CN102718896A - Loaded metallocene catalyst and preparation method thereof - Google Patents
Loaded metallocene catalyst and preparation method thereof Download PDFInfo
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- CN102718896A CN102718896A CN201110080343XA CN201110080343A CN102718896A CN 102718896 A CN102718896 A CN 102718896A CN 201110080343X A CN201110080343X A CN 201110080343XA CN 201110080343 A CN201110080343 A CN 201110080343A CN 102718896 A CN102718896 A CN 102718896A
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- alkylaluminoxane
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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.Because to reach the required MAO of high reactivity (MAO) consumption big for the homogeneous phase metallocene catalyst, production cost is high, and the polymkeric substance that obtains do not have particle shape, can't on widely used slurry process or gas phase polymerization technology, use.And the activity of metallocene catalyst is very high, and it is very fast in polymerization process, to be easy to take place local polymerization velocity, and then causes implode.
The effective way that addresses the above problem is carried out the load processing to the solubility metallocene catalyst exactly.At present, relevant metallocene catalyst load research report is very many, wherein with SiO
2For the research of the report of carrier at most, for example: 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 the evenly regular one dimension or the material of solid netted sieve aperture, and surfactivity is higher, absorption property good, have tangible molecule shape selectivity ability, and its 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, monomeric inserted mode is different with freeboard with propagation process in the polymerization process, and double-basis terminated chance has been reduced in limited space to a certain extent, makes polyreaction show the characteristic of " living polymerization ".
Olefin polymerization catalysis is carried on molecular sieve, has following advantage:
(1) molecular sieve of synthetic does not contain the impurity that is prone to make polymer degradation, with the ageing resistance that improves polyolefine material;
(2) the molecular sieve nano pore has the dual-use function of carrier and reactor drum, and catalyst cupport efficient is high, and polymerization process is controlled easily, and can in the skeleton of polymerization reactor, key in the active site, accelerates reaction process, improves productive rate;
(3) insertion has three-dimensional selection effect with polyreaction to monomer, can improve polyolefinic molecular weight and fusing point.
This shows that 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 (aperture is the molecular sieve of 2-50nm) has bigger specific surface area and relatively large aperture, can handle bigger molecule or group, can make catalyzer bring into play its due catalytic activity well.The mesoporous material that granularity at present commonly used is the 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, can cause to a certain degree infringement to the equipment of vinyl polymerization.Therefore, if can obtain the catalyst activity height and when vinyl polymerization, be difficult for settled catalyzer, will exert far reaching influence this petrochemical industry important step of vinyl polymerization.
Summary of the invention
The objective of the invention is to overcome the still low granularity problem of smaller with mesoporous material of the catalytic activity of loaded metallocene silica-gel catalyst of prior art, provide a kind of high reactivity oarse-grained carried metallocene catalyst.
Contriver of the present invention finds; Through mesoporous material and silica gel is compound; Can the advantage of the activity of mesoporous material and the macrobead degree of silica gel (20-80 micron) be combined, formation has highly active matrix material, can solve the problem of catalyst activity and granularity thus.
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 the said carrier; Said carrier is a sphericity mesoporous silicon dioxide; Wherein, the average particle diameter of said carrier is the 20-80 micron, and the specific surface area of carrier is the 400-700 meters squared per gram; Pore volume is 0.3-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer; Said metallocene compound has the structure shown in the 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 the hafnium, X is a halogen.
The present invention also provides a kind of method for preparing above-mentioned carried metallocene catalyst, and this 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; Said metallocene compound has sandwich structure, and has substituting group on the cyclopentadienyl moiety, and said carrier granule degree and aperture are all bigger; Both guarantee the granularity of catalyzer thus, guaranteed the catalytic activity of catalyzer again.
Particularly, carried metallocene catalyst according to the present invention is when being used for catalysis in olefine polymerization, and catalytic efficiency (can reach 2409g PE/gcath (that is, 6.2 * 10
7G PE/ (mol Zrh)), and under the identical situation of other conditions, the catalytic efficiency (during metallocene compound that 955 silica gel loads have the structure shown in the formula 1 be merely 1295g PE/gcath (, 3.3 * 10
7GPE/ (mol Zrh)).Explain that thus sphericity mesoporous silicon dioxide cooperates with the said metallocene compound with the structure shown in the formula 1 and has synergy, obtained unexpected technique effect, and, when not changing catalytic activity, can significantly reduce production costs.
Description of drawings
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 an 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)
2The adsorption desorption graphic representation, wherein, X-coordinate is a 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 the aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g.
A among Fig. 7
1And a
2Be the stereoscan photograph of sphericity mesoporous silicon dioxide GJ-MBQ, b
1And b
2Be the stereoscan photograph of carried metallocene catalyst MAO/GJ-MBQ-BU, c
1And c
2Carry out the polymerisate that obtains behind the vinyl polymerization for carried metallocene catalyst MAO/GJ-MBQ-BU.
Embodiment
The invention provides a kind of carried metallocene catalyst, wherein, this catalyzer comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier; Said carrier is a sphericity mesoporous silicon dioxide; Wherein, the average particle diameter of said carrier is the 20-80 micron, and the specific surface area of carrier is the 400-700 meters squared per gram; Pore volume is 0.3-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer; Said metallocene compound has the structure shown in the 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 the hafnium, X is a halogen.
According to the present invention, the specific surface area of said carried metallocene catalyst can be the 250-500 meters squared per gram, is preferably the 300-450 meters squared per gram, more preferably 380 meters squared per gram; Pore volume can be 0.1-1 milliliter/gram, is preferably 0.2-0.8 milliliter/gram, more preferably 0.4 milliliter/gram; The most probable aperture can be the 1-20 nanometer, is preferably the 2-10 nanometer, more preferably 3.9 nanometers.
According to carried metallocene catalyst of the present invention, the metallocene compound and the amount of alkylaluminoxane that load on the said carrier can change within a large range.Contriver of the present invention finds; Total amount with said carried metallocene catalyst is a benchmark; The total amount of said metallocene compound and alkylaluminoxane is 10-60 weight %; When the content of said carrier is 40-90 weight %, not only can obtains gratifying catalytic effect, but also can reduce cost.More preferably, be benchmark with the total amount of said carried metallocene catalyst, the total amount of said metallocene compound and alkylaluminoxane is 15-55 weight %, the content of said carrier is 45-85 weight %.Further under the preferable case, be benchmark with the total amount of said carried metallocene catalyst, the total amount of said metallocene compound and alkylaluminoxane is 28-52 weight %, and the content of said carrier is 48-72 weight %.Further under the preferable case, be benchmark with the total amount of said carried metallocene catalyst, the total amount of said metallocene compound and alkylaluminoxane is 35-36 weight %, and the content of said carrier is 64-65 weight %.
According to loaded catalyst of the present invention, the ratio between said alkylaluminoxane and the metallocene compound can be the known content of the technician of field of olefin polymerisation.Particularly, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound can be 100-240: 1, be preferably 147: 1.
According to carried metallocene catalyst of the present invention, what the M in the formula 1 can be in titanium, zirconium and the hafnium is a kind of.M in the different metallocene compound molecules can be identical or different, and preferably, M is a zirconium.
According to carried metallocene catalyst of the present invention, the X in the formula 1 is a halogen.What particularly, the X in the formula 1 can be in fluorine, chlorine, bromine and the iodine is a kind of.Preferably, the X in the formula 1 is a chlorine or bromine.X in the different metallocene compound molecules can be identical or different, and more preferably, the X in the formula 1 is a chlorine.
According to the present invention, in the formula 1, cyclopentadienyl moiety is for forming η with central metal
5Key and have the verivate of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl moiety in the 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.
Among the present invention, said C
1-C
5Alkyl can be in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and the neo-pentyl one or more.
Preferably, the R in the 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, said cyclopentadienyl moiety is n-butyl cyclopentadienyl, sec.-butyl cyclopentadienyl moiety, isobutyl-cyclopentadienyl moiety, tertiary butyl cyclopentadienyl moiety.
Contriver of the present invention finds in research process, the R in formula 1
1And R
1' be normal-butyl, M is a zirconium, X is a chlorine; Be that said metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides; And when alkylaluminoxane is MAO, when said 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 said carrier is the 20-80 micron, and specific surface area is the 400-700 meters squared per gram, and pore volume is 0.3-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer; Under the preferable case, the average particle diameter of said carrier is the 20-80 micron, and specific surface area is the 420-680 meters squared per gram, and pore volume is 0.6-1.2 milliliter/gram, and the most probable aperture is the 3-15 nanometer; More preferably under the situation, the average particle diameter of said carrier is the 20-80 micron, and specific surface area is 602 meters squared per gram, and pore volume is 0.8 a milliliter/gram, and the most probable aperture is 4 nanometers.
According to the present invention, described carrier is a sphericity mesoporous silicon dioxide, and said sphericity mesoporous silicon dioxide can prepare through the method that may further comprise the steps:
(1) with template, N, dinethylformamide and hydrochloric acid are stirred to dissolving under 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy were stirred 1-2 hour under 25-60 ℃ of temperature;
(3) step (2) products therefrom is mixed back crystallization under crystallization condition with silica gel;
(4) with step (3) gained crystallization product heating, removed template method obtains the sphericity mesoporous silicon dioxide of removed template method;
Said template is polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
Said 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 said 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 is preferably 1: 550-650: 10000-13000: 150-480 is preferably 1: 596: 11411: 326 especially.The weight ratio of said 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.
Said template can be the conventional various triblock copolymer polyoxyethylene-polyoxytrimethylenes-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, said silica gel be chosen as general knowledge well known in the art, repeat no more at this, for example can select the trade mark is the silica gel of ES955.
The kind and the content of said carrier, alkylaluminoxane and metallocene compound are described above, repeat no more at this.
Aforesaid method is through adding silica gel before crystallization; And adopt tetraethoxy as the silicon source; Be equipped with polyoxyethylene-polyoxytrimethylene-polyoxyethylene template, the coated with silica that makes teos hydrolysis produce is surperficial at silica gel, constitutes sphericity mesoporous silicon dioxide jointly.
The present invention also provides a kind of method for preparing said carried metallocene catalyst, and this method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
Be included in according to the method for the invention under the 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 the said carrier.Preferably, successively the method at load alkylaluminoxane and metallocene compound on the carrier comprises: under protection of inert gas, said carrier is contacted with first solution, said first solution contains said alkylaluminoxane first solvent; The carrier that has removed first solvent is contacted with second solution, and said second solution contains the said metallocene compound and second solvent, and removes second solvent.Said first solvent and second solvent can be identical or different, preferably are toluene.
The method that the present invention contacts with second solution for the carrier that said carrier is contacted and will remove said first solvent with first solution is not special to be limited, can be for well known to a person skilled in the art the whole bag of tricks, for example: dipping, spraying.The method of employing dipping can be so that solution gets in the duct on the carrier more fully, and therefore, the present invention is preferably flooded.
With not special qualification of condition that the carrier and first solution contact with second solution, for example: carrier can comprise with the condition that said first solution contacts: the time is 1-10 hour, and temperature is 25-80 ℃; The said carrier that has removed first solvent can be comprised with the condition that said 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 make with extra care before use, for example: can be through toluene be made with extra care on sodium in backflow 24-48 hour, with remove desolvate in impurity such as water.
Can also be included in according to the method for the invention before said alkylaluminoxane of load and the said metallocene compound; Under protection of inert gas; Said carrier was heated 7-10 hour under 300-900 ℃ temperature, (for example: water) with the volatile matter that contains in the hydroxyl of removing carrier surface and the carrier.
According to the present invention, chemically interactive all gases can not take place with carrier, alkylaluminoxane, metallocene compound for various in said rare gas element.For example, said rare gas element can be nitrogen, argon gas.
According to the present invention; The feasible total amount with said carried metallocene catalyst of said alkylaluminoxane and the metallocene compound charge capacity on said carrier is a benchmark; The total amount of said metallocene compound and alkylaluminoxane can be 10-60 weight %; Be preferably 15-55 weight %, more preferably 28-52 weight % further is preferably 35-36 weight %; The content of said carrier can be 40-90 weight %, is preferably 45-85 weight %; More preferably 48-72 weight % further is preferably 64-65 weight %; The mol ratio of M in aluminium in the said alkylaluminoxane and the said metallocene compound can be 100-240: 1, be preferably 147: 1.
According to one embodiment of the present invention, the preparation method of said carried metallocene catalyst may further comprise the steps:
In the 1st step, with triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene and N, dinethylformamide (DMF) joins in the aqueous hydrochloric acid, by the mole 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 preferably 1: 596: 11411 especially: 326
Under 25-60 ℃ of temperature, be stirred to dissolving;
The 2nd step added tetraethoxy in a last step gained solution, after stirring 1-2 hour under the 25-60 ℃ of temperature, add silica gel, restir 10-40 hour; The weight ratio of said tetraethoxy and silica gel can be 3-6: 1, be preferably 4-5: and 1, more preferably 4.45: 1.
In the 3rd step,, obtain the former powder of matrix material with the filtration of crystallization after product, washing, drying;
The 4th step, with 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;
In the 5th step, the thermal activation step will go up step gained matrix material under nitrogen protection, in 300-900 ℃ of calcining 7-10 hour, obtain the matrix material after the thermal activation;
The 6th step was transferred to the matrix material after the thermal activation in the reactor drum after nitrogen is fully replaced, and added toluene and alkylaluminoxane; Count in molar ratio, matrix material (in silicon-dioxide): toluene: the amount ratio of alkylaluminoxane is 1: 10-100: 0.1-2 is preferably 1: 20-90: 0.3-1.5; More preferably 1: 28.28: 1.1; In 25-80 ℃ of stirring 1-10 hour, after finishing, use hexane wash again 2 times again; Afterwards solid is dried up with nitrogen, obtain the matrix material of load MAO;
The 7th step under nitrogen protection, joined the matrix material of load MAO in the reactor drum, added stirring solvent and processed slurries; In the container of crossing with nitrogen replacement in advance, solution is processed in the metallocene compound dissolving; Under 25-80 ℃ of agitation condition; Slowly the metallocene compound drips of solution is added in the reactor drum; Count matrix material (in silicon-dioxide): toluene in molar ratio: 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, reaction was left standstill after finishing, and leaches liquid, with toluene and hexane wash, dries up with nitrogen, obtains said carried metallocene catalyst.Wherein the molecular weight of alkylaluminoxane is in RAlO, and wherein R is an alkyl, and for example the molecular weight of MAO is with CH
3The AlO meter is 58.
Said template can be the conventional various triblock copolymer polyoxyethylene-polyoxytrimethylenes-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, said silica gel be chosen as general knowledge well known in the art, repeat no more at this, for example can select the trade mark is the silica gel of ES955.
Below in conjunction with embodiment the present invention is carried out detailed description.
In following examples, P123 is the material of 9003-11-6 in the registration number of U.S. chemical abstract, its average molecular mass Mn=5800; MAO is available from U.S. Albemarle Corporation; Two (n-butyl cyclopentadienyl) zirconium dichloride is available from Alfa Aesar, article No. H27576.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8Advance in the model available from company of German Bruker AXS company; TEM analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model available from company of Dutch FEI Co.; Scanning electron microscope analysis is to carry out on the sem of XL-30 in the model available from company of U.S. FEI Co.; Ultimate analysis is being to carry out on the 7500CX instrument available 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 appearance, sample was 200 ℃ of degassings 4 hours.
Preparation example 1
This preparation example is used for explanation according to carried metallocene catalyst of the present invention and preparation method thereof.
With 2.0 gram P123 and 15 gram N, dinethylformamide (DMF) and 64ml water join in the hydrochloric acid soln of 11.2 grams 37%, are stirred to P123 at 40 ℃ and dissolve fully; Again 4.45 gram tetraethoxys are joined in the above-mentioned solution and stirred 1 hour, add the industrial ES955 silica gel of 1 gram again, through obtaining former powder composite material after filtration, washing, the drying at 40 ℃; With 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.
With above-mentioned matrix material GJ-MBQ 400 ℃ of calcinings 10 hours under nitrogen protection, removing hydroxyl and remaining moisture, thereby obtain matrix material through thermal activation.
0.31 gram is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced through the matrix material of thermal activation, adds 20 milliliters of purified toluene, 0.39 gram MAO in 50 ℃ of stirrings 4 hours.After finishing, use 20 milliliters of hexane wash three times again, at last solid is dried up with nitrogen, obtaining load has the GJ-MBQ of MAO (called after MAO/GJ-MBQ).
Under nitrogen protection, the MAO/GJ-MBQ that obtains is all joined in 250 milliliters of glass reactors, add 20 milliliters of purified toluene, under 30 ℃, slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides of 15.4 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid after the layering,, follow,, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after MAO/GJ-MBQ-BU) with 40 milliliters of hexane wash twice with 10 milliliters of toluene wash three times.Come this carried metallocene catalyst is characterized with XRD, nitrogen adsorption-desorption experiment, ESEM, X-ray energy spectrometer and ICP ultimate analysis.
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 an intensity.Can obviously find out by XRD spectra; Maller angle spectrum peak all appears in sphericity mesoporous silicon dioxide GJ-MBQ and carried metallocene catalyst MAO/GJ-MBQ-BU, explains 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
2The adsorption desorption graphic representation, wherein, X-coordinate is a 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 thermo-isopleth of sharp-pointed capillary condensation speed, and this thermo-isopleth 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 the aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g.Can find out that by Fig. 6 MAO/GJ-MBQ-BU has six sides' meso-hole structure, and the duct is very even.
Fig. 7 is a stereoscan photograph, a
1, a
2Be 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
2Carry out the polymerisate that obtains behind the vinyl polymerization for carried metallocene catalyst MAO/GJ-MBQ-BU.Can find out by figure; The 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 basically, and MAO/GJ-MBQ-BU has mechanical property preferably in loading process.
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 last table 1 can find out that sphericity mesoporous silicon dioxide GJ-MBQ is behind load metallocene, and pore volume, specific surface area and aperture all reduce to some extent, and this explanation metallocene in the 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 MAO (MAO) and metallocene compound be 15.6 weight %; The content of Zr is 0.36 weight %, and the mol ratio of Al/Zr is 147: 1.Learn through converting, be benchmark with the total amount of said carried metallocene catalyst, and the total content of MAO (MAO) and metallocene compound is 35.11 weight %, and the content of carrier is 64.89 weight %.
Embodiment 1
Present embodiment is used for explaining the catalytic activity according to carried metallocene catalyst of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 80 ℃, add 800 milliliters of hexanes again, along with the adding of hexane; The concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol; Then add 60.6 milligrams of MAO/GJ-MBQ-BU, feed ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 146 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.317g/ml, melting index MI
2.16=0.051g/10min.Confirm that through calculating the efficient of catalyzer is 2409g PE/gcath (that is, 6.2 * 10
7G PE/ (mol Zr h)).
Present embodiment is used for explaining the catalytic activity according to carried metallocene catalyst of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then; With still temperature rise to 70 ℃, add 800 milliliters of hexanes again, along with the adding of hexane; The concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of 1 mol; The MAO/GJ-MBQ-BU that then adds 62 milligrams fed ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 141 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.311g/ml, melting index MI
2.16=0.339g/10min.Confirm that through calculating the efficient of catalyzer is 2274g PE/gcath (that is, 5.7 * 10
7G PE/ (mol Zrh)).
Preparation Comparative Examples 1
Will with the 400 ℃ of calcinings 10 hours under nitrogen protection of the industrial ES955 silica gel in preparation example 1 identical source, removing hydroxyl and remaining moisture, thereby obtain silica gel through the ES955 of thermal activation.
Under nitrogen protection, 0.9 gram ES955 silica gel is joined in 250 milliliters of glass reactors, add 1.0 gram MAO and 10mL toluene again; Under 50 ℃ of conditions; Behind the stirring reaction 4 hours,, use 20 milliliters of hexane wash three times again with toluene wash 3 times; At last solid is dried up with nitrogen, obtaining load has the ES955 of MAO (called after MAO/ES955).
Under nitrogen protection; MAO/ES955 is joined in 250 milliliters of glass reactors, add 20 milliliters of purified toluene (refluxing 24 hours), under 30 ℃ with sodium; Slowly drip two (normal-butyl-cyclopentadienyl moiety) zirconium dichlorides of metallocene compound of 44 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid,, follow,, solid is dried up with nitrogen, obtain carried metallocene catalyst (called after MAO/ES955-BU) with 40 milliliters of hexane wash twice with 10 milliliters of toluene wash three times.
Results of elemental analyses shows that the content of the aluminium among the ES955-BU is 32.4 weight %, and the content of Zr is 0.41 weight %, and the mol ratio of Al/Zr is 267: 1.
Comparative Examples 1
Adopt and carry out the homopolymerization of ethene with embodiment 1 identical method; Different is; The catalyzer that adopts adds 60.6 milligrams of ES955-BU for the ES955-BU of preparation Comparative Examples 1 preparation, and the 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.Confirm that through calculating the efficient of catalyzer is 1295g PE/gcath (that is, 3.3 * 10
7GPE/ (mol Zrh)).
Experiment Comparative Examples 2
Adopt and with EXPERIMENTAL EXAMPLE 2 identical methods ethene and hexene are carried out copolymerization, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation, adds 60 milligrams of ES955-BU, obtains 60 gram polymkeric substance.The density of this polymer stacks (BD) is 0.299g/ml, and melting index is MI
2.16=0.679g/10min, the efficient of catalyzer is 1000g PE/gcath (that is, 2.2 * 10
7GPE/ (mol Zr h)).
Claims (13)
1. carried metallocene catalyst, this catalyzer comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier, it is characterized in that; Said carrier is a sphericity mesoporous silicon dioxide; Wherein, the average particle diameter of said carrier is the 20-80 micron, and specific surface area is the 400-700 meters squared per gram; Pore volume is 0.3-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer; Said metallocene compound has the structure shown in the 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 the hafnium; X is a halogen.
2. carried metallocene catalyst according to claim 1 wherein, is a benchmark with the total amount of said carried metallocene catalyst, and the total amount of said metallocene compound and alkylaluminoxane is 10-60 weight %, and the content of said carrier is 40-90 weight %.
3. carried metallocene catalyst according to claim 1 and 2; Wherein, The mol ratio of M in aluminium in the said alkylaluminoxane and the said metallocene compound is 50-200: 1, and the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound is preferably 80-150: 1.
4. according to claim 1 or 3 described carried metallocene catalysts, wherein, M is a zirconium, and X is a chlorine.
5. carried metallocene catalyst according to claim 1, wherein, R
1And R
1' be C independently of one another
1-C
5Alkyl, be preferably normal-butyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
6. according to any described carried metallocene catalyst among the claim 1-3, wherein, the alkyl in the said alkylaluminoxane is C
1-C
5Alkyl, preferred said alkylaluminoxane is a MAO.
7. carried metallocene catalyst according to claim 1, wherein, said metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, said alkylaluminoxane is a MAO.
8. carried metallocene catalyst according to claim 1, wherein, the average particle diameter of said carrier is the 20-80 micron, and specific surface area is the 420-680 meters squared per gram, and pore volume is 0.6-1.2 milliliter/gram, and the most probable aperture is the 3-15 nanometer.
9. according to claim 1 or 8 described carried metallocene catalysts, wherein, said carrier is made by the method that may further comprise the steps:
(1) with template, N, dinethylformamide and hydrochloric acid are stirred to dissolving under 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy were stirred 1-2 hour under 25-60 ℃ of temperature;
(3) step (2) products therefrom is mixed back crystallization under crystallization condition with silica gel;
(4) with the heating of step (3) gained crystallization product, removed template method;
Said template is polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
10. carried metallocene catalyst according to claim 9, wherein, said crystallization condition comprises: crystallization temperature is 25-60 ℃, crystallization time is 10-40 hour; The condition of said removed template method comprises that temperature is 250-800 ℃, and the time is 10-40 hour.
11. according to claim 9 or 10 described carried metallocene catalysts; Wherein, Count in molar ratio; Polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide: water: hydrogenchloride=1: 300-700: 10000-20000: 100-500, said tetraethoxy: the weight ratio of silica gel is 3-6: 1.
12. a method for preparing any described carried metallocene catalyst among the claim 1-11 is characterized in that, this method comprises: under protection of inert gas, and successively load alkylaluminoxane and said metallocene compound on carrier.
13. method according to claim 12, wherein, this method also is included in before the load alkylaluminoxane, under protection of inert gas, said carrier is heated 7-10 hour under 300-900 ℃ temperature.
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|---|---|---|---|---|
| CN105129806A (en) * | 2015-07-29 | 2015-12-09 | 肇庆金三江硅材料有限公司 | High-specific surface area silica for washing powder and its preparation method and use |
| CN109746049A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 (1)
| 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》, vol. 10, 25 December 2008 (2008-12-25) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105129806A (en) * | 2015-07-29 | 2015-12-09 | 肇庆金三江硅材料有限公司 | High-specific surface area silica for washing powder and its preparation method and use |
| CN109746049A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
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