CN102453139A - Olefin polymerization method - Google Patents
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- CN102453139A CN102453139A CN2010105193958A CN201010519395A CN102453139A CN 102453139 A CN102453139 A CN 102453139A CN 2010105193958 A CN2010105193958 A CN 2010105193958A CN 201010519395 A CN201010519395 A CN 201010519395A CN 102453139 A CN102453139 A CN 102453139A
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Abstract
The invention provides an olefin polymerization method, which comprises the following steps that: under an olefin polymerization condition, at least one kind of olefin is contacted with a load type metallocene catalyst. The olefin polymerization method is characterized in that the load type metallocene catalyst comprises a carrier, and a metallocene compound and alkylaluminoxane which are on the carrier, wherein the carrier is a spherical mesoporous silicon dioxide carrier, and the metallocene compound has a structure shown in the formula 1. According to the olefin polymerization method provided by the invention, the activity of the load type metallocene catalyst for catalyzing cinyl polymerization is 1.5*109gPE/(mol Zr h), while the activity of active components with the same load of 955 silica gel generally used in industry is only 5.1*107gPE/(mol Zr h).
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; Eighties particularly; People such as Kaminsky and Sinn develops efficient promotor MAO (MAO), makes 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; Production cost is high; And the polymkeric substance that obtains does not have particle shape; Can't on widely used slurry process or gas phase polymerization technology, use, 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
2As silica gel 955 be carrier report research at most, for example CN1095474C, CN1049439C, CN1157419CUS4808561, US5026797, US5763543, US5661098 all discloses with SiO
2Carried metallocene catalyst 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 the evenly regular one dimension or the mesoporous material of solid netted sieve aperture, and surfactivity is higher, absorption property good, have tangible molecule shape selectivity ability, and its allows the monomer of certain size and the polymkeric substance of formation thereof to insert in the duct of molecular sieve.Especially (aperture=2-50nm), compare with zeolite molecular sieve has bigger specific surface area and relatively large aperture to ordered mesoporous molecular sieve, can handle bigger molecule or group, makes catalyzer well bring into play its due catalytic activity.Because molecular sieve has nano pore, monomeric inserted mode is different with freeboard with propagation process in the polymerization process, and double-basis terminated chance has been reduced in limited space to a certain extent, makes polyreaction show the characteristic 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 is prone to make polymer degradation, with the ageing resistance that improves polyolefine material; (2) the molecular sieve nano pore has the dual-use function of carrier and reactor drum, and catalyst cupport efficient is high, and polymerization process is controlled easily, and can in the skeleton of polymerization reactor, key in the active site, 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.
Have bibliographical information to come catalysed olefin polymerization at present, but the activity of catalyzed ethylene polymerization is merely 10 with the MCM-41 mesoporous material load metallocene catalyst that MAO handles
6G PE/ (mol Zr h) (Chen ST, Guo C Y, Lei L, et al.Polymer, 2005,46:11093).
CN1923862A discloses a kind of olefin polymerization catalysis of mesoporous molecular sieve carriedization, and this catalyzer is upward to obtain through the semi-sandwich alum metallic compound shown in the following formula being loaded on the SBA-15 that handles through MAO,
But the catalytic activity of the disclosed catalyzer of CN1923862A is the highest also has only 10
6G PE/ (molZr h).
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 activity of carried metallocene catalyst that the objective 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 olefine polymerizing process efficiently is provided.
The invention provides a kind of olefine polymerizing process; This method is included under the olefinic polymerization condition, and at least a alkene is contacted with carried metallocene catalyst, it is characterized in that; Said carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier; Said carrier is the sphericity mesoporous silicon dioxide carrier, and said 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 a halogen.
Olefine polymerizing process provided by the invention uses that meso-hole structure is stable, microscopic appearance as dispersiveness preferably, complete spheric carried metallocene catalyst; Olefine polymerizing process compared to prior art; Under the situation of identical catalyst levels, can obtain more olefin polymer.
Can find out that with Comparative Examples 1 in the olefine polymerizing process provided by the invention, every mole carried metallocene catalyst can obtain 1.5 * 10 in 1 hour according to embodiment 1
9GPE, and, under the identical situation of other conditions, only can obtain 5.1 * 10 with the existing olefine polymerizing process of the catalyzer of the identical active ingredient of 955 commonly used silica gel loads of industry
7GPE.
Description of drawings
Fig. 1 is an X-ray diffracting spectrum, and wherein, a is the X-ray diffracting spectrum of JKQ, and b is the X-ray diffracting spectrum of JKQ-BU.
Fig. 2 is nitrogen adsorption-desorption graphic representation, and wherein, X-coordinate is a relative pressure, and unit is p/p
0, a is nitrogen adsorption-desorption graphic representation of JKQ, b is nitrogen adsorption-desorption graphic representation of JKQ-BU.
Fig. 3 is a graph of pore diameter distribution, and wherein, X-coordinate is the aperture, and unit is nm, and a is the graph of pore diameter distribution of JKQ, and b is the graph of pore diameter distribution of JKQ-BU.
Fig. 4 is a transmission electron microscope photo, and wherein, a is the transmission electron microscope photo of JKQ, and b is the transmission electron microscope photo of JKQ-BU.
Fig. 5 is a stereoscan photograph; Wherein, A1 and a2 are the stereoscan photograph of JKQ; B1 and b2 are the stereoscan photograph of JKQ-BU, and c1 and c2 are the stereoscan photograph of the ethylene homo product of JKQ-BU catalysis generation, and d1 and d2 are the ethene of JKQ-BU catalysis generation and the stereoscan photograph of hervene copolymer product.
Embodiment
The invention provides a kind of olefine polymerizing process; This method is included under the olefinic polymerization condition, at least a alkene is contacted with carried metallocene catalyst, wherein; Said carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier; Said carrier is the sphericity mesoporous silicon dioxide carrier, and said 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 a halogen.
According to 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.Preferably, M is a zirconium.
According to the present invention, the X in the formula 1 is a halogen.What particularly, the X in the formula 1 can be in fluorine, chlorine, bromine and the iodine is a kind of.X in the different metallocene compound molecules can be identical or different.Preferably, the X in the formula 1 is a chlorine or bromine.More preferably, the X in the formula 1 is a chlorine.
According to the present invention, in the formula 1, cyclopentadienyl moiety is for forming η with central metal
5Key and have the verivate of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl moiety 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, said 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 at least a.
The specific examples that satisfies the cyclopentadienyl moiety of above-mentioned requirements comprises: methyl cyclopentadienyl, 1,2-dimethyl--cyclopentadienyl moiety, 1,3-dimethyl--cyclopentadienyl moiety, 1; 2,3-trimethylammonium-cyclopentadienyl moiety, 1,2; 4-trimethylammonium-cyclopentadienyl moiety, 1; 2,3,4-tetramethyl--cyclopentadienyl moiety, pentamethyl-cyclopentadienyl moiety, ethyl cyclopentadienyl moiety, 1; 2-diethylammonium-cyclopentadienyl moiety, 1; 3-diethylammonium-cyclopentadienyl moiety, 1,2,4-triethyl-cyclopentadienyl moiety, 1; 3; 5-triethyl-cyclopentadienyl moiety, 1-methyl-2-ethyl-cyclopentadienyl moiety, 1-methyl-3-ethyl-cyclopentadienyl moiety, n-propyl cyclopentadienyl moiety, sec.-propyl cyclopentadienyl moiety, 1,3-di-cyclopentadienyl moiety, 1-methyl-3-n-propyl-cyclopentadienyl moiety, 1,3-di-isopropyl-cyclopentadienyl moiety, 1-methyl-3-sec.-propyl-cyclopentadienyl moiety, n-butyl cyclopentadienyl, sec.-butyl cyclopentadienyl moiety, isobutyl-cyclopentadienyl moiety, tertiary butyl cyclopentadienyl moiety, 1; 3-di-n-butyl-cyclopentadienyl moiety, 1-methyl-3-normal-butyl-cyclopentadienyl moiety, 1; 3-two sec.-butyls-cyclopentadienyl moiety, 1-methyl-3-sec.-butyl-cyclopentadienyl moiety, 1,3-diisobutyl-cyclopentadienyl moiety, 1-methyl 3-isobutyl--cyclopentadienyl moiety, 1,3-di-t-butyl-cyclopentadienyl moiety, the 1-methyl 3-tertiary butyl-cyclopentadienyl moiety, n-pentyl cyclopentadienyl moiety, isopentyl cyclopentadienyl moiety, tert-pentyl cyclopentadienyl moiety, neo-pentyl cyclopentadienyl moiety, 1; 3-two n-pentyls-cyclopentadienyl moiety, 1-methyl-3-n-pentyl-cyclopentadienyl moiety, 1; 3-diisoamyl-cyclopentadienyl moiety, 1-methyl-3-isopentyl-cyclopentadienyl moiety, 1,3-two tert-pentyls-cyclopentadienyl moiety, 1-methyl-3-tert-pentyl-cyclopentadienyl moiety, 1,3-di neo-pentyl-cyclopentadienyl moiety, 1-methyl-3-neo-pentyl-cyclopentadienyl moiety.
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 moiety of above-mentioned requirements comprises: methyl cyclopentadienyl, ethyl cyclopentadienyl moiety, n-propyl cyclopentadienyl moiety, sec.-propyl cyclopentadienyl moiety, n-butyl cyclopentadienyl, sec.-butyl cyclopentadienyl moiety, isobutyl-cyclopentadienyl moiety, tertiary butyl cyclopentadienyl moiety, n-pentyl cyclopentadienyl moiety, isopentyl cyclopentadienyl moiety, tert-pentyl cyclopentadienyl moiety, neo-pentyl cyclopentadienyl moiety.
More preferably, R
1And R
1' be a kind of in normal-butyl, sec.-butyl, isobutyl-and the tertiary butyl.Most preferably, R
1And R
1' be normal-butyl.
According to the present invention, said alkylaluminoxane can be metallocene catalyst field various alkylaluminoxanes commonly used.Usually, the alkyl in the said alkylaluminoxane is C
1-C
5Alkyl.C
1-C
5Alkyl can be above-described various C
1-C
5Alkyl.Preferably, said alkylaluminoxane is a MAO.
Contriver of the present invention finds in research process, the R in formula 1
1And R
1' be normal-butyl, M is a zirconium, X is a chlorine; Be that said metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides; And when alkylaluminoxane is MAO, when said carried metallocene catalyst is used for the polyreaction of catalyzed alkene, demonstrate excellent catalytic activity.
According to the present invention, the metallocene compound and the amount of alkylaluminoxane that load on the said carrier can change within a large range.Contriver of the present invention finds that the total amount of said metallocene compound and alkylaluminoxane is 10-60 weight %, when the content of said carrier is 40-90 weight %, not only can obtain gratifying catalytic effect, but also can reduce cost.More preferably, be benchmark with the total amount of said carried metallocene catalyst, the total amount of said metallocene compound and alkylaluminoxane is 45-55 weight %, the content of said carrier is 45-55 weight %; Most preferably, be benchmark with the total amount of said carried metallocene catalyst, the total amount of said metallocene compound and alkylaluminoxane is 55 weight %, the content of said carrier is 45 weight %.It should be explicitly made clear at this point that the content of metallocene compound and alkylaluminoxane and carrier in the said catalyzer calculates according to the weight of the raw material of each component before the load.
According to loaded catalyst of the present invention, the ratio between said alkylaluminoxane and the metallocene compound can be the known ratio of the technician of field of olefin polymerisation.Particularly, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound can be 10-50: 1, further be preferably 15-40: and 1, most preferably be 15-20: 1.
According to carried metallocene catalyst provided by the invention, wherein, the particle diameter of said carrier can be the 3-20 micron, is preferably the 10-20 micron; Pore volume can be 0.5-1.5 milliliter/gram, is preferably 0.6-1.0 milliliter/gram, most preferably is 0.7 milliliter/gram; The most probable aperture can be the 1.0-3.0 nanometer, is preferably the 1.5-2.5 nanometer, most preferably is 1.9 nanometers; Specific surface area can be the 1000-2000 meters squared per gram, is preferably the 1100-1500 meters squared per gram, most preferably is 1200 meters squared per gram.
According to the present invention; Said sphericity mesoporous silicon dioxide carrier also can prepare through the method that may further comprise the steps: in the presence of template; Silicon ester is contacted with acidic aqueous solution, and will contact back gained mixture crystallization under crystallization condition, the gained crystallization product is heated; Removed template method, said template are cetyl trimethylammonium bromide and polyoxyethylene octyl phenyl ether (having another name called triton x-100).
According to aforesaid method; The acid in said silicon ester, cetyl trimethylammonium bromide, polyoxyethylene octyl phenyl ether (triton x-100), the acidic aqueous solution and the mol ratio of water can change within the specific limits; Preferably; The acid in said silicon ester, cetyl trimethylammonium bromide, polyoxyethylene octyl phenyl ether (triton x-100), the acidic aqueous solution and the mol ratio of water are 1: 0.1-0.6: 0.1-0.5: 5-50: 100-500; More preferably; The acid in said silicon ester, cetyl trimethylammonium bromide, polyoxyethylene octyl phenyl ether (triton x-100), the acidic aqueous solution and the mol ratio of water are 1: 0.2-0.4: 0.2-0.5: 10-20: 200-300; Most preferably, the acid in said silicon ester, cetyl trimethylammonium bromide, polyoxyethylene octyl phenyl ether (triton x-100), the acidic aqueous solution and the mol ratio of water are 1: 0.22: 0.4: 13: 244.
According to aforesaid method, said silicon ester can be tetraethoxy.
The condition of said contact comprises that temperature can be 25-60 ℃, is preferably 30-50 ℃, most preferably is 40 ℃.Time can be 10-60 minute, most preferably is 15 minutes.Said contact is preferably under agitation carried out.
The condition of said crystallization comprises that temperature can be 25-60 ℃, is preferably 30-50 ℃, most preferably is 40 ℃.Time can be 10-40 hour, most preferably is 24 hours.The temperature of said contact and crystallization can be identical or different, as long as in above-mentioned scope.
The method of said removed template method can be calcination method, and the condition of said calcination method comprises that temperature can be 500-700 ℃, is preferably 600 ℃.Time can be 10-40 hour, is preferably 20-30 hour, most preferably is 24 hours.
According to the present invention, said carried metallocene catalyst can be through under protection of inert gas, successively load alkylaluminoxane and metallocene compound and obtain on carrier.The content of alkylaluminoxane and metallocene compound satisfies the described requirement of preamble and gets final product in the carried metallocene catalyst that said alkylaluminoxane and the metallocene compound charge capacity on said carrier make to obtain.
According to the present invention, said carrier, alkylaluminoxane and metallocene compound describe in detail at preamble, repeat no more here.
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 the said carrier.Preferably, successively the method at load alkylaluminoxane and metallocene compound on the carrier comprises: under protection of inert gas, said carrier is contacted with first solution, said first solution contains the said alkylaluminoxane and first solvent; The carrier that has removed said first solvent is contacted with second solution, and said second solution contains the said metallocene compound and second solvent, and removes solvent, and said first solvent and second solvent are toluene.
The present invention does not limit for the method for said contact is special, can be for well known to a person skilled in the art the whole bag of tricks, for example: dipping, spraying.The method of employing dipping can be so that solution gets in the duct on the carrier more fully, and therefore, the present invention is preferably flooded.
With not special qualification of condition that the carrier and first solution contact with second solution, for example: carrier can comprise with the condition that said first solution contacts: be 1-10 hour duration of contact, is preferably 2-6 hour, most preferably is 4 hours.The contact temperature is 25-80 ℃, is preferably 30-60 ℃, most preferably is 50 ℃.The carrier of said load alkylaluminoxane can be comprised with the condition that said second solution contacts: be 0.3-2 hour duration of contact, is preferably 0.4-1 hour, most preferably is 0.5 hour.The contact temperature is 25-80 ℃, is preferably 25-50 ℃, most preferably is 30 ℃.
According to the present invention, the mol ratio of said carrier, first solvent and alkylaluminoxane (in the Al element) can be 1: 30-100: 0.1-2 further is preferably 1: 30-60: 0.8-1.5 most preferably is 1: 33: 1.15.
According to the present invention, the mol ratio of the carrier of said load alkylaluminoxane (in silicon-dioxide), second solvent and metallocene compound can be 1: 20-150: 2 * 10
-3-8 * 10
-3, most preferably be 1: 33: 6.8 * 10
-3
According to the present invention, said solvent preferably adopts the method that well known to a person skilled in the art to make with extra care before use, anhydrates to remove.
Can also be included in according to the method for the invention before said alkylaluminoxane of load and the said metallocene compound; Under protection of inert gas; Said carrier was heated 7-10 hour under 300-900 ℃ temperature; (for example: water), under the preferable case, above-mentioned steps is 400 ℃ of heating 10 hours down with the volatile matter that contains in the hydroxyl of removing carrier surface and the carrier.
According to the present invention, said rare gas element can for various not with all gases of carrier, alkylaluminoxane, metallocene compound generation chemical action.For example, said rare gas element can be nitrogen, argon gas.
According to olefine polymerizing process of the present invention, said alkene can carry out in the presence of solvent with contacting of said carried metallocene catalyst, and said solvent is preferably and replaces or unsubstituted alkane or replacement or unsubstituted aromatic hydrocarbons.When said alkane and aromatic hydrocarbons had substituting group, said substituting group was preferably halogenic substituent.More preferably, said solvent is at least a in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform and the ethylene dichloride.
According to the present invention, chemically interactive all gases can not take place with carrier, alkylaluminoxane, metallocene compound for various in said rare gas element.For example, said rare gas element can be nitrogen, argon gas.
According to olefine polymerizing process of the present invention, contacting preferably containing in the presence of the solution of aluminum alkyls of said alkene and said carried metallocene catalyst carried out, and the concentration of said aluminum alkyls can be 1-5mM, most preferably is 2mM.Said aluminum alkyls can be the known various aluminum alkylss of the technician of field of olefin polymerisation.Preferably, the alkyl in the said aluminum alkyls can be C
1-C
5Alkyl.More preferably, said aluminum alkyls is a triethyl aluminum.
According to olefine polymerizing process of the present invention, what said alkene can be in ethene, terminal olefin and the diolefin is at least a.Preferably, said alkene is ethene, C
3-C
101-alkene, C
4-C
8Diolefin at least a.More preferably, said alkene is at least a in ethene, 1-butylene, 1-amylene and the 1-hexene.
According to olefine polymerizing process of the present invention, because the present invention is through using said carried metallocene catalyst to improve the efficient of polyreaction, so the present invention does not limit for said olefinic polymerization condition is special.Can be the known polymerizing condition of the technician of field of olefin polymerisation.In metallocene compound, the concentration of carried metallocene catalyst can be 1 * 10
-8-1 * 10
-3Mol is preferably 1 * 10
-8-1 * 10
-5Mol; The polymeric temperature can be-78 ℃ to 100 ℃, is preferably 0 ℃-90 ℃, further is preferably 50-90 ℃, most preferably is 70-80 ℃; Pressure can be 0.01-10MPa, is preferably 0.01-2MPa, further is preferably 0.5-1.5MPa, most preferably is 1MPa.
Below in conjunction with embodiment the present invention is carried out detailed description.
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 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 sem of XL-30 in the model available from U.S. FEI Co..Ultimate analysis is carried out on the elemental analyser that available from U.S. An Jielun company model is 7500CX.
Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption appearance, sample was 200 ℃ of degassings 4 hours.
All raw materials are CP.
Preparation example 1
Polyoxyethylene octyl phenyl ether (Triton-X100) contact with 1.5 gram CTAB (cetyl trimethylammonium bromide), 1.5mL with the hydrochloric acid soln of the concentrated hydrochloric acid (concentration is 37 weight %) that contains 29.6 grams with 75 gram water; After being stirred to CTAB under 40 ℃ and dissolving fully; 4.35 gram tetraethoxys are joined in the above-mentioned solution, stirred 15 minutes down, left standstill 24 hours at 40 ℃ at 40 ℃; After filtration, washing, drying, calcined 24 hours down, obtain carrier JKQ at 600 ℃;
Under nitrogen protection, JKQ 400 ℃ of calcinings 10 hours, removing hydroxyl and remaining moisture, thereby is obtained the JKQ through thermal activation;
Activated JKQ is transferred in 250 milliliters of glass reactors after nitrogen is fully replaced with 0.3407 gram; Add 20 milliliters of purified toluene (refluxing 24 hours) and 0.4 gram MAO (available from U.S. Albemarle company), and stirred 4 hours at 50 ℃ via sodium.After reaction is accomplished, leave standstill, leach liquid after the layering, and with 20 milliliters of hexane wash solids three times, at last solid is dried up with nitrogen, obtaining load has the JKQ of MAO (called after MAO/JKQ).
Under nitrogen protection; A last step is obtained whole MAO/JKQ to join in 250 milliliters of glass reactors; Add 20 milliliters of purified toluene (refluxing 24 hours via sodium), under 30 ℃, two (n-butyl cyclopentadienyl) zirconium dichlorides that drip 15.6 milligrams are (available from Alfa Aesar company; Article No. H27576), stirring reaction is 0.5 hour.After reaction finishes, leave standstill, leach liquid after the layering,, follow,, solid is dried up with nitrogen, obtain carried metallocene catalyst (called after JKQ-BU) with 40 milliliters of hexane wash solids twice with 10 milliliters of toluene wash solids three times.With XRD, nitrogen adsorption-desorption experiment, transmission electron microscope and ESEM this carried metallocene catalyst is characterized.
Fig. 1 is an X-ray diffracting spectrum, and wherein, a is the x-ray diffraction pattern of JKQ, and b is the x-ray diffraction pattern of JKQ-BU.Can find out significantly that from XRD spectra JKQ and JKQ-BU all a diffraction peak occurs in little angular region.Explain that JKQ-BU has good mesoporous phase structure (concrete data provide) in table 1.
Fig. 2 is nitrogen adsorption-desorption graphic representation, and wherein, X-coordinate is a relative pressure, and unit is p/p
0, a is nitrogen adsorption-desorption graphic representation of JKQ, b is nitrogen adsorption-desorption graphic representation of JKQ-BU.Fig. 2 shows that JKQ and JKQ-BU are the IV class adsorption-desorption curves of typical IUPAC definition, has proved that JKQ and JKQ-BU have distinctive cube of cage structure (concrete data provide) in table 1.
Fig. 3 is a graph of pore diameter distribution, and wherein, X-coordinate is the aperture, and unit is nm, and a is the graph of pore diameter distribution of JKQ, and b is the graph of pore diameter distribution of JKQ-BU.Fig. 3 shows that JKQ has narrow pore size distribution, and the duct is very even, and same JKQ-BU has also kept narrow pore size distribution and even duct (concrete data provide) in table 1.
Fig. 4 is a transmission electron microscope photo, and wherein, a is the transmission electron microscope picture of JKQ, and b is the transmission electron microscope picture of JKQ-BU.Can be clear that from Fig. 4 JKQ and JKQ-BU have the pore distribution of rule, and compare that the duct shape of JKQ-BU remains unchanged basically with JKQ.
Fig. 5 stereoscan photograph, wherein, a1 and a2 are the stereoscan photograph of JKQ, b1 and b2 are the stereoscan photograph of JKQ-BU; C1 and c2 are the stereoscan photograph of ethylene homo product; D1 and d2 are the stereoscan photograph of ethene and hervene copolymer product, and stereoscan photograph has shown the microscopic appearance of each material.Can know by Fig. 5; The microscopic appearance of JKQ and JKQ-BU is sphere; The spherical morphology that is JKQ-BU keeps better; The pattern of the ethylene homo product that obtains as catalyzer with JKQ-BU and the copolymerized product of ethene and hexene also is intact sphere, but because particle is less, reunion to a certain degree (concrete data provide in table 1) has appearred in polymerization product.
Table 1
| Sample | Specific surface area (m 2/g) | Pore volume (ml/g) | Most probable aperture (nm) |
| JKQ | 1200 | 0.7 | 1.9 |
| JKQ-BU | 762 | 0.45 | 2.1 |
Data from table 1 can find out that the pore structure parameter of JKQ-BU all decreases than JKQ, show that MAO and metallocene compound enter into the duct of JKQ really.
Results of elemental analyses shows that the aluminium content among the JKQ-BU is 0.19 weight %, and the content of Zr is 0.04 weight %, and the mol ratio of Al/Zr is 16.
Embodiment 1
Present embodiment is used for explanation according to olefine polymerizing process 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 hexanes again, along with the adding of hexane; Add triethyl aluminum (TEA is available from the auspicious Dehua of the Zhejiang good fortune worker ltd) hexane solution of 2 milliliter of 1 mol, then add 43.3 milligrams of JKQ-BU; Feed ethene pressure risen to 1.0MPa and to be maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 213 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.306g/ml, melting index MI
2.16=0.026g/10min.Confirm that through calculating the efficient of catalyzer is 4919g PE/gcath (that is, 1.1 * 10
9G PE/ (mol Zr h)).
Present embodiment is used for explanation according to olefine polymerizing process 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 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 40.3 milligrams of JKQ-BU, feed ethene pressure risen to 1.0MPa and to be maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 269 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.321g/ml, melting index MI
2.16=0.384g/10min.Confirm that through calculating the efficient of catalyzer is 6675g PE/gcath (that is, 1.5 * 10
9G PE/ (mol Zr h)).
Preparation Comparative Examples 1
With the 400 ℃ of calcinings 10 hours under nitrogen protection of ES955 silica gel, removing hydroxyl and remaining moisture, thereby obtain silica gel through the ES955 of thermal activation.
Under nitrogen protection; Restrain ES955 silica gel and 1.0 gram MAOs and 10mL toluene (refluxing 24 hours) under 50 ℃ of conditions with 0.9 via sodium; Behind the stirring reaction 4 hours,, use 20 milliliters of hexane wash solids three times again with toluene wash 3 times; At last solid is dried up with nitrogen, obtaining load has the ES955 of MAO (called after MAO/ES955);
Under nitrogen protection; A last step is obtained whole MAO/ES955 to join in 250 milliliters of glass reactors; Add 20 milliliters of purified toluene (refluxing 24 hours) via sodium; Under 30 ℃, drip two (n-butyl cyclopentadienyl) zirconium dichlorides of metallocene catalyst precursors of 49 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid,, follow,, solid is dried up with nitrogen, obtain carried metallocene catalyst (called after ES955-BU) with 40 milliliters of hexane wash solids twice with 10 milliliters of toluene wash solids three times.
Results of elemental analyses shows that the content of the aluminium 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 270.
Comparative Examples 1
Adopt and carry out the homopolymerization of ethene with embodiment 1 identical method, different is that the catalyzer of employing is the ES955-BU of Comparative Examples 1 preparation.The 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.Confirm that through calculating the efficient of catalyzer is 1295g PE/gcath (that is, 2.9 * 10
7G PE/ (mol Zr h)).
Comparative Examples 2
Adopt and with embodiment 2 identical methods ethene and hexene are carried out copolymerization, different is that the catalyzer of employing is the ES955-BU of preparation Comparative Examples 1 preparation.Obtain 76 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.299g/ml, and melting index is MI
2.16=0.679/10min.Confirm that through calculating the efficient of catalyzer is 2260g PE/gcath (that is, 5.1 * 10
7G PE/ (mol Zr h)).
Claims (18)
1. olefine polymerizing process; This method is included under the olefinic polymerization condition, and at least a alkene is contacted with carried metallocene catalyst, it is characterized in that; Said carried metallocene catalyst comprises carrier and loads on metallocene compound and the alkylaluminoxane on the said carrier; Said carrier is the sphericity mesoporous silicon dioxide carrier, and said 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 a halogen.
2. method according to claim 1; Wherein, Total amount with said carried metallocene catalyst is a benchmark; The total amount of said metallocene compound and alkylaluminoxane is 10-60 weight %, and the content of said carrier is 40-90 weight %, and the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound is 10-50: 1.
3. method according to claim 2, wherein, the mol ratio of the M in aluminium in the said alkylaluminoxane and the said metallocene compound is 15-40: 1.
4. method according to claim 3, wherein, the alkyl in the said alkylaluminoxane is C
1-C
5Alkyl.
5. method according to claim 4, wherein, said alkylaluminoxane is a MAO.
6. according to any described method among the claim 1-3, wherein, M is a zirconium.
7. according to any described method among the claim 1-3, wherein, X is a chlorine.
8. method according to claim 1, 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' be hydrogen.
9. method according to claim 8, wherein, R
1And R
1' be the normal-butyl or the tertiary butyl.
10. method according to claim 1, wherein, said metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides, said alkylaluminoxane is a MAO.
11. according to any described method among the claim 1-3, wherein, the particle diameter of said carrier is the 3-20 micron, the most probable aperture is the 1.0-3.0 nanometer, and pore volume is 0.5-1.5 milliliter/gram, and specific surface area is the 1000-2000 meters squared per gram.
12. method according to claim 1, wherein, said alkene is at least a in ethene, terminal olefin and the diolefin.
13. method according to claim 12, wherein, said alkene is ethene, C
3-C
101-alkene, C
4-C
8Diolefin at least a.
14. method according to claim 1, wherein, said olefinic polymerization condition comprises: in metallocene compound, the concentration of carried metallocene catalyst is 1 * 10
-8-1 * 10
-3Mol, temperature are-78 ℃ to 100 ℃, and pressure is 0.01-10MPa.
15. method according to claim 14, wherein, said olefinic polymerization condition comprises: in metallocene compound, the concentration of carried metallocene catalyst is 1 * 10
-8-1 * 10
-5Mol, temperature are 0 ℃-90 ℃, and pressure is 0.01-2MPa.
16. according to any described method among the claim 1-3; Wherein, said carrier is prepared by the method that comprises the steps: in the presence of template, silicon ester is contacted with acidic aqueous solution; And will contact back gained mixture crystallization under crystallization condition; With the heating of gained crystallization product, removed template method, said template is cetyl trimethylammonium bromide and polyoxyethylene octyl phenyl ether.
17. method according to claim 16, wherein, the acid in said silicon ester, cetyl trimethylammonium bromide, polyoxyethylene octyl phenyl ether, the acidic aqueous solution and the mol ratio of water are 1: 0.1-0.6: 0.1-0.5: 5-50: 100-500.
18. method according to claim 17, wherein, said silicon ester is a tetraethoxy, and the condition of said contact comprises that temperature is 25-60 ℃, and the time is 10-60 minute, and the condition of said crystallization comprises that temperature is 25-60 ℃, and the time is 10-40 hour.
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| CN109289936A (en) * | 2017-07-24 | 2019-02-01 | 中国石油化工股份有限公司 | Spherical mesoporous composite material and preparation method and catalyst and its preparation method and application |
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| CN109289936A (en) * | 2017-07-24 | 2019-02-01 | 中国石油化工股份有限公司 | Spherical mesoporous composite material and preparation method and catalyst and its preparation method and application |
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