CN102952217B - Alkene polymerization method - Google Patents
Alkene polymerization method Download PDFInfo
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- CN102952217B CN102952217B CN201110247195.6A CN201110247195A CN102952217B CN 102952217 B CN102952217 B CN 102952217B CN 201110247195 A CN201110247195 A CN 201110247195A CN 102952217 B CN102952217 B CN 102952217B
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- alkylaluminoxane
- magnesium chloride
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Abstract
The invention provides an alkene polymerization method which comprises contacting one or more alkenes with a load-type metallocene catalyst under an alkene polymerization condition, wherein the load-type metallocene catalyst comprises a carrier and an alkyl aluminoxane/magnesium chloride complex and a metallocene compound loaded on the carrier, the carrier is rod-shaped macroporous mesoporous silica, and the metallocene compound has a structure as shown in formula 1. When used for catalyzing the alkene polymerization, the load-type metallocene catalyst provided by the invention has a catalytic efficiency up to 2.7*10<8>gPE/(mol Zr*h) during homopolymerization and a catalytic efficiency up to 4.2*10<8>gPE/(mol Zr*h) during 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 olefine polymerizing process.
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 has an effect as a kind of special part and active centre, 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.
Document 3 (Weckhuysen B M at present, 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.ChemCommun, 1999,445.) in, the mesoporous material of load polyethylene catalysts-metallocene catalyst of report is MCM-41, but activity is only 7.3 × 10 when catalyzed ethylene polymerization
5(mol Zr h) for gPE/; Document 5 (Chen S T, Guo C Y, Lei L, et al.Polymer, 2005,46:11093.) report is taking catalytic activity after the MCM-41 of load metallocene carries out vinyl polymerization again after MAO processes as 10
6(mol Zr h) for gPE/; 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, just there is part to cave at loading process hole wall, 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 processing through MAO upper and obtain.But the catalytic activity of the disclosed carried metallocene catalyst of CN1718596A needs further to improve.
CN1923862A discloses a kind of olefin polymerization catalysis of mesoporous molecular sieve carried, and this catalyzer is that the SBA-15 processing through MAO is upper to be obtained by the semi-sandwich alum metallic compound shown in following formula is loaded on,
But the catalytic activity of the disclosed catalyzer of CN1923862A is the highest also only has 106gPE/ (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 DEG C, 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 in the time 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 that the object of the invention is to the carried metallocene catalyst that overcomes prior art is lower, obtain during for olefinic polymerization is easy to sticky still and the high problem of energy consumption, and a kind of olefine polymerizing process is efficiently provided.
The invention provides a kind of olefine polymerizing process, the method is included under olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, it is characterized in that, described carried metallocene catalyst comprises carrier and loads on alkylaluminoxane/magnesium chloride complex compound and the metallocene compound on described carrier, 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, 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 one, 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 the one in titanium, zirconium and hafnium; X is halogen.
The carried metallocene catalyst adopting according to olefine polymerizing process of the present invention, alkylaluminoxane/magnesium chloride complex compound and metallocene compound are loaded on the macropore mesoporous silicon oxide of wide-aperture and good catalytic adsorption performance, can obtain a Stability Analysis of Structures, the carried metallocene catalyst that catalytic activity is high, therefore has high catalytic activity.
Olefine polymerizing process according to the present invention is because the bar-shaped macropore mesoporous silicon oxide of described carrier adopting has high catalytic activity, thereby method of the present invention has higher polymerization efficiency or catalytic efficiency.
And, no matter for the homopolymerization of alkene, or for the copolymerization of alkene, all demonstrate high catalytic efficiency according to olefine polymerizing process of the present invention.Particularly, while adopting method of the present invention to carry out olefinic polymerization, catalytic efficiency catalytic efficiency in the time of 70 DEG C of homopolymerizations can reach 2.7 × 10
8gPE/ (mol Zrh), when copolymerization, catalytic efficiency can reach 4.2 × 10
8gPE/ (mol Zrh),, and in the situation that other conditions are identical, the catalytic efficiency while using the disclosed semi-sandwich alum metallic compound of CN1923862A to load on the catalyzer on the SBA-15 processing through MAO under 80 DEG C of conditions is 5.1 × 10
7(mol Zr h) for gPE/; Use the open Cp of CN1718596A
2zrCl
2while loading on the catalyzer on the SBA-15 processing through MAO, catalytic efficiency is 10
6gPE/ (mol Zrh).
Brief description of the drawings
Fig. 1 is X-ray diffracting spectrum, and wherein, in Fig. 1, a is the X-ray diffraction curve that in KK-SBA and Fig. 1, b is KK-SBA-Mg-BU, X-coordinate unit be 2 θ (
0), ordinate zou is intensity.
Fig. 2 is N
2adsorption desorption graphic representation, wherein, in Fig. 2 a be adsorption desorption curve that in KK-SBA and Fig. 2, b is KK-SBA-Mg-BU 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.
Concrete preparation method
The invention provides a kind of olefine polymerizing process, the method is included under olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, it is characterized in that, described carried metallocene catalyst comprises carrier and loads on alkylaluminoxane/magnesium chloride complex compound and the metallocene compound on described carrier, described carrier is macropore mesoporous silicon oxide, 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, 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 one, 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 the one in titanium, zirconium and hafnium; X is halogen.
According to 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 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, described alkylaluminoxane/magnesium chloride complex compound and the charge capacity of metallocene compound on described carrier are taking the total amount of described carried metallocene catalyst as 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.Taking the total amount of described alkylaluminoxane/magnesium chloride complex compound as benchmark, 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 the known ratio of technician of field of olefin polymerisation.Particularly, the mol ratio of the aluminium in described alkylaluminoxane/magnesium chloride complex compound and the M in described metallocene compound can be 50-200: 1, be preferably 135-165: and 1, more preferably 140-160: 1, most preferably be 152: 1.
According to the present invention, the M in formula 1 can be the one in titanium, zirconium and hafnium.M in different metallocene compound molecules can be identical or different, and preferably, M is zirconium.
According to the present invention, the X in formula 1 is halogen.Particularly, the X in formula 1 can be the one in fluorine, chlorine, bromine and iodine.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 the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
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 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 the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.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, be ball milling 0.1-100 hour preferred 0.5-72 hour at 15-100 DEG C of preferred 25-50 DEG C by Magnesium Chloride Anhydrous and alkylaluminoxane in temperature.
According to the present invention, the size of described macropore meso-porous titanium dioxide silicon carrier can in very large range change, under preferable case, described macropore mesoporous silicon oxide 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 be by 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, taking the total amount of described carried metallocene catalyst as benchmark, 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.
Taking the total amount of described alkylaluminoxane/magnesium chloride complex compound as benchmark, 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 the known ratio of technician of field of olefin polymerisation.Particularly, the mol ratio of the aluminium in described alkylaluminoxane/magnesium chloride complex compound and the M in described metallocene compound can be 50-200: 1, be preferably 135-165: and 1, more preferably 140-160: 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, the condition of described contact comprises: temperature is 25-60 DEG C, and the time is above extremely dissolving in 25 minutes, and described crystallization condition comprises: crystallization temperature can be 90-180 DEG C, be preferably 140-160 DEG C; 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 DEG C, is preferably 300-600 DEG C; Time can be 5-40 hour, is preferably 15-35 hour.
According to the present invention, in the bar-shaped macropore mesoporous silicon oxide process of preparation, in the time that 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, described carried metallocene catalyst can be by 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, described alkylaluminoxane/magnesium chloride complex compound and the charge capacity of metallocene compound on described carrier are taking the total amount of described carried metallocene catalyst as 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.Taking the total amount of described alkylaluminoxane/magnesium chloride complex compound as benchmark, 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 mol ratio of the aluminium in described alkylaluminoxane/magnesium chloride complex compound and the M in described metallocene compound can be 50-200: 1, be preferably 135-165: and 1, more preferably 140-160: 1, most preferably be 152: 1.
According to the present invention, kind and the content of described carrier, alkylaluminoxane/magnesium chloride complex compound and metallocene compound are described above, do not repeat them here.
According to the present invention, 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 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 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.
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, contact 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.Adopt the method for dipping can make solution enter more fully in the duct on carrier, therefore, the present invention is preferably flooded.
According to the present invention, carrier and the first solution are carried out to first to be contacted with the second solution second condition contacting of carrying out and is 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 DEG C; 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 DEG C.According to the present invention, can adopt the method for well known to a person skilled in the art to remove described the first solvent and the second solvent, for example: can be at the temperature of 20-40 DEG C, purge to remove described the first solvent and the second solvent with nitrogen.
According to the present invention, in the time that described the first solvent and/or the second solvent are toluene, toluene preferably adopts and well known to a person skilled in the art that method refines before use, for example: can within 24-48 hour, refine by toluene is refluxed on sodium, with except impurity such as water in desolventizing.
The method according to this invention be also included in by carrier and the first solution carry out first contact before; under protection of inert gas; described carrier spherical mesoporous material is heated to 7-10 hour at the temperature of 300-900 DEG C; for example, to remove the volatile matter (: water) containing in the hydroxyl of carrier surface and carrier, obtain the rod-like mesoporous material after thermal activation.
According to the present invention, described rare gas element can be variously with carrier, alkylaluminoxane, magnesium chloride, alkylaluminoxane/magnesium chloride complex compound, metallocene compound, chemically interactive various gas not to occur.For example, described rare gas element can be nitrogen, argon gas.
According to the present invention, the preparation method of described carried metallocene catalyst, 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 DEG C 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 DEG C of temperature;
The 3rd step, is placed in closed reactor by previous step gained solution, and crystallization 10-40 hour at 90-180 DEG C 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 bar-shaped previous step gained macropore mesoporous silicon oxide in retort furnace at 300-800 DEG C 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 DEG C of calcining thermal activation in 7-10 hour, obtains the macropore mesoporous silicon oxide after thermal activation by bar-shaped previous step gained macropore mesoporous silicon oxide;
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, be at 15-100 DEG C in temperature, with the rotating speed continuously grinding reaction 0.1-100 hour of 200-1000 rev/min, under nitrogen protection, take out pressed powder, by this pressed powder solvent wash, finally dry up as nitrogen with rare gas element, obtain alkylaluminoxane/magnesium chloride complex compound, can be wherein hexane for the described solvent washing, 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 (taking aluminium content meter): the amount ratio of metallocene compound is 1: 3-10: 0.1-1: 1 × 10
-3-9 × 10
-3, under 25 DEG C to 80 DEG C agitation conditions, slowly metallocene compound solution being added drop-wise in reactor, stirring reaction 0.5-10 hour, after reaction finishes, leaves standstill, and leaches liquid, by toluene wash, dries up with nitrogen, obtains 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 DEG C, 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 DEG C, and the reaction times is preferably 0.3-2 hour.
It should be noted that, in the time that 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 the molecular weight of for example methylaluminoxane is with CH
3alO meter is 58.
According to olefine polymerizing process of the present invention, because the present invention is efficiency by improve polyreaction with described carried metallocene catalyst, therefore the present invention is not particularly limited for described olefinic polymerization condition.It can be the known polymerizing condition of technician of field of olefin polymerisation.Preferably, in metallocene compound, the concentration of described carried metallocene catalyst can be 1 × 10
-8mol/L-1 × 10
-3mol/L, preferred concentration range is 1 × 10
-8mol/L-1 × 10
-5mol/L.
Polymerization temperature be-78 DEG C to 100 DEG C, be preferably 0-90 DEG C, more preferably 70 DEG C.
Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa, more preferably 1.0MPa.
According to olefine polymerizing process of the present invention, described one or more alkene can carry out with contacting of described carried metallocene catalyst under the existence of solvent.Described solvent is preferably and replaces or unsubstituted alkane or replacement or unsubstituted aromatic hydrocarbons.In the time that described alkane and aromatic hydrocarbons have substituting group, described substituting group is preferably halogen.More preferably, described solvent is one or more in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform and methylene dichloride, most preferably is one or more in hexane, toluene and heptane.
The consumption of described solvent can carry out appropriate selection according to concrete use occasion.Preferably, to make the concentration of described carried metallocene catalyst be 1 × 10 to the consumption of described solvent
-8-1 × 10
-3mol/L, is preferably 1 × 10
-8-1 × 10
-5mol/L.
According to olefine polymerizing process of the present invention, described one or more alkene carry out under the solution that contains aluminum alkyls and/or alkylaluminoxane exists with contacting preferably of described carried metallocene catalyst.,, according to olefine polymerizing process of the present invention, preferably, in the time carrying out polymerization, in reaction system, supplement the solution that interpolation contains aluminum alkyls and/or alkylaluminoxane.Play the effect of cleaning reaction poisonous substance in the aluminum alkyls in solution and/or alkylaluminoxane with together with alkylaluminoxane/magnesium chloride complex compound on loading on described carrier, thereby the metallocene compound that makes to load on described carrier can be brought into play katalysis better.
According to olefine polymerizing process of the present invention, when the solution that containing aluminum alkyls and/or alkylaluminoxane with contacting of described carried metallocene catalyst at described one or more alkene carries out under existing, the mol ratio of the M in described aluminum alkyls and described alkylaluminoxane (comprising alkylaluminoxane/magnesium chloride complex compound of loading on described carrier and the alkylaluminoxane in solution) in whole aluminium and described metallocene compound can be 100-3000: 1.
According to the present invention, described aluminum alkyls can be the aluminum alkyls of the known various promotors as metallocene catalyst of the technician of field of olefin polymerisation; Preferably, the alkyl in described aluminum alkyls can be C
1-C
5alkyl; More preferably, can be 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. as the aluminum alkyls of promotor; Further be preferably triethyl aluminum.
According to the present invention, in the time of 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 is a kind of in hexane, toluene, heptane or their mixture.
Alkylaluminoxane in solution can be identical with the kind that loads on the alkylaluminoxane (, the alkylaluminoxane that the supplementary alkylaluminoxane adding contains with described carried metallocene catalyst) on described carrier, also can be different; Be preferably identical.
According to olefine polymerizing process of the present invention, can be polymerization or the copolymerization of alkene, particularly ethylene homo closes or the copolymerization of ethene and other alpha-olefin, and 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 HS and load and metallocene compound, measures the content of aluminium and metal M in carried metallocene catalyst by ultimate analysis.
Below in conjunction with embodiment, the present invention is described in detail.
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.
In following preparation example, X-ray diffraction analysis carries out on the X-ray diffractometer that purchased from the model of German Bruker AXS company is D8 Advance; In the scanning electronic microscope that scanning electron microscope analysis is XL-30 in the model purchased from FEI Co. of the U.S., carry out; Ultimate analysis is being to carry out on 7500CX instrument purchased from the model of An Jielun company of the U.S.; Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption instrument, sample is degassed 4 hours at 200 DEG C.
In following preparation example, 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 company of the U.S. refined treasured (Albemarle); Two (n-butyl cyclopentadienyl) zirconium dichlorides of described metallocene compound are purchased the company from Aldrich.
Preparation example 1
This preparation example is for illustrating according to carried metallocene catalyst of the present invention and preparation 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 DEG C, being stirred to polyoxyethylene-polyoxytrimethylene-polyoxyethylene dissolves completely, afterwards the tetraethoxy of 8.86g is joined in above-mentioned solution, 40 DEG C were stirred after 24 hours, again solution is transferred in teflon-lined reactor, at 150 DEG C baking oven crystallization after 24 hours through filtration, 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 DEG C 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 DEG C 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, wash 3 times each 30 minutes in 30 DEG C of stirrings.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; Calculate according to feed ratio, taking the total amount of described alkylaluminoxane/magnesium chloride complex compound as benchmark, 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 DEG C, 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, leave standstill, 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 calculate according to weight × 100% of the weight/carried metallocene catalyst of the carrier of the content of carrier=add, taking the total amount of described carried metallocene catalyst as 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.
This carried metallocene catalyst is characterized with XRD, the experiment of nitrogen adsorption-desorption, scanning electron microscope, X-ray energy spectrometer and ICP ultimate analysis.
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, 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.
Embodiment 1
The present embodiment is used for illustrating olefine polymerizing process of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with the each displacement of nitrogen and ethene three times, then add 200 milliliters of hexane solvents, by still temperature rise to 70 DEG C, 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 preparation examples 1 to prepare, rose to pressure maintain 1.0MPa, 70 DEG C of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 2.7 × 10
8(h), bulk density (BD) is 0.3g/ml to mol Zr to gPE/, melting index: MI
2.16=0.004g/10min.
Embodiment 2
The present embodiment is used for illustrating olefine polymerizing process of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with the each displacement of nitrogen and ethene three times, then add 200 milliliters of hexane solvents, by still temperature rise to 70 DEG C, 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 preparation examples 1 to prepare, rose to pressure maintain 1.0MPa, 70 DEG C of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 4.2 × 10
8mol Zr is h)), bulk density (BD) is 0.32g/ml, melting index: MI
2.16=0.39g/10min.
Preparation 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, wash three times each 30 minutes in 30 DEG C of stirrings.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 DEG C; 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, leave standstill, 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.
Show by ultimate analysis ICP result, 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.
Comparative example 1
This comparative example is for illustrating the application of the catalyzer prepared of preparation comparative example 1 in olefinic polymerization
Carry out polyreaction according to the method for embodiment 1, different, the Mg-BU that KK-SBA-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 1 of identical weight replaces, 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 using sharp weapon will in reactor, scrape totally.
Comparative example 2
This comparative example is for illustrating the application of the catalyzer prepared of preparation comparative example 1 in olefinic polymerization
Carry out polyreaction according to the method for embodiment 2, different, the Mg-BU that KK-SBA-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 1 of identical weight replaces, 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 using sharp weapon will in reactor, scrape totally.
Preparation comparative example 2
This prepares comparative example for preparation and the application thereof of two (n-butyl cyclopentadienyl) zirconium dichlorides of macropore mesoporous silicon oxide load methylaluminoxane and metallocene compound are described
By 4.0 grams of triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (Aldrich companies, and join in the solution (pH=4.4) of 37% 16.4ml hydrochloric acid and 128ml water P123), at 40 DEG C, being stirred to polyoxyethylene-polyoxytrimethylene-polyoxyethylene dissolves completely, afterwards the tetraethoxy of 8.86g is joined in above-mentioned solution, 40 DEG C were stirred after 24 hours, again solution is transferred in teflon-lined reactor, at 150 DEG C baking oven crystallization after 24 hours through filtration, 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 DEG C 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 DEG C 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 alkylaluminoxane joins in reactor; add 5 milliliters of refining toluene; slurries are made in stirring; at 30 DEG C, 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, leave standstill, 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 DEG C; slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides of 28 milligrams (purchased from Alfa Aesar; article No. H27576), stirring reaction 0.5 hour.After reaction finishes, leave standstill, after layering, leach liquid, by 10 milliliters of toluene wash three times, then, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after MAO/KK-SBA-BU-1).
This carried metallocene catalyst is characterized with XRD, the experiment of nitrogen adsorption-desorption, scanning electron microscope, X-ray energy spectrometer and ICP ultimate analysis.
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.
Comparative example 3
This comparative example is for illustrating the application of the catalyzer prepared of preparation comparative example 2 in olefinic polymerization
Carry out polyreaction according to the method for embodiment 1, different, the catalyzer MAO/KK-SBA-BU-1 that KK-SBA-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 2 of identical weight replaces, and result catalytic efficiency is 3.4 × 10
7(h), poly bulk density (BD) is 0.22g/ml to mol Zr to g PE/, melting index: MI
2.16=0.025g/10min.And observe in discovery polymerization reaction kettle and occur serious sticky still phenomenon need to using sharp weapon will in reactor, scrape totally.
Comparative example 4
This comparative example is for illustrating the application of the catalyzer prepared of preparation comparative example 2 in olefinic polymerization
Carry out polyreaction according to the method for embodiment 2, different, the catalyzer MAO/KK-SBA-BU-1 that KK-SBA-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 2 of identical weight replaces, and result catalytic efficiency is 2.4 × 10
7(h), the bulk density of multipolymer (BD) is 0.205g/ml to mol Zr to g PE/, melting index: MI
2.16=0.058g/10min.And observe in discovery polymerization reaction kettle and occur serious sticky still phenomenon need to using sharp weapon will in reactor, scrape totally.
The polymerization result of embodiment 1-2 and comparative example 1-4 is contrasted 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 of the sticky still of polymerization.
Claims (15)
1. the polymerization process of an alkene, the method is included under olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, it is characterized in that, described carried metallocene catalyst comprises carrier and loads on alkylaluminoxane/magnesium chloride complex compound and the metallocene compound on described carrier, 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, 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 one, 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 the one in titanium, zirconium and hafnium; X is halogen;
Wherein, taking the total amount of described carried metallocene catalyst as benchmark, 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; Taking the total amount of described alkylaluminoxane/magnesium chloride complex compound as benchmark, the content of described alkylaluminoxane is 1-50 % by weight, and the content of described magnesium chloride is 50-99 % by weight;
Wherein, the mol ratio of the aluminium in described alkylaluminoxane/magnesium chloride complex compound and the M in described metallocene compound is 135-165:1.
2. method according to claim 1, wherein, M is zirconium, X is chlorine.
3. method 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. method according to claim 3, wherein, R
1and R
1' be normal-butyl independently of one another.
5. method according to claim 1, wherein, the alkyl in described alkylaluminoxane/magnesium chloride complex compound is C
1-C
5alkyl.
6. method according to claim 5, wherein, described alkylaluminoxane is methylaluminoxane.
7. method according to claim 1, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
8. method 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 method 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. method 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 DEG C, and the time is above extremely dissolving in 25 minutes; The condition of described crystallization comprises: temperature is 90-180 DEG C, and the time is 10-40 hour; The condition of described removed template method comprises: temperature is 300-800 DEG C, and the time is 5-40 hour.
11. methods 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.
12. methods according to claim 1, wherein, described alkene is ethene and/or alpha-olefin, described alpha-olefin is selected from propylene, butylene, amylene, one or more in alkene, octene, 4-methylpentene-1.
13. methods according to claim 12, wherein, described alkene is ethene.
14. methods according to claim 1, wherein, described contact is carried out under solvent exists, and described olefinic polymerization condition comprises: in metallocene compound, the concentration of described carried metallocene catalyst is 1 × 10
-8-1 × 10
-3mol/L, temperature is-78 DEG C to 100 DEG C, pressure is 0.01-10MPa.
15. methods according to claim 14, wherein, described olefinic polymerization condition comprises: in metallocene compound, the concentration of described carried metallocene catalyst is 1 × 10
-8-1 × 10
-5mol/L.
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|---|---|---|---|---|
| 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 |
| EP1799726B1 (en) * | 2004-10-12 | 2011-07-13 | ExxonMobil Chemical Patents Inc. | Trialkylaluminum treated supports |
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2011
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