CN102952216B - Olefin polymerization method - Google Patents
Olefin polymerization method Download PDFInfo
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- CN102952216B CN102952216B CN201110246887.9A CN201110246887A CN102952216B CN 102952216 B CN102952216 B CN 102952216B CN 201110246887 A CN201110246887 A CN 201110246887A CN 102952216 B CN102952216 B CN 102952216B
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- alkylaluminoxane
- magnesium chloride
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- cyclopentadienyl
- sba
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Abstract
The invention provides an olefin polymerization method which comprises the contact of one or more than one olefin with a supported metallocene catalyst under an olefin polymerization condition; the supported metallocene catalyst comprises a carrier, and an alkylaluminoxane/magnesium chloride complex and a metallocene compound which are supported on the carrier; the carrier is rodlike SBA-15; the metallocene compound has a structure as shown in formula 1, wherein M is one of titanium, zirconium and hafnium, and X is halogen. When the method of the invention is used for olefin polymerization, the catalytic efficiency for homopolymerization at 70 DEG C is up to 3.7*10<8>gPE/(mol Zr.h), and the catalytic efficiency for copolymerization at 70 DEG C is up to 3.2*10<8>gPE/(mol Zr.h); the method overcomes the defect of kettle adhesion, has a low polymerization temperature, and thus reduces the energy consumption to some extent. The formula 1 is as follows.
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 low for the polymerization activity of catalyzed polyethylene, 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, Pelgrims J, et al.Chem Eur J, 2000,6:2960.) with document 4 (Rao R R, Weckhuysen B M, Schoonheydt R A.Chem Commun, 1999,445.) in, the mesoporous material of load polyethylene catalysts-metallocene catalyst of report is MCM-41, but activity is only 7.3 × 10 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 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 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 the defect and the low carried metallocene catalyst of polymerization temperature that, how to obtain a kind of high catalytic activity and when for olefinic polymerization, can overcome sticky still remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The polymkeric substance that the catalytic activity 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 polymerization temperature, and a kind of olefine polymerizing process is efficiently provided.
The invention provides a kind of method of olefinic polymerization, 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 metallocene compound and the alkylaluminoxane/magnesium chloride complex compound on described carrier, described carrier is bar-shaped SBA-15, and 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 bar-shaped SBA-15 of 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 SBA-15 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, in the time of 70 DEG C, when homopolymerization, catalytic efficiency can reach 3.7 × 10
8gPE/ (mol Zrh), when copolymerization, catalytic efficiency can reach 3.2 × 10
8gPE/ (mol Zrh), uses 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, wherein, the x-ray diffraction pattern that a is SBA-15, the x-ray diffraction pattern that b is SBA-15-Mg-BU, X-coordinate unit be 2 θ (°), ordinate zou is intensity.
Fig. 2 is pore size distribution curve, wherein, the pore size distribution curve figure that a is SBA-15, the graph of pore diameter distribution that b is SBA-15-Mg-BU, X-coordinate is aperture, and unit is nm, and ordinate zou is dv/dlog, and unit is cm
3/ g.
Fig. 3 is N
2adsorption desorption graphic representation, wherein, wherein, the adsorption desorption graphic representation that a is SBA-15, the adsorption desorption graphic representation that b is SBA-15-Mg-BU, X-coordinate is relative pressure, unit is p/p
0, ordinate zou is pore volume absorption, unit is cm
3/ gSTP.
Fig. 4 is stereoscan photograph, wherein, and a
1and a
2(be a
1partial enlarged drawing) be the stereoscan photograph of SBA-15, b
1and b
2(be b
1partial enlarged drawing) be the stereoscan photograph of SBA-15-Mg-BU.
Embodiment
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 metallocene compound and the alkylaluminoxane/magnesium chloride complex compound on described carrier, described carrier is bar-shaped SBA-15, and 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 100-200 meters squared per gram, more preferably 150 meters squared per gram; Pore volume can be 0.2-0.8 ml/g, more preferably 0.5 ml/g; Most probable aperture can 2-8 nanometer, more preferably 5.0 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 90-150: and 1, more preferably 110-130: 1, most preferably be 119: 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.
According to 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.
According to the present invention, 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 magnesium chloride as the carrier loaded material of metallocene auxiliary agent; 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, described carrier is bar-shaped SBA-15.SBA-15 is a kind of mesoporous material, conventionally has various microscopic appearances, as bar-shaped, donut-like etc.The present inventor's discovery, bar-shaped SBA is as carrier and alkylaluminoxane/magnesium chloride complex compound and metallocene compound mating reaction, and the catalyzer of acquisition can solve the sticky still problem of prior art.Under preferable case, the length of described bar-shaped SBA-15 is 30-150 micron, and aspect ratio can be 2-12: 1; The most probable aperture of described SBA-15 can be 6-10 nanometer, is preferably 6-7 nanometer, more preferably 6.2 nanometers; Pore volume can be 0.5-1.5 ml/g, is preferably 0.8-1.2 ml/g, more preferably 1.0 mls/g; Specific surface area can be 600-700 meters squared per gram, is preferably 630-660 meters squared per gram, more preferably 646 meters squared per gram.
The mesoporous material SBA-15 of above-mentioned specification has the wide aperture of high-sequential, larger specific surface area and relatively large pore volume, high mechanical strength and good catalytic adsorption performance, can process larger molecule or group, in load after alkylaluminoxane/magnesium chloride complex compound and metallocene compound, can obtain a Stability Analysis of Structures, bar-shaped metallocene catalyst, this stable structure makes alkylaluminoxane/magnesium chloride complex compound of load and metallocene compound can be good at bringing into play its catalytic activity.
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, is further preferably 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, is further preferably 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.The mol ratio of aluminium in described alkylaluminoxane/magnesium chloride complex compound and the M in described metallocene compound can be 50-200: 1, be preferably 90-150: and 1, more preferably 110-130: 1, most preferably be 119: 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; bar-shaped described carrier SBA-15 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 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 10-70 DEG C, is further 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.
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 base 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.
According to the present invention, in the time of polymerization, 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, described alkene can be one or more in ethene, alpha-olefin and diolefin.Preferably, described alkene is ethene, C
3-C
101-alkene, C
4-C
8diolefin in one or more.More preferably, described alkene is one or more in ethene, 1-butylene, 1-amylene and 1-hexene.
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 S BA-15 and load and metallocene compound, measures the content of aluminium and metal M in carried metallocene catalyst by ultimate analysis.
Below by concrete preparation example, the present invention is further described.
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.
Described bar-shaped SBA-15 is available commercially from high-tech share company limited of Changchun Jilin University; Described methylaluminoxane is purchased from company of the U.S. 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 method thereof.
(1) thermal activation step, under nitrogen protection, in 400 DEG C of calcinings 10 hours, obtains the bar-shaped SBA-15 after thermal activation by bar-shaped SBA-15;
(2) under nitrogen protection, 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, add 30 milliliters of refining toluene, wash 2 times in 30 DEG C of stirrings, within each 30 minutes, 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.
(3) under nitrogen protection; bar-shaped SBA-15 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 also by this carried metallocene catalyst called after SBA-15-Mg-BU.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, and 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 the XRD Structure Comparison figure of bar-shaped SBA-15 and SBA-15-Mg-BU.The XRD spectra that wherein in figure, a is bar-shaped SBA-15, the XRD spectra that in figure, b is SBA-15-Mg-BU.From XRD spectra, can find out significantly that sample SBA-15 and SBA-15-Mg-BU all occur diffraction peak in little angular region, illustrate that bar-shaped SBA-15 and SBA-15-Mg-BU have the hexagonal hole road structure of good long-range order.
Fig. 2 is the graph of pore diameter distribution of bar-shaped SBA-15 and SBA-15-Mg-BU, wherein, and the graph of pore diameter distribution that a is SBA-15, the graph of pore diameter distribution that b is SBA-15-Mg-BU.SBA-15-Mg-BU has narrow pore size distribution as can be seen from Figure 2, with bibliographical information (Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50to300AngstromPores.D.Y.Zhao in full accord, J.L.Feng, Q.S.Huo, N.Melosh, G.H.Fredrickson, B.F.Chmelka, G.D.Stucky, Science 279 (1998) 548).
Fig. 3 is the N of bar-shaped SBA-15 and SBA-15-Mg-BU
2adsorption desorption graphic representation, wherein, the N that a is SBA-15
2adsorption desorption graphic representation, the N that b is SBA-15-Mg-BU
2adsorption desorption graphic representation, can find out that SBA-15-Mg-BU has the IV type thermoisopleth of sharp-pointed capillary condensation speed, this thermoisopleth has H1 hysteresis loop, and this shows that SBA-15-Mg-BU has the aperture size distribution of homogeneous, and this conclusion is also confirmed in pore size distribution curve spectrogram.
Fig. 4 is the microscopic appearance figure of bar-shaped SBA-15 and SBA-15-Mg-BU.Wherein scheme a
1and a
2(be a
1partial enlarged drawing) be the microscopic appearance figure of bar-shaped SBA-15, b
1and b
2(be b
1partial enlarged drawing) be the microscopic appearance figure of SBA-15-Mg-BU, as seen from the figure, the microscopic appearance figure of bar-shaped SBA-15 and SBA-15-Mg-BU is bar-shaped.
Table 1 is bar-shaped SBA-15 and SBA-15-Mg-BU pore structure parameter.
Table 1
Data by upper table 1 can be found out, bar-shaped SBA-15 all reduces to some extent at pore structure parameter after alkylaluminoxane/magnesium chloride complex compound and two (n-butyl cyclopentadienyl) zirconium dichloride (BUCP) loads of metallocene compound, and this result shows that alkylaluminoxane/magnesium chloride complex compound and two (n-butyl cyclopentadienyl) zirconium dichlorides (BUCP) of metallocene compound enter into mesoporous material duct really.
Show by ultimate analysis ICP result, the aluminium content of the bar-shaped SBA-15 of two (n-butyl cyclopentadienyl) zirconium dichlorides (BUCP) of load alkylaluminoxane/magnesium chloride complex compound and metallocene compound is 6.0 % by weight, the content of Zr is 0.17 % by weight, and the mol ratio of Al/Zr is 119: 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 add 80 milligrams of SBA-15-Mg-BU prepared by preparation example 1, pressure is risen to and maintained 1.0MPa, 70 DEG C of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 3.7 × 10
8gPE/ (mol Zrh), bulk density (BD) is 0.234g/ml, melting index: MI
216=0.06g/10min.And observe and find the sticky still phenomenon of the interior not appearance of polymerization reaction kettle.
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 add 85 milligrams of SBA-15-Mg-BU, pressure is risen to and maintained 1.0MPa, 70 DEG C of reactions 1 hour.After polyreaction finishes, catalytic efficiency is 3.2 × 10
8gPE/ (mol Zrh), bulk density (BD) is 0.211g/ml, melting index: MI
2.16=0.146g/10min.Observe and find the sticky still phenomenon of the interior not appearance of polymerization reaction kettle.
Preparation comparative example 1
This prepares comparative example for 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 are described
Under anhydrous and oxygen-free condition, 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 this and prepare carried metallocene catalyst prepared by comparative example 1 also by this carried metallocene catalyst called after Mg-BU.
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 94: 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 SBA-15-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 1 of identical weight replaces, and result catalytic efficiency is 7.8 × 10
7gPE/ (mol Zrh), bulk density (BD) is 0.277g/ml, melting index: MI
216=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 SBA-15-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 1 of identical weight replaces, and result catalytic efficiency is 2.9 × 10
7gPE/ (mol Zrh), bulk density (BD) is 0.221g/ml, melting index: MI
216=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 bar-shaped SBA-15 load methylaluminoxane and metallocene compound are described
By bar-shaped SBA-15 (originating identical with embodiment 1) 400 DEG C of calcinings 10 hours (thermal activation) under nitrogen protection, remove hydroxyl and remaining moisture, obtain the rod-like mesoporous material after thermal activation;
0.4 gram of rod-like mesoporous material after thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, adds 10 milliliters of refining toluene, 0.47 gram of methylaluminoxane auxiliary agent stirs 4 hours in 50 DEG C.After, then with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen, obtain methylaluminoxane/SBA-15 complex compound carrier (MAO/SBA-15).
Under nitrogen protection; methylaluminoxane/SBA-15 complex compound carrier is joined in reactor; add 20 milliliters of refining toluene; slurries are made in stirring; at 30 DEG C; the toluene solution of two (n-butyl cyclopentadienyl) zirconium dichlorides of metallocene compound that slowly dropping 10ml contains 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, 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 this and prepare carried metallocene catalyst prepared by comparative example 2 and by this carried metallocene catalyst called after SBA-15-MAO-BU.
Results of elemental analyses shows, load the content of aluminium of bar-shaped SBA-15 of two (n-butyl cyclopentadienyl) zirconium dichlorides of promotor methylaluminoxane (MAO) and metallocene compound be 21.3 % by weight, the content of Zr is 0.70 % by weight, and the mol ratio of Al/Zr is 102: 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 catalyst S BA-15-MAO-BU that SBA-15-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 2 of identical weight replaces, and result catalytic efficiency is 8.4 × 10
7gPE/ (mol Zrh), bulk density (BD) is 0.326g/ml, melting index: MI
216=0.061g/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 catalyst S BA-15-MAO-BU that SBA-15-Mg-BU prepared by preparation example 1 is prepared by the preparation comparative example 2 of identical weight replaces, and result catalytic efficiency is 7.5 × 10
7gPE/ (mol Zrh), bulk density (BD) is 0.293g/ml, melting index: MI
216=0.401g/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 SBA-15, this catalyzer could solve the problem of the sticky still of polymerization.
Claims (12)
1. the method for an olefinic polymerization, 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 metallocene compound and the alkylaluminoxane/magnesium chloride complex compound on described carrier, wherein, described carrier is bar-shaped SBA-15, the length of described bar-shaped SBA-15 is 30-150 micron, aspect ratio is 2-12:1, most probable aperture is 6-7nm, and specific surface area is 630-660m
2/ g, pore volume is 0.8-1.2 ml/g; 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; And
The mol ratio of aluminium in described alkylaluminoxane/magnesium chloride complex compound and the M in described metallocene compound is 110-130:1.
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, described alkene is ethene and/or alpha-olefin, described alpha-olefin is selected from one or more in propylene, butylene, amylene, hexene and octene.
9. method according to claim 8, wherein, described hexene is 4-methylpentene-1.
10. method according to claim 8, wherein, described alkene is ethene.
11. 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.
12. methods according to claim 11, wherein, in metallocene compound, the concentration of described carried metallocene catalyst is 1 × 10
-8-1 × 10
-5mol/L.
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