CN103554308A - Supported metallocene catalyst, its preparation method and application - Google Patents
Supported metallocene catalyst, its preparation method and application Download PDFInfo
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- CN103554308A CN103554308A CN201310479396.8A CN201310479396A CN103554308A CN 103554308 A CN103554308 A CN 103554308A CN 201310479396 A CN201310479396 A CN 201310479396A CN 103554308 A CN103554308 A CN 103554308A
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Abstract
The invention relates to a supported metallocene catalyst and its preparation method. The preparation method comprises the following steps: dissolving a magnesium compound in a solvent in the presence of alcohol so as to obtain a magnesium compound solution, adding a porous carrier which has undergone heat treatment so as to obtain a carrier slurry, drying the carrier slurry to obtain a composite carrier, processing the above composite carrier by the use of an aluminium alkyl reagent so as to obtain an active carrier, and processing the active carrier by the use of a metalloscene compound. The supported metallocene catalyst has characteristics as follows: the preparation method is simple and easy to operate and the preparation cost is low. The invention also relates to an application of the supported metallocene catalyst in alkene homopolymerization/copolymerization.
Description
Technical field
The present invention relates to a kind of carried metallocene catalyst.Particularly, the present invention relates to a kind of carried metallocene catalyst, its preparation method and the application in alkene homopolymerization/copolymerization thereof.
Background technology
Metallocene complex has the advantages such as activity is high, polymer architecture is controlled for catalysis in olefine polymerization, but in polymerization process, also has serious sticky still phenomenon, needs a large amount of expensive methylaluminoxane as promotor simultaneously, and cost is higher.The load technology of metallocene is by metallocene complex on the fixing carrier of means by physics or chemistry, supported catalyst is except keeping the feature of catalyzed by homogeneous metallocene catalyst, also there are many advantages: (1) active centre is fixed on carrier, reduced the probability of bimolecular inactivation and the cancellation of β-hydrogen, the stability of catalyzer is improved, thereby reduced the consumption of methylaluminoxane, also increased in addition the molecular weight of polymkeric substance; (2) possess the characteristic of template moulding, polymerisate form is regular, apparent density improves; (3) may be used on vapour phase polymerization and the slurry polymerization processes of alkene, realize the drop-in technology of existing full scale plant.
There is bibliographical information and processed by methylaluminoxane the method that silica-gel carrier is prepared carried metallocene catalyst, its process is that silica gel is processed and obtained supported catalyst with methylaluminoxane and metallocene complex solution after thermal activation, catalyst activity is higher, good (the < < China Synthetic Rubber Industry > > of polymer morphology, 2004,27 volumes, 287-291); The solution of separately had bibliographical information recycle methylaluminoxane and metallocene complex is for load, with this, reduce method (the < < petrochemical technology and application > > of methylaluminoxane and metallocene complex consumption, 2003,21 volumes, 170-173).But above-mentioned load method still exists methylaluminoxane consumption large, the shortcoming that catalyzer cost is high.
Magnesium chloride is the more a kind of inorganic carrier of industrial application outside silica gel.Their the various single active center of magnesium chloride support load metallocene-titanium catalyst of processing with aluminum alkyls of bibliographical information, effective catalyzed ethylene polymerization under existing without methylaluminoxane (MAO), obtain narrow distribution spherical polymkeric substance (Macromolecular Rapid Communication, 2004,25,1024-1028).But magnesium chloride support intensity is lower, in polymerization and transport process, granules of catalyst is easily broken, thereby affects polymer morphology.
Therefore, still need at present a kind of carried metallocene catalyst, its preparation method is simple, is applicable to suitability for industrialized production, and can overcomes problems of the prior art.
Summary of the invention
The inventor finds through creative research on the basis of existing technology, by manufacturing described carried metallocene catalyst by a kind of specific preparation method, just can solve foregoing problems, and complete thus the present invention.
According to the preparation method of this carried metallocene catalyst, need not add methylaluminoxane, reaction requirement and reaction conditions that also need not be harsh.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
technique effect
Preparation method's technique simple possible of carried metallocene catalyst of the present invention, is suitable for industrial production.
The carried metallocene catalyst that the present invention is prepared, when for catalysis in olefine polymerization, without using expensive methylaluminoxane just can show high olefin polymerizating activity, catalyzer cost and polymerization cost reduce greatly.Porous support in catalyzer, for catalyzer provides higher intensity, is suitable for the various industrialization polymerizing conditions such as gas phase, slurry simultaneously.
Adopt method for preparing catalyst provided by the invention, because complex carrier is that convection drying mode by mixed serum obtains, so in catalyzer, composition and the content of key substance is controlled, and activity is higher.
Embodiment
According to the present invention, relate to a kind of carried metallocene catalyst and preparation method thereof, comprise the following steps: magnesium compound is dissolved in solvent under the existence of alcohol, obtains the step of magnesium compound solution; The optionally porous support of process thermal activation treatment is mixed with described magnesium compound solution, obtain the step of carrier pulp; Described carrier pulp is dried, obtains the step of complex carrier; With aluminum alkyls, process described complex carrier, obtain the step of active carrier; With with Metallocenic compound, process described active carrier, obtain the step of loaded catalyst.
To obtaining the step of described magnesium compound solution, be specifically described below.
According to this step, make magnesium compound under the existence of alcohol, be dissolved in suitable solvent (for dissolving the solvent of described magnesium compound), thereby obtain described magnesium compound solution.
As described solvent, such as enumerating C
6-12aromatic hydrocarbon, ester and ether equal solvent.Specifically such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, ethyl acetate and tetrahydrofuran (THF) etc.Wherein, preferred C
6-12aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF).
These solvents can be used separately a kind of, also can use with the multiple mixing of ratio arbitrarily.
According to the present invention, term " alcohol " is used the common concept in this area, refers to C
1-30monohydroxy-alcohol.
As described alcohol, such as enumerating fatty alcohol, aromatic alcohol and alicyclic ring alcohol, wherein preferred fat alcohol, more preferably ethanol and butanols.
As described fatty alcohol, such as enumerating methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, amylalcohol, 2-methyl amyl alcohol, 2-ethylpentanol, 2-hexyl butanols, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanols and 2-Ethylhexyl Alcohol.
As described aromatic alcohol, such as enumerating phenylcarbinol, phenylethyl alcohol and methylbenzyl alcohol etc., preferred phenylethyl alcohol wherein.
As described alicyclic ring alcohol, such as enumerating hexalin, cyclopentanol, ring octanol, methylcyclopentanol, ethyl cyclopentanol, propyl group cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, propyl group hexalin, methyl ring octanol, ethyl ring octanol and propyl group ring octanol etc., wherein preferably hexalin and methyl-cyclohexanol.
These alcohol can be used separately a kind of, also can multiple mixing use.When the form with multiple mixing is used, the ratio between any two kinds of alcohol in described alcohol mixture can be to determine arbitrarily, is not particularly limited.
According to the present invention, as described magnesium compound, such as enumerating magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium and alkyl halide magnesium.
Particularly, magnesium halide is selected from magnesium chloride (MgCl
2), magnesium bromide (MgBr
2), magnesium iodide (MgI
2) and magnesium fluoride (MgF
2) etc., preferred magnesium chloride.
Alkoxyl group magnesium halide is selected from methoxyl group chlorination magnesium (Mg (OCH
3) Cl), oxyethyl group magnesium chloride (Mg (OC
2h
5) Cl), n-butoxy magnesium chloride (Mg (OC
4h
9) Cl) and isobutoxy magnesium chloride (Mg (i-OC
4h
9) Cl) etc., wherein preferably oxyethyl group magnesium chloride and isobutoxy magnesium chloride.
Alkoxyl magnesium is selected from magnesium methylate (Mg (OCH
3)
2), magnesium ethylate (Mg (OC
2h
5)
2), propoxy-magnesium (Mg (OC
3h
7)
2), butoxy magnesium (Mg (OC
4h
9)
2) and isobutoxy magnesium (Mg (i-OC
4h
9)
2) etc., wherein preferably magnesium ethylate and isobutoxy magnesium.
Alkyl halide magnesium is selected from methylmagnesium-chloride (Mg (CH
3) Cl), ethylmagnesium chloride (Mg (C
2h
5) Cl), propyl group magnesium chloride (Mg (C
3h
7) Cl), normal-butyl chlorination magnesium (Mg (C
4h
9) Cl), isobutyl-chlorination magnesium (Mg (i-C
4h
9) Cl), methyl-magnesium-bromide (Mg (CH
3) Br), ethylmagnesium bromide (Mg (C
2h
5) Br), propyl group magnesium bromide (Mg (C
3h
7) Br), normal-butyl bromination magnesium (Mg (C
4h
9) Br), selenium alkynide (Mg (i-C
4h
9) Br) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-chlorination magnesium.
These magnesium compounds can be used separately a kind of, also can multiple mixing use, not special restriction.If while using with the form of multiple mixing, the mol ratio between two kinds of magnesium compounds in described magnesium compound mixture is such as being 0.1～10:1, preferably 0.2～5:1.
In order to prepare described magnesium compound solution, magnesium compound can be dissolved in the mixed solvent being formed by described solvent and described alcohol, or magnesium compound is added in described solvent, and simultaneously or add subsequently alcohol and dissolve, but be not limited to this.
When the described magnesium compound solution of preparation, take the magnesium compound (solid) of magnesium elements and the mol ratio of described alcohol is 1:0.02-4.00, preferred 1:0.05-3.50, more preferably 1:0.10-3.00, and be generally 1mol:75-400ml in the magnesium compound (solid) of magnesium elements and the ratio of described solvent, preferred 1mol:150-300ml, more preferably 1mol:200-250ml.
To the preparation time of described magnesium compound solution (being the dissolution time of magnesium compound), there is no particular limitation, as long as obtain the solution of homogeneous.
By described porous support is mixed with described magnesium compound solution, obtain thus carrier pulp.
According to the present invention, the mixing process of described porous support and described magnesium compound solution can adopt usual method to carry out, and there is no particular limitation.Such as enumerating, at normal temperature under the preparation temperature of described magnesium compound solution, in described magnesium compound solution, be metered into described porous support, or be metered into described magnesium compound solution in described porous support, mix 0.1-8h, preferred 0.5-4h, optimum 1-2h(is if desired by stirring).
According to the present invention, as the consumption of described porous support, make magnesium compound (in the magnesium compound solid containing in described magnesium compound solution) and the mass ratio of described porous support reach 1:0.1-20, preferably 1:0.5-10, more preferably 1:1-5.
According to the present invention, described carrier pulp is a kind of half dry system.Although unessential, in order to ensure the homogeneity of system, this carrier pulp is preferably carried out the airtight standing of certain hour (2-48h, preferably 4-24h, most preferably 6-18h) afterwards in preparation.
Below described porous support is specifically described.
As porous support, such as can enumerate this area when manufacturing supported olefin polymerization catalyst as carrier and conventional those porosu solids that use, such as silicon-dioxide (claiming again silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white or Thorotrast, clay, molecular sieve, mica, polynite, kaolin, wilkinite and diatomite etc.Preferred silicon-dioxide, aluminum oxide, magnesium oxide, oxidation sial, oxidation magnalium, titanium oxide silicon, titanium dioxide, molecular sieve and polynite etc., most preferably silicon-dioxide.
Porosu solid is the optional thermal activation treatment of carrying out before use, such as under reduced pressure or under inert atmosphere, porosu solid being carried out to heat treated.Wherein inert atmosphere can be selected from nitrogen or inert gas atmosphere, and the temperature of thermal activation is 200-800 ℃, and preferably 400～700 ℃, most preferably 400～650 ℃, heat-up time is such as being 0.5～24h, preferably 2～12h, most preferably 4～8h.
There is no particular limitation for the surface-area of porous support, but be generally 10～1000m
2/ g(BET method is measured), preferred 100～600m
2/ g; The pore volume of this porous support (determination of nitrogen adsorption) is generally 0.1～4cm
3/ g, preferably 0.2～2cm
3/ g, and its median size (laser particle analyzer mensuration) preferably 1～500mm, more preferably 1～100mm.Porous support can be form arbitrarily, such as micropowder, granular, spherical, aggregate or other form.
By porous support (optional through thermal activation) is mixed with magnesium compound solution, obtain thus carrier pulp.
According to the present invention, by described carrier pulp convection drying, or through filtering, washing and dry, preferred convection drying, can obtain a kind of solid product of good fluidity, i.e. described complex carrier.
When described carrier pulp is carried out to convection drying, described convection drying can adopt ordinary method to carry out, such as heat drying under dry under dry under inert gas atmosphere, vacuum atmosphere or vacuum atmosphere etc., and preferred heat drying under vacuum atmosphere wherein.At the temperature of the low 5-15 of boiling point ℃ of the described dry solvent generally containing in than described mixed serum (being generally 30-160 ℃, preferably 60-130 ℃), carry out, and be generally 2-24h time of drying, but be sometimes not limited to this.
Described carrier pulp is being filtered, washed and when dry, for described filtration, washing and dry method, be not particularly limited, can use as required conventional those that use in this area.As required, described washing is generally carried out 1-6 time, preferably 2-3 time.Wherein, washer solvent is preferably used and contained identical solvent in described mixed serum, but also can be different.Described being dried can adopt ordinary method to carry out, and the situation during preferably with aforementioned convection drying is identical.
Then, with alkyllithium reagent, process described complex carrier, obtain thus active carrier.
According to the present invention, by described complex carrier being carried out to chemical treatment with alkyllithium reagent, can make alcohol contained in described alkyllithium reagent and this complex carrier react, thereby on carrier, generate magnesium compound-alkoxyl group chlorine complex with activator metal cyclopentadinyl compound, obtain thus described active carrier.
Below described alkyllithium reagent is specifically described.
As described aluminum alkyls, such as enumerating the compound shown in following general formula:
Al(R)
3
Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from independently of one another C
1-C
8alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Particularly, as described aluminum alkyls, such as enumerating trimethyl aluminium (Al (CH
3)
3), triethyl aluminum (Al (CH
3cH
2)
3), tri-propyl aluminum (Al (C
3h
7)
3), triisobutyl aluminium (Al (i-C
4h
9)
3), three n-butylaluminum (Al (C
4h
9)
3), triisopentyl aluminium (Al (i-C
5h
11)
3), three n-pentyl aluminium (Al (C
5h
11)
3), three hexyl aluminium (Al (C
6h
13)
3), three isohexyl aluminium (Al (i-C
6h
13)
3), diethylmethyl aluminium (Al (CH
3) (CH
3cH
2)
2) and dimethyl ethyl aluminium (Al (CH
3cH
2) (CH
3)
2) etc., wherein preferably trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, further preferably triethyl aluminum and triisobutyl aluminium.
These aluminum alkylss can be used separately a kind of, or are used in combination multiple with ratio arbitrarily.
According to the present invention, described alkyllithium reagent is generally to use with the form of solution.When the solution of the described alkyllithium reagent of preparation, to the solvent that now used, there is no particular limitation, as long as it can dissolve this alkyllithium reagent.
Particularly, as described solvent, such as enumerating C
5-12alkane and C
6-12aromatic hydrocarbons etc., such as enumerating pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, hexanaphthene, toluene, ethylbenzene, dimethylbenzene etc., wherein preferably pentane, hexane, decane and toluene, most preferably hexane and toluene.
Clearly, now can not select and have the solvent (such as ether solvent is such as tetrahydrofuran (THF) etc.) of dissolving power to dissolve described alkyllithium reagent to described magnesium compound.
These solvents can be used separately a kind of, or are used in combination multiple with ratio arbitrarily.
In addition, there is no particular limitation for the concentration to described alkyllithium reagent in its solution, can suitably select as required, as long as its described alkyllithium reagent that can realize with predetermined amount carries out described processing.
As the method for carrying out described processing, such as enumerating, first prepare the solution of described alkyllithium reagent, then at the temperature of-30-60 ℃ (preferably-20-30 ℃), in the described complex carrier of intending processing with described alkyllithium reagent, be metered into (preferably dripping) described alkyllithium reagent solution (the described alkyllithium reagent that contains predetermined amount), or be metered into described complex carrier in described alkyllithium reagent solution, form thus reaction mixture, make its reaction 1-8h, preferred 2-6h, most preferably 3-4h(is if desired by stirring).Then, obtained pre-treatment product process is filtered, washed (1-6 time, preferably 1-3 time) and optionally drying, and separate from this reaction mixture.
According to the present invention, as the consumption of described alkyllithium reagent, make to reach 1:0.2-8 in the magnesium compound of Mg element and the mol ratio of described alkyllithium reagent in Al element, preferably 1:0.4-6, more preferably 1:0.5-3.
Then, with Metallocenic compound, process described active carrier, thereby obtain carried metallocene catalyst of the present invention.
Below described Metallocenic compound is specifically described.
According to the present invention, described Metallocenic compound refers to the IVB family organometallics that contains cyclopentadienyl or substituted cyclopentadienyl in chemical structure.
Particularly, as described Metallocenic compound, such as enumerating half metallocene or indenes title complex, cyclopentadienyl, substituted cyclopentadienyl, Bridged-Dicyclopentadiene base, indenyl, substituted indenyl and the bridging indenyl title complex of preferred titanium or zirconium, more preferably cyclopentadienyl titanium dichloride, bis cyclopentadienyl zirconium dichloride, dichloro two indenes zirconiums, Dichloroethyl bridging two indenes titaniums, Dichloroethyl bridging two indenes zirconiums, the luxuriant titanium of dichloro methylene bridge di-, dichloro methylene-bridged zirconocene.
According to the present invention, described Metallocenic compound is generally to use with the form of solution.When the solution of the described Metallocenic compound of preparation, to the solvent that now used, there is no particular limitation, as long as it can dissolve this Metallocenic compound and not react with described active carrier.
Particularly, as described solvent, such as enumerating C
6-12aromatic hydrocarbons, C
1-6halogenated alkane, C
6-12halogenated aryl hydrocarbon etc., such as enumerating toluene, ethylbenzene, dimethylbenzene, methylene dichloride, trichloromethane, chlorobenzene, dichlorobenzene etc., wherein preferably toluene and methylene dichloride, most preferably toluene.
These solvents can be used separately a kind of, or are used in combination multiple with ratio arbitrarily.
In addition, there is no particular limitation for the concentration to described Metallocenic compound in its solution, can suitably select as required, as long as its described Metallocenic compound that can realize with predetermined amount carries out described processing.
As the method for carrying out described processing, such as enumerating, first prepare the solution of described Metallocenic compound, then at the temperature of-30-100 ℃ (preferably 0-80 ℃), in the described active carrier of intending processing with described Metallocenic compound, be metered into described Metallocenic compound solution (the described Metallocenic compound that contains predetermined amount), or be metered into described complex carrier in described Metallocenic compound solution, form thus reaction mixture, make its reaction 1-8h, preferred 2-6h, most preferably 3-4h(is if desired by stirring).Then, obtained processing product process is filtered, washed (1-6 time, preferably 1-3 time) and optionally drying, and separate from this reaction mixture.
According to the present invention, as the consumption of described Metallocenic compound, make to reach 1:0.0001-1 in the magnesium compound of Mg element with the mol ratio with Metallocenic compound, preferably 1:0.0002-0.4, more preferably 1:0.0008-0.2, further preferred 1:0.001-0.1.
Known to those skilled in the art, aforementioned all method stepss all preferably carry out under the condition of anhydrous anaerobic substantially.Here said anhydrous anaerobic substantially refers to the content of water and oxygen in system and continues to be less than 10ppm.And carried metallocene catalyst of the present invention needs pressure-fired in confined conditions to save backup in preparation afterwards conventionally.
In one embodiment, the invention still further relates to the carried metallocene catalyst by preparation method's manufacture of aforesaid carried metallocene catalyst.
In a further embodiment, the present invention relates to a kind of alkene homopolymerization/copolymerization process, wherein using carried metallocene catalyst of the present invention as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.
With regard to this alkene homopolymerization/copolymerization process involved in the present invention, except the content particularly pointing out below, other contents of not explaining (such as the addition manner of reactor, alkene consumption, catalyzer and alkene for polymerization etc.), can directly be suitable for conventional known those in this area, not special restriction, at this, the description thereof will be omitted.
According to homopolymerization/copolymerization process of the present invention, take carried metallocene catalyst of the present invention as Primary Catalysts, take that to be selected from one or more in aluminum alkyls be promotor, make alkene homopolymerization or copolymerization.
Primary Catalysts and promotor can be first to add Primary Catalysts to the mode that adds in polymerization reaction system, and then add promotor, or first add promotor, and then add Primary Catalysts, or both add after first contacting mixing together, or add respectively simultaneously.Primary Catalysts and promotor are added respectively and fashionablely both can in same reinforced pipeline, be added successively, also can in the reinforced pipeline of multichannel, add successively, and both add respectively simultaneously and fashionablely should select the multichannel pipeline that feeds in raw material.For continous way polyreaction, preferably the reinforced pipeline of multichannel adds simultaneously continuously, and for intermittence type polymerization reaction, preferably both add together after first mixing in same reinforced pipeline, or in same reinforced pipeline, first add promotor, and then add Primary Catalysts.
According to the present invention, to the reactive mode of described alkene homopolymerization/copolymerization process, there is no particular limitation, can adopt well known in the art those, such as enumerating slurry process, substance law and vapor phase process etc., wherein preferred slurries method and vapor phase process.
According to the present invention, as described alkene, such as enumerating C
2-C
10monoolefine, diolefin, cyclic olefin and other ethylenically unsaturated compounds.
Particularly, as described C
2-C
10monoolefine, such as enumerating ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and vinylbenzene etc.; As described cyclic olefin, such as enumerating 1-cyclopentenes and norbornylene etc.; As described diolefin, such as enumerating Isosorbide-5-Nitrae-divinyl, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as described other ethylenically unsaturated compounds, such as enumerating vinyl acetate and (methyl) acrylate etc.Wherein, the homopolymerization of optimal ethylene, or the copolymerization of ethene and propylene, 1-butylene or 1-hexene.
According to the present invention, homopolymerization refers to only a kind of polymerization of described alkene, and copolymerization refers to the polymerization between two or more described alkene.
According to the present invention, according to the difference of the reactive mode of described alkene homopolymerization/copolymerization process, sometimes need to use polymerization solvent.As described polymerization solvent, can use this area conventional those that use when carrying out alkene homopolymerization/copolymerization, not special restriction.Such as enumerating C
4-10alkane (such as butane, pentane, hexane, heptane, octane, nonane or decane etc.), halo C
1-10alkane (such as methylene dichloride), aromatic hydrocarbon solvent (such as toluene and dimethylbenzene), ether solvent (such as ether or tetrahydrofuran (THF)), esters solvent (such as ethyl acetate) and ketones solvent (such as acetone) etc.Wherein preferably use hexane as described polymerization solvent.
These polymerizations can be used separately a kind of with solvent, or are used in combination multiple with ratio arbitrarily.
According to the present invention, the polymerization pressure of described alkene homopolymerization/copolymerization process is generally 0.1-10MPa, preferred 0.1-6MPa, and more preferably 1-5MPa, but be sometimes not limited to this.According to the present invention, polymeric reaction temperature is generally-40 ℃-200 ℃, and preferably 10 ℃-100 ℃, more preferably 40 ℃-90 ℃, but be sometimes not limited to this.
In addition, according to the present invention, described alkene homopolymerization/copolymerization process can carry out under the condition that has hydrogen to exist.The dividing potential drop of hydrogen can be the 0.01%-99% of described polymerization pressure, preferred 0.01%-50%, but be sometimes not limited to this.
According to the present invention, when carrying out described alkene homopolymerization/copolymerization process, in the mol ratio of the described carried metallocene catalyst of the described promotor Yu YiⅣ B family metal of aluminium, be generally 1:1-1000, preferably 1:1-500, more preferably 1:10-500, but be sometimes not limited to this.
Embodiment
Below adopt embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiment.
(unit is g/cm to polymer stacks density
3) mensuration with reference to CNS GB 1636-79, carry out.
The polymerization activity of catalyzer calculates in accordance with the following methods: after polyreaction finishes, polymerisate in reactor is filtered and is dried, then weigh the quality of this polymerisate, with this polymerisate quality, divided by the ratio of the quality of carried metallocene catalyst used, represent the polymerization activity (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) of this catalyzer.
Molecular weight Mw, the Mn of polymkeric substance and molecular weight distribution (Mw/Mn) adopt the GPC V2000 type gel chromatography analyser of U.S. WATERS company to measure, and with 1,2.4-trichlorobenzene, for solvent, temperature during mensuration is 150 ℃.
Embodiment 1
Porous support adopts silicon-dioxide, i.e. silica gel, and model is the ES757 of Ineos company.First silica gel is continued to roasting 4h and thermal activation under 600 ℃, nitrogen atmosphere.Magnesium compound adopts magnesium chloride, and alcohol adopts butanols, and the solvent of dissolved magnesium compound adopts tetrahydrofuran (THF), and Metallocenic compound adopts cyclopentadienyl titanium dichloride, and alkyllithium reagent adopts triethyl aluminum.
Take 2.5g Magnesium Chloride Anhydrous, add a certain amount of butanols and tetrahydrofuran (THF), be heated to after 60 ℃ of dissolvings, add silica gel to form carrier pulp, stir after 2 hours, at homogeneous heating to 90 ℃, directly vacuumize dryly, obtain complex carrier.
Measure 25ml hexane solvent, join in described complex carrier, under agitation condition, with 15 minutes, be added dropwise to triethyl aluminum, at 60 ℃, react after 4 hours, filter, hexane washing 3 times, each 25ml, finally vacuumizes the dry active carrier that obtains.
Measure 25ml toluene solvant, join in Metallocenic compound, after dissolving with 15 minutes under agitation condition, under agitation condition, add active carrier, at 30 ℃, react after 4 hours, filter, toluene wash 3 times, each 25ml, finally vacuumizes the dry carried metallocene catalyst that obtains.
Proportioning is: magnesium compound and butanols mol ratio are 1:3; The tetrahydrofuran solvent proportioning of magnesium compound and dissolved magnesium compound is 1mol:200ml; The mol ratio of magnesium compound and Metallocenic compound is 1:0.004; The quality proportioning 1:2 of magnesium compound and porous support silica gel; Magnesium compound and alkyllithium reagent triethyl aluminum and mol ratio be 1:2.
This catalyzer is designated as CAT-1.
Embodiment 2
Substantially the same manner as Example 1, but have following change:
Magnesium compound changes magnesium ethylate into, and alcohol changes ethanol into, and Metallocenic compound adopts bis cyclopentadienyl zirconium dichloride, and magnesia mixed oxide is continued to roasting 4h under 600 ℃, argon gas atmosphere.Carrier pulp be at 80 ℃, vacuumize dry.
Proportioning is: magnesium compound and alcohol mol ratio are 1:1; The solvent burden ratio of magnesium compound and dissolved magnesium compound is 1mol:240ml; The mol ratio of magnesium compound and Metallocenic compound is 1:0.006; The quality proportioning 1:1 of magnesium compound and porous support; Magnesium compound and alkyllithium reagent and mol ratio be 1:1.
This catalyzer is designated as CAT-2.
Embodiment 3
Substantially the same manner as Example 1, but have following change:
Magnesium compound changes isobutoxy magnesium chloride into, and alcohol is changed into propyl alcohol, and the solvent of dissolved magnesium compound changes toluene into, and it is the compound of dichloro two indenes zirconiums that Metallocenic compound adopts structural formula, and porous support adopts aluminium sesquioxide.Aluminium sesquioxide is continued under 700 ℃, nitrogen atmosphere to roasting 6h.Mixed serum be at 100 ℃, vacuumize dry.
Alkyllithium reagent is changed into triisobutyl aluminium, is first dissolved in 25ml toluene, then in 15 minutes, be added drop-wise in complex carrier, and toluene wash three times, each 25ml, is heated to 120 ℃ and vacuumizes dry.
Proportioning is: magnesium compound and alcohol mol ratio are 1:2; The solvent burden ratio of magnesium compound and dissolved magnesium compound is 1mol:100ml; The mol ratio of magnesium compound and Metallocenic compound is 1:0.003; The quality proportioning 1:3 of magnesium compound and porous support; Magnesium compound and alkyllithium reagent and mol ratio be 1:3.
This catalyzer is designated as CAT-3.
Embodiment 4
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into magnesium ethide, and alcohol is changed into isooctyl alcohol, and the solvent of dissolved magnesium compound changes ethylbenzene into, and Metallocenic compound adopts dichlorodicyclopentadienyl titanium, and porous support adopts aluminum oxide.Aluminum oxide is continued under 400 ℃, nitrogen atmosphere to roasting 8h.Mixed serum is dry under nitrogen purging at 130 ℃.Alkyllithium reagent is changed into trimethyl aluminium.
Proportioning is: magnesium compound and alcohol mol ratio are 1:0.25; The solvent burden ratio of magnesium compound and dissolved magnesium compound is 1mol:300ml; The mol ratio of magnesium compound and Metallocenic compound is 1:0.010; The quality proportioning 1:0.5 of magnesium compound and porous support; Magnesium compound and alkyllithium reagent and mol ratio be 1:0.5.
This catalyzer is designated as CAT-4.
Embodiment 5
Substantially the same manner as Example 1, but have following change:
Magnesium compound is changed into oxyethyl group magnesium chloride, and alcohol is changed into amylalcohol, and the solvent of dissolved magnesium compound changes dimethylbenzene into, and porous support adopts aluminium sesquioxide.Aluminium sesquioxide is continued under 700 ℃, nitrogen atmosphere to roasting 6h.Metallocenic compound adopts dichloro ethylene indenes zirconium, mixed serum be at 60 ℃, vacuumize dry.Alkyllithium reagent is changed into tri-n-n-propyl aluminum.
Proportioning is: magnesium compound and alcohol mol ratio are 1:3; The solvent burden ratio of magnesium compound and dissolved magnesium compound is 1mol:350ml; The mol ratio of magnesium compound and Metallocenic compound is 1:0.001; The quality proportioning 1:10 of magnesium compound and porous support; Magnesium compound and alkyllithium reagent and mol ratio be 1:6.
This catalyzer is designated as CAT-5.
Comparative example A
Substantially the same manner as Example 1, but have following change:
Do not add porous support silica gel.
Catalyzer is designated as CAT-1-A.
Embodiment 6(Application Example)
Take respectively carried metallocene catalyst CAT-1-5, CAT-A, carry out in accordance with the following methods under the following conditions respectively homopolymerization, the copolymerization of ethene with promotor.
Homopolymerization is: 2 liters of polymerization autoclaves, slurry polymerization processes, 1 liter of hexane solvent, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.001MPa, 2 hours reaction times.First 1 liter of hexane is joined in polymerization autoclave, open and stir, then add 10mg carried metallocene catalyst and catalyst mixture, then add hydrogen to 0.001MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
Copolymerization is: 2 liters of polymerization autoclaves, slurry polymerization processes, 1 liter of hexane solvent, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.001MPa, 2 hours reaction times.First 1 liter of hexane is joined in polymerization autoclave, open and stir, then add 10mg carried metallocene catalyst and catalyst mixture, the disposable hexene-1 comonomer 25g that adds, add again hydrogen to 0.001MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.
table 1. carried metallocene catalyst is for olefinic polyreaction effect table look-up
From the obtained effect comparison of table 1, catalyzer has higher and adjustable polymerization activity, and the polymkeric substance obtaining is thus higher, and form is better, and contrast sequence number 1 and 3 is visible, and promotor consumption is less on the molecular weight distribution impact of polymkeric substance;
From sequence number in table 11 and contrast sequence number 9, adopt expensive methylaluminoxane as promotor, although the polymerization activity of catalyzer increases, the bulk density of polymkeric substance significantly reduces, morphology is poor.
Known by sequence number in table 11 and 8 obtained effect comparison, in catalyst preparation process, do not add porous support, the catalyzer of preparation also has higher activity and close molecular weight distribution to vinyl polymerization, but polymer stacks density significantly reduces, polymer morphology variation.
Known by sequence number in table 11 and 3 obtained effect comparison, catalyzer has certain copolymerization effect, the Copolymerization activity that is catalyzer is active higher than homopolymerization, and copolyreaction can improve the bulk density of polymkeric substance, improve the particle form of polymkeric substance, but less on the impact of the molecular weight distribution of polymkeric substance.
Claims (10)
1. a preparation method for carried metallocene catalyst, it comprises the following steps:
Magnesium compound is dissolved in solvent under the existence of alcohol, obtains magnesium compound solution, then add through heat treated porous support, obtain the step of carrier pulp;
Described carrier pulp is dry, the step of acquisition complex carrier;
With alkyllithium reagent, process above-mentioned complex carrier, obtain the step of active carrier; With
With Metallocenic compound, process described active carrier, obtain the step of described carried metallocene catalyst.
2. according to the preparation method of a kind of carried metallocene catalyst claimed in claim 1, it is characterized in that, described magnesium compound is selected from magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium and alkyl halide magnesium, described alcohol is selected from fatty alcohol, aromatic alcohol and alicyclic ring alcohol, described porous support is selected from silicon-dioxide, aluminum oxide, magnesium oxide, oxidation sial, oxidation magnalium, titanium dioxide, molecular sieve and the polynite through thermal activation treatment, described Metallocenic compound is selected from half metallocene and the indenes title complex of IV B family metal, and described solvent is selected from C
6-12aromatic hydrocarbon, ester and ether.
3. according to the preparation method of a kind of carried metallocene catalyst claimed in claim 1, it is characterized in that, described magnesium compound is selected from magnesium halide, described alcohol is selected from fatty alcohol, described porous support is selected from silicon-dioxide and aluminum oxide, described Metallocenic compound is selected from cyclopentadienyl, substituted cyclopentadienyl, Bridged-Dicyclopentadiene base, indenyl, substituted indenyl and the bridging indenyl title complex of titanium or zirconium, and described solvent is selected from C
6-12aromatic hydrocarbon and tetrahydrofuran (THF).
4. according to the preparation method of a kind of carried metallocene catalyst claimed in claim 1, it is characterized in that, described magnesium compound is selected from magnesium chloride, described alcohol is selected from ethanol and butanols, described porous support is selected from silicon-dioxide, described Metallocenic compound is selected from cyclopentadienyl titanium dichloride, bis cyclopentadienyl zirconium dichloride, dichloro two indenes zirconiums, Dichloroethyl bridging two indenes titaniums, and described solvent is selected from toluene and tetrahydrofuran (THF).
5. according to the preparation method of a kind of carried metallocene catalyst claimed in claim 1, it is characterized in that, described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohexyl aluminium, diethylmethyl aluminium and dimethyl ethyl aluminium.
6. according to the preparation method of a kind of carried metallocene catalyst claimed in claim 5, it is characterized in that, described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium.
7. according to the preparation method of a kind of carried metallocene catalyst claimed in claim 1, it is characterized in that, take the described magnesium compound of Mg element and the mol ratio of described Metallocenic compound is 1:0.0001-1, the ratio of described magnesium compound and described solvent is 1mol:75-400ml, take the described magnesium compound of Mg element and the mol ratio of described alcohol is 1:0.02-4.00, take the described magnesium compound of magnesium compound solid and the mass ratio of described porous support is 1:0.1-205, and in the described magnesium compound of Mg element with take the mol ratio of described aluminum alkyls as 1:0.2-8.
8. according to the preparation method of a kind of carried metallocene catalyst claimed in claim 1, it is characterized in that, take the described magnesium compound of Mg element and the mol ratio of described Metallocenic compound is 1:0.0002-0.4, the ratio of described magnesium compound and described solvent is 1mol:150-300ml, take the described magnesium compound of Mg element and the mol ratio of described alcohol is 1:0.05-3.50, take the described magnesium compound of magnesium compound solid and the mass ratio of described porous support is 1:0.5-10, and in the described magnesium compound of Mg element with take the mol ratio of described aluminum alkyls as 1:0.4-6.
9. a carried metallocene catalyst, it is to be manufactured by the preparation method according to described in claim 1-8 any one.
10. alkene homopolymerization/copolymerization process, is characterized in that, take according to carried metallocene catalyst claimed in claim 9 is Primary Catalysts, take that to be selected from one or more in aluminum alkyls be promotor, makes alkene homopolymerization or copolymerization.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109485758A (en) * | 2017-09-11 | 2019-03-19 | 中国石油化工股份有限公司 | Load type non-metallocene catalyst, preparation method and its application |
| CN111171196A (en) * | 2020-01-09 | 2020-05-19 | 山东清河化工科技有限公司 | Supported catalyst for preparing polyethylene wax by catalyzing ethylene polymerization and preparation method and application thereof |
| CN116023539A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Supported metallocene catalyst suitable for solution polymerization and preparation method and application thereof |
| CN114249775A (en) * | 2021-12-03 | 2022-03-29 | 国家能源集团宁夏煤业有限责任公司 | Metallocene compound, preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof |
| CN114249775B (en) * | 2021-12-03 | 2024-04-16 | 国家能源集团宁夏煤业有限责任公司 | Metallocene compound and preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof |
| CN115772236A (en) * | 2022-12-12 | 2023-03-10 | 辽宁石油化工大学 | Catalyst for preparing elastomer composition and preparation method of catalyst |
| CN115772236B (en) * | 2022-12-12 | 2024-09-10 | 辽宁石油化工大学 | Catalyst for preparing elastomer composition and preparation method of catalyst |
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