CN102453121B - Supported metallocene catalyst and preparation method thereof - Google Patents
Supported metallocene catalyst and preparation method thereof Download PDFInfo
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- CN102453121B CN102453121B CN 201010519268 CN201010519268A CN102453121B CN 102453121 B CN102453121 B CN 102453121B CN 201010519268 CN201010519268 CN 201010519268 CN 201010519268 A CN201010519268 A CN 201010519268A CN 102453121 B CN102453121 B CN 102453121B
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Abstract
The invention provides a supported metallocene catalyst which is characterized by comprising a supporter, and alkylaluminoxane and a metallocene compound that are loaded on the supporter, wherein, the supporter is a compound formed by hollow spherical mesoporous silica and silica gel. The invention also provides a method for preparing the supported metallocene catalyst, and the method comprises the steps of successively loading alkylaluminoxane and the metallocene compound on the supporter under the protection of inert gas. According to the invention, the metallocene compound has a sandwich structure and has substituent on its cyclopentadienyl groups, and the compound of hollow spherical mesoporous silica and silica gel has highly ordered large aperture (3 to 20 nanometer) and pore volume, good mechanical strength and good macro-molecular catalytic adsorption performance; therefore, the catalyst has high catalytic activity.
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 methylaluminoxane of high reactivity (MAO) consumption big for the homogeneous phase metallocene catalyst, the production cost height, and the polymkeric substance that obtains do not have particle shape, can't use at widely used slurry process or gas phase polymerization technology.And the activity of metallocene catalyst is very high, and it is very fast to be easy to take place local polymerization velocity in polymerization process, 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 evenly regular one dimension or the material of solid netted sieve aperture, and surfactivity is higher, absorption property good, have tangible 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, the inserted mode of monomer is different with freeboard with propagation process in the polymerization process, and 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 molecular sieve, has following advantage:
(1) molecular sieve of synthetic does not contain the impurity that easily makes polymer degradation, will improve the ageing resistance of polyolefine material;
(2) the molecular sieve nano pore has the dual-use function of carrier and reactor, catalyst cupport efficient height, and polymerization process is controlled easily, and can key in the active centre in the skeleton of polymerization reactor, 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 zeolite molecular sieve, 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.
At present the mesoporous material of the load metallocene catalyst of reporting on the document is MCM-41, but activity only is 7.3 * 10 during catalyzed ethylene polymerization
5GPE/ (mol Zrh), and after handling with MAO again the MCM-41 of load metallocene carry out that catalytic activity also only is 10 behind the vinyl polymerization
6GPE/ (mol Zrh).
Therefore, the carried metallocene catalyst that how to obtain high catalytic efficiency remains a technical problem that needs to be resolved hurrily.
Summary of the invention
The objective of the invention is to overcome the catalytic activity lower problem still of the carried metallocene catalyst of prior art, a kind of highly active carried metallocene catalyst is provided.
The invention provides a kind of carried metallocene catalyst, it is characterized in that, this catalyzer comprises carrier and the alkylaluminoxane and the metallocene compound that load on the described carrier, described carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, described 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 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, described metallocene compound has sandwich structure, and has substituting group on the cyclopentadienyl, the mixture of described hollow ball mesoporous silicon oxide and silica gel has wide aperture (3-20 nanometer), pore volume, excellent mechanical intensity and the good bulky molecular catalysis absorption property of high-sequential, therefore has high catalytic activity.
Particularly, carried metallocene catalyst according to the present invention is when being used for catalysis in olefine polymerization, and catalytic efficiency can reach 4659g PE/gcath (that is, 1.9 * 10
8G PE/ (mol Zr h)), and under the identical situation of other conditions, the catalytic efficiency during metallocene compound that industrial 955 silica gel loads have the structure shown in the formula 1 only for 1295g PE/gcath (, 2.9 * 10
7GPE/ (mol Zr h)), the mixture that hollow ball mesoporous silicon oxide and silica gel is described thus cooperates with the described metallocene compound with the structure shown in the formula 1 and has synergy, obtained unexpected technique effect, and, the mixture of hollow ball mesoporous silicon oxide and silica gel is compared with the hollow ball mesoporous silicon oxide, when not changing catalytic activity, can significantly reduce production costs.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, and Fig. 2 is the x-ray diffraction pattern of carried metallocene catalyst MAO/MS-GJ-BU-1.
Fig. 3 and Fig. 4 are respectively the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and the N2 adsorption desorption graphic representation of carried metallocene catalyst MAO/MS-GJ-BU-1, and wherein, X-coordinate is relative pressure, and unit is p/p
0
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of mixture MS-GJ-1 and the carried metallocene catalyst MAO/MS-GJ-BU-1 of hollow ball mesoporous silicon oxide and silica gel, and wherein, X-coordinate is the aperture, and unit is 0.1nm.
Fig. 7 is stereoscan photograph, a1, a2 are the stereoscan photograph of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, b1 is the stereoscan photograph of carried metallocene catalyst MAO/MS-GJ-BU-1 of the present invention, b2 is the hollow ball-shape mesoporous material load MAO of employing embodiment 1 preparation and the stereoscan photograph behind the metallocene compound, and b3 is the stereoscan photograph behind 955 silica gel load MAO and the metallocene compound.
Embodiment
The invention provides a kind of carried metallocene catalyst, wherein, this catalyzer comprises carrier and loads on metallocene compound and alkylaluminoxane on the described carrier, described carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, described 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 halogen.
According to carried metallocene catalyst of the present invention, loading on metallocene compound on the described carrier and the amount of alkylaluminoxane can change within a large range.The present inventor finds, total amount with described carried metallocene catalyst is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 10-60 weight %, when the content of described carrier is 10-60 weight %, not only can obtain gratifying catalytic effect, but also can reduce cost.More preferably, be benchmark with the total amount of described carried metallocene catalyst, the total amount of described metallocene compound and alkylaluminoxane is 45-55 weight %, the content of described carrier is 45-55 weight %.Further under the preferable case, be benchmark with the total amount of described carried metallocene catalyst, the total amount of described metallocene compound and alkylaluminoxane is 48-52 weight %, and the content of described carrier is 48-52 weight %.Further under the preferable case, be benchmark with the total amount of described carried metallocene catalyst, the total amount of described metallocene compound and alkylaluminoxane is 50 weight %, and the content of described carrier is 50 weight %.
According to loaded catalyst of the present invention, the ratio between described alkylaluminoxane and the metallocene compound can be the known content of the technician of field of olefin polymerisation.Particularly, in element, the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described metallocene compound can be 100-500: 1; Be preferably 100-300: 1,200-300 more preferably: 1, further be preferably 250-300: 1, most preferably be 292: 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 zirconium.
According to carried metallocene catalyst of the present invention, the X in the formula 1 is 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 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 chlorine.
According to the present invention, in the formula 1, cyclopentadienyl is for forming η with central metal
5Key and have the derivative of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl 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, described 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.
The specific examples that satisfies the cyclopentadienyl of above-mentioned requirements comprises: methyl-cyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,2,3-trimethylammonium-cyclopentadienyl, 1,2,5-trimethylammonium-cyclopentadienyl, 1,2,3,4-tetramethyl--cyclopentadienyl, 1,2,3,5-tetramethyl--cyclopentadienyl, the pentamethyl-cyclopentadienyl, ethyl-cyclopentadienyl, 1,2-diethyl-cyclopentadienyl, 1,3-diethyl-cyclopentadienyl, 1,2,4-triethyl-cyclopentadienyl, 1,3,5-triethyl-cyclopentadienyl, methyl-2-ethyl-cyclopentadienyl, 1-methyl-3-ethyl-cyclopentadienyl, n-propyl-cyclopentadienyl, 1,3-di-cyclopentadienyl, 1-methyl-3-n-propyl-cyclopentadienyl, 1,3-di-isopropyl-cyclopentadienyl, 1-methyl-3-sec.-propyl-cyclopentadienyl, normal-butyl-cyclopentadienyl, 1,3-di-n-butyl-cyclopentadienyl, 1-methyl-3-normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, 1,3-two sec-butyls-cyclopentadienyl, 1-methyl-3-sec-butyl-cyclopentadienyl, 1-isobutyl--cyclopentadienyl, 1,3-diisobutyl-cyclopentadienyl, 1-methyl 3-isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, 1,3-di-t-butyl-cyclopentadienyl, the 1-methyl 3-tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, 1,3-two n-pentyls-cyclopentadienyl, 1-methyl-3-n-pentyl-cyclopentadienyl, 1-isopentyl-cyclopentadienyl, 1,3-diisoamyl-cyclopentadienyl, 1-methyl-3-isopentyl-cyclopentadienyl, 1-tert-pentyl-cyclopentadienyl, 1,3-two tert-pentyls-cyclopentadienyl, 1-methyl-3-tert-pentyl-cyclopentadienyl, neo-pentyl-cyclopentadienyl, 1,3-di neo-pentyl-cyclopentadienyl, 1-methyl-3-neo-pentyl-cyclopentadienyl.
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.
The specific examples that satisfies the cyclopentadienyl of above-mentioned requirements comprises: methyl-cyclopentadienyl, ethyl-cyclopentadienyl, n-propyl-cyclopentadienyl, sec.-propyl-cyclopentadienyl, normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, isopentyl-cyclopentadienyl, tert-pentyl-cyclopentadienyl, neo-pentyl-cyclopentadienyl.
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.
According to loaded metallocene composite catalyst of the present invention, described alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in the described alkylaluminoxane is aforesaid C
1-C
5Alkyl.Preferably, described alkylaluminoxane is methylaluminoxane.
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 the 3-20 micron, and specific surface area is the 200-300 meters squared per gram, and pore volume is 0.5-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer; Under the preferable case, the average particle diameter of described carrier is the 4-18 micron, and specific surface area is the 220-280 meters squared per gram, and pore volume is 0.6-1.2 milliliter/gram, and the most probable aperture is the 5-15 nanometer; Further under the preferable case, the average particle diameter of described carrier is the 5-18 micron, and specific surface area is the 250-270 meters squared per gram, and pore volume is 0.7-0.9 milliliter/gram, and the most probable aperture is the 8-11 nanometer; Under the most preferred case, the average particle diameter of described carrier is the 5-15 micron, and specific surface area is 261 meters squared per gram, and pore volume is 0.8 milliliter/gram, and the most probable aperture is 9.8 nanometers.
The present invention also provides a kind of method for preparing described carried metallocene catalyst, and this method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
The method according to this invention, described carrier can be the mixture of hollow ball mesoporous silicon oxide and silica gel.In the mixture of described hollow ball mesoporous silicon oxide and silica gel, the weight ratio of hollow ball mesoporous silicon oxide and silica gel can be 1: 0.2-5 is preferably 1: 1: 0.4-3, more preferably 1: 0.5-2 most preferably is 1: 0.5.
The mixture of described hollow ball mesoporous silicon oxide and silica gel can prepare by the method that may further comprise the steps: in the presence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution, and will contact back gained mixture crystallization under crystallization condition, the gained crystallization product is heated, removed template method, described template are triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol; The product of gained removed template method is mixed with silica gel.
Described template can be the conventional various triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol 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.
According to the present invention, the kind of described acidic aqueous solution has no particular limits, and its pH value can be 1-6, is preferably 3-5; Be the acetic acid of 1-6 and the buffered soln of sodium acetate for the pH value for example.
The condition of described contact can comprise that temperature is 10-60 ℃, and can be 10-72 hour duration of contact.Described contact is preferably carried out under agitation condition.
According to the present invention, the condition of described crystallization can comprise: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour.
The condition of described removed template method comprises that temperature can be 90-600 ℃, and the time can be 10-80 hour.
According to the present invention, in the process of the mixture for preparing hollow ball mesoporous silicon oxide and silica gel, triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol, ethanol, the weight ratio of trimethylpentane and tetramethoxy-silicane can change within the specific limits, preferably, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene, tetramethoxy-silicane, trimethylpentane, the weight ratio of ethanol and acidic aqueous solution can be 1: 2-3: 3-10: 1-5: 10-50, be preferably 1: 2-2.5: 4-8: 1-3: 20-40, further be preferably 1: 2-2.2: 5-7: 1-2: 25-35 most preferably is 1: 2.13: 6: 1.69: 28.
The product of described removed template method and the weight ratio of silica gel can be 1: 0.2-5 is preferably 1: 1: 0.4-3, more preferably 1: 0.5-2 most preferably is 1: 0.5.
According to the preparation method of carried metallocene catalyst of the present invention, described alkylaluminoxane, metallocene compound are described above, do not repeat them here.
The method according to this invention is included 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 described carrier.Preferably, successively the method at load alkylaluminoxane and metallocene compound on the carrier comprises: under protection of inert gas, described carrier is contacted with first solution, described first solution contains described alkylaluminoxane and toluene; The carrier that has removed toluene is contacted with second solution, and described second solution contains described metallocene compound and toluene, and removes toluene.Count in molar ratio, carrier: toluene: the amount ratio of alkylaluminoxane is 1: 30-100: 0.1-2.Count in molar ratio, carrier: toluene: the amount ratio of metallocene compound is 1: 20-150: 2 * 10
-3-9 * 10
-3
The present invention is not particularly limited for the method for described contact, can be for well known to a person skilled in the art the whole bag of tricks, for example: dipping, spraying.Adopt the method for dipping can be so that solution enters in the duct on the carrier more fully, therefore, the present invention be preferably flooded.
Carrier is not particularly limited with the condition that second solution contacts with first solution, and for example: carrier can comprise with the condition that described first solution contacts: the time is 1-10 hour, and temperature is 25-80 ℃; The described carrier that has removed toluene can be comprised with the condition that described 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, with except anhydrating etc.
The method according to this invention can also be included in before the described alkylaluminoxane of load and the described metallocene compound; under protection of inert gas; described carrier was heated 7-10 hour under 300-900 ℃ temperature, with the volatile matter that contains in the hydroxyl of removing carrier surface and the carrier (for example: water).
According to the present invention, chemically interactive all gases can not take place 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, the feasible total amount with described carried metallocene catalyst of described alkylaluminoxane and the metallocene compound charge capacity on described carrier is benchmark, the total amount of described metallocene compound and alkylaluminoxane can be 10-60 weight %, be preferably 45-55 weight %, more preferably 48-52 weight % further is preferably 50 weight %; The content of described carrier can be 10-60 weight %, is preferably 45-55 weight %, and more preferably 48-52 weight % further is preferably 50 weight %; The mol ratio of M in aluminium in the described alkylaluminoxane and the described metallocene compound can be 100-500: 1, be preferably 100-300: and 1,200-300 more preferably: 1, further be preferably 250-300: 1, most preferably be 292: 1.
A preferred embodiment of the invention, the preparation method of described carried metallocene catalyst comprises:
In the 1st step, with triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol and ethanol, join pH value and be under 10-60 ℃ of temperature, to be stirred to dissolving in the buffered soln of the acetic acid of 1-6 and sodium acetate;
The 2nd step added trimethylpentane in previous step gained solution, stirred 1-20 hour under 10-60 ℃ of temperature;
The 3rd step added tetramethoxy-silicane in previous step gained solution, stirred 10-72 hour under 10-60 ℃ of temperature;
In the 4th step, will go up step gained solution and place closed reaction vessel, under 30-150 ℃ of temperature crystallization 10-72 hour;
In the 5th step, with the filtration of crystallization after product, washing, drying, obtain the hollow ball-shape mesoporous material raw powder;
The 6th step, gained hollow ball-shape mesoporous material to be calcined 10 hours-80 hours with 90-600 ℃ of temperature in retort furnace, removed template method obtains hollow mesoporous silicon oxide; Should mix with silica gel by hollow mesoporous silicon oxide then;
In the 7th step, the thermal activation step under nitrogen protection, in 300-900 ℃ of calcining 7-10 hour, obtains hollow ball mesoporous silicon oxide after the thermal activation and the mixture of silica gel with the mixture of gained hollow ball mesoporous silicon oxide of last step and silica gel;
The 8th step, the mixture of the hollow ball mesoporous silicon oxide after the thermal activation and silica gel is transferred in the reactor after nitrogen is fully replaced, add solvent and alkylaluminoxane, count in molar ratio, the mixture of hollow ball mesoporous silicon oxide and silica gel: solvent: the amount ratio of alkylaluminoxane is 1: 30-100: 0.1-2, stirred 1-10 hour in 25-80 ℃ again, after finishing, use hexane wash again 2 times, afterwards solid is dried up with nitrogen, obtain the hollow ball mesoporous silicon oxide of load methylaluminoxane and the mixture of silica gel;
The 9th step under nitrogen protection, joined the hollow ball mesoporous silicon oxide of load methylaluminoxane and the mixture of silica gel in the reactor, added stirring solvent and made slurries; In the container of crossing with nitrogen replacement in advance, solution is made in the metallocene compound dissolving, under 25-80 ℃ of agitation condition, slowly the metallocene compound drips of solution is added in the reactor, count the mixture of hollow ball mesoporous silicon oxide and silica gel: toluene in molar ratio: the amount ratio of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of metallocene 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, dried up with nitrogen, obtained described carried metallocene catalyst.
Be described in detail below in conjunction with the present invention of embodiment.
In following examples, X-ray diffraction analysis is that the X-ray diffractometer of D8Advance carries out in the model available from company of German Bruker AXS company; TEM (transmission electron microscope) analysis is that the transmission electron microscope of Tecnai 20 carries out in the model available from company of Dutch FEI Co.; Scanning electron microscope analysis is that the scanning electronic microscope of XL-30 is carried out in the model available from company of U.S. FEI Co..Ultimate analysis is carried out at the model 7500CX instrument available from U.S. An Jielun company.
Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption instrument, sample was 200 ℃ of degassings 4 hours.
Embodiment 1
Present embodiment is used for explanation according to carried metallocene catalyst of the present invention and preparation method thereof.
Restrain triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol (available from Aldrich with 1.0, P123) and 1.69 gram ethanol join in the buffered soln of the acetic acid of pH=4.4 of 28ml and sodium acetate, being stirred to polyethylene glycol-glycerol-polyoxyethylene glycol under 15 ℃ dissolves fully, trimethylpentane with 6g joins in the above-mentioned solution afterwards, 15 ℃ were stirred after 8 hours, again 2.13 gram tetramethoxy-silicanes are joined in the above-mentioned solution, 15 ℃ were stirred after 20 hours, solution is transferred in the teflon-lined reactor, 60 ℃ of following crystallization after 24 hours through filtering, use distilled water wash, obtain the former powder of hollow ball mesoporous silicon oxide after the drying.
The former powder of hollow ball mesoporous silicon oxide was calcined 24 hours in retort furnace at 550 ℃, obtain the hollow ball mesoporous silicon oxide, sneak into the silica gel (ES955) of the 50 weight % that are equivalent to the former grain weight amount of hollow ball mesoporous silicon oxide again, obtain the mixture (called after MS-GJ-1) of hollow ball mesoporous silicon oxide and silica gel.
With the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel 400 ℃ of calcinings 10 hours under nitrogen protection, removing hydroxyl and remaining moisture, thereby obtain through the hollow ball mesoporous silicon oxide of thermal activation and the mixture of silica gel.
0.50 gram in the mixture of the hollow ball mesoporous silicon oxide of thermal activation and silica gel is transferred to 250 milliliters of glass reactors after nitrogen is fully replaced, is added 20 milliliters of refining toluene, 0.51 gram methylaluminoxane (available from U.S. Albemarle company) stirred 4 hours in 50 ℃.After finishing, use 20 milliliters of hexane wash three times again, at last solid is dried up with nitrogen, obtaining load has the MS-GJ-1 of methylaluminoxane (called after MAO/MS-GJ-1).
Under nitrogen protection, MAO/MS-GJ-1 is joined in 250 milliliters of glass reactors, add 20 milliliters of refining toluene, under 30 ℃, slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides of 28 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid after the layering, with 10 milliliters of toluene wash three times, then, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtain restraining according to carried metallocene catalyst of the present invention (called after MAO/MS-GJ-BU-1).Come this carried metallocene catalyst is characterized with XRD, nitrogen adsorption-desorption experiment, scanning electron microscope and ICP ultimate analysis.
Fig. 1 is the x-ray diffraction pattern of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, and Fig. 2 is the x-ray diffraction pattern of carried metallocene catalyst MAO/MS-GJ-BU-1.Can obviously be found out by XRD spectra, Small angle spectrum peak all appears in the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and carried metallocene catalyst MAO/MS-GJ-BU-1, illustrates that MAO/MS-GJ-BU-1 has the hexagonal hole road structure of the peculiar 2D of mesoporous material.
Fig. 3 and Fig. 4 are respectively the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and the N of carried metallocene catalyst MAO/MS-GJ-BU-1
2The adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0Fig. 4 shows that MAO/MS-GJ-BU-1 has the IV type thermoisopleth of sharp-pointed capillary condensation speed, and this thermoisopleth has the H1 hysteresis loop, and this shows that MAO/MS-GJ-BU-1 has the aperture size distribution of homogeneous.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of mixture MS-GJ-1 and the carried metallocene catalyst MAO/MS-GJ-BU-1 of hollow ball mesoporous silicon oxide and silica gel, and wherein, X-coordinate is the aperture, and unit is 0.1nm.As seen from Figure 6, MAO/MS-GJ-BU-1 has six sides' meso-hole structure, and the duct is very even.
Fig. 7 is stereoscan photograph, a1, a2 are the stereoscan photograph of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, the stereoscan photograph of b1 carried metallocene catalyst MAO/MS-GJ-BU-1 of the present invention, b2 is the stereoscan photograph behind 955 silica gel load MAO and the metallocene compound, and b3 is the stereoscan photograph behind hollow ball-shape mesoporous material load MAO and the metallocene compound.As seen from the figure, the MS-GJ-1 particle diameter is 5-15 μ m, and particle diameter and the MS-GJ-1 of MAO/MS-GJ-BU-1 are basic identical, this explanation MS-GJ-1 particle size dispersion, and MAO/MS-GJ-BU-1 has mechanical property preferably.
Table 1 is the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and the pore structure parameter of carried metallocene catalyst MAO/MS-GJ-BU-1,
Table 1 pore structure parameter
By the data of last table 1 as can be seen, the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel is behind load metallocene, pore volume, specific surface area and aperture all reduce to some extent, and this explanation metallocene in the load-reaction process enters into the spheroid inside of hollow ball-shape mesoporous material.
Ultimate analysis ICP result shows, load the aluminium content of mixture MAO/MS-GJ-BU-1 of the hollow ball mesoporous silicon oxide of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of promotor methylaluminoxane (MAO) and cyclopentadienyl catalyst precursor and silica gel be weight 19.04%, the content of Zr is weight 0.22%, and the mol ratio of Al/Zr is 292: 1.Learning through conversion, is benchmark with the total amount of catalyzer, and the total content of methylaluminoxane (MAO) and metallocene compound is 50 weight %, and the content of carrier is 50 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating 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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol, then adds 85.5 milligrams of MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 412 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.323g/ml, melting index MI
2.16=0.005g/10min.Determine that as calculated the efficient of catalyzer is 4819g PE/gcath (that is, 2 * 10
8G PE/ (mol Zr h)).
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating 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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of 1 mol, then adds 61.6 milligrams MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 287 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.313g/ml, melting index MI
2.16=0.465g/10min.Determine that as calculated the efficient of catalyzer is 4659g PE/gcath (that is, 1.9 * 10
8G PE/ (mol Zr h)).
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for illustrating 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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol, then adds 41.3 milligrams of MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 80 ℃ of reactions 1 hour.Obtain 141 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.320g/ml, melting index MI
2.16=0.070g/10min.Determine that as calculated the efficient of catalyzer is 3414g PE/gcath (that is, 1.4 * 10
8G PE/ (mol Zr h)).
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for illustrating 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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of 1 mol, then adds 43.1 milligrams MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 80 ℃ of reactions 1 hour.Obtain 69 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.275g/ml, melting index MI
2.16=0.409g/10min.Determine that as calculated the efficient of catalyzer is 1601g PE/gcath (that is, 6.8 * 10
7G PE/ (mol Zr h)).
Comparative Examples 1
With the 400 ℃ of calcinings 10 hours under nitrogen protection of ES955 silica gel, removing hydroxyl and remaining moisture, thereby obtain the 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 methylaluminoxane and 10mL toluene again; under 50 ℃ of conditions; behind the stirring reaction 4 hours, use toluene wash 3 times, use 20 milliliters of hexane wash three times again; at last 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), under 30 ℃; slowly drip two (normal-butyl-cyclopentadienyl) zirconium dichlorides of metallocene catalyst precursors of 44 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtain carried metallocene catalyst (called after MAO/ES955-BU).
Results of elemental analyses shows that the aluminium content among the MAO/ES955-BU is 32.4 weight %, and the content of Zr is 0.41 weight %, and the mol ratio of Al/Zr is 270: 1.
Experiment Comparative Examples 1
Adopt the method identical with EXPERIMENTAL EXAMPLE 1 to carry out the homopolymerization of ethene, different is that the catalyzer of employing is the ES955-BU that Comparative Examples 1 prepares.The result obtains 65g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.331g/ml, melting index: MI
2.16=0.119g/10min.Determine that as calculated the efficient of catalyzer is 1295g PE/gcath (that is, 2.9 * 10
7GPE/ (mol Zr h)).
Experiment Comparative Examples 2
Adopt the method identical with EXPERIMENTAL EXAMPLE 2 that ethene and hexene are carried out copolymerization, different is that the catalyzer of employing is the ES955-BU that Comparative Examples 1 prepares.Obtain 76 gram polymkeric substance, the density of this polymer stacks (BD) is 0.299g/ml, and melting index is MI
2.16=0.679/10min.Determine that as calculated the efficient of catalyzer is 2260g PE/gcath (that is, 5.1 * 10
7GPE/ (mol Zr h)).
Claims (16)
1. carried metallocene catalyst, it is characterized in that, this catalyzer comprises carrier and the alkylaluminoxane and the metallocene compound that load on the described carrier, described carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, described metallocene compound has the structure shown in the formula 1, wherein, in the mixture of described hollow ball mesoporous silicon oxide and silica gel, the weight ratio of hollow ball mesoporous silicon oxide and silica gel is 1:0.2-5, the average particle diameter of described carrier is the 3-20 micron, specific surface area is the 200-300 meters squared per gram, pore volume is 0.5-1.5 milliliter/gram, the most probable aperture is the 3-20 nanometer, and described specific surface area adopts nitrogen adsorption-desorption measuring
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 halogen.
2. carried metallocene catalyst according to claim 1 wherein, is benchmark with the total amount of described carried metallocene catalyst, and the total amount of described metallocene compound and alkylaluminoxane is 45-55 weight %, and the content of described carrier is 45-55 weight %.
3. carried metallocene catalyst according to claim 1 and 2, wherein, the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described metallocene compound is 100-500:1.
4. carried metallocene catalyst according to claim 3, wherein, the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described metallocene compound is 100-300:1.
5. according to claim 1 or 4 described carried metallocene catalysts, wherein, M is zirconium.
6. carried metallocene catalyst according to claim 1, wherein, X is chlorine.
7. carried metallocene catalyst according to claim 1, wherein, R
1, R
1' be C
1-C
5Alkyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
8. carried metallocene catalyst according to claim 7, wherein, R
1, R
1' be normal-butyl.
9. according to any described carried metallocene catalyst in claim 1-2 and 4, wherein, the alkyl in the described alkylaluminoxane is C
1-C
5Alkyl.
10. carried metallocene catalyst according to claim 9, wherein, described alkylaluminoxane is methylaluminoxane.
11. carried metallocene catalyst according to claim 1, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, and described alkylaluminoxane is methylaluminoxane.
12. carried metallocene catalyst according to claim 1, wherein, described carrier is made by the method that may further comprise the steps: in the presence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution, and will contact back gained mixture crystallization under crystallization condition, with the heating of gained crystallization product, removed template method, described template is polyethylene glycol-glycerol-polyoxyethylene glycol; The product of gained removed template method is mixed with silica gel.
13. carried metallocene catalyst according to claim 12, wherein, described acidic aqueous solution is the buffered soln of acetic acid and sodium acetate, and the pH value of described damping fluid is 1-6; The condition of described contact comprises that temperature is 10-60 ℃, and the time is 10-72 hour; Described crystallization condition comprises: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour; The condition of described removed template method comprises that temperature is 90-600 ℃, and the time is 10-80 hour; When the product of removed template method mixes with silica gel, the product of removed template method and the weight ratio of silica gel are 1:0.2-5, wherein, the average particle diameter of described carrier is the 3-20 micron, specific surface area is the 200-300 meters squared per gram, pore volume is 0.5-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer, and described specific surface area adopts nitrogen adsorption-desorption measuring.
14. carried metallocene catalyst according to claim 12, wherein, the weight ratio of polyethylene glycol-glycerol-polyoxyethylene glycol, tetramethoxy-silicane, trimethylpentane, ethanol and acidic aqueous solution is 1:2-3:3-10:1-5:10-50.
15. a method for preparing any described carried metallocene catalyst among the claim 1-14 is characterized in that, this method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
16. method according to claim 15, wherein, this method also is included in before the load alkylaluminoxane, under protection of inert gas, described carrier is 300-900 ℃ in temperature heated 7-10 hour down.
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| CN105884971B (en) * | 2014-09-05 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of olefine-cyclic olefine copolymer |
| CN105524193B (en) * | 2014-09-29 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of carried metallocene catalyst and preparation method thereof |
| CN104693327A (en) * | 2015-02-15 | 2015-06-10 | 北京化工大学 | Bi-metal semi-metallocene catalyst and preparation method and application thereof |
| CN108017731B (en) * | 2016-11-02 | 2020-04-07 | 中国石油化工股份有限公司 | Spherical mesoporous composite material, supported catalyst and preparation method thereof |
| CN109289847B (en) * | 2017-07-24 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for catalyzing propane dehydrogenation reaction, preparation method thereof and method for preparing propylene by propane dehydrogenation |
| CN109289935B (en) * | 2017-07-24 | 2019-11-12 | 中国石油化工股份有限公司 | The method of complex mesoporous material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
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