CN102453138B - Olefin polymerization method - Google Patents
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- CN102453138B CN102453138B CN201010519335.6A CN201010519335A CN102453138B CN 102453138 B CN102453138 B CN 102453138B CN 201010519335 A CN201010519335 A CN 201010519335A CN 102453138 B CN102453138 B CN 102453138B
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Abstract
The invention provides a high-efficiency olefin polymerization method, which comprises a step of: contacting one or more olefins with a supported metallocene composite catalyst under the olefin polymerization conditions, wherein the supported metallocene composite catalyst comprises a carrier, and specific metallocene compound and alkyl aluminoxane which are supported on the carrier; and the carrier is a complex of SBA-15 like a bread circle and silica gel. When the supported metallocene composite catalyst prepared by supporting the metallocene which has a sandwich structure and of which the cpcyclopentadienyl has substituent to a methyl aluminoxane (MAO) treated carrier, namely the complex of the SBA-15 like a bread circle and the silica gel is used for olefin polymerization, the olefin polymerization efficiency is greatly improved.
Description
Technical field
The present invention relates to a kind of olefine polymerizing process.
Background technology
The Application and Development of metallocene catalyst is after traditional Ziegler-Natta catalyst, the another important breakthrough in olefin polymerization catalysis field, particularly in the eighties, the people such as Kaminsky and Sinn develops efficient promotor methylaluminoxane (MAO), makes the research of metallocene catalyst enter into a stage developed rapidly.Due to catalyzed by homogeneous metallocene catalyst, to reach the required MAO consumption of high reactivity large, and production cost is high, and can not obtain granular polymkeric substance, can't on widely used slurry process or gas phase polymerization technique, use.In order addressing the above problem, usually to adopt the solubility metallocene catalyst is loaded to the method for carrying out supported metallocene on carrier.At present, at relevant supported metallocene, study in report with SiO
2report most study for carrier.Especially aspect support/catalyst/co-catalyst system research, remarkable progress having been arranged, promoted further developing of carried catalyst and polyolefin industry.
Molecular sieve is to have evenly regular one dimension or the material of solid netted sieve aperture, and surfactivity is higher, absorption property good, have obvious molecule shape selectivity energy, and it allows the monomer of certain size and the polymkeric substance of formation thereof to insert in the duct of molecular sieve.Because molecular sieve has nano pore, in polymerization process, the inserted mode of monomer is different from freeboard with propagation process, and the chance that double-basis stops has been reduced in limited space to a certain extent, makes polyreaction show the feature of " living polymerization ".Especially ordered mesoporous molecular sieve (aperture=2～50nm), it is compared with zeolite molecular sieve, 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.
While after olefin polymerization catalysis is carried on to molecular sieve, being applied to olefinic polymerization, there is following advantage:
(1) molecular sieve of synthetic does not contain the impurity that easily makes polymer degradation, can improve the ageing resistance of polyolefine material;
(2) the molecular sieve 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 three-dimensional selection effect is arranged, can improve polyolefinic molecular weight and fusing point.
As can be seen here, the olefin coordination polymerization that appears as of molecular sieve carried olefin polymerization catalysis has been opened up a new field.
The molecular sieve carried metallocene catalyst of reporting on document at present is mainly catalyzer ((a) Weckhuysen B M, Rao R R, Pelgri J, et al.Chem.Eur.J., 2000, the 6:2960 of the upper load metallocene of ordered mesoporous material MCM-41; (b) Rao R R, Weckhuysen B M, Schoonheydt R A.Chem.Commun., 1999,445), but the activity of this catalyzer when catalyzed ethylene polymerization is only 7.3 * 10
5gPE/ (mol Zr h) (Chen S T, Guo C Y, Lei L, et al.Polymer, 2005,46:11093.), and process after MCM-41 again with MAO the catalytic activity that the resulting catalyzer of load metallocene carries out vinyl polymerization, also only have 1 * 10
6gPE/ (mol Zrh) is still lower.
Therefore, how to obtain the carried metallocene catalyst of high catalytic activity, and then carry out efficiently olefinic polymerization and remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The catalytic activity of olefin polymerization catalysis that the object of the invention is to overcome prior art is still lower, causes adopting the not high problem of efficiency of olefinic polyreaction, and a kind of efficient olefine polymerizing process is provided.
In order to address the above problem, the present inventor finds through further investigation, use on cyclopentadienyl while having substituent metallocene as olefin polymerization catalysis, show different catalysis behaviors when there is no substituent metallocene as olefin polymerization catalysis on cyclopentadienyl, there is substituent metallocene when loading on catalyzer on the Mesoporous silica MCM 41 that MAO processed and carrying out vinyl polymerization on cyclopentadienyl, its catalytic activity with on cyclopentadienyl, do not have substituent metallocene to load on catalyzer on the Mesoporous silica MCM 41 that MAO processed to compare and there is no considerable change, be still 1 * 10
6gPE/ (mol Zrh) left and right, this is likely that hole wall structure thermostability and the hydrothermal stability of Mesoporous silica MCM 41 is poor, at the loading process hole wall, just there is part to cave in, affected load effect, to such an extent as to affected catalytic activity, but there is substituent metallocene on cyclopentadienyl when loading on catalyzer on the mixture of SBA-15 that MAO processed and silica gel and carrying out olefinic polymerization, with the catalyzer not have substituent metallocene to load on the mixture of SBA-15 that MAO processed and silica gel on cyclopentadienyl, compare, catalytic activity but obviously improves, can reach 5.1 * 10
7g PE/ (molZr h), this is likely that substituting group on the cyclopentadienyl of metallocene has played certain effect when metallocene loads on carrier, has improved load effect, thereby has made catalytic activity greatly improve.Completed the present invention based on above-mentioned cognition.
The invention provides a kind of olefine polymerizing process, the method is included under the olefinic polymerization condition, a kind of alkene is contacted with supported metallocene catalyst, it is characterized in that, described supported metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on carrier, the mixture that described carrier is donut-like SBA-15 and silica gel, 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, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl, M is a kind of in titanium, zirconium and hafnium, X is halogen.
According to olefine polymerizing process of the present invention, to there is sandwich structure by using, and there is substituent metallocene on cyclopentadienyl while loading to the supported metallocene catalyst that obtains on the mixture of carrier donut-like SBA-15 that MAO processed and silica gel as olefinic polymerization, greatly improved olefinic polymerization efficiency.
The accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, wherein, and the x-ray diffraction pattern that figure a is donut-like SBA-15, the x-ray diffraction pattern that figure b is supported metallocene catalyst SBA-15-M-GJ-BU-1;
Fig. 2 be donut-like SBA-15 (a1) and supported metallocene catalyst SBA-15-M-GJ-BU-1 (a2) nitrogen adsorption-(X-coordinate is relative pressure p/p to the desorption graphic representation
0), and the pore size distribution curve figure of donut-like SBA-15 (b1) and supported metallocene catalyst SBA-15-M-GJ-BU-1 (b2) (X-coordinate is nm);
Fig. 3 is scanning electron microscope microscopic appearance photo, is (a1) and (a2) the microscopic appearance photo of donut-like SBA-15; (b1) be and (b2) the microscopic appearance photo of supported metallocene catalyst SBA-15-M-GJ-BU-1;
Fig. 4 is transmission electron microscope photo, is (a1) and (a2) the pore passage structure transmission electron microscope photo of donut-like SBA-15; (b1) be and (b2) the pore passage structure transmission electron microscope photo of supported metallocene catalyst SBA-15-M-GJ-BU-1.
Embodiment
According to olefine polymerizing process provided by the invention, the method is included under the olefinic polymerization condition, a kind of alkene is contacted with supported metallocene catalyst, it is characterized in that, described supported metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on carrier, the mixture that described carrier is donut-like SBA-15 and silica gel, 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, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl, M is a kind of in titanium, zirconium and hafnium, X is halogen.
According to olefine polymerizing process of the present invention, what the M in formula 1 can be in titanium, zirconium and hafnium is a kind of.M in different metallocene compound molecules can be identical or different, and preferably, M is zirconium.
According to olefine polymerizing process of the present invention, the X in formula 1 is halogen.Particularly, the X in formula 1 can be 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 and/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 one or more 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, 1,2,5-trimethylammonium-cyclopentadienyl, 1,2,3,4-tetramethyl--cyclopentadienyl, 1,2,3,5-tetramethyl--cyclopentadienyl, the pentamethyl-cyclopentadienyl, ethyl-cyclopentadienyl, 1,2-diethyl-cyclopentadienyl, 1,3-diethyl-cyclopentadienyl, 1,2,4-triethyl-cyclopentadienyl, 1,3,5-triethyl-cyclopentadienyl, methyl-2-ethyl-cyclopentadienyl, 1-methyl-3-ethyl-cyclopentadienyl, n-propyl-cyclopentadienyl, 1,3-diη-propyl-cyclopentadienyl, 1-methyl-3-n-propyl-cyclopentadienyl, 1,3-di-isopropyl-cyclopentadienyl, 1-methyl-3-sec.-propyl-cyclopentadienyl, normal-butyl-cyclopentadienyl, 1,3-di-n-butyl-cyclopentadienyl, 1-methyl-3-normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, 1,3-di-sec-butyl-cyclopentadienyl, 1-methyl-3-sec-butyl-cyclopentadienyl, 1-isobutyl--cyclopentadienyl, 1,3-diisobutyl-cyclopentadienyl, 1-methyl 3-isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, 1,3-di-t-butyl-cyclopentadienyl, the 1-methyl 3-tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, 1,3-, bis-n-pentyls-cyclopentadienyl, 1-methyl-3-n-pentyl-cyclopentadienyl, 1-isopentyl-cyclopentadienyl, 1,3-diisoamyl-cyclopentadienyl, 1-methyl-3-isopentyl-cyclopentadienyl, 1-tert-pentyl-cyclopentadienyl, 1,3-, bis-tert-pentyls-cyclopentadienyl, 1-methyl-3-tert-pentyl-cyclopentadienyl, neo-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, normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, isopentyl-cyclopentadienyl, tert-pentyl-cyclopentadienyl, neo-pentyl-cyclopentadienyl.
According to olefine polymerizing process of the present invention, described alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in described alkylaluminoxane is C as above
1-C
5alkyl.Preferably, described alkylaluminoxane 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 (n-butyl cyclopentadienyl) zirconium dichlorides, and, when alkylaluminoxane is methylaluminoxane, when described supported metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent catalytic activity.
According to olefine polymerizing process of the present invention, loading on metallocene compound on described carrier and the mol ratio of described carrier can change within a large range.The present inventor finds, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is % by weight, when the content of described carrier is the 90-40 % by weight, not only can obtain gratifying catalytic effect, but also can reduce costs.More preferably, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is the 45-55 % by weight, 50 % by weight more preferably, and the content of described carrier is the 55-45 % by weight, more preferably 50 % by weight.
According to olefine polymerizing process of the present invention, the donut-like SBA-15 in described carrier and silica gel weight ratio can change within a large range.The present inventor's discovery, in described carrier, the weight ratio of donut-like SBA-15 and silica gel is 0.5-20: 1 o'clock, not only can obtain gratifying catalytic effect, but also can reduce costs.More preferably, in described carrier, the weight ratio of donut-like SBA-15 and silica gel is 1-10: 1.
According to olefine polymerizing process of the present invention, the ratio between described alkylaluminoxane and metallocene compound can be the known content of the technician of field of olefin polymerisation.Particularly, the mol ratio of the aluminium in described alkylaluminoxane and the M in described metallocene compound can be 30-100: 1.
In the present invention, described carrier is donut-like SBA-15 and silica gel, can be by under atmosphere of inert gases, donut-like SBA-15 and silica gel being mixed and roasting obtains.The temperature of described roasting can be 300-900 ℃, and the time of roasting can be 7-10 hour.The internal diameter of described donut-like SBA-15 and the ratio of external diameter can be 0.3-0.9, and median size can be 3-20 μ m, and mean thickness can be 0.1-2 μ m.The various donut-like that donut-like described in the present invention can it has been generally acknowledged that for this area, for example can be for thering is opening or not thering is the various circular of opening or class is circular, described internal diameter and external diameter refer to respectively the radius of circle at interior all places of described bagel and the radius of periphery place circle; The thickness of each donut-like SBA-15 refers to the mean thickness of each position of this donut-like SBA-15.The most probable aperture of described donut-like SBA-15 can be 7-10nm, is preferably 8-9nm, more preferably 8.4nm; Specific surface area is the 600-1000 meters squared per gram, is preferably the 650-800 meters squared per gram, more preferably 706 meters squared per gram; Pore volume is 0.5-3 ml/g, is preferably 1-2 ml/g, more preferably 1.5 ml/gs.Described donut-like SBA-15 can be commercially available, also can be synthetic according to the conventional synthetic method of donut-like SBA-15 in this area.Such as synthesizing by the following method donut-like SBA-15: by triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (as P123) and N, dinethylformamide (DM F), join in aqueous hydrochloric acid, by mole feed ratio, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide (DMF): water: hydrogenchloride=1: 300～700: 10000～20000: 100～500 are stirred to dissolving at 25 ℃～60 ℃ temperature; Add tetraethoxy in gained solution, at 25 ℃～60 ℃ temperature, stir and within 10 hours～40 hours, carry out crystallization; By the filtration of crystallization after product, washing, drying, obtain the donut-like mesoporous material raw powder; By gained donut-like mesoporous material raw powder in retort furnace 250 ℃～800 ℃ temperature lower calcinations 10 hours～40 hours, remove the masterplate agent, obtain the donut-like SBA-15 of removed template method.Described silica gel can directly be commercially available, and preferably, the median size of described silica gel is 10-30 μ m, and specific surface area is the 100-300 meters squared per gram, as 955 silica gel.
The preparation method of supported metallocene catalyst of the present invention, be included under atmosphere of inert gases, successively alkylaluminoxane and metallocene compound loaded on carrier.
Described carrier, alkylaluminoxane and metallocene compound define hereinbefore, hereinafter repeat no more.
According to the method for the described supported metallocene catalyst of preparation of the present invention, be included under protection of inert gas, successively load alkylaluminoxane and metallocene compound on carrier.Can adopt the method for well known to a person skilled in the art that alkylaluminoxane and metallocene compound are loaded on described carrier.Preferably, successively on carrier, the method for load alkylaluminoxane and metallocene compound comprises: under protection of inert gas, described carrier is contacted with the first solution, described the first solution contains described alkylaluminoxane and the first solvent; The carrier that has removed described the first solvent is contacted with the second solution, and described the second solution contains described metallocene compound and the second solvent, and desolvation, described the first solvent and the second solvent toluene of respectively doing for oneself.
The present invention is not particularly limited the whole bag of tricks that can be known to the skilled person for the method for described contact, for example: dipping, spraying.The method of employing dipping can be so that solution enters in the duct on carrier more fully, and therefore, the present invention is preferably flooded.
Carrier is not particularly limited with the condition that the second solution contacts with the first solution, and for example: carrier can comprise with the condition that described the first solution contacts: the time is 1-10 hour, and temperature is 25-80 ℃; The described carrier that has removed the first solvent can be comprised with the condition that described the second solution contacts: the time is 0.3-2 hour, and temperature is 25-80 ℃.
Preferably; before the method for preparing described supported metallocene catalyst also is included in the load alkylaluminoxane; under protection of inert gas; described carrier is heated at the temperature of 300-900 ℃ to 7-10 hour, with the volatile matter that contains in the hydroxyl of removing carrier surface and carrier (for example: water).
Prepare in the method for described supported metallocene catalyst, chemically interactive various gas can not occur with carrier, alkylaluminoxane, metallocene compound for various in described rare gas element.For example, described rare gas element can be nitrogen, argon gas.
Method according to the described supported metallocene catalyst of described preparation, with molar ratio computing, it is 1: 2 * 10 that the charge capacity of described metallocene compound on described carrier (take silicon-dioxide) makes the amount ratio mol ratio of described carrier and described metallocene compound
-3-9 * 10
-3, be preferably 1: 3 * 10
-3-8 * 10
-3the total amount that can realize take described carried metallocene catalyst is benchmark, the total amount of described metallocene compound and alkylaluminoxane can be the 10-60 % by weight, be preferably the 45-55 % by weight, 50 % by weight more preferably, the content of described carrier can be the 90-40 % by weight, be preferably the 55-45 % by weight, more preferably 50 % by weight; In described carrier, the weight ratio of donut-like SBA-15 and silica gel can be 0.5-20: 1, be preferably 0.5-10: and 1, more preferably 0.5: 1; The mol ratio of M in aluminium in described alkylaluminoxane and described metallocene compound can be 100-200: 1, be preferably 120-180: and 1,150-170 more preferably: 1, be particularly preferably 164: 1.
According to olefine polymerizing process of the present invention, described alkene can be the various alkene with polymerizable double bond, for example, 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.Described C
3-C
101-alkene be propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.Described C
4-C
8diolefin be 1,3-butadiene, 1,3-pentadiene, Isosorbide-5-Nitrae-pentadiene, 1,3-hexadiene, Isosorbide-5-Nitrae-hexadiene, 1,3-heptadiene, Isosorbide-5-Nitrae-heptadiene, 1,3-octadiene and Isosorbide-5-Nitrae-octadiene etc.
According to olefine polymerizing process of the present invention, described olefinic polymerization condition can be carried out under the condition of field of olefin polymerisation routine, and preferably, described olefinic polymerization condition comprises that temperature can be-78 ℃ to 100 ℃, and pressure can be 0.01-10MPa.Described olefinic polymerization is carried out under solvent exists, and described olefinic polymerization condition comprises: in metallocene compound, the concentration of described carried metallocene catalyst can be 1 * 10
-8-1 * 10
-5mol/L, temperature can be-78 ℃ to 100 ℃, is preferably-20 ℃ to 90 ℃, more preferably 20 ℃ to 80 ℃, more preferably 70 ℃, pressure can be 0.01-10MPa, is preferably 0.1-5MPa, more preferably 1MPa.Described solvent can be hexane.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, on the X-ray diffractometer that X-ray diffraction analysis is D8 Advance in the model purchased from company of German Bruker AXS company, carry out; On the transmission electron microscope that TEM (transmission electron microscope) analysis is Tecnai 20 in the model purchased from company of Dutch FEI Co., carry out; On the scanning electronic microscope that scanning electron microscope analysis is XL-30 in the model purchased from company of U.S. FEI Co., carry out.The ultimate analysis of U.S. An Jielun company is carried out on purchased from model 7500CX instrument.
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 ℃.
Preparation example 1
The preparation of donut-like SBA-15: by 2.0 gram triblock copolymer polyoxyethylene-polyoxytrimethylenes-polyoxyethylene (P123, the registration number of U.S. chemical abstract is 9003-11-6, average molecular mass Mn=5800, purchased from lark prestige Science and Technology Ltd., goods number 1546106) and 15 gram N, dinethylformamide (DMF) is (purchased from lark prestige Science and Technology Ltd., goods number 287533) join in the solution of the hydrochloric acid of 11.2 grams 37% and 64ml water, being stirred to P123 at 40 ℃ dissolves fully, again 4.45 gram tetraethoxys are joined in gained solution and stir 24 hours at 40 ℃.Obtain former powder mesoporous material after filtration, washing, drying.By the former powder mesoporous material of gained in retort furnace 600 ℃ the calcining 24 hours, remove the masterplate agent, obtain donut-like SBA-15 (wherein, the internal diameter of bagel and the ratio of external diameter are 0.5, and median size is 5 μ m, and mean thickness is 2 μ m).
Donut-like SBA-15 and 955 silica gel be take to weight ratio as mixing in 1: 2, and by their mixture under nitrogen protection 400 ℃ the calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the carrier complexes (called after SBA-15-M) through thermal activation;
By 0.51 gram, activated carrier complexes is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, the refining toluene and the 0.52 gram methylaluminoxane (MAO) (purchased from U.S. Albemarle company) that add 20 milliliters, and stir 4 hours at 50 ℃.After having reacted, standing, leach liquid after layering, and, with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen, obtaining load has the carrier complexes of methylaluminoxane (called after MAO/SBA-15-M-GJ).
Under nitrogen protection; MAO/SBA-15-M-GJ is joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene; under 30 ℃; slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides of 25 milligrams (purchased from Alfa Aesar company; goods number is H27576), stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid after layering, 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 supported metallocene catalyst of the present invention (called after SBA-15-M-GJ-BU-1).By XRD, nitrogen adsorption-desorption experiment, transmission electron microscope and scanning electron microscope, this supported metallocene catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum, wherein, and the x-ray diffraction pattern that figure a is donut-like SBA-15, the x-ray diffraction pattern that figure b is supported metallocene catalyst SBA-15-M-GJ-BU-1.Can find out significantly that from XRD spectra SBA-15 1 diffraction peak occurs in little angular region, illustrate that donut-like macroporous/mesoporous material SBA-15-M has good mesoporous phase structure, and there is two-dimentional hexagonal structure, the mesoporous material XRD spectra of this and bibliographical information is consistent, and after load metallocene, can find out in little angular region an obvious diffraction spectra peak in the XRD spectra of sample SBA-15-M-GJ-BU-1, this explanation mesoporous material structure in loading process remains unchanged substantially.
Fig. 2 be donut-like SBA-15 (a1) and supported metallocene catalyst SBA-15-M-GJ-BU-1 (a2) nitrogen adsorption-(X-coordinate is relative pressure p/p to the desorption graphic representation
0), and the pore size distribution curve figure of donut-like SBA-15 (b1) and supported metallocene catalyst SBA-15-M-GJ-BU-1 (b2) (X-coordinate is nm), in Fig. 2, nitrogen adsorption-desorption isotherm shows that the donut-like mesoporous material of donut-like macroporous/mesoporous material SBA-15 and load metallocene is the IV class adsorption-desorption thermoisopleth of typical IUPAC definition, proved that donut-like macroporous/mesoporous material SBA-15 has the mesoporous material of the distinctive one dimension column pore passage structure of bibliographical information, and the nitrogen adsorption-desorption thermoisopleth of the donut-like SBA-15-M-GJ-BU-1 of load metallocene slightly changes, this is that in loading process, metallocene enters the mesoporous material duct and causes.Can find out that by graph of pore diameter distribution donut-like macroporous/mesoporous material SBA-15 has narrow pore size distribution, and duct is very even, sample after load keeps narrow pore size distribution and even duct substantially, shows that the metallocene loading process does not destroy to some extent to the meso-hole structure of donut-like mesoporous material.
Fig. 3 is scanning electron microscope microscopic appearance photo, is (a1) and (a2) the microscopic appearance photo of donut-like SBA-15; (b1) be and (b2) the microscopic appearance photo of supported metallocene catalyst SBA-15-M-GJ-BU-1.As seen from the figure, the microscopic appearance figure of the donut-like mesoporous material of donut-like macroporous/mesoporous material SBA-15 and load metallocene is donut-like, and the ratio of the internal diameter of described SBA-15 and external diameter is 0.5, and median size is 5 μ m, and mean thickness is 2 μ m.Microscopic appearance after load-reaction remains unchanged substantially, still keeps donut-like preferably, do not occur the MCM-41 carrier the phenomenon of caving in that often occurs.The spheroidal particle of 955 silica gel after load metallocene is high-visible.
Fig. 4 is transmission electron microscope photo, is (a1) and (a2) the pore passage structure transmission electron microscope photo of donut-like SBA-15; (b1) be and (b2) the pore passage structure transmission electron microscope photo of supported metallocene catalyst SBA-15-M-GJ-BU-1.Can know that from Fig. 4 the donut-like macroporous/mesoporous material of seeing sample donut-like macroporous/mesoporous material SBA-15 and load metallocene has more regular pore distribution figure.
The pore structure parameter that table 1 is donut-like SBA-15 and supported metallocene catalyst SBA-15-M-GJ-BU-1.
Table 1
Data from table 1 can find out, the pore structure parameter of SBA-15-M-GJ-BU-1 all reduces to some extent than SBA-15, shows that methylaluminoxane and metallocene compound enter into the duct of SBA-15 really.
Results of elemental analyses shows, load in the supported metallocene catalyst SBA-15-M-GJ-BU-1 of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of methylaluminoxane (MAO) and metallocene compound aluminium content be 18.73 % by weight, the content of Zr is 0.39 % by weight, and the mol ratio of Al/Zr is 164.The total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 50 % by weight, and the content of described carrier is 50 % by weight.
This EXPERIMENTAL EXAMPLE is used for illustrating olefine polymerizing process of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, then add 800 milliliters of hexanes, along with adding of hexane, the triethyl aluminum of 2 milliliter of 1 mol/L (TEA) (purchased from Fu Rui Dehua, Zhejiang work company limited) hexane solution is added, then add 85.2 milligrams of SBA-15-M-GJ-BU-1, pass into ethene and pressure is risen to and maintains 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 184 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.29g/ml, and melting index is MI
2.16=0.026g/10min.As calculated, the efficiency of catalyzer is 2160g PE/gcat.h (5.1 * 107g PE/ (mol Zr h)).
This EXPERIMENTAL EXAMPLE is used for illustrating olefine polymerizing process of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 200 milliliters of hexanes, by still temperature rise to 80 ℃, then add 800 milliliters of hexanes, along with adding of hexane, the triethyl aluminum of 2 milliliter of 1 mol/L (TEA) (purchased from Fu Rui Dehua, Zhejiang work company limited) hexane solution and 10 milliliters of hexenes are added, then add 79.3 milligrams of SBA-15-M-GJ-BU-1, pass into ethene and pressure is risen to and maintains 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 101 gram multipolymers, the bulk density of this multipolymer (BD) is 0.28g/ml, melting index: MI2.16=0.34g/10min, and the efficiency of catalyzer is 1274g PE/gcat.h (3 * 107g PE/ (mol Zrh)).
Comparative Examples 1
By ES955 silica gel under nitrogen protection 400 ℃ the calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the ES955 silica gel after thermal activation.
Under nitrogen protection; 0.9 gram ES955 silica gel is joined in 250 milliliters of glass reactors; add 1.0 gram methylaluminoxane (MAO) (purchased from U.S. Albemarle company) and 10ml toluene solution; under 50 ℃ of conditions, stirring reaction is after 4 hours, by 30 milliliters of toluene wash 3 times; after; with 20 milliliters of hexane washings 3 times, finally solid is dried up with nitrogen, obtaining load has the ES955 of alkylaluminoxane (called after MAO/ES955) again.
Under nitrogen protection; MAO/ES955 is joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene (refluxing 24 hours with sodium); stir; under 30 ℃; slowly drip the solution of two (n-butyl cyclopentadienyl) zirconium dichlorides (purchased from Alfa Aesar company, goods number is H27576) of metallocene compound that contain 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen.By the carried metallocene catalyst of gained (called after ES955-BU).
The results of elemental analyses demonstration, the aluminium content in ES955-BU is weight 32.4%, and the content of Zr is weight 0.41%, and the mol ratio of Al/Zr is 270.
Comparative Examples 2
Adopt the method identical with embodiment 1 to carry out the homopolymerization of ethene, different, the ES955-BU that the catalyzer of employing is Comparative Examples 1 preparation.Result obtains 65g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.33g/ml, melting index: MI
2.16=0.12g/10min.Determine as calculated, the efficiency of catalyzer is 1295gPE/gcath (that is, 2.9 * 10
7gPE/ (mol Zr h)).
Comparative Examples 3
Two (n-butyl cyclopentadienyl) zirconium dichlorides of silica gel (ES955-BU) load metallocene catalyst) preparation for ethylene copolymer
Polymerization process is with embodiment 2, and polymerization result: result obtains 76g polyethylene particle powder, and catalyst efficiency is 2260g PE/gcath (5.1 * 10
7gPE/ (mol Zr h)), bulk density (BD) is 0.299g/ml, melting index: MI
2.16=0.679g/10min.
Claims (15)
1. an olefine polymerizing process, the method is included under the olefinic polymerization condition, one or more alkene are contacted with supported metallocene catalyst, it is characterized in that, described supported metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on carrier, the mixture that described carrier is donut-like SBA-15 and silica gel, the internal diameter of described donut-like SBA-15 and the ratio of external diameter are 0.3-0.9, median size is 3-20 μ m, mean thickness is 0.1-2 μ m, the most probable aperture of described donut-like SBA-15 is 8-9nm, specific surface area is the 650-800 meters squared per gram, pore volume is 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, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl, M is a kind of in titanium, zirconium and hafnium, X is halogen.
2. olefine polymerizing process according to claim 1, wherein, the total amount of composite catalyst of take is benchmark, and the total content of described metallocene compound and alkylaluminoxane is the 10-60 % by weight, and the content of described carrier is the 90-40 % by weight.
3. olefine polymerizing process according to claim 1, wherein, in described carrier, the weight ratio of donut-like SBA-15 and silica gel is 0.5-20:1.
4. according to claim 1,2 or 3 described olefine polymerizing process, wherein, described contact is carried out under the solution that contains aluminum alkyls and/or alkylaluminoxane exists, and in described aluminum alkyls and described alkylaluminoxane, whole aluminium and the mol ratio of the M in described metallocene compound are 100-200:1.
5. olefine polymerizing process according to claim 4, wherein, the C that respectively does for oneself of the alkyl in described aluminum alkyls and described alkylaluminoxane
1-C
5alkyl.
6. olefine polymerizing process according to claim 5, wherein, described aluminum alkyls is triethyl aluminum.
7. olefine polymerizing process according to claim 5, wherein, described alkylaluminoxane is methylaluminoxane.
8. olefine polymerizing process according to claim 1 and 2, wherein, M is zirconium.
9. olefine polymerizing process according to claim 1 and 2, wherein, X is chlorine.
10. olefine polymerizing process according to claim 1 and 2, wherein, R
1, R
2, R
3, R
4and R
5in any one be normal-butyl or the tertiary butyl, R
1', R
2', R
3', R
4' and R
5' in any one be normal-butyl or the tertiary butyl.
11. olefine polymerizing process according to claim 10, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
12. olefine polymerizing process according to claim 1, wherein, described alkene is one or more in ethene, alpha-olefin and diolefin.
13. olefine polymerizing process according to claim 12, wherein, described alkene is ethene, C
3-C
101-alkene, C
4-C
8diolefin in one or more.
14. olefine polymerizing process according to claim 1, wherein, described olefinic polymerization condition comprises that temperature is-78 ℃ to 100 ℃, and pressure is 0.01-10MPa.
15. olefine polymerizing process according to claim 1, wherein, described olefinic polymerization is carried out under solvent exists, and described olefinic polymerization condition comprises: in metallocene compound, the concentration of described supported metallocene catalyst is 1 * 10
-8-1 * 10
-5mol/L, temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MPa.
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