CN102731686B - Supported metallocene catalyst and its preparation method - Google Patents
Supported metallocene catalyst and its preparation method Download PDFInfo
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- CN102731686B CN102731686B CN201110080394.2A CN201110080394A CN102731686B CN 102731686 B CN102731686 B CN 102731686B CN 201110080394 A CN201110080394 A CN 201110080394A CN 102731686 B CN102731686 B CN 102731686B
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- 0 CC(C)(C)c(cc(C)cc1C(C)(C)C)c1O*(*1C(*)=C(*)C(*)=C1*)(N)N Chemical compound CC(C)(C)c(cc(C)cc1C(C)(C)C)c1O*(*1C(*)=C(*)C(*)=C1*)(N)N 0.000 description 1
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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 a rod-shaped macroporous mesoporous silicon dioxide, the most probable pore size of which is 11-20 nanometers. The metallocene compound has a structure as shown in the formula 1, in which M is one selected from the group consisting 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 1245g 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
2for the carried metallocene catalyst of carrier.But, 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.
Compared with industrial silica gel, ordered mesoporous molecular sieve (molecular sieve that aperture is 2-50nm), there is 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 SBA-15 processing 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 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).
Therefore, how to obtain the carried metallocene catalyst with high catalytic activity and remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The catalytic activity lower problem relatively that the object of the invention is to the carried metallocene catalyst that overcomes prior art, provides carried metallocene catalyst that a kind of catalytic activity is relatively higher and preparation method thereof.
The present inventor finds, the mesoporous material that suitably increases (if aperture is 11-20 nanometer) by employing aperture is as carrier, the activity of the catalyzer obtaining can obviously improve, trace it to its cause, the aperture that may be the mesopore molecular sieve as carrier of existing catalyzer employing generally is 5-7 nanometer, in loading process, metallocene compound enters duct and is easy to stop up, and causes the catalytic activity of catalyzer not give full play of.
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 bar-shaped macropore mesoporous silicon oxide, wherein, the most probable aperture of described bar-shaped macropore mesoporous silicon oxide is 11-20 nanometer, and described metallocene compound has the structure shown in formula 1
Wherein, M is the one 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 wide-aperture and good catalytic adsorption performance, can obtain 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 1245g PE/ (gcath), and in the situation that other conditions are identical, the catalytic efficiency when 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 macropore meso-porous titanium dioxide silicon carrier KKSBA-15, X-coordinate unit be 2 θ (
0), ordinate zou is intensity;
Fig. 2 is the x-ray diffraction pattern (b) of carried metallocene catalyst KKSBA-15-YIN, X-coordinate unit be 2 θ (
0), ordinate zou is intensity;
Fig. 3 is the N of macropore meso-porous titanium dioxide silicon carrier KKSBA-15
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 N of carried metallocene catalyst KKSBA-15-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. 5 is the graph of pore diameter distribution of macropore meso-porous titanium dioxide silicon carrier KKSBA-15, and wherein, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g;
Fig. 6 is the graph of pore diameter distribution of carried metallocene catalyst KKSBA-15-YIN, and wherein, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g;
In Fig. 7, a is the stereoscan photograph of macropore meso-porous titanium dioxide silicon carrier KKSBA-15, and b is the stereoscan photograph of carried metallocene catalyst KKSBA-15-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 bar-shaped macropore mesoporous silicon oxide, wherein, the most probable aperture of described bar-shaped macropore mesoporous silicon oxide is 11-20 nanometer, and described metallocene compound has the structure shown in formula 1
Wherein, M is the one in titanium, zirconium and hafnium, and X is halogen.
According to carried metallocene catalyst of the present invention, the M in formula 1 can be the one in titanium, zirconium and hafnium.Preferably, M is zirconium.
According to carried metallocene catalyst of the present invention, the X in formula 1 is halogen.Particularly, the X in formula 1 can be the one in fluorine, chlorine, bromine and iodine.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, when the M in formula 1 is zirconium, when X is chlorine, when described carried metallocene catalyst is used 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 100-300 meters squared per gram, is preferably 150-250 meters squared per gram, more preferably 154 meters squared per gram.Pore volume can be 0.1-1 ml/g, is preferably 0.2-0.8 ml/g, more preferably 0.3 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, 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, take the total amount of described carried metallocene catalyst as 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, take the total amount of described carried metallocene catalyst as benchmark, 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, take the total amount of described carried metallocene catalyst as benchmark, 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, take the total amount of described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane is 30-31 % by weight, and the content of described carrier is 69-70 % by weight.
According to carried metallocene catalyst of the present invention, the ratio between described alkylaluminoxane and metallocene compound can be the known content of technician of field of olefin polymerisation.Particularly, the mol ratio of the zirconium in the aluminium in described alkylaluminoxane and described metallocene compound can be 50-200: 1, be preferably 60-190: and 1, more preferably 70-180: 1, be further preferably 80-170: 1, most preferably be 142: 1.
According to carried metallocene catalyst of the present invention, wherein, the length of described carrier is 2-20 micron, and length-to-diameter ratio is 2-8: 1, and most probable aperture is 11-20 nanometer, and pore volume is 0.3-1.5 ml/g, and specific surface area is 300-600 meters squared per gram.Under preferable case, the length of described carrier is 3-15 micron, and length-to-diameter ratio is 3-7: 1, and most probable aperture is 11-15 nanometer, and pore volume is 0.5-1.2 ml/g, and specific surface area is 300-500 meters squared per gram; More preferably in situation, the length of described carrier is 3-9 micron, and length-to-diameter ratio is 4-6: 1, and most probable aperture is 11-13 nanometer, and pore volume is 0.8-1.2 ml/g, and specific surface area is 300-400 meters squared per gram.
According to the present invention, described carrier is bar-shaped macropore mesoporous silicon oxide, and described bar-shaped macropore mesoporous silicon oxide can prepare by the method comprising the following steps:
(1) template is stirred to dissolving in hydrochloric acid at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred more than 25 minutes 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 polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
Described crystallization condition comprises: crystallization temperature can be 90-180 ℃, is preferably 110-150 ℃, more preferably 150 ℃; Crystallization time can be 10-40 hour, is preferably 15-30 hour, more preferably 24 hours; The condition of described removed template method comprises that temperature can be 300-1200 ℃, is preferably 400-800 ℃, more preferably 600 ℃; Time is 10-40 hour, is preferably 15-35 hour, more preferably 10 hours.
Meter in molar ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrogenchloride: tetraethoxy=1: 9000-15000: 100-500: 50-80, be preferably 1: 10000-14000: 200-400: 55-65, is particularly preferably 1: 10311: 241: 62.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 that use in this area, for example, can be the template of commodity P123 by name.
Kind and the content of described carrier, alkylaluminoxane and metallocene compound are described above, do not repeat them here.
Aforesaid method, by adopting tetraethoxy as silicon source, is equipped with polyoxyethylene-polyoxytrimethylene-polyoxyethylene template, has made bar-shaped macropore mesoporous silicon oxide.
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.Adopt the method for dipping can make solution enter more fully in the duct on carrier, 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 and well known to a person skilled in the art that method refines 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, to remove the volatile matter (: water) containing in the hydroxyl of carrier surface and carrier.
According to the present invention, described rare gas element can be variously with carrier, alkylaluminoxane, metallocene compound, chemically interactive various gas not to occur.For example, described rare gas element can be nitrogen, argon gas.
According to the present invention, described alkylaluminoxane and the metallocene compound charge capacity on described carrier makes total amount take described carried metallocene catalyst as benchmark, 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 30-31 % 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 69-70 % by weight; The mol ratio of M in aluminium in described alkylaluminoxane and described metallocene compound can be 500-200: 1, elect 60-190 as: and 1, more preferably 70-180: 1, be further preferably 80-170: 1, most preferably be 142: 1.
According to one embodiment of the present invention, the preparation method of described carried metallocene catalyst comprises the following steps:
(1) template and hydrochloric acid are stirred to template dissolving at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred more than 25 minutes 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, obtains macropore mesoporous silicon oxide;
(5) by the macropore mesoporous silicon oxide thermal activation after the removed template method of step (4) gained;
(6) the macropore mesoporous silicon oxide after the thermal activation of step (5) gained is reacted with toluene and alkylaluminoxane;
(7) macroporous/mesoporous material of load methylaluminoxane step (6) being obtained and metallocene compound solution reaction, obtain described carried metallocene catalyst.
Described template is polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
Described crystallization condition comprises: crystallization temperature can be 90-180 ℃, is preferably 110-150 ℃, more preferably 150 ℃; Crystallization time can be 10-40 hour, is preferably 15-30 hour, more preferably 24 hours; The condition of described removed template method comprises that temperature can be 300-1200 ℃, is preferably 400-800 ℃, more preferably 600 ℃; Time is 10-40 hour, is preferably 15-35 hour, more preferably 10 hours.
Meter in molar ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrogenchloride: tetraethoxy=1: 9000-15000: 100-500: 50-80, be preferably 1: 10000-14000: 200-400: 55-65, is particularly preferably 1: 10311: 241: 62.
Described thermal activation condition comprises: heat activation temperature can be 25-80 ℃, is preferably 30-75 ℃, more preferably 50 ℃; The thermal activation time can be 1-10 hour, is preferably 2-8 hour, more preferably 4 hours; In thermal activation reaction process, macroporous/mesoporous material (in silicon-dioxide), toluene and alkylaluminoxane after described thermal activation, be calculated in molar ratio as 1: 10-100: 0.1-2, is preferably 1: 20-90: 0.3-1.5, more preferably 1: 28.28: 1.1.Wherein the molecular weight of alkylaluminoxane is in RAlO, and wherein R is alkyl, and the molecular weight of for example methylaluminoxane is with CH
3alO meter is 58.
The macroporous/mesoporous material of described load methylaluminoxane and metallocene compound solution reaction condition comprise: temperature of reaction can be 25-80 ℃, is preferably 30-75 ℃, more preferably 30 ℃; Reaction times can be 0.3-2 hour, is preferably 0.5-2.5 hour, more preferably 0.5 hour; Meter in molar ratio, described macroporous/mesoporous material (take silicon-dioxide): toluene: the amount ratio of two (1-indenyl) zirconium dichlorides of metallocene compound rac-ethene is 1: 20-150: 2 × 10
-3-9 × 10
-3, be preferably 1: 25-140: 3 × 10
-3-8 × 10
-3, more preferably 1: 28.28: 6 × 10
-3.
Described template can be the conventional various triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene template that use in this area, for example, can be the template of commodity P123 by name.
The present invention is the structure of loaded catalyst by X-ray diffraction method, nitrogen adsorption desorption method and the scanning electron microscope method methylaluminoxane of having measured or characterized described carrier macropore mesoporous silicon oxide and load and the carrier with metallocene compound.Measure the content of aluminium and metal M in loaded catalyst by ultimate analysis.
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 Albemarle Corporation of the U.S.; Two (1-indenyl) zirconium dichlorides of rac-ethene are purchased from Alfa Aesar.
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 FEI Co. of the U.S.; Elemental analyser is purchased from the model 7500CX of An Jielun company of the U.S..
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 ℃.
The present embodiment is for illustrating according to carried metallocene catalyst of the present invention and preparation method thereof.
4.0 grams of P123 and 128ml water are joined in the hydrochloric acid soln that 16.4ml concentration is 37 % by weight, be stirred to P123 at 40 ℃ and dissolve completely; Again 8.86 grams of tetraethoxys are joined in above-mentioned solution at 40 ℃ and stir 24 hours, gained solution is transferred in teflon-lined reactor, 150 ℃ of crystallization 24 hours, after filtration, washing, obtain former powder mesoporous material after dry; By matrix material in retort furnace 600 ℃ calcining 24 hours, removed template method, obtains bar-shaped macropore mesoporous silicon oxide (called after KKSBA-15).
By above-mentioned mesoporous material KKSBA-15 under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the large pore material through thermal activation.
0.4 gram of large pore material through thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 20 milliliters of refining toluene (with sodium backflow 24 hours), 0.42 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 macroporous/mesoporous material of methylaluminoxane (called after MAO/KKSBA-15).
Under nitrogen protection; the MAO/KKSBA-15 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 17 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, after layering, leach liquid, by 10 milliliters of toluene wash three times, then, 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 KKSBA-15-YIN).This carried metallocene catalyst is characterized with XRD, the experiment of nitrogen adsorption-desorption, scanning electron microscope and ICP ultimate analysis.
Fig. 1 is the little angle x-ray diffraction pattern of macropore meso-porous titanium dioxide silicon carrier KKSBA-15, and Fig. 2 is the little angle x-ray diffraction pattern of carried metallocene catalyst KKSBA-15-YIN, wherein, X-coordinate unit be 2 θ (
0), ordinate zou is intensity.Can obviously be found out by XRD spectra, all there is Small angle spectrum peak in macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-YIN, illustrates that the macroporous/mesoporous material KKSBA-15-YIN 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 macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-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 shows that carried metallocene catalyst KKSBA-15-YIN has the IV type thermoisopleth of sharp-pointed capillary condensation speed, and this thermoisopleth has H
1hysteresis loop, this shows that carried metallocene catalyst KKSBA-15-YIN has the aperture size distribution of homogeneous.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-YIN, and wherein, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g.Can be found out by Fig. 5 and Fig. 6, macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-YIN have six sides' meso-hole structure, and pore distribution is comparatively even.
Fig. 7 is stereoscan photograph, and a is the stereoscan photograph of macropore meso-porous titanium dioxide silicon carrier KKSBA-15, the stereoscan photograph of b carried metallocene catalyst KKSBA-15-YIN.As seen from Figure 7, the microscopic appearance of macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-YIN is bar-shaped, and in loading process, KKSBA-15 has good mechanical property.
Table 1 is the pore structure parameter of macropore meso-porous titanium dioxide silicon carrier KKSBA-15 and carried metallocene catalyst KKSBA-15-YIN.
Table 1 pore structure parameter
Data by upper table 1 can find out, macropore meso-porous titanium dioxide silicon carrier KKSBA-15 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 macropore meso-porous titanium dioxide silicon carrier.
Ultimate analysis ICP result shows, load the macropore meso-porous titanium dioxide silicon carrier of two (1-indenyl) zirconium dichlorides of methylaluminoxane (MAO) and metallocene compound rac-ethene be that the content of the aluminium element of carried metallocene catalyst KKSBA-15-YIN is 13.4 % by weight, the content of Zr element is 0.32 % by weight, and the mol ratio of Al/Zr is 142: 1.Learn through converting, take the total amount of catalyzer as benchmark, the total content of methylaluminoxane (MAO) and metallocene compound is 30.25 % by weight, and the content of carrier is 69.75 % 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 the each displacement of nitrogen and ethene 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 KKSBA-15-YIN that adds 53.8 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 67 grams of polyethylene particle powders, the bulk density (BD) of this polyethylene particle powder is 0.295g/ml, melting index MI
2.16=0.069g/10min.Determine as calculated, the efficiency of catalyzer is 1245g PE/ (gcath) (, 3.5 × 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 the each displacement of nitrogen and ethene 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 KKSBA-15-YIN that adds above-described embodiment 1 of 56.2 milligrams to make, pass into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 34 grams of polymkeric substance, the bulk density (BD) of this polymkeric substance is 0.199g/ml, melting index MI
2.16=0.004g/10min.Determine as calculated, the efficiency of catalyzer is 605g PE/ (gcath) (, 1.7 × 10
7g PE/ (mol Zrh)).
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, leave standstill, 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
This experiment comparative example is used for illustrating the catalytic activity of the carried metallocene catalyst 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 ES955-YIN prepared by comparative example 1.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 (BD) of this polyethylene particle powder is 0.316g/mL, melting index MI
2.16=0.006g/10min.Determine as calculated, the efficiency of catalyzer is 660g PE/ (gcath) (, 1.5 × 10
7g PE/ (mol Zrh)).
Experiment comparative example 2
This experiment comparative example is used for illustrating the catalytic activity of the carried metallocene catalyst 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 ES955-YIN prepared by comparative example 1.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 (BD) of this polymkeric substance is 0.263g/mL, and melting index is MI
2.16=0.031/10min.Determine as calculated, the efficiency of catalyzer is 358g PE/ (gcath) (, 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 KKSBA-15-Cp).Results of elemental analyses demonstration, in KKSBA-15-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
This experiment comparative example is used for illustrating the catalytic activity of the carried metallocene catalyst 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 KKSBA-15-Cp prepared by comparative example 2.The carried metallocene catalyst KKSBA-15-Cp that adds 93.75 milligrams of above-mentioned comparative examples 2 to make, result obtains 36g polyethylene particle powder, and the bulk density (BD) of this polyethylene particle powder is 0.30g/ml, melting index: MI
2.16=0.011g/10min.Determine as calculated, the efficiency of catalyzer is 384g PE/gcath (, 3.5 × 10
6g PE/ (mol Zrh)).
Experiment comparative example 4
This experiment comparative example is used for illustrating the catalytic activity of the carried metallocene catalyst 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 KKSBA-15-Cp prepared by comparative example 2.The carried metallocene catalyst KKSBA-15-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 (BD) of the multipolymer of this ethene and hexene 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 (, 4.0 × 10
6g PE/ (mol Zrh)).
Claims (10)
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 bar-shaped macropore mesoporous silicon oxide, and wherein, the excellent length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, length-to-diameter ratio is 2-8:1, the most probable aperture of described carrier is 11-15 nanometer, and pore volume is 0.3-1.5 ml/g, and specific surface area is 300-600 meters squared per gram; Described metallocene compound has the structure shown in formula 1,
Wherein, M is the one in titanium, zirconium and hafnium, and X is halogen.
2. carried metallocene catalyst according to claim 1, wherein, take the total amount of described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane is 10-60 % by weight, the content of described carrier is 40-90 % by weight, and the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound is 50-200:1.
3. carried metallocene catalyst according to claim 1, wherein, M is zirconium, X is chlorine.
4. carried metallocene catalyst according to claim 1 and 2, wherein, the alkyl in described alkylaluminoxane is C
1-C
5alkyl.
5. carried metallocene catalyst according to claim 4, wherein, described alkylaluminoxane is methylaluminoxane.
6. 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) template is stirred to dissolving in hydrochloric acid at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred more than 25 minutes 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 polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
7. carried metallocene catalyst according to claim 6, wherein, described crystallization condition comprises: crystallization temperature is 90-180 ℃, crystallization time is 10-40 hour; The condition of described removed template method comprises that temperature is 300-1200 ℃, and the time is 10-40 hour.
8. carried metallocene catalyst according to claim 6, wherein, meter in molar ratio, polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrogenchloride: tetraethoxy=1:9000-15000:100-500:50-80.
9. a method of preparing the carried metallocene catalyst described in any one in claim 1-8, is characterized in that, the method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
10. method according to claim 9 wherein, before the method is also included in load alkylaluminoxane, under protection of inert gas, heats 7-10 hour by described carrier at 300-900 ℃ of temperature.
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| Mesoporous silica as nanoreactor for olefin polymerization;Tsuneji Sano et al;《Catalysis Surveys from Asia》;20041231;第8卷(第4期);295-304 * |
| Tsuneji Sano et al.Mesoporous silica as nanoreactor for olefin polymerization.《Catalysis Surveys from Asia》.2004,第8卷(第4期), |
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