CN102952211B - Supported metallocene catalyst and preparation method and application thereof - Google Patents
Supported metallocene catalyst and preparation method and application thereof Download PDFInfo
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- CN102952211B CN102952211B CN201110247085.XA CN201110247085A CN102952211B CN 102952211 B CN102952211 B CN 102952211B CN 201110247085 A CN201110247085 A CN 201110247085A CN 102952211 B CN102952211 B CN 102952211B
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Abstract
The invention provides a supported metallocene catalyst which comprises a carrier, and an alkylaluminoxane/magnesium chloride complex and a metallocene compound which are supported on the carrier; the carrier is rodlike macroporous mesoporous silica which has a length of 2-20 microns, an aspect ratio of 2-8:1, a specific surface area of 320-380 square meter/g, and a pore volume of 0.5-1.5 ml/g. The metallocene compound has a structure as shown in formula 1. When the supported metallocene catalyst of the invention is used for catalyzing olefin polymerization, the catalytic efficiency for homopolymerization at 70 DEG C is up to 2.7*10<8> gPE/(mol Zr.h), and the catalytic efficiency for copolymerization at 70 DEG C is up to 4.2*10<8> gPE/(mol Zr.h); the supported metallocene catalyst overcomes the defect of kettle adhesion, has a low polymerization temperature, and thus reduces the energy consumption to some extent. Formula 1 is 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, PelgriKK-SBA J, et al.Chem EurJ, 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, obtain a kind of high catalytic activity and when for olefinic polymerization, can overcome the defect of sticky still and catalyzer that polymerization temperature is low realizes secondary load to magnesium chloride remains 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, provides that a kind of catalytic activity is high, 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 bar-shaped macropore mesoporous silicon oxide, the length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, and aspect ratio is 2-8: 1, and specific surface area is 320-380 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 7-17 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 bar-shaped macropore mesoporous silicon oxide, and the length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, aspect ratio is 2-8: 1, specific surface area is 320-380 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and most probable aperture is 7-17 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.
The present invention also provides the application of above-mentioned carried metallocene catalyst in vinyl 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 4.2 * 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 bar-shaped macropore mesoporous silicon oxide 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, in Fig. 1 a be X-ray diffraction curve that in KK-SBA and Fig. 1, b is KK-SBA-Mg-BU as shown in indicating in figure, X-coordinate unit be 2 θ (°), ordinate zou is intensity.
Fig. 2 is N2 adsorption desorption graphic representation, wherein, in Fig. 2 a be in KK-SBA and Fig. 2 b be the adsorption desorption curve of KK-SBA-Mg-BU (b) as shown in indicating in figure, X-coordinate is relative pressure, unit is p/p
0, ordinate zou is pore volume absorption, unit is cm
3/ gSTP.
Fig. 3 is pore size distribution curve, wherein, the pore size distribution curve figure that in Fig. 3, a is KK-SBA, the graph of pore diameter distribution that in Fig. 3, b is KK-SBA-Mg-BU, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g.
Fig. 4 is stereoscan photograph, wherein, and the stereoscan photograph that in Fig. 4, a is KK-SBA, the stereoscan photograph that in Fig. 4, b is KK-SBA-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 macropore mesoporous silicon oxide, wherein, described carrier is bar-shaped macropore mesoporous silicon oxide, the length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, aspect ratio is 2-8: 1, specific surface area is 320-380 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 7-17 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 carried metallocene catalyst of the present invention, the specific surface area of described carried metallocene catalyst can be 20-100 meters squared per gram, is preferably 40-80 meters squared per gram, more preferably 60 meters squared per gram; Pore volume can be 0.1-0.5 ml/g, is preferably 0.1-0.3 ml/g, more preferably 0.1 ml/g; Most probable aperture can be 5-12 nanometer, is preferably 7-11 nanometer, more preferably 9.2 nanometers.
According to carried metallocene catalyst of the present invention, 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 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 carried metallocene catalyst of 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 135-165: and 1,140-160 more preferably: 1, most preferably be 152: 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 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 the present invention; described alkylaluminoxane/magnesium chloride complex compound is the magnesium chloride support that load aluminum alkyls is supported alkane; can prepare by following method: under protection of inert gas and/or under air tight condition; by Magnesium Chloride Anhydrous and alkylaluminoxane, in temperature, being ball milling 0.1-100 hour at 15-100 ℃, is preferably ball milling 0.5-72 hour at 25-50 ℃ in temperature.
According to carried metallocene catalyst of the present invention, the size of described macropore mesoporous silicon oxide can in very large range change, under preferable case, described macropore meso-porous titanium dioxide silicon carrier is bar-shaped macropore mesoporous silicon oxide, the length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, and aspect ratio is 2-8: 1, and specific surface area can be 320-380 meters squared per gram, pore volume can be 0.5-1.5 ml/g, and most probable aperture can be 7-17 nanometer; More preferably, the length of described bar-shaped macropore mesoporous silicon oxide is 3-15 micron, and specific surface area can be 340-360 meters squared per gram, and pore volume can be 0.8-1.2 ml/g, and most probable aperture can be 10-14 nanometer; More preferably, the length of described bar-shaped macropore mesoporous silicon oxide is 3-9 micron, and specific surface area can be 351 meters squared per gram, and pore volume can be 1.0 mls/g, and most probable aperture can be 12 nanometers.
According to carried metallocene catalyst of 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, 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 can be 10-60 % by weight, is 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 carried metallocene catalyst of 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 135-165: and 1,140-160 more preferably: 1, most preferably be 152: 1.
According to the present invention, described bar-shaped macropore mesoporous silicon oxide is made by the method comprising the following steps: under template exists, tetraethoxy is contacted with acidic aqueous solution, and gained mixture crystallization under crystallization condition after contacting, gained crystallization product is heated, removed template method, described template is triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene, described acidic aqueous solution is preferably hydrochloric acid.
According to the present invention, the kind of described acidic aqueous solution has no particular limits, and its pH value can be 1-6, and more preferably pH is 3-5.
According to the present invention, in the bar-shaped macropore mesoporous silicon oxide process of preparation, when described acidic aqueous solution is hydrochloric acid, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: HCl: the mol ratio of tetraethoxy is preferably 1: 9000-15000: 100-500: 50-80, more preferably 1: 10000-14000: 200-400: 55-65.Wherein, the mole number of polyoxyethylene-polyoxytrimethylene-polyoxyethylene calculates according to the molecular-weight average of polyoxyethylene-polyoxytrimethylene-polyoxyethylene.
According to the present invention, the condition of described contact comprises: temperature is 25-60 ℃, and the time is above extremely dissolving in 25 minutes, and described crystallization condition comprises: crystallization temperature can be 90-180 ℃, is preferably 140-160 ℃; 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 5-40 hour, is preferably 15-35 hour.
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 bar-shaped macropore mesoporous silicon oxide, and the length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, and specific surface area is 320-380 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 7-17 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, and can respectively do for oneself one or more in hexane, pentane, heptane, benzene and toluene of described organic solvent, 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 and content, 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, 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 and contact, obtain the carrier after the second contact, described the second solution contains described metallocene compound and the second solvent, and then removes the second solvent.
Preparation in accordance with 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.
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; before load alkylaluminoxane/magnesium chloride complex compound; under protection of inert gas; described bar-shaped macropore mesoporous silicon oxide is heated to 7-10 hour at the temperature of 300-900 ℃; for example, (: water), obtain the macropore mesoporous silicon oxide 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 triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene, joins in the aqueous hydrochloric acid that pH value is 1-6, by molar feed ratio,
The mol ratio of triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene, water, hydrogenchloride is 1: 9000-15000: 100-500, is preferably 1: 10000-14000: 200-400.
At 25-60 ℃ of temperature, be stirred to dissolving;
The 2nd step adds tetraethoxy in previous step gained solution, stirs above extremely dissolving in 25 minutes at 25-60 ℃ of temperature;
The 3rd step, is placed in closed reactor by previous step gained solution, and crystallization 10-40 hour at 90-180 ℃ of temperature filters crystallization after product, wash, be dried, and obtains the former powder of macropore mesoporous silicon oxide;
The 4th step, by the former powder of the bar-shaped macropore mesoporous silicon oxide of previous step gained in retort furnace at 300-800 ℃ of temperature lower calcination 5-40 hour, removed template method, obtains the macropore mesoporous silicon oxide of removed template method;
The 5th step, under nitrogen protection, in 300-900 ℃ of calcining thermal activation in 7-10 hour, obtains the macropore mesoporous silicon oxide after thermal activation by the bar-shaped macropore mesoporous silicon oxide of previous step gained;
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, bar-shaped macropore mesoporous silicon oxide and alkylaluminoxane/magnesium chloride complex compound that bar-shaped macropore mesoporous silicon oxide is preferably after thermal activation are transferred in the reaction vessel after nitrogen is fully replaced, add organic solvent, be 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, bar-shaped macropore mesoporous silicon oxide (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 25 ℃ to 80 ℃ agitation conditions, slowly metallocene compound solution is added drop-wise in reactor, stirring reaction 0.5-10 hour, 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 hexyl 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 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, hexene, 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 KK-SBA 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, on the X-ray diffractometer that X-ray diffraction analysis is D8Advance in the model purchased from German Bruker AXS company, carry out; 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, and triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (Aldrich company, P123), the material that is 9003-11-6 in the registration number of U.S. chemical abstract, its average molecular mass Mn=5800; Methylaluminoxane is purchased from the U.S. refined treasured (Albemarle) company; Two (n-butyl cyclopentadienyl) zirconium dichlorides of described metallocene compound are purchased the company from Aldrich.
Embodiment 1
The present embodiment is for illustrating according to carried metallocene catalyst of the present invention and preparation method thereof.
By 4.0 grams of triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (Aldrich companies, P123) join in the solution (pH=4.4) of 16.4ml hydrochloric acid that concentration is 37 % by weight and 128ml water, at 40 ℃, being stirred to polyoxyethylene-polyoxytrimethylene-polyoxyethylene dissolves completely, afterwards the tetraethoxy of 8.86g is joined in above-mentioned solution, 40 ℃ were stirred after 24 hours, solution is transferred in teflon-lined reactor again, at 150 ℃ baking oven crystallization after 24 hours through filtering, distilled water wash, after dry, obtain the former powder of macropore mesoporous silicon oxide.
By the former powder of previous step gained macropore mesoporous silicon oxide in retort furnace 600 ℃ of temperature lower calcinations 24 hours, removed template method, obtains the macropore mesoporous silicon oxide of removed template method.
By the macropore mesoporous silicon oxide of above-mentioned removed template method under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the macropore mesoporous silicon oxide (called after KK-SBA) through thermal activation.
Under anhydrous and oxygen-free, take 7.0g Magnesium Chloride Anhydrous and 3.5g methylaluminoxane 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 3 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; macropore mesoporous silicon oxide KK-SBA 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 the supported catalyst called after KK-SBA-Mg-BU of gained, 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 X-ray diffracting spectrum, wherein, the X-ray diffraction curve that in Fig. 1, a is KK-SBA, the X-ray diffraction curve that in Fig. 1, b is KK-SBA-Mg-BU, can find out that from XRD spectra KK-SBA and KK-SBA-Mg-BU all occur a diffraction peak in little angular region significantly.Illustrate that KK-SBA has good mesoporous phase structure (concrete data provide in table 1).
Fig. 2 is nitrogen adsorption-desorption graphic representation, and wherein, X-coordinate is relative pressure, and unit is p/p
0, the adsorption desorption curve that in Fig. 2, a is KK-SBA, the adsorption desorption curve that in Fig. 2, b is KK-SBA-Mg-BU.Can find out that KK-SBA and KK-SBA-Mg-BU have the IV type thermoisopleth of sharp-pointed capillary condensation speed, this thermoisopleth has H
1hysteresis loop, this shows that KK-SBA and KK-SBA-Mg-BU have the aperture size distribution of homogeneous.
Fig. 3 is graph of pore diameter distribution, and wherein, X-coordinate is aperture, and unit is nm, the graph of pore diameter distribution that in Fig. 3, a is KK-SBA, the graph of pore diameter distribution that in Fig. 3, b is KK-SBA-Mg-BU.Can find out that KK-SBA has narrow pore size distribution, same KK-SBA-Mg-BU also has narrow pore size distribution.
Fig. 4 is stereoscan photograph, wherein, and the stereoscan photograph that in Fig. 4, a is KK-SBA, the stereoscan photograph that in Fig. 4, b is KK-SBA-Mg-BU; Stereoscan photograph has shown the microscopic appearance of each material.As shown in Figure 4, the microscopic appearance of KK-SBA and KK-SBA-Mg-BU is bar-shaped, and in electromicroscopic photograph, the length of rod is 2-20 micron, and the Rod-like shape of KK-SBA-Mg-BU remains unchanged, and still keeps bar-shaped (concrete data provide in table 1) preferably.
Table 1
Data from table 1 can find out, the pore structure parameter of KK-SBA-Mg-BU all decreases compared with KK-SBA, shows that methylaluminoxane/magnesium chloride complex compound and metallocene compound enter into the duct of KK-SBA really.
Results of elemental analyses demonstration, the aluminium content in KK-SBA-Mg-BU is 5.9 % by weight, and the content of Zr is 0.13 % by weight, and the mol ratio of Al/Zr is 152: 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 the KK-SBA-Mg-BU that adds 90.4 milligrams of embodiment, 1 preparation, rose to pressure maintain 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 2.7 * 10
8gPE/ (mol Zr h), bulk density (BD) is 0.3g/ml, melting index: MI
2.16=0.004g/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 the KK-SBA-Mg-BU that adds 80 milligrams of embodiment, 1 preparation, rose to pressure maintain 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 4.2 * 10
8mol Zr h), bulk density (BD) is 0.32g/ml, melting index: MI
2.16=0.39g/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 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, obtain catalyzer and by the supported catalyst called after Mg-BU of gained.
By ultimate analysis ICP result, show, the aluminium content of two (n-butyl cyclopentadienyl) zirconium dichlorides (BUCP) 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 93: 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 KK-SBA-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 1.5 * 10
8gPE/ (mol Zrh)), bulk density (BD) is 0.277g/ml, melting index: MI
2.16=0.083g/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 KK-SBA-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 8.1 * 10
7gPE/ (mol Zrh)), bulk density (BD) is 0.221g/ml, melting index: MI
2.16=0.269g/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 macropore mesoporous silicon oxide load methylaluminoxane and two (n-butyl cyclopentadienyl) zirconium dichlorides of metallocene compound
By 4.0 grams of triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (Aldrich companies, P123) and join in the solution (pH=4.4) of 37% 16.4ml hydrochloric acid and 128ml water, at 40 ℃, being stirred to polyoxyethylene-polyoxytrimethylene-polyoxyethylene dissolves completely, afterwards the tetraethoxy of 8.86g is joined in above-mentioned solution, 40 ℃ were stirred after 24 hours, solution is transferred in teflon-lined reactor again, at 150 ℃ baking oven crystallization after 24 hours through filtering, distilled water wash, after dry, obtain the former powder of macropore mesoporous silicon oxide.
By the former powder of previous step gained macropore mesoporous silicon oxide in retort furnace 600 ℃ of temperature lower calcinations 24 hours, removed template method, obtains the macropore mesoporous silicon oxide of removed template method.
By the macropore mesoporous silicon oxide of above-mentioned removed template method under nitrogen protection 400 ℃ calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the macropore mesoporous silicon oxide (called after KK-SBA) through thermal activation.
Under nitrogen protection; macropore mesoporous silicon oxide KK-SBA after 0.1 gram of thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced; 0.1 gram of methylaluminoxane 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, obtaining load has the KK-SBA-1 of methylaluminoxane (called after MAO/KK-SBA-1).
Under nitrogen protection; MAO/KK-SBA-1 is joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene; at 30 ℃; slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides of 28 milligrams (purchased from Alfa Aesar; article No. H27576), stirring reaction is 0.5 hour.After reaction finishes, standing, after layering, leach liquid, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after MAO/KK-SBA-BU-1).
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.
Table 2 is the pore structure parameter of macropore meso-porous titanium dioxide silicon carrier KK-SBA and carried metallocene catalyst MAO/KK-SBA-BU-1,
Table 2
Data by upper table 2 can be found out, macropore meso-porous titanium dioxide silicon carrier KK-SBA is after load methylaluminoxane and metallocene, pore volume, specific surface area and aperture all reduce to some extent, and this explanation metallocene in load-reaction process enters into the spheroid inside of coarse pored mesoporous silicon oxide.
Ultimate analysis ICP result shows, load the aluminium content of macropore mesoporous silicon oxide of two (n-butyl cyclopentadienyl) zirconium dichlorides (BUCP) of methylaluminoxane (MAO) and metallocene compound be 14.6%, the content of Zr is that the mol ratio of 0.5%, Al/Zr is 204: 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 KK-SBA-Mg-BU of embodiment 1 preparation is replaced by the catalyzer MAO/KK-SBA-BU-1 of comparative example 2 preparations of identical weight, and result catalytic efficiency is 3.4 * 10
7g PE/ (mol Zr h), poly bulk density (BD) is 0.22g/ml, melting index: MI
2.16=0.025g/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 KK-SBA-Mg-BU of embodiment 1 preparation is replaced by the catalyzer MAO/KK-SBA-BU-1 of comparative example 2 preparations of identical weight, and result catalytic efficiency is 2.4 * 10
7g PE/ (mol Zr h), the bulk density of multipolymer (BD) is 0.205g/ml, melting index: MI
2.16=0.058g/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 bar-shaped macropore mesoporous silicon oxide, this catalyzer could solve the problem that still is glued in polymerization.
Claims (20)
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 bar-shaped macropore mesoporous silicon oxide, the length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, and aspect ratio is 2-8:1, and specific surface area is 320-380 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 7-17 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; And
Aluminium in described alkylaluminoxane/magnesium chloride complex compound and the mol ratio of the M in described metallocene compound are 135-165:1.
2. catalyzer according to claim 1, wherein, M is zirconium, X is chlorine.
3. 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.
4. catalyzer according to claim 3, wherein, R
1and R
1' be normal-butyl independently of one another.
5. catalyzer according to claim 1, wherein, the alkyl in described alkylaluminoxane/magnesium chloride complex compound is C
1-C
5alkyl.
6. catalyzer according to claim 5, wherein, described alkylaluminoxane is methylaluminoxane.
7. catalyzer according to claim 1, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
8. catalyzer according to claim 1, wherein, the length of described bar-shaped macropore mesoporous silicon oxide is 3-15 micron, aspect ratio is 3-7:1, specific surface area is 340-360 meters squared per gram, and pore volume is 0.8-1.2 ml/g, and most probable aperture is 10-14 nanometer.
9. according to the catalyzer described in any one in claim 1-8, wherein, described bar-shaped macropore mesoporous silicon oxide is made by the method comprising the following steps: under template exists, tetraethoxy is contacted with acidic aqueous solution, and gained mixture crystallization under crystallization condition after contacting, by the heating of gained crystallization product, removed template method, described template is triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene, and described acidic aqueous solution is hydrochloric acid.
10. catalyzer according to claim 9, wherein, the pH value of described acidic aqueous solution is 1-6; The condition of described contact comprises: temperature is 25-60 ℃, and the time is within 25 minutes, to make above to dissolve; The condition of described crystallization comprises: temperature is 90-180 ℃, and the time is 10-40 hour; The condition of described removed template method comprises: temperature is 300-800 ℃, and the time is 5-40 hour.
11. catalyzer according to claim 9, wherein, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: water: hydrochloric acid: the mol ratio of tetraethoxy is 1:9000-15000:100-500:50-80.
The preparation method of 12. 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 bar-shaped macropore mesoporous silicon oxide, and the length of described bar-shaped macropore mesoporous silicon oxide is 2-20 micron, aspect ratio is 2-8:1, specific surface area is 320-380 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and most probable aperture is 7-17 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; And
Aluminium in described alkylaluminoxane/magnesium chloride complex compound and the mol ratio of the M in described metallocene compound are 135-165:1.
13. methods according to claim 12, wherein, the method be also included in 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 ℃.
14. methods according to claim 12, 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.
15. methods according to claim 12, wherein, respectively do for oneself one or more in hexane, pentane, heptane, benzene and toluene of described the first solvent and the second solvent.
16. methods according to claim 15, wherein, described the first solvent and the second solvent toluene of respectively doing for oneself.
17. methods according to claim 16, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, described alkylaluminoxane is methylaluminoxane.
18. methods according to claim 17, wherein, count in molar ratio bar-shaped macropore mesoporous silicon oxide: 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
-3-9 * 10
-3.
19. methods according to claim 12, 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 application of carried metallocene catalyst in 20. claim 1-11 described in any one in vinyl polymerization.
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| CN101423575A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst component and preparation method thereof and use |
| CN101723396A (en) * | 2009-11-26 | 2010-06-09 | 上海大学 | Hexagonal flaky sequential silicon-based mesoporous material SBA-15 and preparation method thereof |
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| CN101423575A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Supported metallocene catalyst component and preparation method thereof and use |
| CN101723396A (en) * | 2009-11-26 | 2010-06-09 | 上海大学 | Hexagonal flaky sequential silicon-based mesoporous material SBA-15 and preparation method thereof |
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| A. Carrero et al..Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials.《POLYMER ENGINEERING AND SCIENCE》.2008,第48卷(第3期), * |
| Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials;A. Carrero et al.;《POLYMER ENGINEERING AND SCIENCE》;20080122;第48卷(第3期);第606-616页 * |
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