CN102453142B - Olefin polymerization method - Google Patents
Olefin polymerization method Download PDFInfo
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- CN102453142B CN102453142B CN201010519682.9A CN201010519682A CN102453142B CN 102453142 B CN102453142 B CN 102453142B CN 201010519682 A CN201010519682 A CN 201010519682A CN 102453142 B CN102453142 B CN 102453142B
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- cyclopentadienyl
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Abstract
The invention provides an olefin polymerization method, comprising a step of contacting one or more kinds of olefins with a supported metallocene catalyst under an olefin polymerization condition. The method is characterized in that the supported metallocene catalyst comprises a carrier as well as a metallocene compound and alkylaluminoxane supported on the carrier, and the carrier is a hollow sphere mesoporous silicon oxide carrier. According to the olefin polymerization method provided by the invention, because the metallocene compound in the used catalyst has a sandwich structure and cyclopentadienyl has a substituent group, the hollow sphere mesoporous silicon oxide carrier has highly ordered large pore diameter (3-20 nanometers) and pore volume, good mechanical strength and good macromolecular catalyzed sorption property, thereby having high polymerization efficiency.
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.Due to catalyzed by homogeneous metallocene catalyst, to reach the required methylaluminoxane of high reactivity (MAO) consumption large, and production cost is high, and the polymkeric substance obtained can't be used without particle shape on widely used slurry process or gas phase polymerization technique.And the activity of metallocene catalyst is very high, is easy to occur local polymerization velocity very fast in polymerization process, and then causes implode.
The effective way addressed the above problem is carried out the load processing to the solubility metallocene catalyst exactly.At present, relevant Methods for Immobilization of Metallocene Catalysts research report is very many, wherein with SiO
2for the report most study of carrier, for example: CN1095474C, CN1049439C, CN1157419C, US4808561, US5026797, US5763543 and US5661098 all disclose with SiO
2carried metallocene catalyst for carrier.Yet, 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 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.And, because molecular sieve has nano pore, in polymerization process, the inserted mode of monomer is different from freeboard with propagation process, the chance that double-basis stops has been reduced in limited space to a certain extent, makes polyreaction show the feature of " living polymerization ".
Olefin polymerization catalysis is carried on to molecular sieve, there is following advantage:
(1) molecular sieve of synthetic does not contain the impurity that easily makes polymer degradation, will 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.
With zeolite molecular sieve, compare, ordered mesoporous molecular sieve (molecular sieve that aperture is 2-50nm), have larger specific surface area and relatively large aperture, can process larger molecule or group, can make catalyzer bring into play well its due catalytic activity.
The mesoporous material of the load metallocene catalyst of reporting on document at present is MCM-41, but activity is only 7.3 * 10 during catalyzed ethylene polymerization
5gPE/ (mol Zr h), and take MAO process after again the MCM-41 of load metallocene to carry out catalytic activity after vinyl polymerization be only also 10
6gPE/ (mol Zr h).
Therefore, how to obtain the carried metallocene catalyst of high catalytic efficiency, and then carry out efficiently olefinic polymerization and remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The catalytic efficiency of carried metallocene catalyst that the object of the invention is to overcome prior art is still lower, causes adopting the not high problem of efficiency of the olefinic polyreaction of carried metallocene catalyst, and a kind of efficient olefine polymerizing process is provided.
The invention provides a kind of olefine polymerizing process, the method is included under the 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 on described carrier, described carrier is the hollow ball mesoporous silicon oxide, and 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, because metallocene compound described in used catalyst has sandwich structure, and there is substituting group on cyclopentadienyl, described hollow ball mesoporous silicon oxide has the wide aperture (3-20 nanometer), pore volume of high-sequential, good physical strength and good bulky molecular catalysis absorption property, therefore has high polymerization efficiency or catalytic efficiency.
Particularly, according to olefine polymerizing process of the present invention, carried metallocene catalyst according to the present invention is for catalysis in olefine polymerization the time, and catalytic efficiency can reach 6122g PE/gcath (that is, 1.05 * 10
8g PE/ (mol Zr h)), and in the situation that other conditions are identical, catalytic efficiency during metallocene compound that industrial 955 silica gel loads have the structure shown in formula 1 only for 1295g PE/gcath (, 2.9 * 10
7gPE/ (mol Zr h)).
The accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of hollow ball meso-porous titanium dioxide silicon carrier MS-1, and Fig. 2 is the x-ray diffraction pattern of carried metallocene catalyst MAO/MS-BU-1.
Fig. 3 and Fig. 4 are respectively the N of hollow ball meso-porous titanium dioxide silicon carrier MS-1 and carried metallocene catalyst MAO/MS-BU-1
2the adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of hollow ball meso-porous titanium dioxide silicon carrier MS-1 and carried metallocene catalyst MAO/MS-BU-1, and wherein, X-coordinate is aperture, and unit is 0.1nm.
Fig. 7 is stereoscan photograph, the stereoscan photograph that a1, a2 are hollow ball meso-porous titanium dioxide silicon carrier MS, the stereoscan photograph of b1, b2 carried metallocene catalyst MAO/MS-BU-1.
Fig. 8 is X-ray energy spectrometer (EDS) the ultimate analysis spectrogram of carried metallocene catalyst MAO/MS-BU-1.
Embodiment
The invention provides a kind of olefine polymerizing process, the method is included under the olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, wherein, described carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on described carrier, described carrier is the hollow ball mesoporous silicon oxide, and 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 the present invention, what the M in formula 1 can be in titanium, zirconium and hafnium is a kind of.M in different metallocene compounds can be identical or different, and preferably, M is zirconium.
According to the present invention, the X in formula 1 is halogen.What particularly, the X in formula 1 can be in fluorine, chlorine, bromine and iodine is a kind of.Preferably, the X in formula 1 is chlorine or bromine.X in different metallocene compounds can be identical or different, and more preferably, the X in formula 1 is chlorine.
According to the present invention, in formula 1, cyclopentadienyl is to form η with central metal M
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
1, R
1' and 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.
More preferably, R
1and R
1' be C
4alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.Particularly, described cyclopentadienyl is n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl, isobutyl-cyclopentadienyl, tertiary butyl cyclopentadienyl.
According to 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 carried metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent catalytic activity.
According to the present invention, loading on metallocene compound on described carrier and the amount of alkylaluminoxane 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 the 10-60 % by weight, when the content of described carrier is the 10-60 % 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, and the content of described carrier is the 45-55 % by weight.Further under preferable case, the total amount of described carried metallocene catalyst of take is benchmark, and the total amount of described metallocene compound and alkylaluminoxane is the 48-52 % by weight, and the content of described carrier is the 48-52 % by weight.Further under preferable case, 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.
According to the present invention, the described alkylaluminoxane and the ratio between metallocene compound that load on described carrier can be the known ratio of the technician of field of olefin polymerisation.Preferably, in element, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound can be 50-200: 1, be preferably 80-120: and 1,90-115 more preferably: 1, further be preferably 95-110: 1, most preferably be 105: 1.
According to the present invention, the average particle diameter of described carrier is the 3-20 micron, and specific surface area is the 200-300 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and the most probable aperture is the 3-20 nanometer; Under preferable case, the average particle diameter of described carrier is the 4-18 micron, and specific surface area is the 220-280 meters squared per gram, and pore volume is 0.6-1.2 ml/g, and the most probable aperture is the 5-15 nanometer; Further, under preferable case, the average particle diameter of described carrier is the 5-18 micron, and specific surface area is the 250-270 meters squared per gram, and pore volume is 0.7-0.9 ml/g, and the most probable aperture is the 8-11 nanometer; Under most preferred case, the average particle diameter of described carrier is the 5-15 micron, and specific surface area is 261 meters squared per gram, and pore volume is 0.8 ml/g, and the most probable aperture is 9.8 nanometers.
According to the present invention, described carried metallocene catalyst can be by under protection of inert gas, successively load alkylaluminoxane and metallocene compound and obtain on carrier.Described alkylaluminoxane and the metallocene compound charge capacity on described carrier makes in the carried metallocene catalyst of acquisition the content of alkylaluminoxane and metallocene compound meet previously described requirement and gets final product.
According to the present invention, the kind of described alkylaluminoxane and metallocene compound describes in detail above, repeats no more herein.
According to the present invention, described carrier can be the hollow ball mesoporous silicon oxide.
In addition, described hollow ball mesoporous silicon oxide can prepare by the method comprised the following steps: under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution, and gained mixture crystallization under crystallization condition after contacting, the gained crystallization product is heated, removed template method, described template is triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol.
Described template can be the conventional various triblock copolymer polyethylene glycol-glycerol of using in this area-polyoxyethylene glycol template, can be for example the template of commodity P123 by name.
According to the present invention, the kind of described acidic aqueous solution has no particular limits, and its pH value can be 1-6, is preferably 3-5; Be for example the pH value acetic acid that is 1-6 and the buffered soln of sodium acetate.
According to the present invention, the condition of described crystallization can comprise: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour.
The condition of described contact can comprise that temperature is 10-60 ℃, and can be 10-72 hour duration of contact.Described contact is preferably carried out under agitation condition.
The condition of described removed template method comprises that temperature is 90-600 ℃, and the time is 10-80 hour.
According to the present invention, in the process for preparing the hollow ball mesoporous silicon oxide, triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol, ethanol, the weight ratio of trimethylpentane and tetramethoxy-silicane can change within the specific limits, preferably, triblock copolymer polyoxyethylene-polyoxytrimethylene-polyoxyethylene, tetramethoxy-silicane, trimethylpentane, the weight ratio of ethanol and acidic aqueous solution can be 1: 2-3: 3-10: 1-5: 10-50, be more preferably 1: 2-2.5: 4-8: 1-3: 20-40, further be preferably 1: 2-2.2: 5-7: 1-2: 25-35, most preferably be 1: 2.13: 6: 1.69: 28.
According to the present invention, 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 toluene; The carrier that has removed described toluene is contacted with the second solution, and described the second solution contains described metallocene compound and toluene, and removes toluene.
Under preferable case, count in molar ratio, carrier: toluene: the amount ratio of alkylaluminoxane is 1: 30-100: 0.1-2.
Under preferable case, count in molar ratio, carrier: toluene: the amount ratio of metallocene compound is 1: 20-150: 2 * 10
-3-9 * 10
-3.
The present invention is not particularly limited for the method for described contact, the whole bag of tricks that can be known to the skilled person, for example: dipping, spraying.The method of employing dipping can be so that solution enters in the duct on carrier more fully, and therefore, the present invention is preferably flooded.
Carrier 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 toluene can be comprised with the condition that described the second solution contacts: the time is 0.3-2 hour, and temperature is 25-80 ℃.
According to the present invention, toluene preferably adopts and well known to a person skilled in the art that method is made with extra care before use, to remove, anhydrates.
According to the present invention; also preferably before the described alkylaluminoxane of load and described metallocene compound; 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).
According to the present invention, 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.
According to the present invention, described alkylaluminoxane and the metallocene compound charge capacity on described carrier makes that to take the total amount of described carried metallocene catalyst be benchmark, the total amount of described metallocene compound and alkylaluminoxane can be the 10-60 % by weight, be preferably the 45-55 % by weight, more preferably the 48-52 % by weight, further be preferably 50 % by weight; The content of described carrier can be the 10-60 % by weight, is preferably the 45-55 % by weight; More preferably the 48-52 % by weight, further be preferably 50 % by weight; The mol ratio of M in aluminium in described alkylaluminoxane and described metallocene compound can be 50-200: 1 is preferably 80-120: 1, and 90-115 more preferably: 1, further be preferably 95-110: 1, most preferably be 105: 1.
A preferred embodiment of the invention, the preparation method of described carried metallocene catalyst comprises:
The 1st step, by triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol and ethanol, join in the buffered soln of pH value for the acetic acid of 1-6 and sodium acetate, is stirred to dissolving at 10-60 ℃ of temperature;
The 2nd step adds trimethylpentane in previous step gained solution, stirs 1-20 hour at 10-60 ℃ of temperature;
The 3rd step adds tetramethoxy-silicane in previous step gained solution, stirs 10-72 hour at 10-60 ℃ of temperature;
The 4th step, be placed in closed reaction vessel by upper step gained solution, crystallization 10-72 hour at 30-150 ℃ of temperature;
The 5th step, by the filtration of crystallization after product, washing, drying, obtain the hollow ball-shape mesoporous material raw powder;
The 6th step is calcined gained hollow ball-shape mesoporous material 10 hours-80 hours with 90 ℃ of-600 ℃ of temperature in retort furnace, removes the masterplate agent;
The 7th step, the thermal activation step, the spherical mesoporous material that upper step gained is hollow, under nitrogen protection, in 300-900 ℃ of calcining 7-10 hour, obtains the hollow spherical mesoporous material after thermal activation;
The 8th step, hollow spherical mesoporous material after thermal activation is transferred in the reactor after nitrogen is fully replaced, add solvent and alkylaluminoxane, count in molar ratio, hollow spherical mesoporous material: solvent: the amount ratio of alkylaluminoxane is 1: 30-100: 0.1-2, then stir 1-10 hour in 25-80 ℃, after, with hexane washing 2 times, afterwards solid is dried up with nitrogen again, obtain the hollow spherical mesoporous material of load methylaluminoxane;
The 9th step, under nitrogen protection, join the hollow spherical mesoporous material of load methylaluminoxane in reactor, adds stirring solvent to make slurries; In the container of crossing with nitrogen replacement in advance, metallocene compound is dissolved and makes solution, under 25-80 ℃ of agitation condition, slowly metallocene compound solution is added drop-wise in reactor, count in molar ratio hollow spherical mesoporous material: toluene: the amount ratio of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of metallocene is 1: 20-150: 2 * 10
-3-9 * 10
-3, stirring reaction 0.3-2 hour, after reaction finishes, standing, leach liquid, with toluene and hexane washing, with nitrogen, dry up, obtain described carried metallocene catalyst.
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, and described solvent is preferably and replaces or unsubstituted alkane or replacement or unsubstituted aromatic hydrocarbons.When described alkane and aromatic hydrocarbons have substituting group, described substituting group is preferably halogenic substituent.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, be 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.That is,, according to olefine polymerizing process of the present invention, preferably, when 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 on loading on described carrier, thereby make the metallocene compound loaded on described carrier can bring into play better katalysis.
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, in described aluminum alkyls and described alkylaluminoxane (comprising the alkylaluminoxane that loads on described carrier and the alkylaluminoxane in solution), whole aluminium and the mol ratio of the M in described metallocene compound can be 100-3000: 1.
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, described aluminum alkyls is triethyl aluminum.
Alkylaluminoxane in solution can be identical with the kind that loads on the alkylaluminoxane (that is, the alkylaluminoxane that the supplementary alkylaluminoxane added 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.
According to olefine polymerizing process of the present invention, because the present invention is efficiency by improve polyreaction with described carried metallocene catalyst, so the present invention is not particularly limited for described olefinic polymerization condition.It can be the known polymerizing condition of the technician of field of olefin polymerisation.Preferably, in metallocene compound, the concentration of described carried metallocene catalyst can be 1 * 10
-8-1 * 10
-5mol/L.The temperature of polymerization can be-78 ℃ to 100 ℃, is preferably 0 ℃-90 ℃; Pressure can be 0.01-10MPa, is preferably 0.01-2MPa.
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.Ultimate analysis is carried out on the model 7500CX instrument purchased from U.S. An Jielun company.
Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption instrument, sample is degassed 4 hours at 200 ℃.
Preparation example 1
This preparation example is for the preparation of the carried metallocene catalyst used in olefine polymerizing process according to the present invention.
By 1.0 gram three down section multipolymer polyethylene glycol-glycerol-polyoxyethylene glycol (purchased from Aldrich, trade mark P123) and 1.69 gram ethanol join in the buffered soln of acetic acid that the pH of 28ml is 4.4 and sodium acetate, being stirred to polyethylene glycol-glycerol-polyoxyethylene glycol under 15 ℃ dissolves fully, afterwards the trimethylpentane of 6g is joined in above-mentioned solution, 15 ℃ were stirred after 8 hours, again 2.13 gram tetramethoxy-silicanes are joined in above-mentioned solution, 15 ℃ were stirred after 20 hours, solution is transferred in the teflon-lined reactor, 60 ℃ of lower crystallization after 24 hours through filtering, use distilled water wash, obtain the former powder of hollow ball mesoporous silicon oxide after drying.
The former powder of hollow ball mesoporous silicon oxide is calcined 24 hours in retort furnace at 550 ℃, obtained hollow ball mesoporous silicon oxide (called after MS-1).
By hollow ball mesoporous silicon oxide MS-1 under nitrogen protection 400 ℃ the calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the hollow ball mesoporous silicon oxide through thermal activation.
Hollow ball mesoporous silicon oxide by 0.50 gram through thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, and adds 20 milliliters of refining toluene, 0.51 gram methylaluminoxane (purchased from U.S. Albemarle company) to stir 4 hours in 50 ℃.After, then, with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen, obtaining load has the MS-1 of methylaluminoxane (called after MAO/MS-1).
Under nitrogen protection, MAO/MS-1 is joined in 250 milliliters of glass reactors, add 20 milliliters of refining toluene; under 30 ℃; slowly drip two (n-butyl cyclopentadienyl) zirconium dichlorides (purchased from Alfa Aesar, article No. H27576) of 28 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid after layering, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after MAO/MS-BU-1).With XRD, nitrogen adsorption-desorption experiment, scanning electron microscope, X-ray energy spectrometer and ICP ultimate analysis, this carried metallocene catalyst is characterized.
The x-ray diffraction pattern that Fig. 1 is hollow ball meso-porous titanium dioxide silicon carrier MS-1, the x-ray diffraction pattern that Fig. 2 is carried metallocene catalyst MAO/MS-BU-1.By XRD spectra, can obviously be found out, Small angle spectrum peak all appears in hollow ball meso-porous titanium dioxide silicon carrier MS-1 and carried metallocene catalyst MAO/MS-BU-1, illustrates that MAO/MS-BU-1 has the hexagonal hole road structure of the peculiar 2D of mesoporous material.
Fig. 3 and Fig. 4 are respectively the N of hollow ball meso-porous titanium dioxide silicon carrier MS-1 and carried metallocene catalyst MAO/MS-BU-1
2the adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0.Fig. 4 shows that MAO/MS-BU-1 has the IV type thermoisopleth of sharp-pointed capillary condensation speed, and this thermoisopleth has the H1 hysteresis loop, and this shows that MAO/MS-BU-1 has the aperture size distribution of homogeneous.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of hollow ball meso-porous titanium dioxide silicon carrier MS-1 and carried metallocene catalyst MAO/MS-BU-1, and wherein, X-coordinate is aperture, and unit is 0.1nm.As seen from Figure 6, MAO/MS-BU-1 has six sides' meso-hole structure, and duct is very even.
Fig. 7 is stereoscan photograph, the stereoscan photograph that a1, a2 are hollow ball meso-porous titanium dioxide silicon carrier MS-1, the stereoscan photograph of b1, b2 carried metallocene catalyst MAO/MS-BU-1.As seen from the figure, the MS-1 particle diameter is 5-15 μ m, and particle diameter and the MS-1 of MAO/MS-BU-1 are basic identical, this explanation MS-1 particle size dispersion, and MAO/MS-BU-1 has mechanical property preferably.
Fig. 8 is X-ray energy spectrometer (EDS) the ultimate analysis spectrogram of carried metallocene catalyst MAO/MS-BU-1.That by spectrogram, can find out the MAO/MS-BU-1 surface contains Al and Zr, and it is comparatively even to distribute, methylaluminoxane MAO and two (n-butyl cyclopentadienyl) zirconium dichloride (BUCP) that this explanation loads on the surface of mesoporous material MS distribute very even.
The pore structure parameter that table 1 is hollow ball meso-porous titanium dioxide silicon carrier MS-1 and carried metallocene catalyst MAO/MS-BU-1,
Table 1 pore structure parameter
| Sample | Specific surface area (m 2/g) | Pore volume (ml/g) | Most probable aperture (nm) |
| MS-1 | 261 | 0.8 | 9.8 |
| MAO/MS-BU-1 | 230 | 0.3 | 4.8 |
Data by upper table 1 can find out, hollow ball meso-porous titanium dioxide silicon carrier MS-1 after load metallocene, pore volume, specific surface area and aperture all reduce to some extent, this explanation metallocene in the load-reaction process enters into the spheroid inside of hollow ball-shape mesoporous material.
Ultimate analysis ICP result shows, load two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of promotor methylaluminoxane (MAO) and cyclopentadienyl catalyst precursor) the aluminium content of hollow ball mesoporous material MAO/MS-BU-1 be 16.7%, the mol ratio that the content of Zr is 0.53%, Al/Zr is 105: 1.Through conversion, learn, the total amount of catalyzer of take is benchmark, and the total content of methylaluminoxane (MAO) and metallocene compound is 50 % by weight, and the content of carrier is 50 % by weight.
The present embodiment is used for explanation according to 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, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L, then add 60.6 milligrams of MAO/MS-BU-1, pass into ethene pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 371 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.031g/ml, melting index MI
2.16=0.323g/10min.Determine as calculated, the efficiency of catalyzer is 6122g PE/gcath (that is, 1.05 * 10
8g PE/ (mol Zr h)).
The present embodiment is used for explanation according to 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, triethyl aluminum (TEA) hexane solution that the concentration that adds 2 milliliters is 1 mol/L and 10 milliliters of hexenes, the MAO/MS-BU-1 that then adds 44.6 milligrams, passed into ethene pressure risen to 1.0MPa and is maintained 1.0MPa, 80 ℃ of reactions 1 hour.Obtain 267.5 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.499g/ml, melting index MI
2.16=0.301g/10min.Determine as calculated, the efficiency of catalyzer is 5998g PE/gcath (that is, 1.03 * 10
8g PE/ (mol Zr h)).
Preparation Comparative Examples 1
By ES955 silica gel under nitrogen protection 400 ℃ the calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the silica gel through the ES955 of thermal activation.
Under nitrogen protection; 0.9 gram ES955 silica gel is joined in 250 milliliters of glass reactors; add again 1.0 gram methylaluminoxane and 10mL toluene; under 50 ℃ of conditions; after stirring reaction 4 hours, use toluene wash 3 times, then wash three times with 20 milliliters of hexanes; finally solid is dried up with nitrogen, obtaining load has the ES955 of methylaluminoxane (called after MAO/ES955).
Under nitrogen protection; MAO/ES955 is joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene (refluxing 24 hours with sodium); under 30 ℃; slowly drip two (normal-butyl-cyclopentadienyl) zirconium dichlorides of metallocene catalyst precursors of 44 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, obtain carried metallocene catalyst (called after ES955-BU).
The results of elemental analyses demonstration, the content of the aluminium in ES955-BU is 32.4 % by weight, and the content of Zr is 0.41 % by weight, and the mol ratio of Al/Zr is 270.
Comparative Examples 1
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 0.331g/ml, melting index: MI
2.16=0.119g/10min.Determine as calculated, the efficiency of catalyzer is 1295g PE/gcath (that is, 2.9 * 10
7gPE/ (mol Zr h)).
Comparative Examples 2
Adopt the method identical with embodiment 2 that ethene and hexene are carried out to copolymerization, different, the ES955-BU that the catalyzer of employing is Comparative Examples 1 preparation.Obtain 76 gram polymkeric substance, the density of this polymer stacks (BD) is 0.299g/ml, and melting index is MI
2.16=0.679/10min.Determine as calculated, the efficiency of catalyzer is 2260g PE/gcath (that is, 5.1 * 10
7gPE/ (mol Zr h)).
Preparation Example 2
The hollow ball mesoporous silicon oxide MS-1 that Preparation Example 1 is obtained under nitrogen protection 400 ℃ the calcining 10 hours, to remove hydroxyl and remaining moisture, thereby obtain the hollow ball mesoporous silicon oxide through thermal activation.
Hollow ball mesoporous silicon oxide by 0.17 gram through thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, and adds 20 milliliters of refining toluene, 0.17 gram methylaluminoxane to stir 4 hours in 50 ℃.After, then, with 20 milliliters of hexane washings three times, finally solid is dried up with nitrogen, obtaining load has the MS-2 of methylaluminoxane (called after MAO/MS-2).
Under nitrogen protection; MAO/MS-2 is joined in 250 milliliters of glass reactors, add 20 milliliters of refining toluene, under 30 ℃; slowly drip two (1-methyl-3-butyl-cyclopentadienyl) zirconium dichlorides (purchased from Alfa Aesar) of 10 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid after layering, by 10 milliliters of toluene wash three times, follow, by 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after MAO/MS-BM).Ultimate analysis ICP result shows, load the aluminium content of hollow ball mesoporous material MAO/MS-BM of two (1-methyl-3-butyl-cyclopentadienyl) zirconium dichlorides of promotor methylaluminoxane (MAO) and metallocene compound be 19 % by weight, the content of Zr is 0.22 % by weight, and the mol ratio of Al/Zr is 291: 1.
Adopt the method identical with embodiment 1 to carry out the homopolymerization of ethene, different, the MAO/MS-BM that the catalyzer of employing is Preparation Example 2 preparations.Result obtains 118g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.257g/ml, melting index (MI
2.16) be 0.001g/10min.Determine as calculated, the efficiency of catalyzer is 1297g PE/gcath (that is, 5.4 * 10
7gPE/ (mol Zr h)).
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, triethyl aluminum (TEA) hexane solution and the 10 milliliters of hexenes that add 2 milliliter of 1 mol/L, then add 40.3 milligrams of MAO/MS-BM, pass into ethene pressure risen to 1.0MPa and to be maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain the polymkeric substance of 43.36 gram ethene and hexene, the bulk density of the polymkeric substance of this ethene and hexene (BD) is 0.259g/ml, melting index MI
2.16=0.025g/10min.Determine as calculated, the efficiency of catalyzer is 1076g PE/gcath (7.5 * 10
7gPE/ (mol Zr h)).
Claims (16)
1. an olefine polymerizing process, the method is included under the 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 on described carrier, described carrier is the hollow ball mesoporous silicon oxide, and described metallocene compound has the structure shown in formula 1
Formula 1
Wherein, R
1, R
1' be C
1-C
5alkyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' being hydrogen, M is a kind of in titanium, zirconium and hafnium, X is halogen;
The average particle diameter of described carrier is the 3-20 micron, specific surface area is the 200-300 meters squared per gram, pore volume is 0.5-1.5 ml/g, and the most probable aperture is the 3-20 nanometer, and described most probable aperture, pore volume and specific surface area are by nitrogen adsorption-desorption measuring.
2. method according to claim 1, wherein, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is the 10-60 % by weight, the content of described carrier is the 10-60 % by weight, and the total amount of described metallocene compound, described alkylaluminoxane and described carrier is 100 % by weight, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound is 50-200:1.
3. method according to claim 2, wherein, the total amount of described carried metallocene catalyst of take is benchmark, the total amount of described metallocene compound and alkylaluminoxane is the 45-55 % by weight, the content of described carrier is the 45-55 % by weight, and the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound is 80-120:1.
4. according to claim 1,2 or 3 described methods, wherein, the alkyl in described alkylaluminoxane is C
1-C
5alkyl.
5. method according to claim 4, wherein, described alkylaluminoxane is methylaluminoxane.
6. according to the described method of claim 1 or 3, wherein, M is zirconium.
7. method according to claim 1, wherein, X is chlorine.
8. method according to claim 7, wherein, R
1, R
1' be normal-butyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
9. method according to claim 1, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, described alkylaluminoxane is methylaluminoxane.
10. method according to claim 1, wherein, described carrier is made by the method comprised the following steps: under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution, and gained mixture crystallization under crystallization condition after contacting, by the heating of gained crystallization product, removed template method, described template is polyethylene glycol-glycerol-polyoxyethylene glycol.
11. method according to claim 10, wherein, the buffered soln that described acidic aqueous solution is acetic acid and sodium acetate, and the pH value of described damping fluid is 1-6; The condition of described contact comprises that temperature is 10-60 ℃, and the time is 10-72 hour; Described crystallization condition comprises: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour; The condition of described removed template method comprises that temperature is 90-600 ℃, and the time is 10-80 hour.
12. method according to claim 11, wherein, the weight ratio of polyethylene glycol-glycerol-polyoxyethylene glycol, tetramethoxy-silicane, trimethylpentane, ethanol and acidic aqueous solution is 1:2-3:3-10:1-5:10-50.
13. method according to claim 1, wherein, described alkene is one or more in ethene, alpha-olefin and diolefin.
14. method according to claim 1, wherein, described alkene is ethene, C
3-C
101-alkene, C
4-C
8diolefin in one or more.
15. method according to claim 1, wherein, described olefinic polymerization condition comprises: temperature is-78 ℃ to 100 ℃, and pressure is 0.01-10MPa.
16. method according to claim 1, wherein, described contact is carried out in solvent, and described olefinic polymerization condition comprises: in metallocene compound, the concentration of described carried metallocene catalyst is 1 * 10
-8-1 * 10
-5mol/L, temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MPa.
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