CN1174849A, CN1356343A, US4,808,561, US5,026,797, US5,763,543, 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 carried 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.The mesoporous material that at present conventional granularity is 5-20 micron is as support of the catalyst.Adopt catalyzer that above-mentioned carrier makes free settling not when vinyl polymerization, powder is too many, to the equipment of vinyl polymerization, can cause to a certain degree infringement.Therefore, if obtain catalyst activity high and when vinyl polymerization the catalyzer of free settling not, will exert far reaching influence to this petrochemical industry important step of vinyl polymerization.
Summary of the invention
The catalytic activity lower and less problem of granularity mesoporous material still that the object of the invention is to overcome the loaded metallocene silica-gel catalyst of prior art, provides a kind of high reactivity oarse-grained carried metallocene catalyst.
The present inventor finds, by mesoporous material and silica gel is compound, the advantage of the macrobead degree of the activity of mesoporous material and silica gel (20-80 micron) can be combined, form and there is highly active matrix material, can solve thus the problem of catalyst activity and granularity.
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 20-80 micron, and the specific surface area of carrier is 400-700 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 3-20 nanometer; Described metallocene compound has the structure shown in formula 1:
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl, M is a kind of in titanium, zirconium and hafnium, X is halogen.
The present invention also provides a kind of method of preparing above-mentioned 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, and has substituting group on cyclopentadienyl, and described carrier granule degree and aperture are all larger, both guarantee thus the granularity of catalyzer, guaranteed again the catalytic activity of catalyzer.
Particularly, carried metallocene catalyst according to the present invention is when for catalysis in olefine polymerization, and catalytic efficiency can reach 2409g PE/gcath (that is, 6.2 * 10
7g PE/ (mol Zrh)), and in the situation that other conditions are identical, catalytic efficiency when 955 silica gel loads have the metallocene compound of the structure shown in formula 1 only for 1295g PE/gcath (, 3.3 * 10
7gPE/ (mol Zrh)).Illustrate that thus sphericity mesoporous silicon dioxide coordinates and has synergy with the described metallocene compound with the structure shown in formula 1, obtained unexpected technique effect, and, when not changing catalytic activity, can significantly reduce production costs.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern (a) of sphericity mesoporous silicon dioxide GJ-MBQ, and Fig. 2 is the x-ray diffraction pattern (b) of carried metallocene catalyst MAO/GJ-MBQ-BU, X-coordinate unit be 2 θ (°), ordinate zou is intensity.
Fig. 3 and Fig. 4 are respectively the N of sphericity mesoporous silicon dioxide GJ-MBQ (a) and carried metallocene catalyst MAO/GJ-MBQ-BU (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.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution (b) of sphericity mesoporous silicon dioxide GJ-MBQ (a) and carried metallocene catalyst MAO/GJ-MBQ-BU, 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. 7
1and a
2for the stereoscan photograph of sphericity mesoporous silicon dioxide GJ-MBQ, b
1and b
2for the stereoscan photograph of carried metallocene catalyst MAO/GJ-MBQ-BU, c
1and c
2for carried metallocene catalyst MAO/GJ-MBQ-BU carries out the polymerisate obtaining after vinyl polymerization.
Embodiment
The invention provides a kind of carried metallocene catalyst, wherein, 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 20-80 micron, and the specific surface area of carrier is 400-700 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 3-20 nanometer; Described metallocene compound has the structure shown in formula 1,
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl, M is a kind of in titanium, zirconium and hafnium, X is halogen.
According to the present invention, the specific surface area of described carried metallocene catalyst can be 250-500 meters squared per gram, is preferably 300-450 meters squared per gram, more preferably 380 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 1-20 nanometer, is preferably 2-10 nanometer, more preferably 3.9 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 28-52 % by weight, and the content of described carrier is 48-72 % 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 35-36 % by weight, and the content of described carrier is 64-65 % 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 100-240: 1, be preferably 147: 1.
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.M in different metallocene compound molecules can be identical or different, and 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.X in different metallocene compound molecules can be identical or different, and more preferably, the X in formula 1 is chlorine.
According to the present invention, in formula 1, cyclopentadienyl is for forming η with central metal
5key and with the derivative of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl in formula 1
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl.
In the present invention, described C
1-C
5alkyl can be one or more in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
Preferably, the R in formula 1
1, R
1' and be C independently of one another
1-C
5alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
More preferably, R
1and R
1' be C
4alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.Particularly, described cyclopentadienyl is n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl, isobutyl-cyclopentadienyl, tertiary butyl cyclopentadienyl.
The present inventor finds in research process, the R in formula 1
1and R
1' be normal-butyl, M is zirconium, X is chlorine, be that described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, and when alkylaluminoxane is methylaluminoxane, when described carried metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent catalytic activity.
According to carried metallocene catalyst of the present invention, wherein, the average particle diameter of described carrier is 20-80 micron, and specific surface area is 400-700 meters squared per gram, and pore volume is 0.3-1.5 ml/g, and most probable aperture is 3-20 nanometer; Under preferable case, the average particle diameter of described carrier is 20-80 micron, and specific surface area is 420-680 meters squared per gram, and pore volume is 0.6-1.2 ml/g, and most probable aperture is 3-15 nanometer; More preferably in situation, the average particle diameter of described carrier is 20-80 micron, and specific surface area is 602 meters squared per gram, and pore volume is 0.8 ml/g, and most probable aperture is 4 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) template, DMF and hydrochloric acid are stirred to dissolving at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred to 1-2 hour at 25-60 ℃ of temperature;
(3) step (2) products therefrom is mixed with silica gel after under crystallization condition crystallization;
(4), by step (3) gained crystallization product heating, removed template method, obtains the sphericity mesoporous silicon dioxide of removed template method;
Described template is polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
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, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide: water: HCl=1: 300-700: 10000-20000: 100-500, be preferably 1: 550-650: 10000-13000: 150-480, is particularly preferably 1: 596: 11411: 326.The weight ratio of described tetraethoxy and silica gel can be 3-6: 1, be preferably 4-5: and 1, more preferably 4.45: 1.Wherein, the mole number of polyoxyethylene-polyoxytrimethylene-polyoxyethylene calculates according to the molecular-weight average of polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
Described template can be the conventional various triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene template used in this area, for example, can be the template of commodity P123 by name.
According to the present invention, the various silica gel that described silica gel can be used for carrier for olefin polymerization catalyst, described silica gel be chosen as general knowledge well known in the art, do not repeat them here, for example can select the trade mark is the silica gel of ES955.
Kind and the content of described carrier, alkylaluminoxane and metallocene compound are described above, do not repeat them here.
Aforesaid method by adding silica gel before crystallization, and adopt tetraethoxy as silicon source, be equipped with polyoxyethylene-polyoxytrimethylene-polyoxyethylene template, make the coated with silica of teos hydrolysis generation at Silica Surface, jointly form sphericity mesoporous silicon dioxide.
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 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 can be 10-60 % by weight, be preferably 15-55 % by weight, more preferably 28-52 % by weight, is further preferably 35-36 % by weight; The content of described carrier can be 40-90 % by weight, is preferably 45-85 % by weight; More preferably 48-72 % by weight, is further preferably 64-65 % by weight; The mol ratio of M in aluminium in described alkylaluminoxane and described metallocene compound can be 100-240: 1, be preferably 147: 1.
According to one embodiment of the present invention, the preparation method of described carried metallocene catalyst comprises the following steps:
The 1st step, by triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene and DMF (DMF), joins in aqueous hydrochloric acid, by molar feed ratio,
Triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide (DMF): water: hydrogenchloride=1: 300-700: 10000-20000: 100-500, be preferably 1: 550-650: 10000-13000: 150-480, be particularly preferably 1: 596: 11411: 326
At 25-60 ℃ of temperature, be stirred to dissolving;
The 2nd step adds tetraethoxy in previous step gained solution, adds silica gel after stirring 1-2 hour, then stir 10-40 hour at 25-60 ℃ of temperature; The weight ratio of described tetraethoxy and silica gel can be 3-6: 1, be preferably 4-5: and 1, more preferably 4.45: 1.
The 3rd step, filters crystallization after product, wash, be dried, and obtains the former powder of matrix material;
The 4th step, by the former powder of gained matrix material in retort furnace at 250-800 ℃ of temperature lower calcination 10-40 hour, removed template method, obtains the sphericity mesoporous silicon dioxide of removed template method;
The 5th step, thermal activation step, under nitrogen protection, in 300-900 ℃ of calcining 7-10 hour, obtains the matrix material after thermal activation by upper step gained matrix material;
The 6th step, matrix material after thermal activation is transferred in the reactor after nitrogen is fully replaced, add toluene and alkylaluminoxane, count in molar ratio, matrix 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: 28.28: 1.1, in 25-80 ℃, stir 1-10 hour again, after, with hexane washing 2 times, afterwards solid is dried up with nitrogen again, obtain the matrix material of load methylaluminoxane;
The 7th step, under nitrogen protection, joins the matrix material of 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 25-80 ℃ of agitation condition, slowly metallocene compound solution is added drop-wise in reactor, meter in molar ratio, matrix material (take silicon-dioxide): toluene: the amount ratio of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of metallocene compound is 1: 20-150: 2 * 10
-3-9 * 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.
Described template can be the conventional various triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene template used in this area, for example, can be the template of commodity P123 by name.
The various silica gel that described silica gel can be used for carrier for olefin polymerization catalyst, described silica gel be chosen as general knowledge well known in the art, do not repeat them here, for example can select the trade mark is the silica gel of ES955.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, P123, the material that is 9003-11-6 in the registration number of U.S. chemical abstract, its average molecular mass Mn=5800; Methylaluminoxane is purchased from U.S. Albemarle Corporation; Two (n-butyl cyclopentadienyl) zirconium dichloride is purchased from Alfa Aesar, article No. H27576.
In following examples, on the X-ray diffractometer that X-ray diffraction analysis is D8Advance in the model purchased from company of German Bruker AXS company, carry out; TEM (transmission electron microscope) analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model purchased from company of Dutch FEI Co.; In the scanning electronic microscope that scanning electron microscope analysis is XL-30 in the model purchased from company of U.S. FEI Co., carry out; Ultimate analysis is being to carry out on 7500CX instrument purchased from U.S. An Jielun company model.
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.
2.0 grams of P123 and 15 grams of DMFs (DMF) and 64ml water are joined in the hydrochloric acid soln of 11.2 gram 37%, at 40 ℃, be stirred to P123 and dissolve completely; Again 4.45 grams of tetraethoxys are joined in above-mentioned solution and stir 1 hour at 40 ℃, then add 1 gram of industrial ES955 silica gel, after filtering, wash, being dried, obtain former powder composite material; By matrix material 600 ℃ of calcinings 24 hours in retort furnace, removed template method, obtains the sphericity mesoporous silicon dioxide (called after GJ-MBQ) of final product.
By above-mentioned matrix material GJ-MBQ under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the matrix material through thermal activation.
0.31 gram of matrix material through thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 20 milliliters of refining toluene, 0.39 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 GJ-MBQ of methylaluminoxane (called after MAO/GJ-MBQ).
Under nitrogen protection, the MAO/GJ-MBQ obtaining is all joined in 250 milliliters of glass reactors, add 20 milliliters of refining toluene, at 30 ℃, slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides of 15.4 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 MAO/GJ-MBQ-BU).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 GJ-MBQ, and Fig. 2 is the little angle x-ray diffraction pattern of carried metallocene catalyst MAO/GJ-MBQ-BU, X-coordinate unit be 2 θ (°), ordinate zou is intensity.By XRD spectra, can obviously be found out, all there is Small angle spectrum peak in sphericity mesoporous silicon dioxide GJ-MBQ and carried metallocene catalyst MAO/GJ-MBQ-BU, illustrates that the matrix material MAO/GJ-MBQ-BU of load metallocene has the peculiar two-dimentional hexagonal hole of mesoporous material road structure.
Fig. 3 and Fig. 4 are respectively the N of sphericity mesoporous silicon dioxide GJ-MBQ and carried metallocene catalyst MAO/GJ-MBQ-BU
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 shows that MAO/GJ-MBQ-BU has the IV type thermoisopleth of sharp-pointed capillary condensation speed, and this thermoisopleth has H
1hysteresis loop, this shows that MAO/GJ-MBQ-BU has the aperture size distribution of homogeneous.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of sphericity mesoporous silicon dioxide GJ-MBQ and carried metallocene catalyst MAO/GJ-MBQ-BU, and wherein, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g.As seen from Figure 6, MAO/GJ-MBQ-BU has six sides' meso-hole structure, and duct is very even.
Fig. 7 is stereoscan photograph, a
1, a
2for the stereoscan photograph of sphericity mesoporous silicon dioxide GJ-MBQ, b
1, b
2the stereoscan photograph of carried metallocene catalyst MAO/GJ-MBQ-BU, c
1and c
2for carried metallocene catalyst MAO/GJ-MBQ-BU carries out the polymerisate obtaining after vinyl polymerization.As seen from the figure, GJ-MBQ particle diameter is 20-80 μ m, and particle diameter and the GJ-MBQ of MAO/GJ-MBQ-BU are basic identical, this explanation load metallocene GJ-MBQ particle size dispersion, pattern is spherical substantially, and in loading process, MAO/GJ-MBQ-BU has good mechanical property.
Table 1 is the pore structure parameter of sphericity mesoporous silicon dioxide GJ-MBQ and carried metallocene catalyst MAO/GJ-MBQ-BU.
Table 1 pore structure parameter
| Sample | Specific surface area (m 2/g) | Pore volume (ml/g) | Most probable aperture (nm) |
| GJ-MBQ | 602 | 0.8 | 4.0 |
| GJ-MBQ-BU | 380 | 0.4 | 3.9 |
Data by upper table 1 can find out, sphericity mesoporous silicon dioxide GJ-MBQ is after load metallocene, and pore volume, specific surface area and aperture all reduce to some extent, and this explanation metallocene in load-reaction process enters into the inside of matrix material.
Ultimate analysis ICP result shows, load the aluminium content of complex mesoporous material MAO/GJ-MBQ-BU of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of methylaluminoxane (MAO) and metallocene compound be 15.6 % by weight, the content of Zr is 0.36 % by weight, and the mol ratio of Al/Zr is 147: 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 35.11 % by weight, and the content of carrier is 64.89 % by weight.
Embodiment 1
The present embodiment 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 add 60.6 milligrams of MAO/GJ-MBQ-BU, pass into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 146 grams of polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.317g/ml, melting index MI
2.16=0.051g/10min.Determine as calculated, the efficiency of catalyzer is 2409g PE/gcath (that is, 6.2 * 10
7g PE/ (mol Zr h)).
The present embodiment 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 ℃, then add 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 MAO/GJ-MBQ-BU that adds 62 milligrams, passed into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 141 grams of polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.311g/ml, melting index MI
2.16=0.339g/10min.Determine as calculated, the efficiency of catalyzer is 2274g PE/gcath (that is, 5.7 * 10
7g PE/ (mol Zrh)).
Preparation comparative example 1
By the industrial ES955 silica gel with preparation example 1 identical source under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the silica gel through the ES955 of thermal activation.
Under nitrogen protection; 0.9 gram of ES955 silica gel is joined in 250 milliliters of glass reactors; add again 1.0 grams of methylaluminoxane and 10mL toluene; under 50 ℃ of conditions; after stirring reaction 4 hours, use toluene wash 3 times, then wash three times with 20 milliliters of hexanes; finally solid is dried up with nitrogen, obtaining load has the ES955 of methylaluminoxane (called after MAO/ES955).
Under nitrogen protection; MAO/ES955 is joined in 250 milliliters of glass reactors, add 20 milliliters of refining toluene (refluxing 24 hours with sodium), at 30 ℃; slowly drip two (normal-butyl-cyclopentadienyl) zirconium dichlorides of metallocene compound of 44 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, obtain carried metallocene catalyst (called after MAO/ES955-BU).
Results of elemental analyses demonstration, the content of the aluminium in ES955-BU is 32.4 % by weight, and the content of Zr is 0.41 % by weight, and the mol ratio of Al/Zr is 267: 1.
Comparative example 1
Adopt the method identical with embodiment 1 to carry out the homopolymerization of ethene, different is, the catalyzer adopting is the ES955-BU of preparation comparative example 1 preparation, add 60.6 milligrams of ES955-BU, result obtains 78.5g polyethylene particle powder, the bulk density of this polyethylene particle powder (BD) is 0.331g/ml, melting index: MI
2.16=0.119g/10min.Determine as calculated, the efficiency of catalyzer is 1295g PE/gcath (that is, 3.3 * 10
7gPE/ (mol Zrh)).
Experiment comparative example 2
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-BU of comparative example 1 preparation, adds 60 milligrams of ES955-BU, obtains 60 grams of polymkeric substance.The density of this polymer stacks (BD) is 0.299g/ml, and melting index is MI
2.16=0.679g/10min, the efficiency of catalyzer is 1000g PE/gcath (that is, 2.2 * 10
7gPE/ (mol Zr h)).
Claims (16)
1. a carried metallocene catalyst, this catalyzer comprises carrier and loads on metallocene compound and the alkylaluminoxane on described carrier, it is characterized in that, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 20-80 micron, and specific surface area is 400-700 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 3-20 nanometer; Described metallocene compound has the structure shown in formula 1:
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; 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 amount of described metallocene compound and alkylaluminoxane is 10-60 % by weight, and the content of described carrier is 40-90 % by weight.
3. carried metallocene catalyst according to claim 1 and 2, wherein, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound is 50-200:1.
4. carried metallocene catalyst according to claim 3, wherein, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound is 80-150:1.
5. carried metallocene catalyst according to claim 1, wherein, M is zirconium, X is chlorine.
6. carried metallocene catalyst according to claim 1, wherein, R
1and R
1' be C independently of one another
1-C
5alkyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
7. carried metallocene catalyst according to claim 6, wherein, R
1and R
1' be normal-butyl independently of one another.
8. carried metallocene catalyst according to claim 1 and 2, wherein, the alkyl in described alkylaluminoxane is C
1-C
5alkyl.
9. carried metallocene catalyst according to claim 8, wherein, described alkylaluminoxane is methylaluminoxane.
10. carried metallocene catalyst according to claim 1, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, described alkylaluminoxane is methylaluminoxane.
11. carried metallocene catalysts according to claim 1, wherein, the average particle diameter of described carrier is 20-80 micron, and specific surface area is 420-680 meters squared per gram, and pore volume is 0.6-1.2 ml/g, and most probable aperture is 3-15 nanometer.
12. according to the carried metallocene catalyst described in claim 1 or 11, and wherein, described carrier is made by the method comprising the following steps:
(1) template, DMF and hydrochloric acid are stirred to dissolving at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred to 1-2 hour at 25-60 ℃ of temperature;
(3) step (2) products therefrom is mixed with silica gel after under crystallization condition crystallization;
(4) by the heating of step (3) gained crystallization product, removed template method;
Described template is polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
13. carried metallocene catalysts according to claim 12, 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.
14. carried metallocene catalysts according to claim 12, wherein, count in molar ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide: water: hydrogenchloride=1:300-700:10000-20000:100-500, described tetraethoxy: the weight ratio of silica gel is 3-6:1.
15. 1 kinds of methods of preparing the carried metallocene catalyst described in any one in claim 1-14, is characterized in that, the method comprises: under protection of inert gas, and successively load alkylaluminoxane and described metallocene compound on carrier.
16. methods according to claim 15 wherein, before the method is also included in load alkylaluminoxane, under protection of inert gas, heat 7-10 hour by described carrier at the temperature of 300-900 ℃.
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| EP1283222A1 (en) * | 2001-03-30 | 2003-02-12 | Toho Catalyst Co., Ltd. | Solid catalyst ingredient and catalyst each for olefin polymerization and propylene block copolymer |
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| EP1283222A1 (en) * | 2001-03-30 | 2003-02-12 | Toho Catalyst Co., Ltd. | Solid catalyst ingredient and catalyst each for olefin polymerization and propylene block copolymer |
Non-Patent Citations (2)
| Title |
|---|
| Cristian Covarrubias et al.High catalytic activity of SBA-15-supported metallocene toward ethylene polymerization: The effect of the ordered porous structure of the support.《Catalysis Communications》.2008,第10卷 |
| High catalytic activity of SBA-15-supported metallocene toward ethylene polymerization: The effect of the ordered porous structure of the support;Cristian Covarrubias et al;《Catalysis Communications》;20081225;第10卷;995–1001 * |
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