CN102453121A - Supported metallocene catalyst and preparation method thereof - Google Patents
Supported metallocene catalyst and preparation method thereof Download PDFInfo
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- CN102453121A CN102453121A CN2010105192688A CN201010519268A CN102453121A CN 102453121 A CN102453121 A CN 102453121A CN 2010105192688 A CN2010105192688 A CN 2010105192688A CN 201010519268 A CN201010519268 A CN 201010519268A CN 102453121 A CN102453121 A CN 102453121A
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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 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 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.
The mesoporous material of the load metallocene catalyst of reporting on the document at present is MCM-41, but activity is merely 7.3 * 10 during catalyzed ethylene polymerization
5GPE/ (mol Zrh), and also be merely 10 with catalytic activity after the MCM-41 of load metallocene carries out vinyl polymerization again after the MAO processing
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 still lower problem of catalytic activity 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 loads on alkylaluminoxane and the metallocene compound on the said carrier; Said carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, and said metallocene compound has the structure shown in the 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; The mixture of said 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 be merely 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 said 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 a relative pressure, and unit is p/p
0
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of the 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 a 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 the alkylaluminoxane on the said carrier; Said carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, and said metallocene compound has the structure shown in the 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 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 10-60 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 45-55 weight %, the content of said carrier is 45-55 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 48-52 weight %, and the content of said carrier is 48-52 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 50 weight %, and the content of said carrier is 50 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, in element, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said 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 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.
The specific examples that satisfies the cyclopentadienyl moiety of above-mentioned requirements comprises: methyl-cyclopentadienyl moiety, 1,2-dimethyl--cyclopentadienyl moiety, 1,3-dimethyl--cyclopentadienyl moiety, 1; 2,3-trimethylammonium-cyclopentadienyl moiety, 1,2; 5-trimethylammonium-cyclopentadienyl moiety, 1,2,3; 4-tetramethyl--cyclopentadienyl moiety, 1,2,3; 5-tetramethyl--cyclopentadienyl moiety, pentamethyl-cyclopentadienyl moiety, ethyl-cyclopentadienyl moiety, 1,2-diethylammonium-cyclopentadienyl moiety, 1,3-diethylammonium-cyclopentadienyl moiety, 1; 2; 4-triethyl-cyclopentadienyl moiety, 1,3,5-triethyl-cyclopentadienyl moiety, methyl-2-ethyl-cyclopentadienyl moiety, 1-methyl-3-ethyl-cyclopentadienyl moiety, n-propyl-cyclopentadienyl moiety, 1; 3-di-cyclopentadienyl moiety, 1-methyl-3-n-propyl-cyclopentadienyl moiety, 1; 3-di-isopropyl-cyclopentadienyl moiety, 1-methyl-3-sec.-propyl-cyclopentadienyl moiety, normal-butyl-cyclopentadienyl moiety, 1,3-di-n-butyl-cyclopentadienyl moiety, 1-methyl-3-normal-butyl-cyclopentadienyl moiety, sec.-butyl-cyclopentadienyl moiety, 1,3-two sec.-butyls-cyclopentadienyl moiety, 1-methyl-3-sec.-butyl-cyclopentadienyl moiety, 1-isobutyl--cyclopentadienyl moiety, 1; 3-diisobutyl-cyclopentadienyl moiety, 1-methyl 3-isobutyl--cyclopentadienyl moiety, the tertiary butyl-cyclopentadienyl moiety, 1; 3-di-t-butyl-cyclopentadienyl moiety, the 1-methyl 3-tertiary butyl-cyclopentadienyl moiety, n-pentyl-cyclopentadienyl moiety, 1,3-two n-pentyls-cyclopentadienyl moiety, 1-methyl-3-n-pentyl-cyclopentadienyl moiety, 1-isopentyl-cyclopentadienyl moiety, 1,3-diisoamyl-cyclopentadienyl moiety, 1-methyl-3-isopentyl-cyclopentadienyl moiety, 1-tert-pentyl-cyclopentadienyl moiety, 1; 3-two tert-pentyls-cyclopentadienyl moiety, 1-methyl-3-tert-pentyl-cyclopentadienyl moiety, neo-pentyl-cyclopentadienyl moiety, 1,3-di neo-pentyl-cyclopentadienyl moiety, 1-methyl-3-neo-pentyl-cyclopentadienyl moiety.
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 moiety of above-mentioned requirements comprises: methyl-cyclopentadienyl moiety, ethyl-cyclopentadienyl moiety, n-propyl-cyclopentadienyl moiety, sec.-propyl-cyclopentadienyl moiety, normal-butyl-cyclopentadienyl moiety, sec.-butyl-cyclopentadienyl moiety, isobutyl--cyclopentadienyl moiety, the tertiary butyl-cyclopentadienyl moiety, n-pentyl-cyclopentadienyl moiety, isopentyl-cyclopentadienyl moiety, tert-pentyl-cyclopentadienyl moiety, neo-pentyl-cyclopentadienyl moiety.
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.
According to loaded metallocene composite catalyst of the present invention, said alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in the said alkylaluminoxane is aforesaid C
1-C
5Alkyl.Preferably, said alkylaluminoxane is a MAO.
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 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 said 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 said 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 said carrier is the 5-15 micron, and specific surface area is 261 meters squared per gram, and pore volume is 0.8 a milliliter/gram, and the most probable aperture is 9.8 nanometers.
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.
According to the method for the invention, said carrier can be the mixture of hollow ball mesoporous silicon oxide and silica gel.In the mixture of said 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 further is preferably 1: 0.5-2 most preferably is 1: 0.5.
The mixture of said hollow ball mesoporous silicon oxide and silica gel can prepare through the method that may further comprise the steps: in the presence of template, trimethylpentane and alcoholic acid; 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, said template is triblock copolymer polyethylene glycol-USP Kosher-polyoxyethylene glycol; The product of gained removed template method is mixed with silica gel.
Said template can be the conventional various triblock copolymer polyethylene glycol-USP Kosher-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, 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.
According to the present invention, the kind of said acidic aqueous solution has no particular limits, and its pH value can be 1-6, is preferably 3-5; Be the acetate of 1-6 and the buffered soln of sodium acetate for example for the pH value.
The condition of said contact can comprise that temperature is 10-60 ℃, and can be 10-72 hour duration of contact.Said contact is preferably carried out under agitation condition.
According to the present invention, the condition of said crystallization can comprise: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour.
The condition of said 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; The weight ratio of triblock copolymer polyethylene glycol-USP Kosher-polyoxyethylene glycol, ethanol, trimethylpentane and tetramethoxy-silicane can change within the specific limits; Preferably, the weight ratio of triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene, tetramethoxy-silicane, trimethylpentane, ethanol and acidic aqueous solution can be 1: 2-3: 3-10: 1-5: 10-50 is 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 said removed template method and the weight ratio of silica gel can be 1: 0.2-5 is preferably 1: 1: 0.4-3 further is preferably 1: 0.5-2 most preferably is 1: 0.5.
According to the preparation method of carried metallocene catalyst of the present invention, said alkylaluminoxane, metallocene compound are described above, repeat no more at this.
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 and toluene; The carrier that has removed toluene is contacted with second solution, and said second solution contains said 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 does not limit for the method for said contact is special, 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 toluene 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, anhydrates etc. to remove.
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 45-55 weight %, more preferably 48-52 weight % further is preferably 50 weight %; The content of said 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 said alkylaluminoxane and the said 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 said carried metallocene catalyst comprises:
In the 1st step,, join pH value and be under 10-60 ℃ of temperature, to be stirred to dissolving in the buffered soln of acetate and sodium acetate of 1-6 triblock copolymer polyethylene glycol-USP Kosher-polyoxyethylene glycol and ethanol;
The 2nd step added trimethylpentane in a last step gained solution, under 10-60 ℃ of temperature, stirred 1-20 hour;
The 3rd step added tetramethoxy-silicane in a last step gained solution, under 10-60 ℃ of temperature, stirred 10-72 hour;
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,, obtain the hollow ball-shape mesoporous material raw powder with the filtration of crystallization after product, washing, drying;
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, is calcined the mixture of gained hollow ball mesoporous silicon oxide of last step and silica gel 7-10 hour in 300-900 ℃, obtains hollow ball mesoporous silicon oxide and the mixture of silica gel after the thermal activation;
The 8th step; The mixture of hollow ball mesoporous silicon oxide after the thermal activation and silica gel is transferred in the reactor drum after nitrogen is fully replaced, adds solvent and alkylaluminoxane, in molar ratio meter; The mixture of hollow ball mesoporous silicon oxide and silica gel: solvent: the amount ratio of alkylaluminoxane is 1: 30-100: 0.1-2; 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 hollow ball mesoporous silicon oxide of load MAO and the mixture of silica gel;
The 9th step under nitrogen protection, joined the hollow ball mesoporous silicon oxide of load MAO and the mixture of silica gel 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 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, dries up with nitrogen, obtains said carried metallocene catalyst.
Below in conjunction with embodiment the present invention is carried out detailed description.
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 carried out on 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 appearance, sample was 200 ℃ of degassings 4 hours.
Present embodiment is used for explanation according to carried metallocene catalyst of the present invention and preparation method thereof.
Restrain triblock copolymer polyethylene glycol-USP Kosher-polyoxyethylene glycol (available from Aldrich with 1.0; P123) and 1.69 gram ethanol join in the buffered soln of acetate and sodium acetate of pH=4.4 of 28ml; Under 15 ℃, be stirred to polyethylene glycol-USP Kosher-polyoxyethylene glycol and dissolve fully, the trimethylpentane with 6g joins in the above-mentioned solution afterwards, and 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 reaction kettle, 60 ℃ of following crystallization after 24 hours through filtering, obtaining the former powder of hollow ball mesoporous silicon oxide after with distilled water wash, 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 is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced through the hollow ball mesoporous silicon oxide of thermal activation and the mixture of silica gel, adds 20 milliliters of purified toluene, 0.51 gram MAO (available from U.S. Albemarle company) 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 MS-GJ-1 of MAO (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 purified 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,, then,, solid is dried up with nitrogen, obtain restraining according to carried metallocene catalyst of the present invention (called after MAO/MS-GJ-BU-1) 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 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 find out by XRD spectra; Maller 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, explains 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 a relative pressure, unit is p/p
0Fig. 4 shows that MAO/MS-GJ-BU-1 has the IV type thermo-isopleth of sharp-pointed capillary condensation speed, and this thermo-isopleth 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 the 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.Can find out that by Fig. 6 MAO/MS-GJ-BU-1 has six sides' meso-hole structure, and the duct is very even.
Fig. 7 is a 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.Can find out that by figure the MS-GJ-1 particle diameter is 5-15 μ m, 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
Data by last table 1 can be found out; 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 hollow ball mesoporous silicon oxide and silica gel of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of promotor MAO (MAO) and cyclopentadienyl catalyst precursor be weight 19.04%; The content of Zr is weight 0.22%, and the mol ratio of Al/Zr is 292: 1.Learn through converting, be benchmark with the total amount of catalyzer, and the total content of MAO (MAO) and metallocene compound is 50 weight %, and the content of carrier is 50 weight %.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE 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 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.Confirm that through calculating 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 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 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.Confirm that through calculating 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 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 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.Confirm that through calculating 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 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 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.Confirm that through calculating 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 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 catalyst precursors 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 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 and carry out the homopolymerization of ethene with EXPERIMENTAL EXAMPLE 1 identical method, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation.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.Confirm that through calculating the efficient of catalyzer is 1295g PE/gcath (that is, 2.9 * 10
7GPE/ (mol Zr h)).
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.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.Confirm that through calculating the efficient of catalyzer is 2260g PE/gcath (that is, 5.1 * 10
7GPE/ (mol Zr h)).
Claims (19)
1. carried metallocene catalyst; It is characterized in that this catalyzer comprises carrier and load on alkylaluminoxane and the metallocene compound on the said carrier that said carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel; 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.
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 10-60 weight %.
3. carried metallocene catalyst according to claim 2 wherein, is a benchmark with the total amount of said carried metallocene catalyst, and the total amount of said metallocene compound and alkylaluminoxane is 45-55 weight %, and the content of said carrier is 45-55 weight %.
4. according to claim 1,2 or 3 described carried metallocene catalysts, wherein, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound is 100-500: 1.
5. carried metallocene catalyst according to claim 4, wherein, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound is 100-300: 1.
6. according to claim 1 or 5 described carried metallocene catalysts, wherein, M is a zirconium.
7. carried metallocene catalyst according to claim 1, wherein, X is a chlorine.
8. 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.
9. carried metallocene catalyst according to claim 8, wherein, R
1, R
1' be normal-butyl.
10. according to any described carried metallocene catalyst in claim 1-3 and 5, wherein, the alkyl in the said alkylaluminoxane is C
1-C
5Alkyl.
11. carried metallocene catalyst according to claim 10, wherein, said alkylaluminoxane is a MAO.
12. carried metallocene catalyst according to claim 1, wherein, said metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, and said alkylaluminoxane is a MAO.
13. carried metallocene catalyst according to claim 1 and 2, wherein, the average particle diameter of said 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.
14. carried metallocene catalyst according to claim 13, wherein, in the mixture of said 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.
15. according to claim 1 or 14 described carried metallocene catalysts; Wherein, said carrier is made by the method that may further comprise the steps: in the presence of template, trimethylpentane and alcoholic acid, 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, said template is polyethylene glycol-USP Kosher-polyoxyethylene glycol; The product of gained removed template method is mixed with silica gel.
16. carried metallocene catalyst according to claim 15, wherein, said acidic aqueous solution is the buffered soln of acetate and sodium acetate, and the pH value of said damping fluid is 1-6; The condition of said contact comprises that temperature is 10-60 ℃, and the time is 10-72 hour; Said crystallization condition comprises: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour; The condition of said removed template method comprises that temperature is 90-600 ℃, and the time is 10-80 hour; When the product of removed template method mixed with silica gel, the product of removed template method and the weight ratio of silica gel were 1: 0.2-5, wherein; The average particle diameter of said carrier is the 3-20 micron; 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.
17. carried metallocene catalyst according to claim 15, wherein, the weight ratio of polyethylene glycol-USP Kosher-polyoxyethylene glycol, tetramethoxy-silicane, trimethylpentane, ethanol and acidic aqueous solution is 1: 2-3: 3-10: 1-5: 10-50.
18. a method for preparing any described carried metallocene catalyst among the claim 1-17 is characterized in that, this method comprises: under protection of inert gas, and successively load alkylaluminoxane and metallocene compound on carrier.
19. method according to claim 18, wherein, this method also is included in before the load alkylaluminoxane, under protection of inert gas, said carrier is 300-900 ℃ in temperature heated 7-10 hour down.
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| CN105330766A (en) * | 2014-06-09 | 2016-02-17 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method thereof |
| CN105524193A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method therefor |
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| CN108017731A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | Spherical mesoporous composite material and loaded catalyst and preparation method thereof |
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| 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 |
| CN108017731A (en) * | 2016-11-02 | 2018-05-11 | 中国石油化工股份有限公司 | Spherical mesoporous composite material and loaded catalyst and preparation method thereof |
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