CN102453140B - Load type metallocene catalyst and preparation method thereof - Google Patents
Load type metallocene catalyst and preparation method thereof Download PDFInfo
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- CN102453140B CN102453140B CN 201010519429 CN201010519429A CN102453140B CN 102453140 B CN102453140 B CN 102453140B CN 201010519429 CN201010519429 CN 201010519429 CN 201010519429 A CN201010519429 A CN 201010519429A CN 102453140 B CN102453140 B CN 102453140B
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Abstract
The invention provides a load type metallocene catalyst, which comprises a carrier, and a metallocene compound and alkylaluminoxane which are on the carrier, wherein the carrier is a bagel-shaped SBA-15. The invention also provides a preparation method of the load type metallocene catalyst, which comprises the following step of: under the inert gas atmosphere, sequentially loading alkylaluminoxane and the metallocene compound on the carrier. According to the invention, when the load type metallocene catalyst is used for catalyzing olefin homopolymerization, the catalytic efficiency can reach 3.7*108-6.0*108gPE/(mol Zr h); and when the load type metallocene catalyst is used for catalyzing olefin polymerization, the catalytic efficiency can reach 6.0*107-9.0*108gPE/(mol Zr h).
Description
Technical field
The present invention relates to a kind of load metallocene type Catalysts and its preparation method.
Background technology
The Application and Development of metallocene catalyst is after traditional Ziegler-Natta catalyst, the another important breakthrough in olefin polymerization catalysis field, and particularly in the eighties, people such as Kaminsky and Sinn (Angew.Chem., 1980,19,390; Adv.Organoment.Chem., 1980,18,99.) develop efficient promotor methylaluminoxane (MAO), make the research of metallocene catalyst enter into a stage that develops rapidly.Because it is big that the homogeneous phase metallocene catalyst reaches the required MAO consumption of high reactivity, the production cost height, and the polymkeric substance that obtains does not have particle shape, can't use at widely used slurry process or gas phase polymerization technology, the effective way that addresses the above problem is carried out the load processing to the solubility metallocene catalyst exactly.At present, relevant metallocene load research report is very many, wherein with SiO
2Report research maximum (CN1174848, CN1174849, CN1356343, US4808561, US5026797, US5763543, US5661098) for carrier.For furtheing investigate new support/catalyst/co-catalyst system, be necessary to attempt different carriers, to promote 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 tangible 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.Especially ordered mesoporous molecular sieve (aperture=2～50nm) ((a) Tudor J, Willington L, O ' Hare D, et al.Chem Commun, 1996,17:2031. (b) Bergman J S, Chen H, Giannelis E P, et al.Chem Commun, 1999,21:2179. (c) Beck J S, Vartuli J C, Roth WJ, et at.J Am Chem Soc, 1992,114:10834. (d) Corma A.Chem Rev, 1997,97:2373. (e) Ying J Y, Mehnert C P, Wong M S.Angew Chem Int Ed, 1999,38:56. (f) Xu Ruren. molecular sieve and porous material chemistry, Beijing. the .2004. of Science Press), compare with zeolite molecular sieve, have bigger specific surface area and relatively large aperture, can handle bigger molecule or group, can make catalyzer well bring into play its due catalytic activity.Because molecular sieve has nano pore, the inserted mode of monomer is different with freeboard with propagation process in the polymerization process, the chance that double-basis stops has been reduced in limited space to a certain extent, polyreaction is shown " living polymerization " feature ((a) Ng SM, Ogino S, Aida T, et al.Macromol Rapid Commun, 1997,18:991; (b) Kageyama K, Ng SM, Ichikawa H, et al.Macromol Symp, 2000,157:137; (c) Kageyama K, Ogino S, Tatsumi T, et al.Macromolecules, 1995,28:1320; (d) Kageyama K, Ogino S, Aida T, Macromolecules, 1998,31:4069.).
Olefin polymerization catalysis is carried on molecular sieve, has following advantage:
(1) molecular sieve of synthetic does not contain the impurity that easily makes polymer degradation, has improved the ageing resistance of polyolefine material;
(2) the molecular sieve nano pore has the dual-use function of carrier and reactor, catalyst cupport efficient height, and polymerization process is controlled easily, and can key in the active centre in the skeleton of polymerization reactor, accelerates reaction process, improves productive rate;
(3) insertion has three-dimensional selection effect with polyreaction to monomer, can improve polyolefinic molecular weight and fusing point.
This shows that the olefin coordination polymerization that appears as of molecular sieve carried olefin polymerization catalysis has been opened up a new field.
At present the mesoporous material of the load metallocene catalyst of reporting on the document is MCM-41, but activity only is 7.3 * 10 during catalyzed ethylene polymerization
5GPE/ (mol Zr h) ((a) Weckhuysen B M, Rao R R, Pelgrims J, et al.Chem Eur J, 2000,6:2960; (b) Rao R R, Weckhuysen B M, Schoonheydt R A.Chem Commun, 1999,445), and after handling with MAO again the MCM-41 of load metallocene carry out that catalytic activity is 10 behind the vinyl polymerization
6GPE/ (mol Zr h) (Chen S T, GuoC Y, Lei L, et al.Polymer, 2005,46:11093.).The hole wall structure thermostability and the hydrothermal stability that carry out the lower reason of ethylene polymerization activity behind the mesoporous material MCM-41 supported catalyst and mainly be MCM-41 are relatively poor, just there is part to cave at the loading process hole wall, influenced load effect, to such an extent as to influenced catalytic activity.Therefore press for the high catalyzer of a kind of catalytic activity of exploitation.
Summary of the invention
The object of the present invention is to provide the high carried metallocene catalyst of a kind of catalytic activity.
Another object of the present invention is to provide a kind of preparation method of carried metallocene catalyst.
In order to address the above problem, the present inventor finds through further investigation, use when having substituent metallocene as alkene homopolymerization catalyzer on the cyclopentadienyl, show different catalysis behaviors when not having substituent metallocene as alkene homopolymerization catalyzer on the cyclopentadienyl, load on catalyzer on the mesoporous material MCM-41 that MAO handled when carrying out vinyl polymerization having substituent metallocene with cyclopentadienyl, not having substituent metallocene to load on catalyzer on the mesoporous material MCM-41 that MAO handled on its catalytic activity and the cyclopentadienyl and compare and do not have considerable change, still is 1 * 10
6About gPE/ (mol Zr h), this might be that hole wall structure thermostability and the hydrothermal stability of mesoporous material MCM-41 is relatively poor, just there is part to cave at the loading process hole wall, influenced load effect, to such an extent as to influenced catalytic activity, the bar-shaped microscopic appearance of mesoporous material MCM-41 causes its flowability relatively poor in addition, also catalytic activity has been produced certain influence, but have substituent metallocene on cyclopentadienyl and load on catalyzer on the mesoporous material SBA-15 that MAO handled when carrying out the alkene homopolymerization, with compare with the catalyzer that does not have substituent metallocene to load on the mesoporous material SBA-15 that MAO handled on the cyclopentadienyl, catalytic activity but obviously improves, and can reach 5.1 * 10
7G PE/ (molZr h), this might be that substituting group on the cyclopentadienyl of metallocene has played certain effect when metallocene loads on the carrier, has improved load effect, thereby has made catalytic activity improve greatly.The present inventor has finished the present invention on the basis of above-mentioned cognition through further investigation.
The invention provides a kind of carried metallocene catalyst, wherein, this catalyzer comprises carrier and the metallocene compound and the alkylaluminoxane that load on the described carrier, and described carrier is donut-like SBA-15, described metallocene compound has the structure shown in the 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 the hafnium, X is halogen.
The present invention also provides a kind of preparation method of carried metallocene catalyst, and wherein, this method is included under the atmosphere of inert gases, successively alkylaluminoxane and metallocene compound is loaded on the carrier.
According to carried metallocene catalyst of the present invention, described metallocene compound has sandwich structure, and has more than one substituting group on the cyclopentadienyl, therefore has high catalytic activity.In addition, because described carrier is donut-like SBA-15, its pore diameter range is at 7-0nm, and microscopic appearance remains unchanged substantially behind the load metallocene compound, still keeps the donut-like of disperseing.Particularly, carried metallocene catalyst of the present invention is when being used for the catalyzed alkene homopolymerization, and catalytic efficiency can reach 3.7 * 10
8-6.0 * 10
8GPE/ (mol Zr h), carried metallocene catalyst of the present invention is when being used for the catalyzed alkene copolymerization, and catalytic efficiency can reach 6.0 * 10
7-9.0 * 10
8GPE/ (mol Zr h), and under the identical situation of other conditions, catalytic efficiency during metallocene compound that silica gel 955 loads have the structure shown in the formula 1 only is 1295gPE/ (mol Zr h), illustrate that thus donut-like SBA-15 carrier cooperates with the described metallocene compound with the structure shown in the formula 1 and has synergy, has obtained unexpected technique effect.
Description of drawings
Fig. 1 is X-ray diffracting spectrum, and wherein Fig. 1 a is that X-ray diffracting spectrum, Fig. 1 b of donut-like SBA-15 are the X-ray diffracting spectrum of carried metallocene catalyst SBA-15-BU.
Fig. 2 is N
2The adsorption desorption graphic representation, wherein a is the N of donut-like SBA-15
2Adsorption desorption graphic representation, b are the N of carried metallocene catalyst SBA-15-BU
2The adsorption desorption graphic representation.Wherein, X-coordinate is relative pressure, and unit is p/p
0
Fig. 3 is graph of pore diameter distribution, and wherein a is that graph of pore diameter distribution, the b of donut-like SBA-15 are the graph of pore diameter distribution of carried metallocene catalyst SBA-15-BU.Wherein, X-coordinate is the aperture, and unit is nm.
Fig. 4 is pore structure synoptic diagram (transmission electron microscope TEM), and wherein a1 and a2 are that pore structure synoptic diagram, b1 and the b2 of donut-like SBA-15 are the pore structure synoptic diagram of carried metallocene catalyst SBA-15-BU.
Fig. 5 is microscopic appearance figure (scanning electron microscope sem), and wherein a1 and a2 are microscopic appearance figure, the b1 of donut-like SBA-15 and the microscopic appearance figure that b2 is carried metallocene catalyst SBA-15-BU.
Fig. 6 is X-ray energy spectrometer (EDS) ultimate analysis of donut-like macroporous/mesoporous material SBA-15-BU.
Embodiment
The invention provides a kind of carried metallocene catalyst, wherein, this catalyzer comprises carrier and the metallocene compound and the alkylaluminoxane that load on the described carrier, and described carrier is donut-like SBA-15, described metallocene compound has the structure shown in the 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 the hafnium, X is halogen.
According to carried metallocene catalyst of the present invention, what the M in the formula 1 can be in titanium, zirconium and the hafnium is a kind of.M in the different metallocene compound molecules can be identical or different, and preferably, M is zirconium.
According to carried metallocene catalyst of the present invention, the X in the formula 1 is halogen.Particularly, the X in the formula 1 can be fluorine atom, chlorine atom, bromine atoms and iodine atom.Preferably, the X in the formula 1 is chlorine and/or bromine.X in the different metallocene compound molecules can be identical or different, and more preferably, the X in the formula 1 is chlorine.
According to the present invention, in the formula 1, cyclopentadienyl is for forming η with central metal
5The derivative of the cyclopentadienyl of key.Preferably, the R on the cyclopentadienyl in the 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.
Among the present invention, described C
1-C
5Alkyl can be in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and the neo-pentyl one or more.
The specific examples that satisfies 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-di-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-two sec-butyls-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-two 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-two 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 the 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 satisfies 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.
More preferably, R
1And R
1' be normal-butyl or the tertiary butyl.Particularly, described cyclopentadienyl is normal-butyl-cyclopentadienyl or the tertiary butyl-cyclopentadienyl.
According to carried metallocene catalyst of the present invention, described alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in the described alkylaluminoxane is aforesaid C
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 or the tertiary butyl, M is zirconium, X is chlorine, be that described metallocene compound is two (normal-butyl-cyclopentadienyl) zirconium dichlorides, and when alkylaluminoxane is methylaluminoxane, when described carried metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent catalytic activity.
According to carried metallocene catalyst of the present invention, loading on metallocene compound on the described carrier and the amount of alkylaluminoxane can change within a large range.The present inventor finds, total amount with described carried metallocene catalyst is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 10-60 weight %, when the content of described carrier is 90-40 weight %, not only can obtain gratifying catalytic effect, but also can reduce cost.More preferably, total amount with described carried metallocene catalyst is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 45-55 weight %, more preferably 50 weight %, the content of described carrier is 55-45 weight %, more preferably 50 weight %.
According to loaded catalyst of the present invention, the ratio between described alkylaluminoxane and the metallocene compound can be the known content of the technician of field of olefin polymerisation.Particularly, the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described metallocene compound can be 300-1000: 1, be preferably 400-800: and 1,500-750 more preferably: 1,550-655 more preferably: 1, be preferably 651: 1 especially.
According to the present invention, preferably, described SBA-15 is donut-like, and the ratio of the internal diameter of described donut-like SBA-15 and external diameter is preferably 0.3-0.9, be preferably 0.5-0.85, especially preferred 0.5, median size is preferably 3-20 μ m, is preferably 3-10 μ m, especially be preferably 5 μ m, mean thickness is preferably 0.1-2 μ m, is preferably 1-2 μ m, especially is preferably 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 having opening or not having the various circular of opening or class is circular, described internal diameter and external diameter refer to the radius of circle at interior all places of described bagel and the radius of periphery place circle respectively; Described mean thickness refers to the average thickness value of a plurality of donut-like SBA-15.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 SBA-15 can be 7-10nm, is preferably 8-9nm, more preferably 8.4nm; Pore volume can be 0.5-3 milliliter/gram, is preferably 1-2 milliliter/gram, more preferably 1.5 milliliters/gram; Specific surface area can be the 600-1000 meters squared per gram, is preferably the 650-800 meters squared per gram, more preferably 706 meters squared per gram.
The present invention also provides a kind of method for preparing described carried metallocene catalyst, and this method comprises: under protection of inert gas, successively alkylaluminoxane and metallocene compound are loaded on the carrier.
Described carrier, alkylaluminoxane and metallocene compound are described above, hereinafter repeat no more.
Can adopt the method for well known to a person skilled in the art that alkylaluminoxane and metallocene compound are loaded on the described carrier.Preferably, successively the method at load alkylaluminoxane and metallocene compound on the carrier comprises: under protection of inert gas, described carrier is contacted with first solution, described first solution contains described alkylaluminoxane and first solvent; The carrier that has removed described first solvent is contacted with second solution, and described second solution contains described metallocene compound and second solvent, and removes solvent, respectively do for oneself in the toluene one or more of described first solvent and second solvent.
The present invention is not particularly limited for the method for described contact can be for well known to a person skilled in the art the whole bag of tricks, for example: dipping, spraying.Adopt the method for dipping can be so that solution enters in the duct on the carrier more fully, therefore, the present invention be preferably flooded.
Carrier is not particularly limited with the condition that second solution contacts with first solution, and for example: carrier can comprise with the condition that described first solution contacts: be 1-10 hour duration of contact, and the contact temperature is 25-80 ℃; The described carrier that has removed first solvent can be comprised with the condition that described second solution contacts: be 0.3-2 hour duration of contact, and the contact temperature is 25-80 ℃.
The method according to this invention can also be included in before the described alkylaluminoxane of load and the described metallocene compound; under protection of inert gas; described carrier was heated 7-10 hour under 300-900 ℃ temperature, with the volatile matter that contains in the hydroxyl of removing carrier surface and the carrier (for example: water).
According to the present invention, chemically interactive all gases can not take place with carrier, alkylaluminoxane, metallocene compound for various in described rare gas element.For example, described rare gas element can be nitrogen, argon gas.
According to the present invention, with molar ratio computing, described carrier (in silicon-dioxide) is generally 1 with the amount ratio of described alkylaluminoxane and described metallocene compound: 0.1-0.5: 2 * 10
-3-9 * 10
-3, be preferably 1: 0.2-0.4: 3 * 10
-3-8 * 10
-3, be preferably 1: 0.31: 7.83 * 10
-3
The SBA-15 of carrier donut-like of the present invention can obtain by variety of way, for example can be commercially available, and also can obtain according to existing prepared in various methods, for example can adopt the method that may further comprise the steps to prepare:
The 1st step, with triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (as P123) and N, dinethylformamide (DMF), join in the aqueous hydrochloric acid, by the mole feed ratio, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene: N, dinethylformamide (DMF): water: hydrogenchloride=1: 300-700: 10000-20000: 100-500 is stirred to dissolving under 25-60 ℃ of temperature;
The 2nd step added tetraethoxy in previous step gained solution, stirred 10-40 hour under 25-60 ℃ of temperature;
In the 3rd step, with the filtration of crystallization after product, washing, drying, obtain the donut-like mesoporous material raw powder;
The 4th the step, with gained donut-like mesoporous material raw powder in retort furnace at 250-800 ℃ of temperature lower calcination 10-40 hour, remove the masterplate agent, obtain donut-like SBA-15.Be described in detail below in conjunction with the present invention of embodiment.
In following examples, X-ray diffraction analysis is available from German Bruker AXS company, and model is to carry out on the X-ray diffractometer of D8Advance; TEM (transmission electron microscope) analysis is available from Dutch FEI Co., and model is to carry out on the transmission electron microscope of Tecnai 20; Scanning electron microscope analysis is available from U.S. FEI Co., and model is to carry out on the scanning electronic microscope of XL-30.Ultimate analysis is carried out on the model 7500CX of the company instrument available from U.S. An Jielun.
Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption instrument, sample was 200 ℃ of degassings 4 hours.
Present embodiment is used for explanation according to carried metallocene catalyst of the present invention and preparation method thereof.
The preparation of donut-like SBA-15 carrier: with 2.0 gram triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene (P123, the registration number of U.S. chemical abstract is 9003-11-6, average molecular mass Mn=5800) and 15 the gram N, dinethylformamide (DMF) joins in the solution of 11.2 gram 37% hydrochloric acid and 64ml water, be stirred to P123 at 40 ℃ and dissolve fully, 4.45 gram tetraethoxys are joined in the gained solution stirred 24 hours at 40 ℃ again.Obtain former powder mesoporous material after filtration, washing, the drying.With the former powder mesoporous material of gained in retort furnace 600 ℃ the calcining 24 hours, remove the masterplate agent, obtain donut-like mesoporous material 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).
With above-mentioned synthetic whole donut-like SBA-15 400 ℃ of calcinings 10 hours (thermal activation) under nitrogen protection, to remove hydroxyl and remaining moisture, obtain the donut-like SBA-15 after the thermal activation;
The activated donut-like SBA-15 of above-mentioned synthetic whole 0.3675 grams is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, add 20 milliliters of refining toluene (refluxing 24 hours with sodium) and 0.3321 gram methylaluminoxane MAO (available from the auspicious Dehua of Zhejiang good fortune worker company limited) auxiliary agent, and stirred 4 hours at 50 ℃.After reaction is finished, leave standstill, layering leaches liquid, and with 20 milliliters of hexane wash three times, at last solid dried up with nitrogen, obtaining load has the SBA-15 of methylaluminoxane (called after MAO/SBA-15).
Under nitrogen protection; MAO/SBA-15 is joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene (refluxing 24 hours with sodium); under 30 ℃; slowly drip two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of the metallocene that contains 19.6 milligrams (available from Alfa Aesar; article No. H27576) toluene solution, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid after the layering, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after SBA-15-BU).
Table 1 is the pore structure parameter of SBA-15 and SBA-15-BU, wherein a is that pore structure parameter, the b of SBA-15 are SBA-15-BU, find out that by table the SBA-15-BU pore structure parameter behind the load metallocene all reduces to some extent, this shows that metallocene enters in the mesoporous material duct.
Show by ultimate analysis ICP result, load the aluminium content among the MAO/SBA-15-BU of donut-like SBA-15 of two (n-butyl cyclopentadienyl) zirconium dichlorides (BUCP) of promotor methylaluminoxane (MAO) and cyclopentadienyl catalyst precursor be that the content of 17.4 weight %, Zr is 0.09 weight %, the mol ratio of Al/Zr is 651.Total amount with described carried metallocene catalyst is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is 50 weight %, and the content of described carrier is 50 weight %.
Fig. 1 is X-ray diffracting spectrum, and wherein Fig. 1 a is that X-ray diffracting spectrum, Fig. 1 b of donut-like SBA-15 are the X-ray diffracting spectrum of carried metallocene catalyst SBA-15-BU.
Can find out significantly that from XRD spectra sample SBA-15-BU 1 diffraction peak occurs in little angular region, (Fig. 1 is a) consistent with SBA-15.Illustrate that donut-like SBA-15-BU has good meso-hole structure; and has two-dimentional hexagonal structure; consistent (the Sun Jinyu of XRD spectra of the mesoporous material SBA-15 of this and bibliographical information; Zhao Dongyuan; " bagel " shape high-sequential big-pore mesoporous molecular sieve SBA-15's is synthetic; SCI, 2000,1 (21): 21～23).
Fig. 2 is N
2The adsorption desorption graphic representation, wherein a is the N of donut-like SBA-15
2Adsorption desorption graphic representation, b are the N of carried metallocene catalyst SBA-15-BU
2The adsorption desorption graphic representation.Wherein, X-coordinate is relative pressure, and unit is p/p
0Nitrogen adsorption-desorption thermoisopleth shows that donut-like macropore SBA-15 is the IV class adsorption-desorption thermoisopleth of typical IUPAC definition among Fig. 2, and the nitrogen adsorption-desorption thermoisopleth of SBA-15-BU slightly changes, and this is that the loading process of load metallocene causes.
Fig. 3 is graph of pore diameter distribution, and wherein a is that graph of pore diameter distribution, the b of SBA-15 are the graph of pore diameter distribution of carried metallocene catalyst SBA-15-BU.Wherein, X-coordinate is the aperture, and unit is nm.As seen from Figure 3, donut-like SBA-15 has narrow pore size distribution, and the duct is very even, and same SBA-15-BU has narrow pore size distribution, and duct very even (concrete data provide in table 1).
Fig. 4 is transmission electron microscope photo TEM, and wherein a1 and a2 are that pore structure synoptic diagram, b1 and the b2 of donut-like SBA-15 are the pore structure synoptic diagram of carried metallocene catalyst SBA-15-BU.Can know from Fig. 4 and see that SBA-15 has the orderly pore passage structure of six sides, donut-like SBA-15 has the pore distribution figure of rule.Compare with SBA-15, remain unchanged substantially with the duct shape of SBA-15-BU, do not occur MCM-41 the structure that often the occurs phenomenon of caving in.
Fig. 5 is stereoscan photograph SEM, and wherein a1 and a2 are microscopic appearance figure, the b1 of donut-like SBA-15 and the microscopic appearance figure that b2 is carried metallocene catalyst SBA-15-BU.As shown in Figure 5; the microscopic appearance figure of SBA-15 and SBA-15-BU is donut-like; size is micron level; with bibliographical information (Sun Jinyu in full accord; Zhao Dongyuan, " bagel " shape high-sequential big-pore mesoporous molecular sieve SBA-15's is synthetic, SCI; 2000,1 (21): 21～23).
Fig. 6 is X-ray energy spectrometer (EDS) ultimate analysis of donut-like macroporous/mesoporous material SBA-15-BU, by spectrogram as can be seen the Al on SBA-15-BU surface and Zr distribute very evenly, methylaluminoxane MAO and two (n-butyl cyclopentadienyl) zirconium dichloride BUCP that this explanation loads on the surface of mesoporous material SBA-15 distribute very even.
Table 1 pore structure parameter
| Sample | Specific surface area (m 2/g) | Pore volume (ml/g) | Most probable aperture (nm) |
| SBA-15 | 706 | 1.5 | 8.4 |
| SBA-15-BU | 488 | 0.5 | 4.3 |
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity according to carried metallocene catalyst of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then, with still temperature rise to 80 ℃, add 800 milliliters of hexane solvents again, along with the adding of hexane, triethyl aluminum (TEA) hexane solution that adds 2 milliliter of 1 mol, then add 36.9 milligrams of SBA-15-BU, feed ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 30 minutes.Obtain 137 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.238g/ml, melting index: MI
2.16=0.021g/10min determines that as calculated the efficient of catalyzer is 3713g PE/gcath (3.7 * 10
8G PE/ (mol Zr h)).
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity according to carried metallocene catalyst of the present invention.
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexanes then, with still temperature rise to 80 ℃, add all the other 800 milliliters of hexanes again, along with the adding of hexane, triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of adding 2 milliliter of 1 mol, then add 31.5 milligrams of SBA-15-BU, feed ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain the polymkeric substance of 283 grams, the bulk density of this polymkeric substance (BD) is 0.272g/ml, melting index: MI
2.16=0.403g/10min determines that as calculated the efficient of catalyzer is 8984g PE/gcath (9.0 * 10
8G PE/ (mol Zr h)).
Comparative Examples 1
Adopt the method synthetic loaded catalyst identical with embodiment 1, the carrier of employing that different is is ES955 silica gel, obtains loaded catalyst ES955-BU.
Results of elemental analyses shows that the aluminium content among the ES955-BU is 32.4 weight %, and the content of Zr is 0.41 weight %, and the mol ratio of Al/Zr is 267.
Experiment Comparative Examples 1
Adopt the method identical with EXPERIMENTAL EXAMPLE 1 to carry out the homopolymerization of ethene, different is that the catalyzer of employing is the ES955-BU that Comparative Examples 1 prepares.The result obtains 65g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.33g/ml, and melting index is MI
2.16=0.119g/10min, as calculated, catalyst efficiency is 1295g PE/gcath (2.9 * 10
7GPE/ (mol Zr h)).
Experiment Comparative Examples 2
Adopt the method identical with EXPERIMENTAL EXAMPLE 2 that ethene and hexene are carried out copolymerization, different is that the catalyzer of employing is the ES955-BU that Comparative Examples 1 prepares.Obtain 76 gram polymkeric substance, the density of this polymer stacks (BD) is 0.299g/ml, and melting index is MI
2.16=0.679g/10min, catalyst efficiency is 2260g PE/gcath (5.1 * 10 as calculated
7GPE/ (mol Zr h)).
Claims (14)
1. a carried metallocene catalyst is characterized in that, this catalyzer comprises carrier and the metallocene compound and the alkylaluminoxane that load on the described carrier, and described carrier is donut-like SBA-15, and described metallocene compound has the structure shown in the 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, 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 the hafnium, X is halogen.
2. carried metallocene catalyst according to claim 1 wherein, is benchmark with the total amount of described carried metallocene catalyst, and the total amount of described metallocene compound and alkylaluminoxane is 10-60 weight %, and the content of described carrier is 90-40 weight %.
3. carried metallocene catalyst according to claim 1 and 2, wherein, the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described metallocene compound is 300-1000:1.
4. carried metallocene catalyst according to claim 3, wherein, the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described metallocene compound is 500-750:1.
5. according to claim 1 or 4 described carried metallocene catalysts, wherein, M is zirconium.
6. carried metallocene catalyst according to claim 1, wherein, X is chlorine.
7. carried metallocene catalyst according to claim 1, 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.
8. according to claim 1,2 or 4 described carried metallocene catalysts, wherein, the alkyl in the described alkylaluminoxane is C
1-C
5Alkyl.
9. carried metallocene catalyst according to claim 8, wherein, described alkylaluminoxane is methylaluminoxane.
10. carried metallocene catalyst according to claim 1, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, described alkylaluminoxane is methylaluminoxane.
11. carried metallocene catalyst according to claim 1 and 2, wherein, the internal diameter of described donut-like SBA-15 and the ratio of external diameter are 0.3-0.9, and mean thickness is 0.1-2 μ m.
12. carried metallocene catalyst according to claim 11, wherein, the most probable aperture of described carrier is 7-10nm, and pore volume is 0.5-3 milliliter/gram, and specific surface area is the 600-1000 meters squared per gram, and median size is 3-20 μ m.
13. a preparation method who prepares any described carried metallocene catalyst among the claim 1-12 is characterized in that this method is included under the atmosphere of inert gases, successively alkylaluminoxane and metallocene compound is loaded on the carrier.
14. preparation method according to claim 13, wherein, this method also is included in before the load alkylaluminoxane, under protection of inert gas, described carrier is heated 7-10 hour under 300-900 ℃ temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1542025A (en) * | 2003-11-06 | 2004-11-03 | 复旦大学 | Alkene polymerization catalyst loaded by mesoporous materials and method for preparing the same |
| CN1718596A (en) * | 2005-07-21 | 2006-01-11 | 浙江大学 | Method of preparing nano-polyethylene fiber by normal pressure extrusion polymerization |
| CN101668578A (en) * | 2007-06-22 | 2010-03-10 | 道达尔石油化学产品研究弗吕公司 | Process for the polymerisation of olefins |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1542025A (en) * | 2003-11-06 | 2004-11-03 | 复旦大学 | Alkene polymerization catalyst loaded by mesoporous materials and method for preparing the same |
| CN1718596A (en) * | 2005-07-21 | 2006-01-11 | 浙江大学 | Method of preparing nano-polyethylene fiber by normal pressure extrusion polymerization |
| CN101668578A (en) * | 2007-06-22 | 2010-03-10 | 道达尔石油化学产品研究弗吕公司 | Process for the polymerisation of olefins |
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