CN102952212B - Load-type metallocene catalyst, preparation method thereof and application thereof - Google Patents
Load-type metallocene catalyst, preparation method thereof and application thereof Download PDFInfo
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- CN102952212B CN102952212B CN201110247347.2A CN201110247347A CN102952212B CN 102952212 B CN102952212 B CN 102952212B CN 201110247347 A CN201110247347 A CN 201110247347A CN 102952212 B CN102952212 B CN 102952212B
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Abstract
The invention provides a load-type metallocene catalyst which comprises a carrier and an alkyl aluminoxane/magnesium chloride complex and a metallocene compound loaded on the carrier. The carrier is spherical mesoporous silica, and has an average particle diameter of 1 to 10 micrometers, a specific surface area of 1000 to 2000 square meter per gram, a pore volume of 0.3 to 1.5 milliliter per gram, and a most probable pore size of 4 to 20 nanometers. The metallocene compound has a structure as shown in formula 1. The load-type metallocene catalyst provided by the invention has a catalytic efficiency up to 2.7*10<8>gPE/(mol Zr*h) while homopolymerization and a catalytic efficiency up to 2.3*10<8> gPE/(mol Zr*h) while copolymerization under 70 DEG C, overcomes defects of sticking to kettles, is low in a polymerization temperature, and reduces energy consumption to some extent. The formula 1 is as shown in the specification.
Description
Technical field
The present invention relates to a kind of carried metallocene catalyst and its preparation method and application.
Background technology
Olefin polymerization catalysis is the core of polyolefine technical development, and in the innovation of catalyzer, carrier is again a very crucial factor.Carrier not only plays a part carrying, dispersed activity center, also likely as a kind of special part and active centre, has an effect, thereby improves the activity and selectivity of catalyzer.At present, most of olefin polymetiation process processes (as vapour phase polymerization, slurry polymerization etc.) all need working load type catalyzer, to improve the activity of catalyzer.Meet processing requirement, avoid polymkeric substance to stick still phenomenon, improve the form of polymkeric substance.
In supported olefin polymerization catalyst various carriers used, MgCl
2carrier be industrial application up to now at most, the most effective carrier.But in magnesium chloride support, contain the components such as alcohol, water and alkoxyl group, therefore, document 1: Xiao Shijing, Yu Fusheng; Catalysts for Olefin Polymerization and polyolefine, press of Beijing University of Technology, 2002.1-10, records MgCl in P30-42
2before load, need to carry out activation treatment, to increase the specific surface area of carrier, improve charge capacity and the dispersity of active ingredient.At present, MgCl
2activation treatment adopt alcohol adduct method more, as document 2: Wang Yaohua, Zeng Jinlong, Zheng Ronghui; Magnesium chloride support and polyethylene high-efficiency catalyst, Guangxi Normal University's journal, 1986, (1): in 43-49, report, but alcohol adduct method activation MgCl
2complex process, cost higher, and due to the less 13.8m of specific surface area of magnesium chloride
2/ g, the also less (0.017m of pore volume
3/ g), lower as carrier dispersity of active ingredient after loading process finishes, carry out easily sticky still in ethylene polymerisation process, therefore, in the urgent need to development technology novel carriers simple, with low cost, with the good supported olefin polymerization catalyst of processability, magnesium chloride is carried out to secondary load.
With MgCl
2compare, mesoporous material has larger specific surface area and relatively large aperture, can process larger molecule or group, can make catalyzer well bring into play its due catalytic activity, in addition, utilizes mesoporous material as carrier, and tool has the following advantages:
(1) mesoporous material of synthetic does not contain the impurity that easily makes polymer degradation, will improve the ageing resistance of polyolefine material;
(2) mesoporous material nano pore has the dual-use function of carrier and reactor, and catalyst cupport efficiency is high, and polymerization process is easily controlled, and can in the skeleton of polymerization reactor, key in active centre, accelerates reaction process, improves productive rate;
(3) monomer is inserted with polyreaction and has three-dimensional selection effect, can improve polyolefinic molecular weight and fusing point.
As can be seen here, the olefin coordination polymerization that appears as of mesoporous material load olefin polymerization catalysis has been opened up a new field.
Current document 3 (Weckhuysen B M, Rao R R, Pelgrims J, et al.Chem Eur J, 2000,6:2960.) with document 4 (Rao R R, Weckhuysen B M, Schoonheydt R A.Chem Commun, 1999,445.) in, the mesoporous material of load polyethylene catalysts-metallocene catalyst of report is MCM-41, but activity is only 7.3 * 10 during catalyzed ethylene polymerization
5gPE/ (mol Zr h); Document 5 (Chen S T, Guo CY, Lei L, et al.Polymer, 2005,46:11093.) report take MAO process after again the MCM-41 of load metallocene to carry out catalytic activity after vinyl polymerization be 10
6gPE/ (mol Zr h); The hole wall structure thermostability and the hydrothermal stability that after Mesoporous silica MCM 41 supported catalyst, carry out reason that ethylene polymerization activity is lower and be mainly MCM-41 are poor, at loading process hole wall, just there is part to cave in, affect load effect, to such an extent as to affected catalytic activity.
CN1718596A discloses a kind of carried metallocene catalyst, and this catalyzer is by by Cp
2zrCl
2load on the SBA-15 that processes through MAO upper and obtain.But the catalytic activity of the disclosed carried metallocene catalyst of CN1718596A needs further to improve.
CN1923862A discloses a kind of olefin polymerization catalysis of mesoporous molecular sieve carried, and this catalyzer is that the SBA-15 processing through MAO is upper to be obtained by the semi-sandwich alum metallic compound shown in following formula is loaded on,
But the catalytic activity of the disclosed catalyzer of CN1923862A is the highest also only has 10
6gPE/ (molZrh).
CN101172988A discloses a kind of magnesium chloride loaded metallocene catalyst component and method for making and application; CN101173011A discloses a kind of magnesium chloride load non-metallocene schiff base catalyst component and method for making and application; But CN101172988A and CN101173011A all utilize magnesium chloride to carry out metallocene or non-metallocene schiff base catalyst load as carrier, due to the less 13.8m of specific surface area of magnesium chloride
2/ g, the also less (0.017m of pore volume
3/ g), although therefore in polymerization process, polymerization activity is higher, polymerization temperature is 80 ℃, and energy consumption is high, and inhomogeneous in magnesium chloride surface arrangement when metallocene or non-metallocene schiff base catalyst and auxiliary agent load thereof, the polymkeric substance therefore obtaining when carrying out vinyl polymerization is easy to sticky still.
Therefore the defect and the low carried metallocene catalyst of polymerization temperature that, how to obtain a kind of high catalytic activity and when for olefinic polymerization, can overcome sticky still remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The polymkeric substance that the catalytic activity of carried metallocene catalyst that the object of the invention is to overcome prior art is lower, obtain during for olefinic polymerization is easy to sticky still and the high problem of energy consumption, provide a kind of catalytic activity high, not sticky still and the low carried metallocene catalyst of polymerization temperature during for olefinic polymerization.
The invention provides a kind of carried metallocene catalyst, this catalyzer comprises carrier and loads on alkylaluminoxane/magnesium chloride complex compound and the metallocene compound on described carrier, it is characterized in that, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, and specific surface area is 1000-2000 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1:
formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
The present invention also provides a kind of preparation method of carried metallocene catalyst, it is characterized in that, this preparation method comprises: under protection of inert gas, by Magnesium Chloride Anhydrous and alkylaluminoxane, in temperature, be ball milling 0.1-100 hour at 15-100 ℃, then under protection of inert gas, carrier and the first solution are carried out to first and contact, obtain the carrier after the first contact, described the first solution contains ball milling products therefrom and the first solvent; Remove the first solvent on the carrier after the first contact; The carrier that has removed the first solvent is carried out to second with the second solution to be contacted, obtain the carrier after the second contact, described the second solution contains described metallocene compound and the second solvent, wherein, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, specific surface area is 1000-2000 meters squared per gram, and pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1:
formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
The present invention also provides the carried metallocene catalyst being made by aforesaid method, has realized the secondary load to magnesium chloride.
The present invention also provides the application of above-mentioned carried metallocene catalyst in olefinic polymerization.
Specifically, carried metallocene catalyst according to the present invention is when for catalysis in olefine polymerization, and in the time of 70 ℃, during homopolymerization, catalytic efficiency can reach 2.7 * 10
8gPE/ (mol Zrh), during copolymerization, catalytic efficiency can reach 2.3 * 10
8gPE/ (mol Zrh), and the open Cp of CN1718596A
2zrCl
2loading on catalyzer on the SBA-15 processing through MAO catalytic efficiency is under the same conditions 10
6gPE/ (mol Zrh).
The preparation method of carried metallocene catalyst provided by the invention is by carrying out ball milling by alkylaluminoxane and magnesium chloride, thereby obtain alkylaluminoxane/magnesium chloride complex compound, again by this alkylaluminoxane/magnesium chloride complex compound is contacted with spherical mesoporous material together with metallocene compound, thereby made the carried metallocene catalyst with above-mentioned advantage of the present invention.
Accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, wherein, the X-ray diffraction curve of HS and HS-Mg-BU as shown in indicating in figure, X-coordinate unit be 2 θ (
0), ordinate zou is intensity.
Fig. 2 is N
2adsorption desorption graphic representation, wherein, the adsorption desorption curve of HS and HS-Mg-BU is as shown in indicating in figure, and X-coordinate is relative pressure, and unit is p/p
0, ordinate zou is pore volume absorption, unit is cm
3/ gSTP.
Fig. 3 is stereoscan photograph, wherein, and a
1and a
2(be a
1partial enlarged drawing) be the stereoscan photograph of HS, b
1and b
2(be b
1partial enlarged drawing) be the stereoscan photograph of HS-Mg-BU.
Embodiment
The invention provides a kind of carried metallocene catalyst, this catalyzer comprises carrier and loads on alkylaluminoxane/magnesium chloride complex compound and the metallocene compound on described carrier, it is characterized in that, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, and specific surface area is 1000-2000 meters squared per gram, pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1:
formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
According to the present invention, the specific surface area of described carried metallocene catalyst can be 680-820 meters squared per gram, is preferably 700-800 meters squared per gram, more preferably 760 meters squared per gram; Pore volume can be 0.10-0.80 ml/g, is preferably 0.20-0.60 ml/g, more preferably 0.40 ml/g; Most probable aperture can be 1.2-2.0 nanometer, is preferably 1.4-1.8 nanometer, more preferably 1.6 nanometers.
According to the present invention, loading on metallocene compound on described carrier and the amount of alkylaluminoxane/magnesium chloride complex compound can change within a large range.The present inventor finds, it is benchmark that described alkylaluminoxane/magnesium chloride complex compound and the charge capacity of metallocene compound on described carrier be take the total amount of described carried metallocene catalyst, the total content of described metallocene compound and alkylaluminoxane/magnesium chloride complex compound can be 10-60 % by weight, be preferably 45-55 % by weight, more preferably 48-52 % by weight, most preferably is 48.8 % by weight; The content of described carrier can be 40-90 % by weight, is preferably 45-55 % by weight, and more preferably 48-52 % by weight, most preferably is 51.2 % by weight.The total amount of described alkylaluminoxane/magnesium chloride complex compound of take is benchmark, and the content of described alkylaluminoxane is 1-50 % by weight, is preferably 15-45 % by weight, and more preferably 30-40 % by weight, most preferably is 33.33 % by weight; The content of described magnesium chloride is 50-99 % by weight, is preferably 55-85 % by weight, and more preferably 60-70 % by weight, most preferably is 66.67 % by weight.
According to the present invention, the alkylaluminoxane in described alkylaluminoxane/magnesium chloride complex compound and the ratio between metallocene compound can be for the technician of field of olefin polymerisation known ratio.Particularly, the aluminium in described alkylaluminoxane/magnesium chloride complex compound and the mol ratio of the M in described metallocene compound can be 50-200: 1, be preferably 100-200: and 1,130-170 more preferably: 1, most preferably be 153: 1.
According to carried metallocene catalyst of the present invention, what the M in formula 1 can be in titanium, zirconium and hafnium is a kind of.M in different metallocene compound molecules can be identical or different, and preferably, M is zirconium.
According to carried metallocene catalyst of the present invention, the X in formula 1 is halogen.What particularly, the X in formula 1 can be in fluorine, chlorine, bromine and iodine is a kind of.X in different metallocene compound molecules can be identical or different, and preferably, the X in formula 1 is chlorine or bromine.More preferably, the X in formula 1 is chlorine.
According to carried metallocene catalyst of the present invention, in formula 1, cyclopentadienyl is for forming η with central metal
5key and with the derivative of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl in formula 1
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl.
In the present invention, described C
1-C
5alkyl can be in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl a kind of.
The specific examples that meets the cyclopentadienyl of above-mentioned requirements comprises: methyl cyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,2,3-trimethylammonium-cyclopentadienyl, 1,2,4-trimethylammonium-cyclopentadienyl, 1,2,3,4-tetramethyl--cyclopentadienyl, pentamethyl-cyclopentadienyl, ethyl cyclopentadienyl, 1,2-diethyl-cyclopentadienyl, 1,3-diethyl-cyclopentadienyl, 1,2,4-triethyl-cyclopentadienyl, 1,3,5-triethyl-cyclopentadienyl, 1-methyl-2-ethyl-cyclopentadienyl, 1-methyl-3-ethyl-cyclopentadienyl, n-propyl cyclopentadienyl, sec.-propyl cyclopentadienyl, 1,3-diη-propyl-cyclopentadienyl, 1-methyl-3-n-propyl-cyclopentadienyl, 1,3-di-isopropyl-cyclopentadienyl, 1-methyl-3-sec.-propyl-cyclopentadienyl, n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl, isobutyl-cyclopentadienyl, tertiary butyl cyclopentadienyl, 1,3-di-n-butyl-cyclopentadienyl, 1-methyl-3-normal-butyl-cyclopentadienyl, 1,3-di-sec-butyl-cyclopentadienyl, 1-methyl-3-sec-butyl-cyclopentadienyl, 1,3-diisobutyl-cyclopentadienyl, 1-methyl 3-isobutyl--cyclopentadienyl, 1,3-di-t-butyl-cyclopentadienyl, the 1-methyl 3-tertiary butyl-cyclopentadienyl, n-pentyl cyclopentadienyl, isopentyl cyclopentadienyl, tert-pentyl cyclopentadienyl, neo-pentyl cyclopentadienyl, 1,3-, bis-n-pentyls-cyclopentadienyl, 1-methyl-3-n-pentyl-cyclopentadienyl, 1,3-diisoamyl-cyclopentadienyl, 1-methyl-3-isopentyl-cyclopentadienyl, 1,3-, bis-tert-pentyls-cyclopentadienyl, 1-methyl-3-tert-pentyl-cyclopentadienyl, 1,3-di neo-pentyl-cyclopentadienyl, 1-methyl-3-neo-pentyl-cyclopentadienyl.
Preferably, the R in formula 1
1and R
1' 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 meets the cyclopentadienyl of above-mentioned requirements comprises: methyl cyclopentadienyl, ethyl cyclopentadienyl, n-propyl cyclopentadienyl, sec.-propyl cyclopentadienyl, n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl, isobutyl-cyclopentadienyl, tertiary butyl cyclopentadienyl, n-pentyl cyclopentadienyl, isopentyl cyclopentadienyl, tert-pentyl cyclopentadienyl, neo-pentyl cyclopentadienyl.
More preferably, R
1and R
1' for being normal-butyl or the tertiary butyl.The specific examples that meets the cyclopentadienyl of above-mentioned requirements is tertiary butyl cyclopentadienyl, n-butyl cyclopentadienyl.
According to carried metallocene catalyst of the present invention, the alkylaluminoxane in described alkylaluminoxane/magnesium chloride complex compound can be the conventional various alkylaluminoxanes in metallocene catalyst field.Usually, the alkyl in described alkylaluminoxane can be C
1-C
5alkyl.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 neo-pentyl a kind of.Be preferably methyl, the alkylaluminoxane in described alkylaluminoxane/magnesium chloride complex compound 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 (normal-butyl-cyclopentadienyl) zirconium dichlorides, and when described alkylaluminoxane is methylaluminoxane, when described carried metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent especially catalytic activity.
According to carried metallocene catalyst of the present invention, under preferable case, the average particle diameter of described carrier is 1-10 micron, and specific surface area is 1000-2000 meters squared per gram, and pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Under preferable case, the average particle diameter of described carrier is 2-8 micron, and specific surface area is 1100-1800 meters squared per gram, and pore volume is 0.4-0.8 ml/g, and most probable aperture is 4-12 nanometer; More preferably in situation, the average particle diameter of described carrier is 2-8 micron, and specific surface area is 1345 meters squared per gram, and pore volume is 0.6 ml/g, and most probable aperture is 5 nanometers.
According to the present invention, described carrier is sphericity mesoporous silicon dioxide, and described sphericity mesoporous silicon dioxide can prepare by the method comprising the following steps:
(1) cetyl trimethylammonium bromide (CTAB), Triton X-100 (triton x-100) and hydrochloric acid are stirred to dissolving at 25-60 ℃ of temperature;
(2) step (1) gained solution and tetraethoxy are stirred to 10-60 minute to dissolving at 25-60 ℃ of temperature;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) by the heating of step (3) gained crystallization product, removed template method;
Described template is cetyl trimethylammonium bromide and Triton X-100.
Described crystallization condition comprises: crystallization temperature can be 25-60 ℃, is preferably 30-50 ℃; Crystallization time can be 10-40 hour, is preferably 15-30 hour; The condition of described removed template method comprises that temperature can be 300-800 ℃, is preferably 300-600 ℃; Time can be 10-40 hour, is preferably 15-35 hour.
According to the present invention, count in molar ratio, tetraethoxy: Triton X-100: cetyl trimethylammonium bromide (CTAB): hydrogenchloride: water=1: 0.1-0.5: 0.1-0.6: 5-50: 100-500, be preferably 1: 0.1-0.3: 0.1-0.4: 5-20: 100-300, is particularly preferably 1: 0.12: 0.20: 14.39: 199.5.Wherein, the mole number of Triton X-100 calculates according to the molecular-weight average of Triton X-100.
Described Triton X-100 can be the various Triton X-100s that can be used as template, for example triton x-100.
Aforesaid method adopts tetraethoxy as silicon source, is equipped with cetyl trimethylammonium bromide (CTAB) and Triton X-100 (triton x-100) as mixed templates, makes it possible to obtain micron-sized sphericity mesoporous silicon dioxide.
According to the present invention, described carried metallocene catalyst can pass through under protection of inert gas, successively load alkylaluminoxane/magnesium chloride complex compound and metallocene compound on carrier.The content of described alkylaluminoxane/magnesium chloride complex compound and metallocene compound load on described carrier meets previously described requirement.According to the present invention, it is benchmark that described alkylaluminoxane/magnesium chloride complex compound and the charge capacity of metallocene compound on described carrier be take the total amount of described carried metallocene catalyst, the total content of described metallocene compound and alkylaluminoxane/magnesium chloride complex compound can be 10-60 % by weight, be preferably 45-55 % by weight, more preferably 48-52 % by weight, most preferably is 48.8 % by weight; The content of described carrier can be 40-90 % by weight, is preferably 45-55 % by weight, and more preferably 48-52 % by weight, most preferably is 51.2 % by weight.The total amount of described alkylaluminoxane/magnesium chloride complex compound of take is benchmark, and the content of described alkylaluminoxane is 1-50 % by weight, is preferably 15-45 % by weight, and more preferably 30-40 % by weight, most preferably is 33.33 % by weight; The content of described magnesium chloride is 50-99 % by weight, is preferably 55-85 % by weight, and more preferably 60-70 % by weight, most preferably is 66.67 % by weight.Aluminium in described alkylaluminoxane/magnesium chloride complex compound and the mol ratio of the M in described metallocene compound can be 50-200: 1, be preferably 100-200: and 1,130-170 more preferably: 1, most preferably be 153: 1.
According to the present invention; described alkylaluminoxane/magnesium chloride complex compound is that magnesium chloride is as the material of carrier loaded metallocene auxiliary agent structure; can prepare by following method: under protection of inert gas and/or under air tight condition, by Magnesium Chloride Anhydrous and alkylaluminoxane, in temperature, be ball milling 0.1-100 hour preferred 0.5-72 hour at 15-100 ℃ of preferred 25-50 ℃.
The present invention also provides a kind of method of preparing above-mentioned carried metallocene catalyst, this preparation method comprises: under protection of inert gas, by Magnesium Chloride Anhydrous and alkylaluminoxane, in temperature, be ball milling 0.1-100 hour at 15-100 ℃, then under protection of inert gas, carrier and the first solution are carried out to first to be contacted, obtain the carrier after the first contact, described the first solution contains ball milling products therefrom and the first solvent; Remove the first solvent on the carrier after the first contact; The carrier that has removed the first solvent is carried out to second with the second solution to be contacted, obtain the carrier after the second contact, described the second solution contains described metallocene compound and the second solvent, wherein, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, specific surface area is 1000-2000 meters squared per gram, and pore volume is 0.3-1.5 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1:
formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
According to the present invention, described the first solvent and the second solvent are organic solvent, can respectively do for oneself one or more in hexane, pentane, heptane, benzene and toluene of described organic solvent; Described the first solvent and the second solvent can be identical or different, are preferably toluene.
According to the present invention, can there is not chemically interactive various gas with carrier, alkylaluminoxane, magnesium chloride, alkylaluminoxane/magnesium chloride complex compound, metallocene compound for various in described rare gas element.For example, described rare gas element can be nitrogen, argon gas.
Preparation in accordance with the present invention, alkylaluminoxane in described carrier, alkylaluminoxane/magnesium chloride complex compound is described above with kind metallocene compound, does not repeat them here.
The method according to this invention is included under protection of inert gas, successively load alkylaluminoxane/magnesium chloride complex compound and metallocene compound on carrier.Can adopt the method for well known to a person skilled in the art that alkylaluminoxane/magnesium chloride complex compound and metallocene compound are loaded on described carrier.Preferably, successively on carrier, the method for load alkylaluminoxane/magnesium chloride complex compound and metallocene compound comprises: under protection of inert gas, described carrier and the first solution are carried out to first and contact, described the first solution contains described alkylaluminoxane/magnesium chloride complex compound and the first solvent; The carrier that has removed the first solvent is carried out to second with the second solution and contact, described the second solution contains described metallocene compound and the second solvent, and then removes the second solvent.
The present invention contacts and the carrier that has removed described the first solvent is carried out to the second method contacting with the second solution and be not particularly limited for described carrier and the first solution being carried out to first, the whole bag of tricks that can be known to the skilled person, for example: dipping, spraying.The method of employing dipping can be so that solution enters in the duct on carrier more fully, and therefore, the present invention is preferably flooded.
Carrier and the first solution are carried out to first and contact with the second solution second condition contacting of carrying out and be not particularly limited, for example: carrier carries out the first condition contacting with described the first solution and can comprise: the time is 1-10 hour, and temperature is 25-80 ℃; The described carrier that has removed the first solvent is carried out to the second condition contacting with described the second solution can be comprised: the time is 0.3-2 hour, and temperature is 25-80 ℃.
According to the present invention, when described the first solvent and/or the second solvent are toluene, toluene preferably adopts the method that well known to a person skilled in the art to refine before use, for example: can within 24-48 hour, refine by toluene is refluxed on sodium, with except impurity such as water in desolventizing.
The method of the carried metallocene catalyst that preparation of the present invention is above-mentioned; the method be also included in by carrier and the first solution carry out first contact before; under protection of inert gas; described spherical mesoporous material is heated to 7-10 hour at the temperature of 300-900 ℃; for example, (: water), obtain the spherical mesoporous material after thermal activation to remove the volatile matter that contains in the hydroxyl of carrier surface and carrier.
The method of the carried metallocene catalyst that preparation of the present invention is above-mentioned, for example: can comprise the following steps:
The 1st step, by Triton X-100 (triton x-100) and cetyl trimethylammonium bromide (CTAB), joins in aqueous hydrochloric acid, by molar feed ratio,
Tetraethoxy: Triton X-100 (triton x-100): cetyl trimethylammonium bromide (CTAB): hydrogenchloride: water=1: 0.1-0.5: 0.1-0.6: 5-50: 100-500, be preferably 1: 0.1-0.3: 0.1-0.4: 5-20: 100-300, be particularly preferably 1: 0.12: 0.20: 14.39: 199.5
At 25-60 ℃ of temperature, be stirred to dissolving;
The 2nd step adds tetraethoxy in previous step gained solution, stirs 10-60 minute to dissolving at 25-60 ℃ of temperature;
The 3rd step, by previous step products therefrom crystallization 10-40 hour at 25-60 ℃ of temperature, filters crystallization after product, wash, be dried, and obtains the former powder of spherical mesoporous material;
The 4th step, by the former powder of previous step gained spherical mesoporous material in retort furnace at 300-800 ℃ of temperature lower calcination 10-40 hour, removed template method, obtains the spherical mesoporous material of removed template method;
The 5th step, under nitrogen protection, in 300-900 ℃ of calcining thermal activation in 7-10 hour, obtains the spherical mesoporous material after thermal activation by previous step gained spherical mesoporous material;
The 6th step, by anhydrous chlorides of rase magnesium carrier and solid alkylaluminoxane powder, at rare gas element as under nitrogen protection, together join and grind in still, after sealing, still is encased in ball mill, in temperature, be at 15-100 ℃, rotating speed continuously grinding reaction 0.1-100 hour with 200-1000 rev/min, under nitrogen protection, take out pressed powder, by this pressed powder solvent wash, finally with rare gas element, dry up as nitrogen, obtain alkylaluminoxane/magnesium chloride complex compound, for the described solvent washing, can be wherein hexane, pentane, heptane, one or more in benzene and toluene,
The 7th step, spherical mesoporous material and alkylaluminoxane/magnesium chloride complex compound that spherical mesoporous material is preferably after thermal activation are transferred in the reaction vessel after nitrogen is fully replaced, and add organic solvent, are preferably toluene, stir and make slurries; In the container of crossing with nitrogen replacement in advance, metallocene compound is dissolved and makes solution, meter in molar ratio, spherical mesoporous material (in silicon-dioxide): toluene: alkylaluminoxane/magnesium chloride complex compound (take aluminium content meter): the amount ratio of metallocene compound is 1: 3-10: 0.1-1: 1 * 10
-3-9 * 10
-3, under-80 to 150 ℃ of agitation conditions, slowly metallocene compound solution is added drop-wise in reactor, stirring reaction 10 minutes to 4 hours, after reaction finishes, standing, leach liquid, by toluene wash, with nitrogen, dry up, obtain carried metallocene catalyst.
According to the present invention, the temperature range that described anhydrous chlorides of rase magnesium carrier and solid alkylaluminoxane powder grind is altogether preferably 25-50 ℃, and milling time is preferably 0.5-72 hour altogether.
According to the present invention, while dripping metallocene compound, temperature of reaction is preferably 25-80 ℃, and the reaction times is preferably 0.3-2 hour.
It should be noted that, when reaction raw materials adopts the mode dripping to carry out, the described time is from starting to drip beginning timing.
Wherein the molecular weight of alkylaluminoxane is in RAlO, and wherein R is alkyl, and for example the molecular weight of methylaluminoxane is with CH
3alO meter is 58.
Carried metallocene catalyst of the present invention is under promotor effect, for olefinic polymerization.
Promotor of the present invention is aluminum alkyls, as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three base aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride etc., be preferably triethyl aluminum.
According to the present invention, when polymerization, promotor and described carried metallocene catalyst can together join and in polymerization reactor, use or add in polymerization reactor and use respectively.Wherein, the solvent that polymerization is used is selected from alkane, aromatic hydrocarbon or halohydrocarbon.Preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, ethylene dichloride or their mixture, most preferably be a kind of in hexane, toluene, heptane or their mixture.
The concentration of described carried metallocene catalyst when polymerization is 1 * 10
-8mol/L-1 * 10
-3mol/L, preferred concentration range is 1 * 10
-8mol/L-1 * 10
-5mol/L.
Polymerization temperature be-78 ℃ to 100 ℃, be preferably 0-90 ℃, more preferably 10-70 ℃, is further preferably 70 ℃.
Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa, more preferably 1.0MPa.
Carried metallocene catalyst of the present invention can be used on different polymerization processs, as vapour phase polymerization and the polymerization of what slurry etc.
Carried metallocene catalyst of the present invention can be for polymerization or the copolymerization of alkene, be specially adapted to that ethylene homo closes or the copolymerization of ethene and other alpha-olefin, wherein alpha-olefin adopts propylene, butylene, amylene, alkene, octene, 4-methylpentene-1 etc.
The present invention is the structure of carried metallocene catalyst by the carrier of X-ray diffraction method, nitrogen adsorption desorption method and scanning electron microscope method alkylaluminoxane/magnesium chloride complex compound of having measured or characterized carrier HS and load and metallocene compound, measures the content of aluminium and metal M in carried metallocene catalyst by ultimate analysis.
Below by specific embodiment, the present invention is further described, but embodiments of the invention have more than and are limited to following examples.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8 Advance in the model purchased from German Bruker AXS company; In the scanning electronic microscope that scanning electron microscope analysis is XL-30 in the model purchased from U.S. FEI Co., carry out; Ultimate analysis is to carry out on 7500CX instrument in the model purchased 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 is degassed 4 hours at 200 ℃.
In following examples, described Triton X-100 (triton x-100) is purchased from ACROS company of Belgian reagent company; Methylaluminoxane is purchased from the U.S. refined treasured (Albemarle) company; Two (n-butyl cyclopentadienyl) zirconium dichlorides of described metallocene compound are purchased the company from Aldrich; Described cetyl trimethylammonium bromide (CTAB) is purchased from J & K Chemical LTD company, CAS 57-09-0.
Embodiment 1
The present embodiment is for illustrating according to carried metallocene catalyst of the present invention and preparation method thereof.
In the hydrochloric acid soln that the concentrated hydrochloric acid that it is 37 % by weight that the Triton X-100 (triton x-100) that is 1.07g/ml by 1.5 grams of cetyl trimethylammonium bromides (CTAB) and 1.5ml density joins by 29.6 grams of concentration and 75 grams of water form, at 40 ℃, be stirred to CTAB and triton x-100 dissolves completely; Again 4.35 grams of tetraethoxys are joined in above-mentioned solution at 40 ℃ and stir 15 minutes, 40 ℃ standing 24 hours, tetraethoxy dissolves completely, then 40 ℃ of crystallization 24 hours, through filtering, washing, obtain former powder mesoporous material after dry; By former powder mesoporous material in retort furnace 600 ℃ calcining 24 hours, removed template method, obtains carrier spherical mesoporous material (called after HS).
By above-mentioned spherical mesoporous material HS under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the spherical mesoporous material through thermal activation.
Under nitrogen protection, take 7.0g Magnesium Chloride Anhydrous and 3.5g methylaluminoxane solid and together join in grinding still, after sealing, still is encased in ball mill, with the rotating speed continuously grindings reactions of 400 revs/min 12 hours.After grinding stops, the solid product of grinding is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 30 milliliters of refining toluene, in 30 ℃ of stirrings, wash 2 times each 30 minutes.After, then use 40 milliliters of hexane washed twice, and finally solid is dried up with nitrogen, obtain having alkylaluminoxane/magnesium chloride complex compound of good mobility; According to feed ratio, calculate, the total amount of described alkylaluminoxane/magnesium chloride complex compound of take is benchmark, and the content of described alkylaluminoxane is 66.67 % by weight, and the content of described magnesium chloride is 33.33 % by weight.
Under nitrogen protection; spherical mesoporous material HS after 0.1 gram of thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced; 0.1 gram, alkylaluminoxane/magnesium chloride complex compound joins in reactor; add 5 milliliters of refining toluene; slurries are made in stirring; at 30 ℃, 5 milliliters of the toluene solutions of two (n-butyl cyclopentadienyl) zirconium dichlorides of metallocene compound that slowly dropping contains 4.9 milligrams, stirring reaction 1 hour.After reaction finishes, standing, leach liquid, by 10 milliliters of toluene wash 2 times, solid is dried up with nitrogen, obtain 0.2049 gram of target product carried metallocene catalyst and by this carried metallocene catalyst called after HS-Mg-BU, wherein according to weight * 100% of the weight/carried metallocene catalyst of the carrier of the content of carrier=add, calculate, the total amount of described carried metallocene catalyst of take is benchmark, the total content of described metallocene compound and alkylaluminoxane/magnesium chloride complex compound is 51.2 % by weight, the content of described carrier is 48.8 % by weight.
With XRD, the experiment of nitrogen adsorption-desorption, scanning electron microscope, X-ray energy spectrometer and ICP ultimate analysis, this carried metallocene catalyst is characterized.
Fig. 1 is the XRD spectra of spherical mesoporous material HS and HS-Mg-BU.From XRD spectra, can find out significantly that sample HS and HS-Mg-BU all occur diffraction peak in little angular region, illustrate that spherical mesoporous material HS and HS-Mg-BU have good mesoporous phase structure, consistent (the Xuelei Pang of mesoporous material XRD spectra of this and bibliographical information, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1～6).
Fig. 2 is that (X-coordinate is relative pressure (p/p for nitrogen adsorption-desorption graphic representation of spherical mesoporous material product HS and HS-Mg-BU
0)), nitrogen adsorption-desorption thermoisopleth shows that spherical mesoporous material sample HS and HS-Mg-BU are the IV class adsorption-desorption thermoisopleths of typical IUPAC definition, proved that spherical mesoporous material sample HS and HS-Mg-BU have meso-hole structure (the Xuelei Pang of distinctive cube of cage structure of bibliographical information, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1～6; Chengzhong Yu, Bozhi Tian, Jie Fan, Galen D.Stucky, Dongyuan Zhao, J.Am.Chem.Soc.2002,124,4556-4557).
Fig. 3 is the microscopic appearance figure of spherical mesoporous material HS and HS-Mg-BU.Wherein in Fig. 3, a1 and a2 (being the partial enlarged drawing of a1) are the microscopic appearance figure of spherical mesoporous material HS, and b1 and b2 in Fig. 3 (being the partial enlarged drawing of b1) are the microscopic appearance figure of HS-Mg-BU.As seen from the figure, the microscopic appearance figure of spherical mesoporous material HS and HS-Mg-BU is spherical, size is micron level, with bibliographical information (Xuelei Pang in full accord, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1～6), after load-reaction, the microscopic appearance of Mesoporous Spheres remains unchanged substantially, still keeps spherical preferably.
Table 1
Table 1 is spherical mesoporous material HS and HS-Mg-BU pore structure parameter, spherical mesoporous material HS is again through two (n-butyl cyclopentadienyl) zirconium dichlorides of alkoxyl group alumina alkane/magnesium chloride complex compound and metallocene compound) (BUCP) pore structure parameter all reduces to some extent after load, and this result shows that alkoxyl group alumina alkane/magnesium chloride complex compound and metallocene enter into spherical mesoporous material duct really.
By ultimate analysis ICP result, show, two (n-butyl cyclopentadienyl) zirconium dichlorides of load alkoxyl group alumina alkane/magnesium chloride complex compound and metallocene compound) the aluminium content of spherical mesoporous material HS (BUCP) is 5.9%, the content of Zr is that the mol ratio of 0.13%, Al/Zr is 153: 1.
Application examples 1
Should be used for illustrating that the carried metallocene catalyst of embodiments of the invention 1 preparation is in the application of olefinic polymerization by use-case
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexane solvents, by still temperature rise to 70 ℃, then add 800 milliliters of hexane solvents, along with adding of hexane, the triethyl aluminum of 2 milliliter of 1 mol/L (TEA) hexane solution is added, then 98.8 milligrams of HS-Mg-BU that add embodiment 1 preparation, rise to pressure maintain 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 2.7 * 10
8gPE/ (mol Zrh)), bulk density (BD) is 0.325g/ml, melting index: MI
2.16=0.077g/10min.
Application examples 2
Should be used for illustrating that the carried metallocene catalyst of embodiments of the invention 1 preparation is in the application of olefinic polymerization by use-case
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexane solvents, by still temperature rise to 70 ℃, then add 800 milliliters of hexane solvents, along with adding of hexane, the triethyl aluminum of 2 milliliter of 1 mol/L (TEA) hexane solution and 10 milliliters of hexenes are added, then 85 milligrams of HS-Mg-BU that add embodiment 1 preparation, rise to pressure maintain 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 2.3 * 10
8gPE/ (mol Zrh)), bulk density (BD) is 0.322g/ml, melting index: MI
2.16=0.326g/10min.
Comparative example 1
This comparative example is used for illustrating preparation and the application thereof of two (n-butyl cyclopentadienyl) zirconium dichlorides (BUCP) of the carrier loaded metallocene compound of alkylaluminoxane/magnesium chloride complex compound
Under nitrogen protection, take the pretreated Magnesium Chloride Anhydrous of 7.0g and 3.5g methylaluminoxane solid and together join in grinding still, after sealing, still is encased in ball mill, with the rotating speed continuously grindings reactions of 400 revs/min 12 hours.After grinding stops, the solid product of grinding is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 30 milliliters of refining toluene, in 30 ℃ of stirrings, wash three times each 30 minutes.After, then use 40 milliliters of hexane washed twice, and finally solid is dried up with nitrogen, obtain having alkylaluminoxane/magnesium chloride complex compound of good mobility;
Under nitrogen protection; 0.1 gram, alkylaluminoxane/magnesium chloride complex compound is joined in 250 milliliters of glass reactors after nitrogen is fully replaced; add 5 milliliters of refining toluene; slurries are made in stirring; at 30 ℃; 5 milliliters of the toluene solutions of two (n-butyl cyclopentadienyl) zirconium dichlorides of metallocene compound that slowly dropping contains 4.9 milligrams, stirring reaction 1 hour.After reaction finishes, standing, leach liquid, by 10 milliliters of toluene wash 2 times, solid is dried up with nitrogen, the carried metallocene catalyst that obtains preparing comparative example 1 preparation is also by this carried metallocene catalyst called after Mg-BU.
By ultimate analysis ICP result, show, the aluminium content of two (n-butyl cyclopentadienyl) zirconium dichlorides of the carrier loaded metallocene compound of alkylaluminoxane/magnesium chloride complex compound is 12.2 % by weight, the content of Zr is 0.44 % by weight, and the mol ratio of Al/Zr is 94: 1.
Application comparative example 1
This application comparative example is for illustrating that the catalyzer of comparative example 1 preparation is in the application of olefinic polymerization
According to the method for application examples 1, carry out polyreaction, different, the HS-Mg-BU of embodiment 1 preparation is replaced by the Mg-BU of comparative example 1 preparation of identical weight, and result catalytic efficiency is 2.5 * 10
8gPE/ (mol Zrh), bulk density (BD) is 0.325g/ml, melting index: MI
2.16=0.077g/10min.And observe in discovery polymerization reaction kettle and occur serious sticky still phenomenon, need to use sharp weapon will in reactor, scrape totally.
Application comparative example 2
This application comparative example is for illustrating that the catalyzer of comparative example 1 preparation is in the application of olefinic polymerization
According to the method for application examples 2, carry out polyreaction, different, the HS-Mg-BU of embodiment 1 preparation is replaced by the Mg-BU of comparative example 1 preparation of identical weight, and result catalytic efficiency is 2.1 * 10
8gPE/ (mol Zrh), bulk density (BD) is 0.322g/ml, melting index: MI
2.16=0.326g/10min.And observe in discovery polymerization reaction kettle and occur serious sticky still phenomenon, need to use sharp weapon will in reactor, scrape totally.
Comparative example 2
This comparative example is used for illustrating preparation and the application thereof of spherical mesoporous material load methylaluminoxane and two (n-butyl cyclopentadienyl) zirconium dichlorides of metallocene compound
By 1.5 grams of cetyl trimethylammonium bromides (CTAB), be 1.07g/ml with 1.5ml density, in the hydrochloric acid soln that the concentrated hydrochloric acid that it is 37 % by weight that the Triton X-100 of concentration weight 5% (triton x-100) joins by 29.6 grams of concentration and 75 grams of water form, at 40 ℃, be stirred to CTAB and triton x-100 dissolves completely; Again 4.35 grams of tetraethoxys are joined in above-mentioned solution at 40 ℃ and stir 15 minutes, 40 ℃ standing 24 hours, tetraethoxy dissolves completely, then 40 ℃ of crystallization 24 hours, through filtering, washing, obtain former powder mesoporous material after dry; By former powder mesoporous material in retort furnace 600 ℃ calcining 24 hours, removed template method, obtains carrier spherical mesoporous material (called after HS).
By above-mentioned spherical mesoporous material HS under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the spherical mesoporous material through thermal activation.
Under nitrogen protection, the spherical mesoporous material HS after 0.1 gram of thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, add 10 milliliters of refining toluene, 0.47 gram of methylaluminoxane auxiliary agent stirs 4 hours in 50 ℃.After, then with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen, obtain methylaluminoxane/HS complex compound carrier (MAO/HS).
Under nitrogen protection; methylaluminoxane/HS complex compound carrier is joined in reactor; add 20 milliliters of refining toluene; slurries are made in stirring; at 30 ℃; the toluene solution of two (n-butyl cyclopentadienyl) zirconium dichlorides of metallocene compound that slowly dropping 10ml contains 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid, by 10 milliliters of toluene wash three times, then, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, and the carried metallocene catalyst that obtains preparing comparative example 4 preparations is also by this carried metallocene catalyst called after HS-MAO-BU.
Table 2 is spherical mesoporous material HS and HS-MAO-BU pore structure parameter.
Table 2
Data from table 2 can find out, the pore structure parameter of HS-MAO-BU all decreases compared with HS, shows that methylaluminoxane and metallocene compound enter into the duct of JKQ really.
Results of elemental analyses shows, load the content of aluminium of spherical mesoporous material of two (n-butyl cyclopentadienyl) zirconium dichlorides of promotor methylaluminoxane (MAO) and metallocene compound be 0.19 % by weight, the content of Zr is 0.04 % by weight, and the mol ratio of Al/Zr is 16: 1.
Application comparative example 3
This application comparative example is for illustrating that the catalyzer of comparative example 2 preparations is in the application of olefinic polymerization
According to the method for application examples 1, carry out polyreaction, different, the HS-Mg-BU of embodiment 1 preparation is replaced by the catalyzer HS-MAO-BU of comparative example 2 preparations of identical weight, and result catalytic efficiency is 1.1 * 10
8g PE/ (mol Zr h), poly bulk density (BD) is 0.306g/ml, melting index: MI
2.16=0.026g/10min.And observe in discovery polymerization reaction kettle and occur serious sticky still phenomenon, need to use sharp weapon will in reactor, scrape totally.
Application comparative example 4
This application comparative example is for illustrating that the catalyzer of comparative example 2 preparations is in the application of olefinic polymerization
According to the method for application examples 2, carry out polyreaction, different, the HS-Mg-BU of embodiment 1 preparation is replaced by the catalyzer HS-MAO-BU of comparative example 2 preparations of identical weight, and result catalytic efficiency is 1.5 * 10
8g PE/ (mol Zr h), the bulk density of multipolymer (BD) is 0.321g/ml, melting index: MI
2.16=0.384g/10min.And observe in discovery polymerization reaction kettle and occur serious sticky still phenomenon, need to use sharp weapon will in reactor, scrape totally.
The polymerization result of application examples 1-2 and application comparative example 1-4 contrast and can be found out, only have while containing at the same time alkylaluminoxane, magnesium chloride, metallocene and sphericity mesoporous silicon dioxide, this catalyzer could solve the problem that still is glued in polymerization.
Claims (23)
1. a carried metallocene catalyst, this catalyzer comprises carrier and loads on alkylaluminoxane/magnesium chloride complex compound and the metallocene compound on described carrier, it is characterized in that, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, and specific surface area is 1000-2000 meters squared per gram, pore volume is 0.4-0.8 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1:
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen;
Wherein, the total amount of described carried metallocene catalyst of take is benchmark, and the total content of described metallocene compound and alkylaluminoxane/magnesium chloride complex compound is 10-60 % by weight, and the content of described carrier is 40-90 % by weight; The total amount of described alkylaluminoxane/magnesium chloride complex compound of take is benchmark, and the content of described alkylaluminoxane is 1-50 % by weight, and the content of described magnesium chloride is 50-99 % by weight.
2. catalyzer according to claim 1, wherein, the aluminium in described alkylaluminoxane/magnesium chloride complex compound and the mol ratio of the M in described metallocene compound are 50-200:1.
3. catalyzer according to claim 2, wherein, the aluminium in described alkylaluminoxane/magnesium chloride complex compound and the mol ratio of the M in described metallocene compound are 130-170:1.
4. according to the catalyzer described in any one in claim 1-3, wherein, M is zirconium, and X is chlorine.
5. catalyzer according to claim 1, wherein, R
1and R
1' be C independently of one another
1-C
5alkyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
6. catalyzer according to claim 5, wherein, R
1and R
1' be normal-butyl independently of one another.
7. according to the catalyzer described in any one in claim 1-3, wherein, the alkyl in described alkylaluminoxane/magnesium chloride complex compound is C
1-C
5alkyl.
8. catalyzer according to claim 7, wherein, described alkylaluminoxane is methylaluminoxane.
9. according to the catalyzer described in any one in claim 1-3, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
10. catalyzer according to claim 1, wherein, the average particle diameter of described carrier is 2-8 micron, and specific surface area is 1100-1800 meters squared per gram, and most probable aperture is 4-12 nanometer.
11. according to the catalyzer described in claim 1 or 10, and wherein, described carrier is made by the method comprising the following steps:
(1), at 25-60 ℃, template is dissolved in aqueous hydrochloric acid;
(2), at 25-60 ℃, tetraethoxy is dissolved in step (1) gained solution;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) by the heating of step (3) gained crystallization product, removed template method;
Described template is cetyl trimethylammonium bromide and Triton X-100.
12. catalyzer according to claim 11, wherein, described crystallization condition comprises: crystallization temperature is 25-60 ℃, crystallization time is 10-40 hour; The condition of described removed template method comprises that temperature is 300-800 ℃, and the time is 10-40 hour.
13. catalyzer according to claim 11, wherein, count tetraethoxy: Triton X-100: cetyl trimethylammonium bromide: hydrogenchloride: water=1:0.1-0.5:0.1-0.6:5-50:100-500 in molar ratio.
The preparation method of 14. 1 kinds of carried metallocene catalysts, it is characterized in that, this preparation method comprises: under protection of inert gas, by Magnesium Chloride Anhydrous and alkylaluminoxane, in temperature, be ball milling 0.1-100 hour at 15-100 ℃, then under protection of inert gas, carrier and the first solution are carried out to first and contact, obtain the carrier after the first contact, described the first solution contains ball milling products therefrom and the first solvent; Remove the first solvent on the carrier after the first contact; The carrier that has removed the first solvent is carried out to second with the second solution to be contacted, obtain the carrier after the second contact, described the second solution contains described metallocene compound and the second solvent, wherein, described carrier is sphericity mesoporous silicon dioxide, wherein, the average particle diameter of described carrier is 1-10 micron, specific surface area is 1000-2000 meters squared per gram, and pore volume is 0.4-0.8 ml/g, and most probable aperture is 4-20 nanometer; Described metallocene compound has the structure shown in formula 1:
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen;
Wherein, the butt weighing scale of the carrier after the consumption of metallocene compound, alkylaluminoxane and magnesium chloride makes to contact with second, the total content of described metallocene compound and alkylaluminoxane/magnesium chloride complex compound is 10-60 % by weight, and the content of described carrier is 40-90 % by weight; And the total amount of described alkylaluminoxane/magnesium chloride complex compound of take is benchmark, and the content of described alkylaluminoxane is 1-50 % by weight, and the content of described magnesium chloride is 50-99 % by weight.
15. methods according to claim 14, wherein, the method also comprise by carrier and the first solution carry out first contact before, under protection of inert gas, described carrier is heated to 7-10 hour at the temperature of 300-900 ℃.
16. methods according to claim 14, wherein, the temperature of Magnesium Chloride Anhydrous and alkylaluminoxane being carried out to ball milling is 25-50 ℃, the time is 0.5-72 hour.
17. methods according to claim 14, wherein, respectively do for oneself one or more in hexane, pentane, heptane, benzene and toluene of described the first solvent and the second solvent.
18. methods according to claim 17, wherein, described the first solvent and the second solvent toluene of respectively doing for oneself.
19. methods according to claim 14, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, described alkylaluminoxane is methylaluminoxane.
20. methods according to claim 19, wherein, count spherical mesoporous material: toluene: alkylaluminoxane/magnesium chloride complex compound: the amount ratio of two (n-butyl cyclopentadienyl) zirconium dichloride is 1:3-10:0.1-1:1 * 10 in molar ratio
-3-9 * 10
-3.
21. methods according to claim 14, wherein, carrier comprises with described the first solution first condition contacting of carrying out: the time is 1-10 hour, and temperature is 25-80 ℃; The described carrier that has removed the first solvent is comprised with described the second solution second condition contacting of carrying out: the time is 0.3-2 hour, and temperature is 25-80 ℃.
The carried metallocene catalyst that method in 22. claim 14-21 described in any one makes.
The application of carried metallocene catalyst in 23. claim 1-13 and 22 described in any one in vinyl polymerization.
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Citations (2)
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| US20030109377A1 (en) * | 2001-11-15 | 2003-06-12 | Industrial Technology Research Institute | Catalyst composition and process for preparing olefin polymers |
| CN101172988A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Magnesium chloride loaded metallocene catalyst component, prepare method and application of the same |
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