CN107459592A - Modified silica gel carrier and supported metallocene catalyst and preparation method and metallocene catalyst system - Google Patents
Modified silica gel carrier and supported metallocene catalyst and preparation method and metallocene catalyst system Download PDFInfo
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- CN107459592A CN107459592A CN201610393399.3A CN201610393399A CN107459592A CN 107459592 A CN107459592 A CN 107459592A CN 201610393399 A CN201610393399 A CN 201610393399A CN 107459592 A CN107459592 A CN 107459592A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/00—Polymerisation catalysts
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/643—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44 other than an organo-aluminium compound
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
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Abstract
The invention belongs to olefin polymerization catalysis field, is related to a kind of modified silica gel carrier and metallocene catalyst and preparation method and metallocene catalyst system.The modified silica gel carrier includes the reaction product of following components：Silica gel, manganese chloride and alkylaluminoxane, the formula of the alkylaluminoxane are：Wherein, R is selected from C1~C12Alkyl；A be 4~30 integer, preferably 10~30 integer.Described modified silica gel carrier preparation method is simple, and the catalyst granules form prepared is good；In addition, applicability of the supported metallocene catalyst on olefin polymetiation process is wide, polymerization activity is high, and the bulk density of obtained polymer is high, and the molecular chain conformation of polymer is held essentially constant.
Description
Technical field
The invention belongs to olefin polymerization catalysis field, in particular it relates to a kind of modified silica gel carrier and preparation method thereof,
A kind of supported metallocene catalyst and preparation method thereof, and a kind of metallocene catalyst system for olefinic polymerization.
Background technology
The development and application of metallocene catalyst are the olefinic polymerization catalysis after traditional Ziegler-Natta catalyst
The another important breakthrough in agent field, the particularly eighties, and Kaminsky and Sinn et al. (Angew.Chem., 1980,19,390；
Adv.Organoment.Chem., efficient co-catalyst MAO (MAO) 1980,18,99.) is developed so that metallocene
The research of catalyst has entered a fast-developing stage.Because catalyzed by homogeneous metallocene catalyst will reach needed for high activity
MAO dosages are big, and production cost is high, and obtained polymer is amorphous, therefore can not be in widely used slurry process or gas
Used on phase method polymerization technique.And overcome above mentioned problem effective way be exactly soluble metallocene catalyst carry out it is supported
Processing.
At present, relevant supported metallocene research report is very more, wherein with SiO2For the report most study (example of carrier
Such as CN1174848A, CN1174849A, CN1356343A, US4,808,561, US5,026,797, US5,763,543, US5,
661,098), but this kind of carrier preparation method it is complicated, the cost of catalyst load is high, and carrier particle shape is poor, uncontrollable.
Also document (US4265785, US20010006931) directly uses alkyl aluminum and manganous chloride to be used as additive system
Standby catalyst carries out polymerisation, and this significantly improves polymerization activity, but the molecular weight of polymer and its distribution produce it is larger
Change, it can not effectively control the performance of polymer.
The content of the invention
In order to solve above mentioned problem existing for prior art, the invention provides a kind of modified silica gel carrier and its preparation side
Method, a kind of supported metallocene catalyst and preparation method thereof, and a kind of metallocene catalyst system for olefinic polymerization.
The present inventor is had found under study for action, and manganese chloride and alkylaluminoxane are introduced into silica-gel carrier, and with cyclopentadienyl
Metal complex is supported metallocene catalyst prepared by precursor, when for olefinic polymerization, can significantly improve catalytic reaction
Activity, and can keep original metallocene catalyst (not adding manganese chloride) resulting polymers molecular weight distribution and accumulation it is close
Degree etc. is basically unchanged.Found based on more than, propose the present invention.
According to the first aspect of the invention, the invention provides a kind of modified silica gel carrier, the modified silica gel carrier bag
Include the reaction product of following components：Silica gel, manganese chloride and alkylaluminoxane, the formula of the alkylaluminoxane are：
Wherein, R is selected from C1~C12Alkyl；A be 4~30 integer, preferably 10~30 integer.
According to the second aspect of the invention, should the invention provides a kind of method for preparing above-mentioned modified silica gel carrier
Method includes：
1) in the presence of the first solvent, manganese chloride is reacted with silica-gel carrier, carried so as to which manganese chloride/silica gel be made
Body；
2) in the presence of the second solvent, the manganese chloride/silica-gel carrier is made to be reacted with alkylaluminoxane.
According to the third aspect of the present invention, the invention provides a kind of supported metallocene catalyst, the supported cyclopentadienyl
Metallic catalyst includes above-mentioned modified silica gel carrier and the metallocenes being supported on carrier, the metallocenes
Precursor is the metallocene complex shown in formula 1,
Cp* 2(Z)MXnFormula 1,
Wherein, Cp*For substituted or unsubstituted cyclopentadienyl group, indenyl or fluorenyl, its substituent is selected from C1~C20Alkane
Base, C1~C20Alkoxy, C1~C20Silylation, C1~C20Aralkoxy, hydroxyl or halogen；
Z is a kind of connection unit for coupling two luxuriant rings, if the metallocene complex for non-bridging shown in formula 1, Z is not
Represent any element；If it is selected from SiR shown in formula 1 for bridging type metallocene complex, Z* 2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、CR* 2SiR* 2、GeR* 2、BR*Or BR* 2, R therein*It is not more than 20 following base selected from hydrogen or carbon number
Group：Alkyl, aryl, silicyl, haloalkyl, halogenated aryl, aralkyl, alkaryl, haloaralkyl and haloalkylaryl；
M is the transition metal of the 4th race or the 5th race in the periodic table of elements, and n is the integer for meeting M valence states；
N X is identical or different, each is selected from hydrogen, halogen, alkyl, substituted hydrocarbon radical, oxyl, aromatic hydrocarbons epoxide, acid group or amine
Base；
In the supported metallocene catalyst, central metal M content is 0.01~5 weight %, preferably 0.05~2
Weight %.
According to the fourth aspect of the present invention, the invention provides a kind of side for preparing above-mentioned supported metallocene catalyst
Method, this method include：In the presence of the 3rd solvent, the modified silica gel carrier is set to be carried out with the metallocene complex shown in formula 1
Reaction；It is preferred that the condition of the reaction includes：Temperature is 0~40 DEG C, and the time is 1~120 minute；3rd solvent is preferably first
Benzene, benzene, dimethylbenzene, hexane, the more preferably at least one of heptane and hexamethylene, toluene and/or hexane.
According to the fifth aspect of the present invention, the invention provides a kind of metallocene catalyst body for olefinic polymerization
System, the metallocene catalyst system include major catalyst and co-catalyst, and the major catalyst is above-mentioned supported metallocene
Catalyst, the co-catalyst are preferably alkyl aluminum；In the metallocene catalyst system, Al and central metal in alkyl aluminum
M mol ratio is preferably 0.01：1~50000：1；More preferably 1：1~5000：1.
The preparation method of the modified silica gel carrier (that is, alkylaluminoxane/manganese chloride/silica-gel carrier) of the present invention is simple, and
The catalyst granules form of preparation is good, and catalyst particle size can pass through the big minor adjustment of silica gel；In addition, the supported cyclopentadienyl
Applicability of the metallic catalyst on olefin polymetiation process is wide, and polymerization activity is high, and the bulk density of obtained polymer is higher, and
And the molecular chain conformation of polymer is held essentially constant.
Brief description of the drawings
Fig. 1 a- Fig. 1 b are SEM of the supported metallocene catalyst of the preparation of the embodiment of the present invention 1 under different amplification
Figure.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to the first aspect of the invention, the invention provides a kind of modified silica gel carrier, the modified silica gel carrier bag
Include the reaction product of following components：Silica gel, manganese chloride and alkylaluminoxane, the formula of the alkylaluminoxane are：
Wherein, R is selected from C1~C12Alkyl；A be 4~30 integer, preferably 10~30 integer.
C1~C12Alkyl refer to C1~C12Straight chained alkyl and C3~C12Branched alkyl.C1~C12Alkyl non-limit
Property example processed includes：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isoamyl
Base, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, dodecyl.
Under preferable case, the alkylaluminoxane is MAO (MAO) and/or alkyl-modified MAO
(MMAO)。
According to the second aspect of the invention, the invention provides the preparation method of above-mentioned modified silica gel carrier, this method
Including：
1) in the presence of the first solvent, manganese chloride is made to be reacted with silica gel, so as to which manganese chloride/silica-gel carrier be made；
2) in the presence of the second solvent, the manganese chloride/silica-gel carrier is made to be reacted with alkylaluminoxane.
In step 1), on the basis of the gross weight of manganese chloride and silica gel, the dosage of manganese chloride can be 0.1~60 weight
Measure %, preferably 0.5~45 weight %.
In step 1), the reaction is generally carried out under inert gas (for example, nitrogen) protective condition.Described can be used
After one solvent dissolves manganese chloride, add the silica gel and reacted.The reaction can be carried out under agitation, and the condition of reaction can
With including：Temperature is 50~100 DEG C, and the time is 0.5~4 hour.
The silica gel can be the conventional selection in prepared by polyolefin catalyst, and it is mainly formed as silica, preferably
The particle diameter of the silica gel is 0.1~120 μm, and specific surface area is>100m2/g。
Usually, before being reacted, silica gel need to be calcined 1~24 hour at a temperature of 50~800 DEG C.Preferable case
Under, according to temperature from low to high, the roasting is carried out in three stages.The roasting condition in each stage specifically includes, the first stage：Temperature
For 100~200 DEG C, the time is 0.5~3 hour；Second stage：Temperature is 250~450 DEG C, and the time is 0.5~3 hour；3rd
Stage：Temperature is 550~800 DEG C, and the time is 0.5~3 hour.
In step 1), conventional selection when first solvent can be this area modified silica gel carrier, as long as can dissolve
Silica gel and manganese chloride, for example, first solvent can be selected from tetrahydrofuran, it is molten one or more alcohols can also to be selected from
Agent.Preferably, first solvent is selected from tetrahydrofuran, ethanol, methanol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol, ethylene glycol and third
At least one of triol.It is highly preferred that first solvent is tetrahydrofuran.
In step 1), in order to obtain the solid chlorine of good fluidity manganese/silica-gel carrier, after the completion of reaction, the step
Also include the first solvent for removing reaction system.
Removing the process of the first solvent can include：First, solvent is steamed by heating；Then, heating vacuumizes, so as to
Obtain the zinc chloride/silica-gel carrier of solid powdery.Wherein, in order to further obtain the carrier of good fluidity, preferably
The heating vacuumizes to be carried out in two stages, and the condition of first stage includes：Temperature is 80~150 DEG C, and the time is 0.5~3 small
When；The condition of second stage includes：Temperature is 200~400 DEG C, and the time is 6~15 hours.
Preferably, the content of the first solvent is not higher than 0.1 weight % in prepared manganese chloride/silica-gel carrier.In addition, can
To pass through the content of the first solvent in gas chromatographic detection carrier.
In step 2), on the basis of the gross weight of the manganese chloride/silica-gel carrier and alkylaluminoxane, alkylaluminoxane
Dosage can be 1~50 weight %, preferably 10~50 weight %.
In step 2), the reaction is generally also carried out under inert gas (for example, nitrogen) protective condition.The can be utilized
Manganese chloride/silica gel is carried and is dispersed into suspension by two solvents, is added alkylaluminoxane and is reacted.The reaction can be in stirring condition
Lower progress, the condition of reaction can include：Temperature is 30~80 DEG C, and preferably 40~60 DEG C, the time is 3~6 hours.
Second solvent may be selected from aromatic hydrocarbons and/or aliphatic hydrocarbon, be preferably selected from toluene, benzene, dimethylbenzene, hexane, heptane and
At least one of hexamethylene, more preferably toluene.
In addition, after reaction terminates, preferably methods described also includes：The slurries obtained using the second solvent to reaction are washed
Wash, be then dried in vacuo, so as to which the modified silica gel carrier (that is, alkylaluminoxane/chlorination of good fluidity be made
Manganese/silica-gel carrier).
In the present invention, the dosage of first solvent and the second solvent is referred to prior art and selected, herein
Repeat no more.
According to the third aspect of the present invention, the invention provides a kind of supported metallocene catalyst, the supported cyclopentadienyl
Metallic catalyst includes described modified silica gel carrier and the metallocenes being supported on carrier, the metallocenes
Precursor is the metallocene complex shown in formula 1,
Cp* 2(Z)MXnFormula 1,
Wherein, Cp*For substituted or unsubstituted cyclopentadienyl group, indenyl or fluorenyl, its substituent is selected from C1~C20Alkane
Base, C1~C20Alkoxy, C1~C20Silylation, C1~C20Aralkoxy, hydroxyl or halogen；
Z is a kind of connection unit for coupling two luxuriant rings, if the metallocene complex for non-bridging shown in formula 1, Z is not
Represent any element；If it is selected from SiR shown in formula 1 for bridging type metallocene complex, Z* 2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、CR* 2SiR* 2、GeR* 2、BR*Or BR* 2, R therein*It is not more than 20 following groups for hydrogen or carbon number：
Alkyl, aryl, silicyl, haloalkyl, halogenated aryl, aralkyl, alkaryl, haloaralkyl and haloalkylaryl；
M is the transition metal of the 4th race or the 5th race in the periodic table of elements, and n is the integer for meeting M valence states；
N X is identical or different, each is selected from hydrogen, halogen, alkyl, substituted hydrocarbon radical, oxyl, aromatic hydrocarbons epoxide, acid group or amine
Base.
In the supported metallocene catalyst, central metal M content is 0.01~5 weight %, preferably 0.05~2
Weight %.
Under preferable case, if being selected from SiR* shown in formula 1 for bridging type metallocene complex, Z2、CR*2、SiR*2SiR*2、CR*2CR*2, CR*=CR* or CR*2SiR*2, R* therein is selected from the alkyl or virtue of hydrogen or carbon number less than 20
Base.
In formula 1, M is preferably selected from titanium, zirconium or hafnium.
In formula 1, X is preferably selected from hydrogen, halogen, alkyl, pi-allyl, cyclopentadienyl group, alkoxy or aromatic hydrocarbons epoxide, more preferably
Selected from chlorine, bromine, iodine, methoxyl group, ethyoxyl, isopropoxy, isobutoxy, butoxy, phenoxy group, oxy-o-cresyl, a toluene
Epoxide, to toloxyl or naphthoxy.
In formula 1, n can be 1-3 integer, preferably n=2.
The present invention mainly solves often by the way that the precursor of metallocene catalyst is supported on the modified silica gel carrier
The problems such as metallocene catalyst polymerisation activity is not high is advised, being referred to prior art as the specific metallocene complex enters
Row selection, will not be repeated here.
According to described supported metallocene catalyst, in certain scope, with the increase of Mn contents, catalyst
Activity increase.The angle being easily controlled from polymerisation, it is preferable that in the supported metallocene catalyst, Mn's
Content is 0.5~4.0 weight %.In addition, in described supported metallocene catalyst, Al and central metal M mol ratio can
Think 50~150:1.
According to the fourth aspect of the present invention, the invention provides the supported metallocene catalyst described in a kind of prepare
Method, this method include：In the presence of the 3rd solvent, the modified silica gel carrier is set to enter with the metallocene complex shown in formula 1
Row reaction；
Preferably, the condition of the reaction includes：Temperature is 0~40 DEG C, and the time is 1~120 minute；
3rd solvent is preferably at least one of toluene, benzene, dimethylbenzene, hexane, heptane and hexamethylene, more preferably
Toluene and/or hexane.
According to one embodiment of the present invention, preparing the process of the supported metallocene catalyst can include：It is first
First, under inert gas (for example, nitrogen) protection, the modified silica gel carrier is mixed with the 3rd solvent, slurries are made；So
Afterwards, the solution of the metallocene complex shown in formula 1 is slowly dropped in this slurries, at 0~40 DEG C, reacts 1~120 point
Clock, you can obtain the supported metallocene catalyst of slurries state, it is used directly for polymerisation.In addition, terminate in reaction
Afterwards, the solvent in reaction system can be also removed, after product washing is dried, the solid catalyst of mobility is obtained, for polymerizeing
Reaction.
According to the fifth aspect of the present invention, the invention provides a kind of metallocene catalyst body for olefinic polymerization
System, the metallocene catalyst system include major catalyst and co-catalyst, and the major catalyst is above-mentioned supported metallocene
Catalyst.
The co-catalyst is preferably alkyl aluminum.In the present invention, polymerization can be removed by adding alkyl aluminum in the polymerization
Impurity in system, polymerization activity is improved to a certain extent, and make co-catalyst without adding expensive MAO.
In the metallocene catalyst system, the dosage of alkyl aluminum is referred to prior art and selected, and the present invention is right
This is not particularly limited.Preferably, in the metallocene catalyst system, the mol ratio of the Al and central metal M in alkyl aluminum
For 0.01：1~50000：1；More preferably 1：1~5000：1.
Preferably, the alkyl aluminum is selected from trimethyl aluminium, triethyl aluminum (TEA), tri-propyl aluminum, tri-butyl aluminum, three isopropyls
Base aluminium, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, aluminium diethyl monochloride and Dichloroethyl
At least one of aluminium.It is highly preferred that the alkyl aluminum is triethyl aluminum.
Described metallocene catalyst system can be with different polymerizations, such as gas-phase polymerization and slurry polymerization
Deng.Homopolymerization or copolymerization available for alkene, are closed especially suitable for ethylene homo or ethene and other alpha-olefins are total to
The non-limiting examples of polymerisation, wherein alpha-olefin can include propylene, butylene, amylene, hexene, octene and 4- methylpents
Alkene -1 etc..
In polymerization, the alkyl aluminum can add simultaneously with supported metallocene catalyst, can also successively be added to
In polymer reactor.
Solvent used in polymerization can be selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons, preferably hexane, pentane, heptane, benzene,
One kind or their mixture in toluene, dichloromethane, chloroform, dichloroethanes, more preferably hexane.
In terms of central metal M element, concentration of the supported metallocene catalyst in polymerization can be 1 × 10- 8Mol/L~1 × 10-2mol/L。
The temperature of polymerization can be -78 DEG C to 100 DEG C, preferably 0~90 DEG C.
The pressure of polymerization can be 0.01~10.0MPa, preferably 0.01~2.0MPa.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, used silica gel model 2485 (45 microns of average grain diameter), purchased from thunder lattice
This-Davis Co., Ltd, first carry out calcination process using preceding：Under a nitrogen, it is calcined 2.5 hours in 150 DEG C, then heats to 300
DEG C roasting 2 hours, be finally warming up to 600 DEG C be calcined 5 hours.Processing is being dried using preceding in various solvents；MAO is purchased from
Sigma-Aldrich companies, it is 10wt% MAO toluene solution.
The percentage by weight of element determines by the following method in catalyst：Using plasma emission spectrometry (ICP), instrument
Device selects the P1000 type ICP-AES plasma emission spectrometers of PE companies of U.S. production.
Polymer molecular weight determines by the following method with molecular weight distribution：Using gel permeation chromatography (GPC), instrument
Using Waters Alliance GPCV 2000, solvent is 1,2,4- trichloro-benzenes, sample concentration 1mg/mL, and solvent flow rate is
1.0mL/min；Measurement temperature is 150 DEG C.
Polymer bulk density characterizes：With reference to GB/T1033-1986 methods describeds, tested using infusion process.
Embodiment 1
The present embodiment is used for the modified silica gel carrier and supported metallocene catalyst and respective system for illustrating the present invention
Preparation Method.
1) preparation of manganese chloride/silica-gel carrier
Under nitrogen protection, 0.52 gram of anhydrous Manganese chloride is added into glass reactor in room temperature, then adds 350 milliliters
Tetrahydrofuran, stirring is started, 13.9 grams of silica gel are added in reactor, be warming up to 65 DEG C, stirring and dissolving is after 2 hours, 80
Evaporation of solvent at DEG C, obtains white solid powder.White solid powder is dried in vacuo 2 hours at 100 DEG C, then
It is dried in vacuo 10 hours at 300 DEG C, obtains manganese chloride/silica-gel carrier of good fluidity, through gas chromatographic analysis, fails to detect
To tetrahydrofuran.
2) preparation of alkylaluminoxane/manganese chloride/silica-gel carrier
Under nitrogen protection, take 4.64 grams of manganese chloride/silica-gel carrier obtained above to add in glass reactor, add 60
Milliliter toluene, is dispersed into suspension, adds 28 milliliters of 10wt% MAO toluene solution, is warming up to 50 DEG C, stirring reaction 4 is small
When, then washed three times with toluene, then washed with hexane, it is dried in vacuo, obtains the solid powder of good fluidity, i.e. alkyl aluminum
Oxygen alkane/manganese chloride/silica-gel carrier.
3) preparation of supported metallocene catalyst
Under nitrogen protection, above-mentioned alkylaluminoxane/3.5 grams of the manganese chloride/silica-gel carrier prepared is added to glass
In reactor, add 35 milliliters of toluene and slurries are made, be dissolved in 0.173 gram of double (1,3- normal-butyl methyl in 20 milliliters of toluene
Cyclopentadienyl group) solution of zirconium dichloride (BMCP) is added drop-wise in reactor, reacts 30 minutes in 30 DEG C, then washed with toluene
To wash, be dried in vacuo, obtain supported metallocene catalyst A, the microscopic appearance of the product is as shown in Fig. 1 a- Fig. 1 b, as seen from the figure,
The particle shape of catalyst is good.In addition, the content of essential element is as shown in table 1 in catalyst.
Embodiment 2
The present embodiment is used for the modified silica gel carrier and supported metallocene catalyst and respective system for illustrating the present invention
Preparation Method.
1) preparation of manganese chloride/silica-gel carrier
Under nitrogen protection, 0.8 gram of anhydrous Manganese chloride is added into glass reactor in room temperature, then adds 250 milliliter four
Hydrogen furans, stirring is started, 7.0 grams of silica gel are added in reactor, be warming up to 65 DEG C, stirring and dissolving is after 2 hours, at 80 DEG C
Evaporation of solvent, obtain white solid powder.White solid powder is dried in vacuo 2 hours at 100 DEG C, then at 300 DEG C
Lower vacuum drying 10 hours, obtains manganese chloride/silica-gel carrier of good fluidity, through gas chromatographic analysis, fails to detect four
Hydrogen furans.
2) preparation of alkylaluminoxane/manganese chloride/silica-gel carrier
Under nitrogen protection, take 4.13 grams of manganese chloride/silica-gel carrier obtained above to add in glass reactor, add 60
Milliliter toluene, is dispersed into suspension, adds 24 milliliters of 10wt% MAO toluene solution, is warming up to 50 DEG C, stirring reaction 4 is small
When, then washed three times with toluene, then washed with hexane, it is dried in vacuo, obtains the solid powder of good fluidity, i.e. alkyl aluminum
Oxygen alkane/manganese chloride/silica-gel carrier.
3) preparation of supported metallocene catalyst
Under nitrogen protection, above-mentioned alkylaluminoxane/4.89 grams of the manganese chloride/silica-gel carrier prepared is added to glass
In reactor, add 50 milliliters of toluene and slurries are made, the solution for being dissolved in 0.211 gram of BMCP in 24 milliliters of toluene is added drop-wise to instead
Answer in device, react 30 minutes in 30 DEG C, then washed with toluene, be dried in vacuo, obtain supported metallocene catalyst B, it is led
Want the content of element as shown in table 1.
Embodiment 3
The present embodiment is used for the modified silica gel carrier and supported metallocene catalyst and respective system for illustrating the present invention
Preparation Method.
1) preparation of manganese chloride/silica-gel carrier
Under nitrogen protection, 0.81 gram of anhydrous Manganese chloride is added into glass reactor in room temperature, then adds 300 milliliter four
Hydrogen furans, stirring is started, 5.94 grams of silica gel are added in reactor, be warming up to 65 DEG C, stirring and dissolving is after 2 hours, at 80 DEG C
Lower evaporation of solvent, obtains white solid powder.White solid powder is dried in vacuo 2 hours at 100 DEG C, then 300
It is dried in vacuo 10 hours at DEG C, obtains manganese chloride/silica-gel carrier of good fluidity, through gas chromatographic analysis, fails to detect
Tetrahydrofuran.
2) preparation of alkylaluminoxane/manganese chloride/silica-gel carrier
Under nitrogen protection, take 2.67 grams of manganese chloride/silica-gel carrier obtained above to add in glass reactor, add 40
Milliliter toluene, is dispersed into suspension, adds 16 milliliters of 10wt% MAO toluene solution, is warming up to 50 DEG C, stirring reaction 4 is small
When, then washed three times with toluene, then washed with hexane, it is dried in vacuo, obtains the solid powder of good fluidity, i.e. alkyl aluminum
Oxygen alkane/manganese chloride/silica-gel carrier.
3) preparation of supported metallocene catalyst
Under nitrogen protection, above-mentioned alkylaluminoxane/3.72 grams of the manganese chloride/silica-gel carrier prepared is added to glass
In reactor, add 40 milliliters of toluene and slurries are made, the solution for being dissolved in 0.161 gram of BMCP in 24 milliliters of toluene is added drop-wise to instead
Answer in device, react 30 minutes in 30 DEG C, then washed with 50 milliliters of toluene, be dried in vacuo, obtain supported metallocene catalyst
C, the content of its essential element are as shown in table 1.
Comparative example 1
1) preparation of alkylaluminoxane/silica-gel carrier
Under nitrogen protection, take 7.01 grams of silica gel to be added in glass reactor, and add 90 milliliters of toluene thereto, point
Suspension is dissipated into, 40 milliliters of 10wt% MAO toluene solution is then added, is warming up to 50 DEG C, stirring reaction 4 hours, then
Washed three times with toluene, then washed with hexane, be dried in vacuo, obtain the solid powder of good fluidity, i.e. alkylaluminoxane/silicon
Glue carrier.
2) preparation of supported metallocene catalyst
Under nitrogen protection, above-mentioned 3.19 grams of the alkylaluminoxane/silica-gel carrier prepared is added to glass reactor
In, add 32 milliliters of toluene and slurries are made, the solution for being dissolved in 0.140 gram of BMCP in 16 milliliters of toluene is added drop-wise to reactor
In, react 30 minutes at 30 DEG C, then washed with toluene, be dried in vacuo, obtain supported metallocene catalyst D, its main member
The content of element is as shown in table 1.
Test case 1~4
High pressure ethylene polymerization is tested
In 1 liter of stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 500 milliliters oneself
The hexane solution of alkane and 1 milliliter of 1 mol/L triethyl aluminum, then it is separately added into above-described embodiment and the obtained load of comparative example
30 milligrams of metallocene catalyst A-D, is warming up to 70 DEG C, and pressure is risen to and maintains 1.0MPa, reacts 1 hour.Polymerization is anti-
After should terminating, cooling, polyethylene particle powder is collected, is weighed.Polymerization activity and the polymer performance such as institute of table 2 in the experiment
Show.
Table 1
Table 2
Embodiment 1-3 is understood compared with the result of comparative example 1, MnCl2Addition can improve metallocene catalysis
The polymerization activity of agent, moreover it is possible to which the performance such as the bulk density of basic guarantee polymer and molecular weight is basically unchanged；In addition, by embodiment
1-3 understand, in catalyst the raising of Mn contents can further improve the polymerization activity of alkene.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.In addition, it can also enter between a variety of embodiments of the present invention
Row any combination, as long as it without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of modified silica gel carrier, it is characterised in that the modified silica gel carrier includes the reaction product of following components：Silica gel,
Manganese chloride and alkylaluminoxane, the formula of the alkylaluminoxane are：
Wherein, R is selected from C1~C12Alkyl；A be 4~30 integer, preferably 10~30 integer.
2. modified silica gel carrier according to claim 1, wherein, the alkylaluminoxane is MAO and/or alkane
Base modified methylaluminoxane.
A kind of 3. method for preparing the modified silica gel carrier of claim 1 or 2, it is characterised in that this method includes：
1) in the presence of the first solvent, manganese chloride is made to be reacted with silica gel, so as to which manganese chloride/silica-gel carrier be made；
2) in the presence of the second solvent, the manganese chloride/silica gel is made to be reacted with alkylaluminoxane.
4. the method according to claim 11, wherein, in step 1), on the basis of the gross weight of manganese chloride and silica gel, chlorination
The dosage of manganese is 0.1~60 weight %；
In step 2), on the basis of the gross weight of the manganese chloride/silica-gel carrier and alkylaluminoxane, the dosage of alkylaluminoxane
For 1~50 weight %.
5. according to the method for claim 3, wherein, in step 1), first solvent is selected from tetrahydrofuran, ethanol, first
At least one of alcohol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol, ethylene glycol and glycerine, preferably tetrahydrofuran；
In step 2), second solvent is selected from least one of toluene, benzene, dimethylbenzene, hexane, heptane and hexamethylene, excellent
Elect toluene as.
6. according to the method for claim 3, wherein, the reaction condition of step 1) includes：Temperature is 50~100 DEG C, the time
For 0.5~4 hour；
The reaction condition of step 2) includes：Temperature is 30~80 DEG C, preferably 40~60 DEG C；Time is 3~6 hours.
7. a kind of supported metallocene catalyst, it is characterised in that the supported metallocene catalyst includes claim 1 or 2
Described modified silica gel carrier and the metallocenes being supported on carrier, the precursor of the metallocenes is shown in formula 1
Metallocene complex,
Cp* 2(Z)MXnFormula 1,
Wherein, Cp*For substituted or unsubstituted cyclopentadienyl group, indenyl or fluorenyl, its substituent is selected from C1~C20Alkyl, C1
~C20Alkoxy, C1~C20Silylation, C1~C20Aralkoxy, hydroxyl or halogen；
Z is a kind of connection unit for coupling two luxuriant rings, if the metallocene complex for non-bridging shown in formula 1, Z are not represented
Any element；If it is selected from SiR shown in formula 1 for bridging type metallocene complex, Z* 2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、
CR*=CR*、CR* 2SiR* 2、GeR* 2、BR*Or BR* 2, R therein*It is not more than 20 following groups selected from hydrogen or carbon number：Alkane
Base, aryl, silicyl, haloalkyl, halogenated aryl, aralkyl, alkaryl, haloaralkyl and haloalkylaryl；
M is the transition metal of the 4th race or the 5th race in the periodic table of elements, and n is the integer for meeting M valence states；
N X is identical or different, each is selected from hydrogen, halogen, alkyl, substituted hydrocarbon radical, oxyl, aromatic hydrocarbons epoxide, acid group or amido；
In the supported metallocene catalyst, central metal M content is 0.01~5 weight %, preferably 0.05~2 weight
Measure %.
8. supported metallocene catalyst according to claim 7, wherein, if matching somebody with somebody for bridging type metallocene shown in formula 1
Compound, then Z be selected from SiR*2、CR*2、SiR*2SiR*2、CR*2CR*2, CR*=CR* or CR*2SiR*2, R* therein be selected from hydrogen or
Person's carbon number is less than 20 alkyl or aryl；
M is selected from titanium, zirconium or hafnium；
X is selected from hydrogen, halogen, alkyl, pi-allyl, cyclopentadienyl group, alkoxy or aromatic hydrocarbons epoxide, is preferably selected from chlorine, bromine, iodine, first
Epoxide, ethyoxyl, isopropoxy, isobutoxy, butoxy, phenoxy group, oxy-o-cresyl, a toloxyl, to toloxyl
Or naphthoxy；
N=2.
A kind of 9. method for preparing the supported metallocene catalyst described in claim 7 or 8, it is characterised in that this method bag
Include：In the presence of the 3rd solvent, the modified silica gel carrier is set to be reacted with the metallocene complex shown in formula 1；
It is preferred that the condition of the reaction includes：Temperature is 0~40 DEG C, and the time is 1~120 minute；
3rd solvent is preferably at least one of toluene, benzene, dimethylbenzene, hexane, heptane and hexamethylene, more preferably toluene
And/or hexane.
10. a kind of metallocene catalyst system for olefinic polymerization, it is characterised in that the metallocene catalyst system includes master
Catalyst and co-catalyst, the major catalyst are the supported metallocene catalyst described in claim 7 or 8, and described help is urged
Agent is preferably alkyl aluminum；
In the metallocene catalyst system, the mol ratio of the Al and central metal M in alkyl aluminum is preferably 0.01：1~
50000：1；More preferably 1：1~5000：1.
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