CN102453135B - Olefin polymerization method - Google Patents

Olefin polymerization method Download PDF

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CN102453135B
CN102453135B CN 201010519311 CN201010519311A CN102453135B CN 102453135 B CN102453135 B CN 102453135B CN 201010519311 CN201010519311 CN 201010519311 CN 201010519311 A CN201010519311 A CN 201010519311A CN 102453135 B CN102453135 B CN 102453135B
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alkylaluminoxane
cyclopentadienyl
sba
metallocene catalyst
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CN102453135A (en
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邱波
谢伦嘉
亢宇
王洪涛
王彦强
郭顺
郑刚
刘长城
周歆
王伟
邓晓音
王红英
赵思源
姜健准
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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 catalyst under the olefin polymerization conditions, wherein the supported metallocene catalyst comprises a carrier, and a metallocene compound and alkyl aluminoxane which are supported on the carrier, and is characterized in that: the carrier is SBA-15; the metallocene compound has a structure shown as a formula 1; and in the formula, R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' independently refer to hydrogen or alkyl with 1o 5 carbon atoms, at least one of R1, R2, R3, R4 and R5 refers to alkyl with 1 to 5 carbon atoms, at least one of R1', R2', R3', R4' and R5' refers to alkyl with 1 to 5 carbon atoms, M refers to one of titanium, zirconium and hafnium, and X is halogen. In the olefin polymerization method, the catalyst with high catalytic activity is used, and the catalytic efficiency is high, so a great amount of polymer can be obtained through a small amount of catalyst.

Description

A kind of olefine polymerizing process
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.To reach the required methylaluminoxane of high reactivity (MAO) consumption large due to catalyzed by homogeneous metallocene catalyst, and production cost is high, and the polymkeric substance that obtains can't use on widely used slurry process or gas phase polymerization technique without particle shape.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 that addresses 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 2Be 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, 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 ".
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, will improve the ageing resistance of polyolefine hydrocarbon material;
(2) the molecular sieve nano pore has the dual-use function of carrier and reactor, and catalyst cupport efficient is high, and polymerization process is easily controlled, 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, the olefin coordination polymerization that appears as of molecular sieve carried olefin polymerization catalysis has been opened up a new field.
Compare with zeolite molecular sieve, ordered mesoporous molecular sieve (aperture is the molecular sieve of 2-50nm) has 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.
CN1718596A discloses a kind of carried metallocene catalyst, and this catalyzer is by with Cp 2ZrCl 2Load on the SBA-15 that processes through MAO upper and obtain.But the catalytic activity of the disclosed carried metallocene catalyst of CN1718596A awaits further to improve.
CN1923862A discloses a kind of olefin polymerization catalysis of mesoporous molecular sieve carried, and this catalyzer is that the SBA-15 that processes through MAO is upper to be obtained by the semi-sandwich alum metallic compound shown in following formula is loaded on,
Figure BSA00000318708200021
But the catalytic activity of the disclosed catalyzer of CN1923862A is the highest also only has 10 6GPE/ (molZrh).
Therefore, the carried metallocene catalyst that how to obtain to have high catalytic activity remains a technical problem that needs 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 efficient 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, described carried metallocene catalyst comprises carrier and loads on metallocene compound and alkylaluminoxane on described carrier, it is characterized in that, described carrier is SBA-15, and described metallocene compound has the structure shown in formula 1
Figure BSA00000318708200031
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, metallocene compound in the carried metallocene catalyst that adopts has sandwich structure, and has substituting group on cyclopentadienyl, it is loaded on the mesoporous material SBA-15 of high mechanical strength and good catalytic adsorption performance, can access a Stability Analysis of Structures, therefore the carried metallocene catalyst that catalytic activity is high has high catalytic activity.Particularly, according to olefine polymerizing process of the present invention, carried metallocene catalyst is when being used for catalysis in olefine polymerization, and catalytic efficiency can be 4000-7000gPE/ (gcath) (10 7And the catalyzer catalytic efficiency under the same conditions that the disclosed semi-sandwich alum metallic compound of CN1923862A loads on the SBA-15 that MAO processes is 1000gPE/ (gcath) gPE/ (mol Zrh)); The open Cp of CN1718596A 2ZrCl 2The catalyzer catalytic efficiency under the same conditions that loads on the SBA-15 that MAO processes is 10 6GPE/ (molZrh).
Description of drawings
Fig. 1 is X-ray diffracting spectrum, and wherein, a is the x-ray diffraction pattern of SBA-15, and b is the x-ray diffraction pattern of SBA-15-BU-1.
A in Fig. 2 is the attached graphic representation of nitrogen adsorption-desorption of SBA-15-BU-1, and the b in Fig. 2 is the graph of pore diameter distribution of SBA-15-BU-1.
Fig. 3 is transmission electron microscope photo, and wherein, a is the transmission electron microscope photo of SBA-15, and b is the transmission electron microscope photo of SBA-15-BU-1.
Fig. 4 is stereoscan photograph, and wherein, a1 and a2 are the stereoscan photograph of SBA-15, and b1 and b2 are the stereoscan photograph of SBA-15-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, described carried metallocene catalyst comprises carrier and loads on metallocene compound and alkylaluminoxane on described carrier, it is characterized in that, described carrier is SBA-15, and described metallocene compound has the structure shown in formula 1
Figure BSA00000318708200041
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 compound molecules 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 compound molecules 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 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 in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl a kind of.
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, 1,2,4-trimethylammonium-cyclopentadienyl, 1,2,3,4-tetramethyl--cyclopentadienyl, the pentamethyl-cyclopentadienyl, the ethyl cyclopentadienyl, 1,2-diethyl-cyclopentadienyl, 1,3-diethyl-cyclopentadienyl, 1,2,4-triethyl-cyclopentadienyl, 1,3,5-triethyl-cyclopentadienyl, 1-methyl-2-ethyl-cyclopentadienyl, 1-methyl-3-ethyl-cyclopentadienyl, the n-propyl cyclopentadienyl, the sec.-propyl cyclopentadienyl, 1,3-diη-propyl-cyclopentadienyl, 1-methyl-3-n-propyl-cyclopentadienyl, 1,3-di-isopropyl-cyclopentadienyl, 1-methyl-3-sec.-propyl-cyclopentadienyl, n-butyl cyclopentadienyl, the sec-butyl cyclopentadienyl, the isobutyl-cyclopentadienyl, tertiary butyl cyclopentadienyl, 1,3-di-n-butyl-cyclopentadienyl, 1-methyl-3-normal-butyl-cyclopentadienyl, 1,3-di-sec-butyl-cyclopentadienyl, 1-methyl-3-sec-butyl-cyclopentadienyl, 1,3-diisobutyl-cyclopentadienyl, 1-methyl 3-isobutyl--cyclopentadienyl, 1,3-di-t-butyl-cyclopentadienyl, the 1-methyl 3-tertiary butyl-cyclopentadienyl, the n-pentyl cyclopentadienyl, the isopentyl cyclopentadienyl, the tert-pentyl cyclopentadienyl, the neo-pentyl cyclopentadienyl, 1,3-, two n-pentyls-cyclopentadienyl, 1-methyl-3-n-pentyl-cyclopentadienyl, 1,3-diisoamyl-cyclopentadienyl, 1-methyl-3-isopentyl-cyclopentadienyl, 1,3-, two tert-pentyls-cyclopentadienyl, 1-methyl-3-tert-pentyl-cyclopentadienyl, 1,3-di neo-pentyl-cyclopentadienyl, 1-methyl-3-neo-pentyl-cyclopentadienyl.
Preferably, the R in formula 1 1And R 1' be C independently of one another 1-C 5Alkyl, R 2, R 3, R 4, R 5, R 2', R 3', R 4' and R 5' be hydrogen.The specific examples that satisfies the cyclopentadienyl of above-mentioned requirements comprises: methyl cyclopentadienyl, ethyl cyclopentadienyl, n-propyl cyclopentadienyl, sec.-propyl cyclopentadienyl, n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl, isobutyl-cyclopentadienyl, tertiary butyl cyclopentadienyl, n-pentyl cyclopentadienyl, isopentyl cyclopentadienyl, tert-pentyl cyclopentadienyl, neo-pentyl cyclopentadienyl.
More preferably, R 1And R 1' for being normal-butyl or the tertiary butyl.The specific examples that satisfies the cyclopentadienyl of above-mentioned requirements is tertiary butyl cyclopentadienyl, n-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 1-C 5Alkyl.Described C 1-C 5Alkyl be a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.Be preferably methyl, namely 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 (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 especially catalytic activity.
According to the present invention, described alkylaluminoxane and the metallocene compound charge capacity on described carrier makes total amount take described carried metallocene catalyst as 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, most preferably be 50 % by weight.The content of described carrier can be the 40-90 % by weight, is preferably the 45-55 % by weight, and more preferably the 48-52 % by weight, most preferably be 50 % by weight.
According to the present invention, the ratio between described alkylaluminoxane and metallocene compound can be the known ratio of the technician of field of olefin polymerisation.Particularly, the mol ratio of the M in the aluminium in described alkylaluminoxane and described metallocene compound can be 50-200: 1, be preferably 90-110: and 1,95-105 more preferably: 1, most preferably be 102: 1.
According to the present invention, described carrier is SBA-15, and described SBA-15 can be the known SBA-15 with various microscopic appearances of technician in Zeolite synthesis field.Particularly, described SBA-15 is bar-shaped, and the length of rod can be the 30-100 micron; The most probable aperture of described SBA-15 can be the 6-10 nanometer, is preferably the 6-7 nanometer, more preferably 6.2 nanometers; Pore volume can be 0.5-1.5 ml/g, is preferably 0.8-1.2 ml/g, more preferably 1.0 ml/gs; Specific surface area can be the 600-700 meters squared per gram, is preferably the 630-660 meters squared per gram, more preferably 646 meters squared per gram.
The mesoporous material SBA-15 of above-mentioned specification has high mechanical strength that the wide aperture, pore volume of high-sequential, thicker hole wall keep and good catalytic adsorption performance, have larger specific surface area and relatively large aperture, can process larger molecule or group, in load after metallocene compound and alkylaluminoxane, can access a Stability Analysis of Structures, bar-shaped loaded metallocene catalytic, this stable structure makes the metallocene compound and the alkylaluminoxane that load on mesoporous material SBA-15 can be good at bringing into play its catalytic activity.
Above-mentioned carried metallocene catalyst can be by under protection of inert gas, successively load alkylaluminoxane and metallocene compound and prepare on carrier.
According to the present invention, chemically interactive various gases 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.
Described on carrier the method for load alkylaluminoxane and metallocene compound can be various carrying method well known in the art, for example: dipping, spraying.Adopt the method for dipping can be so that solution enters in duct on carrier more fully, therefore, the present invention be preferably flooded.
According to the present invention, in the above-mentioned carried metallocene catalyst of preparation, before also being included in the load alkylaluminoxane, under protection of inert gas, described carrier was heated 5-20 hour at the temperature of 300-500 ℃.
According to the present invention, prepare the method for above-mentioned carried metallocene catalyst, for example: can comprise the following steps:
(1) thermal activation step under nitrogen protection, in 300-500 ℃ of calcining 5-20 hour, obtains the carrier after thermal activation with carrier such as bar-shaped SBA-15;
(2) carrier after thermal activation is transferred in reactor after nitrogen is fully replaced, add toluene, alkylaluminoxane, count in molar ratio, carrier (take silicon-dioxide): toluene: the amount ratio of alkylaluminoxane is 1: 3-10: 0.1-1, then stirred 1-10 hour in 25-80 ℃, after complete, with hexane washing 2 times, at last solid is dried up with nitrogen again, obtain the carrier of load alkylaluminoxane;
(3) under nitrogen protection, the carrier of load alkylaluminoxane is joined in reactor, add toluene, stir and make slurries; In the container of crossing with nitrogen replacement in advance, solution is made in the metallocene compound dissolving, counted in molar ratio, carrier (take silicon-dioxide): toluene: the amount ratio of metallocene compound is 1: 3-15: 2 * 10 -3-5 * 10 -3Under 25-80 ℃ of agitation condition, slowly metallocene compound solution is added drop-wise in reactor, stirring reaction 0.3-2 hour, after reaction finishes, standing, leach liquid, wash 3 times with toluene and hexane, dry up with nitrogen, obtain carried metallocene catalyst, described metallocene compound solution is preferably the toluene solution of metallocene compound.
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, replenish the solution that interpolation contains aluminum alkyls and/or alkylaluminoxane in reaction system.Be in aluminum alkyls in solution and/or alkylaluminoxane and play the effect of cleaning reaction poisonous substance together with alkylaluminoxane on loading on described carrier, thereby make the metallocene compound that loads on described carrier can bring into play better katalysis.
According to olefine polymerizing process of the present invention, when carrying out under the solution that described one or more alkene and contacting of described carried metallocene catalyst are being contained aluminum alkyls and/or alkylaluminoxane exists.In described aluminum alkyls and described alkylaluminoxane (comprise the alkylaluminoxane that loads on described carrier and be in alkylaluminoxane in solution), whole aluminium and the mol ratio of the M in described metallocene compound can be various mol ratios known in the field.Alkyl in described aluminum alkyls and the described alkylaluminoxane C that respectively does for oneself 1-C 5Alkyl.Preferably, described aluminum alkyls is triethyl aluminum, and described alkylaluminoxane is methylaluminoxane.
The alkylaluminoxane that is in solution can be identical with the kind that loads on alkylaluminoxane on described carrier (that is, replenishing the alkylaluminoxane that the alkylaluminoxane that adds and described carried metallocene catalyst contain), also can difference; 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 efficient by improving polyreaction with described loaded catalyst, so the present invention is not particularly limited for described olefinic polymerization condition.Can be the known polymerizing condition of the technician of field of olefin polymerisation.Preferably, described contact is carried out under solvent exists, and to have the compound of the structure shown in formula 1, the concentration of described loaded catalyst in solvent is 1 * 10 -8-1 * 10 -3Mol/L is preferably 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.Described solvent is selected from alkyl or aromatic hydrocarbon or halohydrocarbon.Be preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, ethylene dichloride or their mixture, most preferably be a kind of in hexane, toluene, heptane or their mixture.
The present invention is the structure of loaded catalyst by X-ray diffraction method, nitrogen adsorption desorption method and the scanning electron microscope method alkylaluminoxane of having measured or characterized carrier S BA-15 and load and carrier with metallocene compound.Measure the content of aluminium and metal M in loaded catalyst by ultimate analysis.
Below by specific embodiment, the present invention is further illustrated, but embodiments of the invention have more than and are limited to following examples.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8 Advance in the model available from German Bruker AXS company; TEM (transmission electron microscope) analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model available from Dutch FEI Co.; Scanning electron microscope analysis is to carry out on the scanning electronic microscope of XL-30 in the model available from U.S. FEI Co..Ultimate analysis is to carry out on the 7500CX instrument in the model available 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 ℃.
Embodiment 1
The present embodiment is used for explanation according to carried metallocene catalyst of the present invention and preparation method thereof.
1) rod-like mesoporous material SBA-15 (is available commercially from Changchun high-tech share company limited of Jilin University, the length of rod is the 30-100 micron, its pore structure parameter is as shown in table 1) 400 ℃ of calcinings 10 hours (thermal activation) under nitrogen protection, remove hydroxyl and remaining moisture, obtain the rod-like mesoporous material after thermal activation;
2) rod-like mesoporous material 0.4 gram after thermal activation is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, add 10 milliliters of refining toluene, methylaluminoxane (MAO is purchased the Albemarle company from the U.S.) auxiliary agent 0.47 gram stirred 4 hours in 50 ℃.After complete, then with 20 milliliters of hexane washings three times, at last solid is dried up with nitrogen, obtain alkylaluminoxane/SBA-15 complex compound carrier (MAO/SBA-15).
3) under nitrogen protection; alkylaluminoxane/SBA-15 complex compound carrier is joined in reactor; add 20 milliliters of refining toluene; slurries are made in stirring; under 30 ℃; slowly drip the toluene solution that 10ml contains two (n-butyl cyclopentadienyl) zirconium dichlorides (being purchased the Aesar from Alfa) of metallocene compound of 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain carried metallocene catalyst and with the carried metallocene catalyst called after SBA-15-BU-1 of gained.By X-ray diffraction method, nitrogen adsorption desorption method and scanning electron microscope, carrier S BA-15 and SBA-15-BU-1 are characterized, its result as shown in Figure 1, Figure 2, Figure 3 and Figure 4, the pore structure parameter of SBA-15-BU-1 is as shown in table 1.Measure the content of aluminium and zirconium in loaded catalyst by ultimate analysis.
A in Fig. 1 is the x-ray diffraction pattern of SBA-15, and the b in Fig. 1 is the x-ray diffraction pattern of SBA-15-BU-1.Can find out significantly that from x-ray diffraction pattern sample SBA-15 and SBA-15-BU-1 all diffraction peak occurs in little angular region.(100) diffraction peak intensity of face is high, peak shape is narrow, illustrates that rod-like mesoporous material SBA-15 and SBA-15-BU-1 have good six side's long-range order pore passage structures.
A in Fig. 2 be carried metallocene catalyst SBA-15-BU-1 nitrogen adsorption-(X-coordinate is relative pressure (p/p to the desorption graphic representation 0)), the b in Fig. 2 is graph of pore diameter distribution, shows that by nitrogen adsorption-desorption thermoisopleth in a carried metallocene catalyst SBA-15-BU-1 is the meso-hole structure of typical orderly hexagonal structure.Can find out that by b graph of pore diameter distribution (X-coordinate is the aperture, and unit is 0.1nm) SBA-15-BU-1 has narrow pore size distribution, and the duct is very even.
A in Fig. 3 is the transmission electron microscope picture of SBA-15, and the b in Fig. 3 is the transmission electron microscope picture of SBA-15-BU-1.Can know from Fig. 3 and see that SBA-15 is the orderly pore passage structures of six sides, after load metallocene, SBA-15-BU-1 duct shape remains unchanged substantially.
Fig. 4 is the microscopic appearance figure of SBA-15 and SBA-15-BU-1.Wherein, the a1 in Fig. 4 and a2 are the microscopic appearance figure of SBA-15, and the b1 in Fig. 4 and b2 are the microscopic appearance figure of SBA-15-BU.As shown in Figure 4, the microscopic appearance figure of mesoporous material SBA-15 and SBA-15-BU-1 is bar-shaped.
Table 1
Can find out from the pore structure parameter of the rod-like mesoporous material SBA-15 shown in table 1 and SBA-15-BU-1, mesoporous material SBA-15 is all reducing to some extent through pore structure parameter after the metallocene load, and this result shows that clearly MAO and metallocene enter into the mesoporous material duct really.
Results of elemental analyses shows, load two (n-butyl cyclopentadienyl) zirconium dichlorides of promotor methylaluminoxane (MAO) and metallocene compound) the content of aluminium of rod-like mesoporous material SBA-15 be 21.3 % by weight, the content of Zr is 0.70 % by weight, and the mol ratio of Al/Zr is 102.According to the weight of SBA-15-BU-1 after the weight of carrier S BA-15 before load and load as can be known: take the total amount of carried metallocene catalyst as benchmark, the total content of methylaluminoxane (MAO) and metallocene compound is 50 % by weight, and the content of carrier is 50 % by weight.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity according to loaded catalyst of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, respectively replace three times with nitrogen and ethene, then add 200 milliliters of hexane solvents, with still temperature rise to 80 ℃, then add 800 milliliters of hexane solvents, along with adding of hexane, triethyl aluminum (TEA) hexane solution of 2 milliliter of 1 mol/L is added, then add the SBA-15-BU65.5 milligram, pass into ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, 421 grams of weighing to get, the efficient of catalyzer is 6427gPE/ (gcath) (8.4 * 10 7GPE/ (mol Zrh)), poly bulk density (BD) is 0.326g/ml, melting index: MI 2.16=0.061g/10min.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity according to loaded catalyst of the present invention.
In the stainless steel polymermaking autoclave of 2 liters, respectively replace three times with nitrogen and ethene, then add 200 milliliters of hexane solvents, with still temperature rise to 80 ℃, then add 800 milliliters of hexane solvents, along with adding of hexane, triethyl aluminum (TEA) hexane of 2 milliliter of 1 mol/L and the hexene solution of 10ml are added, then add the SBA-15-BU37.4 milligram, pass into ethene and pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, collected polymer particle powder, 216 grams of weighing to get, the efficient of catalyzer is 5775gPE/ (gcath) (7.5 * 10 7GPE/ (mol Zrh)), the bulk density of polymkeric substance (BD) is 0.293g/ml, melting index: MI 2.16=0.401g/10min.
Comparative Examples 1
Two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of silica gel (ES955) load metallocene catalyst) preparation also is used for ethylene homo
1) with the 400 ℃ of calcinings 10 hours (thermal activation) under nitrogen protection of ES955 silica gel, remove hydroxyl and remaining moisture, obtain the ES955 silica gel after thermal activation;
2) under nitrogen protection; 0.9 gram ES955 silica gel is joined in reactor; add 1.0 gram methylaluminoxane (MAO is purchased the Albemarle company from the U.S.) and 10ml toluene solution, under 50 ℃ of conditions; after stirring reaction 4 hours; with toluene wash 3 times, complete after, then with 20 milliliters of hexanes washings three times; at last solid is dried up with nitrogen, obtain alkylaluminoxane/ES955 silica gel complex compound carrier (MAO/ES955).
3) under nitrogen protection; alkylaluminoxane/ES955 silica gel complex compound carrier is joined in reactor; add 20 milliliters of refining toluene; slurries are made in stirring; under 30 ℃; slowly drip the toluene solution that 10ml contains two (n-butyl cyclopentadienyl) zirconium dichlorides (being purchased the Aesar from Alfa) of metallocene compound of 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane washed twice, solid is dried up with nitrogen.Supported catalyst called after ES955-BU with gained.
Results of elemental analyses shows, load two (n-butyl cyclopentadienyl) zirconium dichlorides of promotor methylaluminoxane (MAO) and cyclopentadienyl catalyst precursor) the content of aluminium of 955 silica gel be 32.4 % by weight, the content of Zr is 0.41 % by weight, and the mol ratio of Al/Zr is 270.
Experiment Comparative Examples 1
Adopt the method identical with implementing embodiment 1 to carry out the homopolymerization of ethene, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation.Result obtains 65g polyethylene particle powder, and catalyst efficiency is 1295gPE/ (gcath) (2.9 * 10 7GPE/ (mol Zrh)), the bulk density of this polyethylene particle powder (BD) 0.331 is g/ml, melting index: MI 2.16=0.119g/10min.
Experiment Comparative Examples 2
Adopt the method identical with implementing embodiment 2 to carry out the copolymerization of ethene, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation.Result obtains 76g polymer beads powder, and catalyst efficiency is 2260gPE/ (gcath) (5.1 * 10 7GPE/ (mol Zrh)), the bulk density of this polymer beads powder (BD) 0.299 is g/ml, melting index: MI 2.16=0.679g/10min.
Comparative Examples 2
With SBA-15 (being purchased from Changchun high-tech share company limited of Jilin University) 400 ℃ of calcinings 10 hours under nitrogen protection, removing hydroxyl and remaining moisture, thereby obtain the SBA-15 through thermal activation;
The SBA-15 that 0.56 gram is activated is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced, add 10 milliliters of refining toluene (refluxing 24 hours with sodium) and 1 gram methylaluminoxane (being purchased the Albemarle company from the U.S.), and stirred 4 hours at 50 ℃.After reaction is completed, standing, leach liquid after layering, and with 20 milliliters of hexane washings three times, at last solid is dried up with nitrogen, obtaining load has the SBA-15-1 of methylaluminoxane (called after MAO/SBA-15-2).
Under nitrogen protection; MAO/SBA-15-2 is joined in 250 milliliters of glass reactors; add 20 milliliters of refining toluene (refluxing 24 hours with sodium); stirred 30 minutes; under 30 ℃; slowly drip the toluene solution that 10ml contains the bicyclic pentadiene zirconium dichloride (being purchased the company from Aldrich) of 60 milligrams, stirring reaction 0.5 hour.After reaction finishes, standing, leach liquid after layering, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane washed twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after SBA-15-Cp).
The results of elemental analyses demonstration, the aluminium content in SBA-15-Cp is 24 % by weight, and the content of Zr is 1 % by weight, and the mol ratio of Al/Zr is 81.
Experiment Comparative Examples 3
Adopt the method identical with embodiment 1 to carry out the homopolymerization of ethene, different is that the catalyzer of employing is the SBA-15-Cp of preparation Comparative Examples 2 preparations.Result obtains 36g polyethylene particle powder, and the bulk density of this polyethylene particle powder (BD) is 0.30g/ml, melting index: MI 2.16=0.011g/10min.Determine as calculated, the efficient of catalyzer is 384gPE/ (gcath) (3.5 * 10 6GPE/ (mol Zrh)).
Experiment Comparative Examples 4
Adopt the method identical with embodiment 2 that ethene and hexene are carried out copolymerization, different is that the catalyzer of employing is the SBA-15-Cp of preparation Comparative Examples 1 preparation.Obtain 43 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.304g/ml, and melting index is MI 2.16=0.077g/10min.Determine as calculated, the efficient of catalyzer is 438gPE/ (gcath) (4.0 * 10 6G PE/ (mol Zrh)).

Claims (12)

1. olefine polymerizing process, the method is included under the olefinic polymerization condition, one or more alkene are contacted with carried metallocene catalyst, described carried metallocene catalyst comprises carrier and loads on metallocene compound and alkylaluminoxane on described carrier, it is characterized in that, described carrier is SBA-15, described carrier is bar-shaped, the length of rod is the 30-100 micron, the most probable aperture of described carrier is the 6-7 nanometer, pore volume is 0.8-1.2 ml/g, specific surface area is the 630-660 meters squared per gram, described most probable aperture, pore volume and specific surface area are to adopt nitrogen adsorption-desorption measuring, described metallocene compound has the structure shown in formula 1,
Figure FDA00002563503100011
Wherein, R 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' being hydrogen, M is a kind of in titanium, zirconium and hafnium, X is halogen,
The mol ratio of M in aluminium in described alkylaluminoxane and described metallocene compound is 90-110:1.
2. method according to claim 1, wherein, take the total amount of described carried metallocene catalyst as benchmark, the total amount of described metallocene compound and alkylaluminoxane is the 10-60 % by weight, the content of described carrier is the 40-90 % by weight.
3. method according to claim 1 and 2, wherein, described alkylaluminoxane is methylaluminoxane.
4. method according to claim 1, wherein, M is zirconium.
5. method according to claim 1, wherein, X is chlorine.
6. method according to claim 1, wherein, R 1And R 1' respectively do for oneself normal-butyl or the tertiary butyl.
7. method according to claim 1 and 2, wherein, described metallocene compound is two (normal-butyl-cyclopentadienyl) zirconium dichlorides, described alkylaluminoxane is methylaluminoxane.
8. method according to claim 1, wherein, described alkene is one or more in ethene, alpha-olefin and diolefin.
9. method according to claim 8, wherein, described alkene is ethene, C 3-C 101-alkene, C 4-C 8Diolefin in one or more.
10. method according to claim 1, wherein, described olefinic polymerization condition comprises: temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MPa.
11. method according to claim 1, wherein, described contact is carried out under solvent exists, and to have the compound of the structure shown in formula 1, the concentration of described carried metallocene catalyst in solvent is 1 * 10 -8-1 * 10 -3Mol/L, described olefinic polymerization condition comprises: temperature is-78 ℃ to 100 ℃, pressure is 0.01-10MPa.
12. method according to claim 11, wherein, to have the compound of the structure shown in formula 1, the concentration of described carried metallocene catalyst in solvent is 1 * 10 -8-1 * 10 -5Mol/L.
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Title
A. Carrero et al.Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials.《POLYMER ENGINEERING AND SCIENCE》.2008,
A. Carrero et al.Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials.《POLYMER ENGINEERING AND SCIENCE》.2008,第48卷(第3期),
Cristian Covarrubias et al.High catalytic activity of SBA-15-supported metallocene toward ethylene polymerization: The effect of the ordered porous structure of the support.《Catalysis Communications》.2008,第10卷
Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials;A. Carrero et al;《POLYMER ENGINEERING AND SCIENCE》;20080331;606-616 *
Ethylene Polymerization Over (nBuCp)2ZrCl2/MAO Catalytic System Supported on Aluminosilicate SBA-15 Mesostructured Materials;A. Carrero et al;《POLYMER ENGINEERING AND SCIENCE》;20080331;第48卷(第3期);606-616 *
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