CN102453144B - Olefin polymerization method - Google Patents
Olefin polymerization method Download PDFInfo
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- CN102453144B CN102453144B CN 201010519725 CN201010519725A CN102453144B CN 102453144 B CN102453144 B CN 102453144B CN 201010519725 CN201010519725 CN 201010519725 CN 201010519725 A CN201010519725 A CN 201010519725A CN 102453144 B CN102453144 B CN 102453144B
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- silica gel
- alkylaluminoxane
- carrier
- cyclopentadienyl
- metallocene compound
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Abstract
The invention provides an olefin polymerization method. The method comprises the step of: contacting one or more olefins with a loaded metallocene catalyst under an olefin polymerization condition, and is characterized in that: the loaded metallocene catalyst comprises a carrier, and a metallocene compound and alkylaluminoxane loaded on the carrier; and the carrier is a compound of hollow sphere mesoporous silicon dioxide and silica gel. In the olefin polymerization method provided by the invention, the metallocene compound in the catalyst in use has a sandwich structure, cyclopentadienyl is provided with a substituent, and the compound of the hollow sphere mesoporous silicon dioxide and the silica gel has a highly-ordered large pore diameter (3-20 nanometers), a large pore size, high mechanical strength and high macromolecular adsorption performance, so that high polymerization efficiency is achieved.
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.Because to reach the required methylaluminoxane of high reactivity (MAO) consumption big for the homogeneous phase metallocene catalyst, the production cost height, and the polymkeric substance that obtains do not have particle shape, can't use at widely used slurry process or gas phase polymerization technology.And the activity of metallocene catalyst is very high, and it is very fast to be easy to take place local polymerization velocity 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 metallocene catalyst load research report is very many, wherein with SiO
2Maximum for the report research 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 tangible molecule shape selectivity energy, and it allows the monomer of certain size and the polymkeric substance of formation thereof to insert in the duct of molecular sieve.And because molecular sieve has nano pore, the inserted mode of monomer is different with freeboard with propagation process in the polymerization 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 material;
(2) the molecular sieve nano pore has the dual-use function of carrier and reactor, catalyst cupport efficient height, and polymerization process is controlled easily, and can key in the active centre in the skeleton of polymerization reactor, accelerates reaction process, improves productive rate;
(3) insertion has three-dimensional selection effect with polyreaction to monomer, can improve polyolefinic molecular weight and fusing point.
This shows that the olefin coordination polymerization that appears as of molecular sieve carried olefin polymerization catalysis has been opened up a new field.
Compare with zeolite molecular sieve, ordered mesoporous molecular sieve (aperture is the molecular sieve of 2-50nm) has bigger specific surface area and relatively large aperture, can handle bigger molecule or group, can make catalyzer bring into play its due catalytic activity well.
At present the mesoporous material of the load metallocene catalyst of reporting on the document is MCM-41, but activity only is 7.3 * 10 during catalyzed ethylene polymerization
5GPE/ (mol Zr h), and after handling with MAO again the MCM-41 of load metallocene carry out that catalytic activity also only is 10 behind the vinyl polymerization
6GPE/ (mol Zr h).
Therefore, how to obtain the carried metallocene catalyst of high catalytic efficiency, and then carry out olefinic polymerization efficiently and remain a technical problem that needs to be resolved hurrily.
Summary of the invention
The catalytic efficiency 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, 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 alkylaluminoxane on the described carrier, described carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, and described metallocene compound has the structure shown in the formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5Alkyl, and R
1, R
2, R
3, R
4And R
5In at least one be C
1-C
5Alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5Alkyl, M is a kind of in titanium, zirconium and the hafnium, X is halogen.
According to olefine polymerizing process of the present invention, because metallocene compound has sandwich structure described in the catalyst system therefor, and has substituting group on the cyclopentadienyl, the mixture of described hollow ball mesoporous silicon oxide and silica gel has wide aperture (3-20 nanometer), pore volume, excellent mechanical intensity and the good bulky molecular catalysis absorption property of high-sequential, 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 when being used for catalysis in olefine polymerization, and catalytic efficiency can reach 4659g PE/gcath (that is, 1.9 * 10
8GPE/ (mol Zr h)), and under the identical situation of other conditions, the catalytic efficiency during metallocene compound that industrial 955 silica gel loads have the structure shown in the formula 1 only for 1295g PE/gcath (, 2.9 * 10
7GPE/ (mol Zr h)), the mixture that hollow ball mesoporous silicon oxide and silica gel is described thus cooperates with the described metallocene compound with the structure shown in the formula 1 and has synergy, olefine polymerizing process of the present invention has been obtained unexpected technique effect, and, the mixture of hollow ball mesoporous silicon oxide and silica gel is compared with the hollow ball mesoporous silicon oxide, when not changing catalytic activity, can significantly reduce production costs.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, and Fig. 2 is the x-ray diffraction pattern of carried metallocene catalyst MAO/MS-GJ-BU-1.
Fig. 3 and Fig. 4 are respectively the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and the N of carried metallocene catalyst MAO/MS-GJ-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 mixture MS-GJ-1 and the carried metallocene catalyst MAO/MS-GJ-BU-1 of hollow ball mesoporous silicon oxide and silica gel, and wherein, X-coordinate is the aperture, and unit is 0.1nm.
Fig. 7 is stereoscan photograph, a1, a2 are the stereoscan photograph of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, b1 is the stereoscan photograph of carried metallocene catalyst MAO/MS-GJ-BU-1 of the present invention, b2 is 955 silica gel load MAO of employing embodiment 1 preparation and the stereoscan photograph behind the metallocene compound, and b3 is the stereoscan photograph behind hollow ball-shape mesoporous material load MAO and the metallocene compound.
Embodiment
The invention provides a kind of olefine polymerizing process, this 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 alkylaluminoxane on the described carrier, described carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, and described metallocene compound has the structure shown in the formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5Alkyl, and R
1, R
2, R
3, R
4And R
5In at least one be C
1-C
5Alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5Alkyl, M is a kind of in titanium, zirconium and the hafnium, X is halogen.
According to 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 compounds can be identical or different, and preferably, M is zirconium.
According to the present invention, the X in the formula 1 is halogen.What particularly, the X in the formula 1 can be in fluorine, chlorine, bromine and the iodine is a kind of.Preferably, the X in the formula 1 is chlorine or bromine.X in the different metallocene compounds can be identical or different, and more preferably, the X in the formula 1 is chlorine.
According to the present invention, in the formula 1, cyclopentadienyl is to form η with central metal M
5Key and have the derivative of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl in the formula 1
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5Alkyl, and R
1, R
2, R
3, R
4And R
5In at least one be C
1-C
5Alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5Alkyl.
Among the present invention, described C
1-C
5Alkyl can be in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and the neo-pentyl one or more.
The specific examples that satisfies the cyclopentadienyl of above-mentioned requirements comprises: methyl-cyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,2,3-trimethylammonium-cyclopentadienyl, 1,2,5-trimethylammonium-cyclopentadienyl, 1,2,3,4-tetramethyl--cyclopentadienyl, 1,2,3,5-tetramethyl--cyclopentadienyl, the pentamethyl-cyclopentadienyl, ethyl-cyclopentadienyl, 1,2-diethyl-cyclopentadienyl, 1,3-diethyl-cyclopentadienyl, 1,2,4-triethyl-cyclopentadienyl, 1,3,5-triethyl-cyclopentadienyl, methyl-2-ethyl-cyclopentadienyl, 1-methyl-3-ethyl-cyclopentadienyl, n-propyl-cyclopentadienyl, 1,3-di-cyclopentadienyl, 1-methyl-3-n-propyl-cyclopentadienyl, 1,3-di-isopropyl-cyclopentadienyl, 1-methyl-3-sec.-propyl-cyclopentadienyl, normal-butyl-cyclopentadienyl, 1,3-di-n-butyl-cyclopentadienyl, 1-methyl-3-normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, 1,3-two sec-butyls-cyclopentadienyl, 1-methyl-3-sec-butyl-cyclopentadienyl, 1-isobutyl--cyclopentadienyl, 1,3-diisobutyl-cyclopentadienyl, 1-methyl 3-isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, 1,3-di-t-butyl-cyclopentadienyl, the 1-methyl 3-tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, 1,3-two n-pentyls-cyclopentadienyl, 1-methyl-3-n-pentyl-cyclopentadienyl, 1-isopentyl-cyclopentadienyl, 1,3-diisoamyl-cyclopentadienyl, 1-methyl-3-isopentyl-cyclopentadienyl, 1-tert-pentyl-cyclopentadienyl, 1,3-two tert-pentyls-cyclopentadienyl, 1-methyl-3-tert-pentyl-cyclopentadienyl, neo-pentyl-cyclopentadienyl, 1,3-di neo-pentyl-cyclopentadienyl, 1-methyl-3-neo-pentyl-cyclopentadienyl.
Preferably, the R in the formula 1
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 satisfies the cyclopentadienyl of above-mentioned requirements comprises: methyl-cyclopentadienyl, ethyl-cyclopentadienyl, n-propyl-cyclopentadienyl, sec.-propyl-cyclopentadienyl, normal-butyl-cyclopentadienyl, sec-butyl-cyclopentadienyl, isobutyl--cyclopentadienyl, the tertiary butyl-cyclopentadienyl, n-pentyl-cyclopentadienyl, isopentyl-cyclopentadienyl, tert-pentyl-cyclopentadienyl, neo-pentyl-cyclopentadienyl.
More preferably, R
1And R
1' be 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 the described alkylaluminoxane is aforesaid C
1-C
5Alkyl.Preferably, described alkylaluminoxane is methylaluminoxane.
The present inventor finds in research process, the R in formula 1
1And R
1' be normal-butyl, 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 the described carrier and the amount of alkylaluminoxane can change within a large range.The present inventor finds, total amount with described carried metallocene catalyst is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 10-60 weight %, when the content of described carrier is 10-60 weight %, not only can obtain gratifying catalytic effect, but also can reduce cost.More preferably, be benchmark with the total amount of described carried metallocene catalyst, the total amount of described metallocene compound and alkylaluminoxane is 45-55 weight %, the content of described carrier is 45-55 weight %.Further under the preferable case, be benchmark with the total amount of described carried metallocene catalyst, the total amount of described metallocene compound and alkylaluminoxane is 48-52 weight %, and the content of described carrier is 48-52 weight %.Further under the preferable case, be benchmark with the total amount of described carried metallocene catalyst, the total amount of described metallocene compound and alkylaluminoxane is 50 weight %, and the content of described carrier is 50 weight %.
According to the present invention, the described alkylaluminoxane and the ratio between the metallocene compound that load on the 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 the described alkylaluminoxane and the described metallocene compound can be 100-500: 1; Be preferably 100-300: 1,200-300 more preferably: 1, further be preferably 250-300: 1, most preferably be 292: 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 milliliter/gram, and the most probable aperture is the 3-20 nanometer.Under the 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 milliliter/gram, and the most probable aperture is the 5-15 nanometer; Further under the 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 milliliter/gram, and the most probable aperture is the 8-11 nanometer; Under the 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 milliliter/gram, 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.The content of alkylaluminoxane and metallocene compound satisfies previously described requirement and gets final product in the carried metallocene catalyst that described alkylaluminoxane and the metallocene compound charge capacity on described carrier make to obtain.
According to the present invention, the kind of described alkylaluminoxane and metallocene compound describes in detail at preamble, repeats no more herein.
According to the present invention, described carrier can be the mixture of hollow ball mesoporous silicon oxide and silica gel.In the mixture of described hollow ball mesoporous silicon oxide and silica gel, the weight ratio of hollow ball mesoporous silicon oxide and silica gel can be 1: 0.2-5 is preferably 1: 1: 0.4-3, more preferably 1: 0.5-2 most preferably is 1: 0.5.
The mixture of described hollow ball mesoporous silicon oxide and silica gel can prepare by the method that may further comprise the steps: in the presence of template, trimethylpentane and ethanol, tetramethoxy-silicane 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, described template are triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol; The product of gained removed template method is mixed with silica gel.
Described template can be the conventional various triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol template used in this area, for example can be the template of commodity P123 by name.
According to the present invention, the various silica gel that described silica gel can be used for carrier for olefin polymerization catalyst, described silica gel be chosen as general knowledge well known in the art, do not repeat them here, for example can select the trade mark is the silica gel of ES955.
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 the acetic acid of 1-6 and the buffered soln of sodium acetate for the pH value for example.
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.
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 removed template method comprises that temperature can be 90-600 ℃, and the time can be 10-80 hour.
According to the present invention, in the process of the mixture for preparing hollow ball mesoporous silicon oxide and silica gel, 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 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 is 1: 2.13: 6: 1.69: 28.
The product of described removed template method and the weight ratio of silica gel can be 1: 0.2-5 is preferably 1: 1: 0.4-3, more preferably 1: 0.5-2 most preferably is 1: 0.5.
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 described carrier.Preferably, successively the method at load alkylaluminoxane and metallocene compound on the carrier comprises: under protection of inert gas, described carrier is contacted with first solution, described first solution contains described alkylaluminoxane and toluene; The carrier that has removed toluene is contacted with second solution, and described second solution contains described metallocene compound and toluene, and removes toluene.Count in molar ratio, carrier: toluene: the amount ratio of alkylaluminoxane is 1: 30-100: 0.1-2.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, can be for well known to a person skilled in the art the whole bag of tricks, for example: dipping, spraying.Adopt the method for dipping can be so that solution enters in the duct on the carrier more fully, therefore, the present invention be preferably flooded.
Carrier is not particularly limited with the condition that second solution contacts with first solution, and for example: carrier can comprise with the condition that described first solution contacts: 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 second solution contacts: the time is 0.3-2 hour, and temperature is 25-80 ℃.
According to the present invention, toluene preferably adopts the method that well known to a person skilled in the art to make with extra care before use, anhydrates to remove.
According to the present invention; also preferably before the described alkylaluminoxane of load and described metallocene compound; under protection of inert gas, described carrier was heated 7-10 hour under 300-900 ℃ temperature, with the volatile matter that contains in the hydroxyl of removing carrier surface and the carrier (for example: water).
According to the present invention, chemically interactive all gases can not take place with carrier, alkylaluminoxane, metallocene compound for various in described rare gas element.For example, described rare gas element can be nitrogen, argon gas.
According to the present invention, the feasible total amount with described carried metallocene catalyst of described alkylaluminoxane and the metallocene compound charge capacity on described carrier is benchmark, the total amount of described metallocene compound and alkylaluminoxane can be 10-60 weight %, be preferably 45-55 weight %, more preferably 48-52 weight % further is preferably 50 weight %; The content of described carrier can be 10-60 weight %, is preferably 45-55 weight %, and more preferably 48-52 weight % further is preferably 50 weight %; The mol ratio of M in aluminium in the described alkylaluminoxane and the described metallocene compound can be 100-500: 1, be preferably 100-300: and 1,200-300 more preferably: 1, further be preferably 250-300: 1, most preferably be 292: 1.
A preferred embodiment of the invention, the preparation method of described carried metallocene catalyst comprises:
In the 1st step, with triblock copolymer polyethylene glycol-glycerol-polyoxyethylene glycol and ethanol, join pH value and be under 10-60 ℃ of temperature, to be stirred to dissolving in the buffered soln of the acetic acid of 1-6 and sodium acetate;
The 2nd step added trimethylpentane in previous step gained solution, stirred 1-20 hour under 10-60 ℃ of temperature;
The 3rd step added tetramethoxy-silicane in previous step gained solution, stirred 10-72 hour under 10-60 ℃ of temperature;
In the 4th step, will go up step gained solution and place closed reaction vessel, under 30-150 ℃ of temperature crystallization 10-72 hour;
In the 5th step, with the filtration of crystallization after product, washing, drying, obtain the hollow ball-shape mesoporous material raw powder;
The 6th step, gained hollow ball-shape mesoporous material to be calcined 10 hours-80 hours with 90 ℃ of-600 ℃ of temperature in retort furnace, removed template method obtains hollow mesoporous silicon oxide; Should mix with silica gel by hollow mesoporous silicon oxide then;
In the 7th step, the thermal activation step under nitrogen protection, in 300-900 ℃ of calcining 7-10 hour, obtains hollow ball mesoporous silicon oxide after the thermal activation and the mixture of silica gel with the mixture of gained hollow ball mesoporous silicon oxide of last step and silica gel;
The 8th step, the mixture of the hollow ball mesoporous silicon oxide after the thermal activation and silica gel is transferred in the reactor after nitrogen is fully replaced, add solvent and alkylaluminoxane, count in molar ratio, the mixture of hollow ball mesoporous silicon oxide and silica gel: solvent: the amount ratio of alkylaluminoxane is 1: 30-100: 0.1-2, stirred 1-10 hour in 25-80 ℃ again, after finishing, use hexane wash again 2 times, afterwards solid is dried up with nitrogen, obtain the hollow ball mesoporous silicon oxide of load methylaluminoxane and the mixture of silica gel;
The 9th step under nitrogen protection, joined the hollow ball mesoporous silicon oxide of load methylaluminoxane and the mixture of silica gel in the reactor, added stirring solvent and made slurries; In the container of crossing with nitrogen replacement in advance, solution is made in the metallocene compound dissolving, under 25-80 ℃ of agitation condition, slowly the metallocene compound drips of solution is added in the reactor, count the mixture of hollow ball mesoporous silicon oxide and silica gel: toluene in molar ratio: 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, reaction was left standstill after finishing, and leaches liquid, with toluene and hexane wash, dried up with nitrogen, obtained described carried metallocene catalyst.
According to olefine polymerizing process of the present invention, described one or more alkene can carry out in the presence of solvent with contacting of described carried metallocene catalyst, and described solvent is preferably and replaces or unsubstituted alkane or replacement or unsubstituted aromatic hydrocarbons.When described alkane and aromatic hydrocarbons had substituting group, described substituting group was preferably halogenic substituent.More preferably, described solvent is one or more in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform and the methylene dichloride.
The consumption of described solvent can carry out appropriate selection according to concrete use occasion.Preferably, the consumption of described solvent makes that the concentration of described carried metallocene catalyst is 1 * 10
-8-1 * 10
-3Mol is preferably 1 * 10
-8-1 * 10
-5Mol.
According to olefine polymerizing process of the present invention, described one or more alkene carry out in the presence of the solution that contains aluminum alkyls and/or alkylaluminoxane 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, replenish the solution that interpolation contains aluminum alkyls and/or alkylaluminoxane.Be in the effect that aluminum alkyls in the solution and/or the alkylaluminoxane of alkylaluminoxane on loading on described carrier play the cleaning reaction poisonous substance, thereby make the metallocene compound that loads on the described carrier can bring into play katalysis better.
According to olefine polymerizing process of the present invention, when described one or more alkene carried out in the presence of the solution that is containing aluminum alkyls and/or alkylaluminoxane with contacting of described carried metallocene catalyst, whole aluminium and the mol ratio of the M in the described metallocene compound can be 100-3000 in described aluminum alkyls and the described alkylaluminoxane (comprise the alkylaluminoxane that loads on the described carrier and be in alkylaluminoxane in the solution): 1.
Described aluminum alkyls can be the known various aluminum alkylss that are used as the promotor of metallocene catalyst of the technician of field of olefin polymerisation.Preferably, the alkyl in the described aluminum alkyls can be C
1-C
5Alkyl.More preferably, described aluminum alkyls is triethyl aluminum.
The alkylaluminoxane that is in the solution can be identical with the kind that loads on alkylaluminoxane on the 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 in ethene, alpha-olefin and the diolefin one or more.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 the 1-hexene.
According to olefine polymerizing process of the present invention, because the present invention is by using described carried metallocene catalyst to improve the efficient of polyreaction, 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, in metallocene compound, the concentration of described carried metallocene catalyst can be 1 * 10
-8-1 * 10
-5Mol.The temperature of polymerization can be-78 ℃ to 100 ℃, is preferably 0 ℃-90 ℃; Pressure can be 0.01-10MPa, is preferably 0.01-2MPa.
Be described in detail below in conjunction with the present invention of embodiment.
In following examples, X-ray diffraction analysis is that the X-ray diffractometer of D8 Advance carries out in the model available from company of German Bruker AXS company; TEM (transmission electron microscope) analysis is that the transmission electron microscope of Tecnai 20 carries out in the model available from company of Dutch FEI Co.; Scanning electron microscope analysis is that the scanning electronic microscope of XL-30 is carried out in the model available from company of U.S. FEI Co..Ultimate analysis is carried out at the model 7500CX instrument 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 was 200 ℃ of degassings 4 hours.
Preparation example 1
This preparation example is for the preparation of the carried metallocene catalyst that uses in the olefine polymerizing process according to the present invention.
Restrain three down section multipolymer polyethylene glycol-glycerol-polyoxyethylene glycol (available from Aldrich with 1.0, trade mark P123) and 1.69 gram ethanol join in the buffered soln of the acetic acid of pH=4.4 of 28ml and sodium acetate, being stirred to polyethylene glycol-glycerol-polyoxyethylene glycol under 15 ℃ dissolves fully, trimethylpentane with 6g joins in the above-mentioned solution afterwards, 15 ℃ were stirred after 8 hours, again 2.13 gram tetramethoxy-silicanes are joined in the above-mentioned solution, 15 ℃ were stirred after 20 hours, solution is transferred in the teflon-lined reactor, 60 ℃ of following crystallization after 24 hours through filtering, distilled water wash, obtain the former powder of hollow ball mesoporous silicon oxide after the drying.
The former powder of hollow ball mesoporous silicon oxide was calcined 24 hours in retort furnace at 550 ℃, obtain the hollow ball mesoporous silicon oxide, sneak into the silica gel (ES955) of the 50 weight % that are equivalent to the former grain weight amount of hollow ball mesoporous silicon oxide again, obtain the mixture (called after MS-GJ-1) of hollow ball mesoporous silicon oxide and silica gel.
With the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel 400 ℃ of calcinings 10 hours under nitrogen protection, removing hydroxyl and remaining moisture, thereby obtain through the hollow ball mesoporous silicon oxide of thermal activation and the mixture of silica gel.
0.50 gram in the mixture of the hollow ball mesoporous silicon oxide of thermal activation and silica gel is transferred to 250 milliliters of glass reactors after nitrogen is fully replaced, is added 20 milliliters of refining toluene, 0.51 gram methylaluminoxane (available from U.S. Albemarle company) stirred 4 hours in 50 ℃.After finishing, use 20 milliliters of hexane wash three times again, at last solid is dried up with nitrogen, obtaining load has the MS-GJ-1 of methylaluminoxane (called after MAO/MS-GJ-1).
Under nitrogen protection, MAO/MS-GJ-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 of 28 milligrams, stirring reaction 0.5 hour.After reaction finishes, leave standstill, leach liquid after the layering, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtain according to carried metallocene catalyst of the present invention (called after MAO/MS-GJ-BU-1).Come this carried metallocene catalyst is characterized with XRD, nitrogen adsorption-desorption experiment, scanning electron microscope and ICP ultimate analysis.
Fig. 1 is the x-ray diffraction pattern of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, and Fig. 2 is the x-ray diffraction pattern of carried metallocene catalyst MAO/MS-GJ-BU-1.Can obviously be found out by XRD spectra, Small angle spectrum peak all appears in the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and carried metallocene catalyst MAO/MS-GJ-BU-1, illustrates that MAO/MS-GJ-BU-1 has the hexagonal hole road structure of the peculiar 2D of mesoporous material.
Fig. 3 and Fig. 4 are respectively the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and the N of carried metallocene catalyst MAO/MS-GJ-BU-1
2The adsorption desorption graphic representation, wherein, X-coordinate is relative pressure, unit is p/p
0Fig. 4 shows that MAO/MS-GJ-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-GJ-BU-1 has the aperture size distribution of homogeneous.
Fig. 5 and Fig. 6 are respectively the graph of pore diameter distribution of mixture MS-GJ-1 and the carried metallocene catalyst MAO/MS-GJ-BU-1 of hollow ball mesoporous silicon oxide and silica gel, and wherein, X-coordinate is the aperture, and unit is 0.1nm.As seen from Figure 6, MAO/MS-GJ-BU-1 has six sides' meso-hole structure, and the duct is very even.
Fig. 7 is stereoscan photograph, a1, a2 are the stereoscan photograph of the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel, the stereoscan photograph of b1 carried metallocene catalyst MAO/MS-GJ-BU-1 of the present invention, b2 is the stereoscan photograph behind 955 silica gel load MAO and the metallocene compound, and b3 is the stereoscan photograph behind hollow ball-shape mesoporous material load MAO and the metallocene compound.As seen from the figure, the MS-GJ-1 particle diameter is 5-15 μ m, and particle diameter and the MS-GJ-1 of MAO/MS-GJ-BU-1 are basic identical, this explanation MS-GJ-1 particle size dispersion, and MAO/MS-GJ-BU-1 has mechanical property preferably.
Table 1 is the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel and the pore structure parameter of carried metallocene catalyst MAO/MS-GJ-BU-1,
Table 1 pore structure parameter
| Sample | Specific surface area (m 2/g) | Pore volume (ml/g) | Most probable aperture (nm) |
| MS-GJ-1 | 261 | 0.8 | 9.8 |
| MAO/MS-BU-GJ-1 | 230 | 0.3 | 4.8 |
By the data of last table 1 as can be seen, the mixture MS-GJ-1 of hollow ball mesoporous silicon oxide and silica gel is behind load metallocene, pore volume, specific surface area and aperture all reduce to some extent, and 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 the aluminium content of mixture MAO/MS-GJ-BU-1 of the hollow ball mesoporous silicon oxide of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of promotor methylaluminoxane (MAO) and cyclopentadienyl catalyst precursor and silica gel be 19.04 weight %, the content of Zr is 0.22 weight %, and the mol ratio of Al/Zr is 292: 1.Learning through conversion, is benchmark with the total amount of catalyzer, and the total content of methylaluminoxane (MAO) and metallocene compound is 50 weight %, and the content of carrier is 50 weight %.
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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol, then adds 85.5 milligrams of MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain 412 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.323g/ml, melting index MI
2.16=0.005g/10min.Determine that as calculated the efficient of catalyzer is 4819g PE/gcath (that is, 2 * 10
8G 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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of 1 mol, then adds 61.6 milligrams MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 70 ℃ of reactions 1 hour.Obtain the polymkeric substance of 287 gram ethene and hexene, the bulk density of the polymkeric substance of this ethene and hexene (BD) is 0.313g/ml, melting index MI
2.16=0.465g/10min.Determine that as calculated the efficient of catalyzer is 4659g PE/gcath (that is, 1.9 * 10
8GPE/ (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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution of 1 mol, then adds 413 milligrams of MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 80 ℃ of reactions 1 hour.Obtain 141 gram polyethylene particle powders, the bulk density of this polyethylene particle powder (BD) is 0.320g/ml, melting index MI
2.16=0.070g/10min.Determine that as calculated the efficient of catalyzer is 3414g PE/gcath (that is, 1.4 * 10
8G PE/ (mol Zr h)).
Embodiment 4
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, adding along with hexane, the concentration that adds 2 milliliters is triethyl aluminum (TEA) hexane solution and 10 milliliters of hexenes of 1 mol, then adds 43.1 milligrams MAO/MS-GJ-BU-1, feeds ethene, pressure is risen to 1.0MPa and is maintained 1.0MPa, 80 ℃ of reactions 1 hour.Obtain 69 gram polymkeric substance, the bulk density of this polymkeric substance (BD) is 0.275g/ml, melting index MI
2.16=0.409g/10min.Determine that as calculated the efficient of catalyzer is 1601g PE/gcath (that is, 6.8 * 10
7G 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 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 1.0 gram methylaluminoxane and 10mL toluene again; under 50 ℃ of conditions; behind the stirring reaction 4 hours, use toluene wash 3 times, use 20 milliliters of hexane wash three times again; at last 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, leave standstill, leach liquid, with 10 milliliters of toluene wash three times, follow, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtain carried metallocene catalyst (called after ES955-BU).
Results of elemental analyses shows that the aluminium content among the ES955-BU is weight 32.4%, and the content of Zr is weight 0.41%, and the mol ratio of Al/Zr is 270: 1.
Comparative Examples 1
Adopt the method identical with embodiment 1 to carry out the homopolymerization of ethene, different is the ES955-BU that the catalyzer of employing prepares for preparation Comparative Examples 1.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.Determine that as calculated the efficient 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 copolymerization, different is that the catalyzer of employing is the ES955-BU that preparation ratio 1 is prepared.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 that as calculated the efficient of catalyzer is 2260g PE/gcath (that is, 5.1 * 10
7GPE/ (mol Zr h)).
Claims (16)
1. olefine polymerizing process, this 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 alkylaluminoxane on the described carrier;
Described carrier is the mixture of hollow ball mesoporous silicon oxide and silica gel, described carrier is made by the method that may further comprise the steps: in template, under the existence of trimethylpentane and ethanol, tetramethoxy-silicane 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, described template is polyethylene glycol-glycerol-polyoxyethylene glycol, described acidic aqueous solution is the buffered soln of acetic acid and sodium acetate, and the pH value of described damping fluid is 1-6, polyethylene glycol-glycerol-polyoxyethylene glycol, tetramethoxy-silicane, trimethylpentane, the weight ratio of ethanol and acidic aqueous solution is 1:2-3:3-10:1-5:10-50; The product of gained removed template method is mixed with silica gel;
Described metallocene compound has the structure shown in the formula 1,
Formula 1
Wherein, R
1And R
1' be C independently of one another
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 the hafnium, X is halogen.
2. method according to claim 1, wherein, total amount with described carried metallocene catalyst is benchmark, the total amount of described metallocene compound and alkylaluminoxane is 10-60 weight %, the content of described carrier is 10-60 weight %, and the mol ratio of the M in the aluminium in the described alkylaluminoxane and the described metallocene compound is 100-300:1.
3. method according to claim 2 wherein, is benchmark with the total amount of described carried metallocene catalyst, and the total amount of described metallocene compound and alkylaluminoxane is 45-55 weight %, and the content of described carrier is 45-55 weight %.
4. according to claim 1,2 or 3 described methods, wherein, the alkyl in the described alkylaluminoxane is C
1-C
5Alkyl.
5. method according to claim 4, wherein, described alkylaluminoxane is methylaluminoxane.
6. method according to claim 1 and 2, wherein, M is zirconium.
7. method according to claim 1, wherein, X is chlorine.
8. method according to claim 1, wherein, R
1, R
1' be normal-butyl.
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 and 2, wherein, 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 milliliter/gram, and the most probable aperture is the 3-20 nanometer.
11. method according to claim 10, wherein, in the mixture of described hollow ball mesoporous silicon oxide and silica gel, the weight ratio of hollow ball mesoporous silicon oxide and silica gel is 1:0.2-5.
12. method according to claim 1, wherein, 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; When the product of removed template method mixed with silica gel, the product of removed template method and the weight ratio of silica gel were 1:0.2-5; Wherein, 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 milliliter/gram, and the most probable aperture is the 3-20 nanometer.
13. method according to claim 1, wherein, described alkene is one or more in ethene, alpha-olefin and the 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, temperature are-78 ℃ to 100 ℃, and pressure is 0.01-10MPa.
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| CN105175586B (en) * | 2014-06-13 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of preparation method of mesoporous composite material and preparation method thereof and catalytic component and polyethylene |
| CN105330767B (en) * | 2014-06-13 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application |
| CN105330768B (en) * | 2014-06-13 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of support type polyethylene catalyst and preparation method thereof and support type polyethylene catalysts and application |
| CN109289935B (en) * | 2017-07-24 | 2019-11-12 | 中国石油化工股份有限公司 | The method of complex mesoporous material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN109289847B (en) * | 2017-07-24 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for catalyzing propane dehydrogenation reaction, preparation method thereof and method for preparing propylene by propane dehydrogenation |
| CN110614110A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with eggshell-shaped mesoporous material silica gel composite material as carrier, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040688A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Application of metallocene catalyst-loaded hexagonal mesoporous material to olefinic polymerization |
-
2010
- 2010-10-19 CN CN 201010519725 patent/CN102453144B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040688A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Application of metallocene catalyst-loaded hexagonal mesoporous material to olefinic polymerization |
Non-Patent Citations (4)
| 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,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;第48卷(第3期);606-616 * |
| High catalytic activity of SBA-15-supported metallocene toward ethylene polymerization: The effect of the ordered porous structure of the support;Cristian Covarrubias et al;《Catalysis Communications》;20081225;第10卷;995–1001 * |
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