CN109320637A - A kind of ethylene polymerization carried metallocene catalyst and preparation method thereof - Google Patents
A kind of ethylene polymerization carried metallocene catalyst and preparation method thereof Download PDFInfo
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- CN109320637A CN109320637A CN201811018261.0A CN201811018261A CN109320637A CN 109320637 A CN109320637 A CN 109320637A CN 201811018261 A CN201811018261 A CN 201811018261A CN 109320637 A CN109320637 A CN 109320637A
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Abstract
The invention discloses a kind of ethylene polymerization carried metallocene catalysts and preparation method thereof, the catalyst includes: polymer microballoon, the metallocene compound and alkyl aluminum that are supported on polymer microballoon, zirconium loading content is 0.1 ~ 5wt% in catalyst, aluminium content is 10 ~ 36wt%, and carrier is 59 ~ 89.9wt%；The arene solution of metallocene compound is added in polymer microballoon when load, using supercritical carbon dioxide swollen polymer microballoon, alkylaluminoxane is added later and carries out activation of catalyst, last drying and moulding.Metallocene catalyst particle shape prepared by the present invention is good, polymerization activity is high, and kinetics of polymerization reaction is steady, and polymer molecular weight is controllable.
Description
Technical field
The invention belongs to carried metallocene catalyst fields, and in particular to a kind of ethylene polymerization loaded metallocene is urged
Agent and use supercritical carbon dioxide treatment porous polymer microsphere, for synthesizing the preparation of carried metallocene catalyst
Method.
Background technique
Metallocene PE (mPE) be the earliest metallocene-polyolefin for realizing industrialized production and current production rate it is maximum,
The metallocene polymers that functionization progress is most fast, the development company that goes in for the study is most.Currently, there are about more than ten large-scale stones in the whole world
Change company can be with industrialized production metallocene product, and China only has Daqing petrochemical company, Dushanzi petrochemical industry, Qilu Petrochemical etc. less
Number manufacture of polyolefins producer produced metallocene PE product.Year ends 2011, the grand celebration of China Petroleum Petroleum Chemical Engineering Institute
Work research center has carried out 14 days by a definite date metallocene PEs on its 50kg/hr gas-phase method total density polyvinyl pilot-plant
The work of Semi-plant scale long-term operation, device are continuously run 276 hours, indicate domestic state-of-the-art polyethylene pilot-plant tool
For the strength of metallocene catalyst long-term operation, technological service preferably can be provided for factory.
The production of metallocene PE be unable to do without metallocene catalyst.The research of domestic metallocene catalyst and polyolefin with
Exploitation starts from the beginning of the nineties in last century, and the R&D institution and universities and colleges that the work is added in recent years gradually increase, wherein in mainly having
Petroleum Petroleum Chemical Engineering Institute of state, Research Institute of Petro-Chemical Engineering, chemistry institute of the Chinese Academy of Sciences, Beijing Chemical Research Institute, Zhejiang University
Deng.In metallocene catalyst exploitation beginning, be to realize olefinic polymerization using homogeneous catalyst system, catalyzed by homogeneous metallocene catalyst exists
While possessing many advantages, there is also some shortcomings, inactivate as bimolecular association easily occurs for the activated centre of catalyst, because
This must be added to a large amount of MAO and keeps apart activated centre, cause the Al/Zr molar ratio of catalyzed by homogeneous metallocene catalyst requirement very
It is high；Meanwhile catalyzed by homogeneous metallocene catalyst be used for olefinic polymerization when, prepared polymer morphology is bad, generates in polymerization process
Polymer seriously glue kettle, constrain the industrial application of metallocene catalyst to a certain extent.
To overcome the above disadvantages, it is attempted to load to metallocene catalyst on carrier, to obtain supported cyclopentadienyl
Metallic catalyst.After metallocene catalyst loads on carrier, activated centre cannot be close to each other, because without bimolecular occurs
Inactivation, can substantially reduce the dosage of MAO, catalyst can be made to keep original substantially under conditions of lower Al/Zr molar ratio
Activity.And the macroscopic form of polyolefin catalyst carrier particle is in the course of the polymerization process on the one hand as the mould of polymer particle
On the other hand plate is affected to the activity of catalyst and catalytic performance.It can prevent bimolecular from losing using loaded catalyst
Elimination reaction that is living and reducing β-H, obtains high molecular weight and dystectic polymer, the polymer thus prepared be expected to have compared with
Good form and biggish heap density.In addition, catalyst activity can be made uniformly to discharge after catalyst is supported, and make polymerization reaction
It is easy to control, slurry and gas-phase polymerization can be carried out, it is easier to be used on existing olefinic polymerization commercial plant.
By metallocene catalyst load to the process on carrier it is usual there are four types of: (1) metallocene complex, co-catalysis
Agent (usually methylaluminoxane) is added simultaneously, and after reacting a period of time, carrier, the metallocene complex in whipping process is added
It is loaded on carrier simultaneously with co-catalyst；(2) metallocene complex and carrier function for a period of time, after loading on carrier,
Co-catalyst is added to be loaded；(3) after co-catalyst and carrier function load on carrier for a period of time, luxuriant gold is added
Metal complex is loaded；(4) make in two reaction kettles metallocene complex and co-catalyst respectively with one section of carrier function
After time, then the two is mixed, both makes to load to together.
The current existing a large amount of research of the load in relation to metallocene catalyst, such as Ge Tengjie is at " synthetic resin and plastics "
1st phase in 2018, " progress of Methods for Immobilization of Metallocene Catalysts ", neat America etc. disclosed by 76-80 pages " chemistry into
Exhibition " the 5th phase in 2014, " metallocene catalyst supported ", model will disclosed by 737-748 page by force etc. " synthetic resin and
Plastics " the 1st phase in 2015, disclosed by page 76~79 " research of the supported mechanism of metallocene catalyst for olefine polymerization into
Exhibition ", Fernando Silveira etc. is in " Macromolecular Reaction Engineering " the 4th phase 139 in 2009
" The Role of the Support in the Performance of Grafted disclosed by page~147
Metallocene Catalysts " and Long Wu etc. are in " Handbook of Transition Metal
Polymerization Catalysts, Second Edition " it 2018 years publishes, " Product disclosed by page 369~400
Morphology in Olefin Polymerization with Polymer-Supported Metallocene
Catalysts " etc. contrasts to this detailed summary.
Load metallocene catalyst is mainly made of metallocene compound, aikyiaiurnirsoxan beta and carrier.Metallocene compound is by matching
Cyclopentadiene and its derivative, bridge chain part, central transition can belong to such as Zr, Hf, Ti and be connected in other on metal on the body of position
Substituent group is formed.Aikyiaiurnirsoxan beta is mainly used as co-catalyst, and price is high, very big to the performance and cost impact of catalyst.It is negative
In the metallocene catalyst of load type, aikyiaiurnirsoxan beta and metallocene compound will be supported on above carrier securely, otherwise polymerize
Cheng Zhonghui falls off and leads to that polymer morphology is poor, fine polymer powder is more, even viscous kettle.In the prior art, alkylaluminoxane and cyclopentadienyl gold
It is not high to belong to load capacity of the compound on carrier, this aspect causes alkylaluminoxane loss in loading process larger, raising
The cost of supported catalyst, on the other hand also reduces the utilization rate of alkylaluminoxane and metallocene compound, in addition in this way
Catalyst catalytic activity it is lower.
Most common catalyst carrier is divided into inorganic carrier and organic polymer carrier two major classes.Commonly inorganic carrier is
Aluminium oxide (Al2O3), magnesium chloride (MgCl2), silica gel (SiO2) etc. macropores hold and specific surface area inorganic matter, wherein with SiO2Such as
955 silica gel of Grace be carrier report most study, such as CN1095474C, CN1049439C, CN1157419C,
US4808561, US5026797, US5763543, US5661098 are disclosed with SiO2It is catalyzed for the loaded metallocene of carrier
Agent.
CN 105622796 discloses a kind of carried metallocene catalyst and preparation method thereof.The content of Al in catalyst
For 5~20wt%；Levels of transition metals is 0.01~0.3wt%.Preparation method mainly includes two steps, and step A loads alkyl aluminum
Oxygen alkane: silica-gel carrier is added in alkylalumoxane solution, and stirring is washed out, filters, dries, and obtaining load has alkyl
The carrier of aikyiaiurnirsoxan beta；Load metallocene compound: the carrier that load has alkylaluminoxane is added to metallocene chemical combination by step B
In object slurries, stirring is washed out, filters, dries, and carried metallocene catalyst is finally made.This method is used carrier
The mode being added in alkylalumoxane solution, eliminates the step of suspension is made in carrier, reduces solvent usage amount, together
When can by control vector be added speed, reduce the possibility of vector aggregation, improve the form of catalyst.But party's legal system
Standby catalyst is mainly used for being catalyzed propylene polymerization.The thermal discharge of vinyl polymerization is high, is the 2 times or more of propylene polymerization thermal discharge,
Cause catalyst for polymerization of propylene to cannot be used for catalytic polymerization ethylene and obtains the polyethylene product of high quality.
CN 105330766 discloses a kind of loaded metallocene catalysis for being supported on spherical montmorillonite mesoporous composite material
Agent and preparation method thereof.The carrier be containing montmorillonite, the meso-porous molecular sieve material with one-dimensional straight channels structure and
Meso-porous molecular sieve material with hexagonal hole road structure, the average grain diameter of carrier are 30-60 microns, specific surface area 150-600
Meters squared per gram, pore volume are 0.5-1.5 mls/g, and aperture is in tri-modal distribution.This method, which mainly passes through, changes catalyst load
The method of body improves the activity of carried metallocene catalyst.But the carrier that this method uses is global molecular sieve, the carrier
Preparation process is complicated, is unfavorable for the industrialized production and application of catalyst.
Due to SiO2、MgCl2、Al2O3Strong electrostatic interaction between equal inorganic carriers and metallocene, on the one hand makes
The catalytic performance for obtaining metallocene catalyst changes；On the other hand polyolefin obtained by these inorganic carrier catalysts is residual
Organic/inorganic substance；Importantly, these hard carrier particle fragments will bring undesirable polymer morphology and purity.It compares
Under, organic polymer supported metallocene catalyst provides a chemical environment similar with homogeneous catalyst.Relative to
The surface of inorganic carrier rigidity, organic carrier and final polymer then seem more there is " affinity ".And organic carrier preparation is more
It is easy, cost is lower, is easier to carry out functionalization to meet specific catalysis and require.The catalysis of organic carrier metallocene catalyst
Polyolefin remnants inorganic impurity it is few, polymer morphology is easier to control, and can satisfy as cable sheathing etc. needs insulating properties
Requirement in high field, therefore organic polymer carrier has progressed into the sight of people.Most common organic polymer carries
Body is expanded polystyrene microballoon, polyethylene powders, polysiloxanes etc..
CN 1624005 discloses a kind of preparation method of the Solid homogenous metallocene catalyst of loaded by polystyrene.The party
Method is by introducing cyclopentadienyl group on linear polystyrene chain, in the presence of metallocene, using between cyclopentadienyl group
Diels-Alder cross-linking reaction loads to metallocene in the polystyrene network of crosslinking.Outside catalyst with this method preparation
Seeing is solid-state, and solvent, which can enter polystyrene network metallocene catalyst is under homogeneous environment, in polymerization process is catalyzed
Olefinic polymerization, the cross-linked network of carrier can be unlocked gradually in the course of the polymerization process, to make the work for being wrapped in carrier inside originally
Property center gradually discharges, and is conducive to the industrial application of catalyst.But the shortcomings that this method is primarily present is: the function unity of carrier
Structure is indefinite, and functional group's being unevenly distributed in the carrier, the catalyst active center after leading to load is in polystyrene microsphere
Be unevenly distributed, the morphology of production is not able to satisfy industrialization demand.
CN 1257875 discloses a kind of preparation method of the metallocene catalyst of producing high-molecular, using with alkene function
The metallocene catalyst of group is copolymerized with styrene, has synthesized a kind of cyclopentadienyl of self-supported producing high-molecular with special construction
Metallic catalyst.But metallocene compound needed for this method needs special structure, to the performance of polymerizate can generate compared with
It is big to influence, it is only used for the polyethylene of production specific structure.In addition, the catalyst active center of this method preparation has focused largely on
Carrier surface, catalyst active center are unevenly distributed, cause in the course of the polymerization process carrier be unevenly crushed, the polymer of production
Particle shape is poor, and fine powder content is high, is unfavorable for the large-scale industrial application of catalyst.
Supercritical fluid is the fluid more than critical-temperature and critical pressure point.In critical-temperature, pressure, no matter
Pressure has much, fluid cannot all liquefy, in gas-liquid regardless of state, but the density of fluid increases with the increase of pressure
Greatly.Supercritical fluid have with density similar in liquid, and viscosity similar in gas, and its diffusion coefficient is bigger than liquid close
100 times, the advantage with the incomparable special hereditary property of other fluids.Supercritical fluid quick expansion (Rapid
Expansion of Supercritical Solution), abbreviation RESS preparation.The method is exactly to utilize the spy of supercritical fluid
Point makes the supercritical fluid containing volatile materials by specific method, in a very short period of time rapid expanding even vacuum,
Due to the variation of pressure, cause fluid solvent power that huge variation occurs, and form very big degree of supersaturation, substance sinks quickly
Analysis.So-called specific method, which refers to, to be expanded through nozzle, capillary etc. to carry out, small-sized due to nozzle, so that it may
Obtain required ultrafine particle.According to classical nucleation theory, degree of supersaturation is bigger, and the particle of formation is thinner.Ye Chunlin etc.
The catalyst of carried metallocene catalyst subparticle is prepared using supercritical fluid technique, is polyolefin catalyst particle
Preparation new method is provided, development to the petrochemical industry in China and promote the application of polyolefin catalyst that there is important meaning
Justice.But the fluid that supercritical fluid quick expansion method uses is supercritical propane, and propane is inflammable and explosive, carrier molding needs are specific
The equipment such as nozzle, particle shape and the particle diameter distribution regulation of catalyst are unsatisfactory, are unfavorable for the form duplication of polymerizate.
Summary of the invention
The first purpose of this invention is to provide a kind of ethylene polymerization carried metallocene catalyst, existing to solve
Catalyst granules form and particle diameter distribution regulation are undesirable, and the morphology of production is poor, is not able to satisfy industrialization demand
Technical problem.
To achieve the above object, the present invention is achieved by the following technical scheme:
A kind of ethylene polymerization carried metallocene catalyst, comprising: carrier, the metallocene compound being supported on carrier
And co-catalyst, the carrier are polymer microballoon, the co-catalyst is alkyl aluminum, and zirconium loading content is 0.1 in catalyst
~5wt%, aluminium content are 10~36wt%, and carrier is 59~89.9wt%；By the arene solution of metallocene compound when load
It is added in polymer microballoon, using supercritical carbon dioxide swollen polymer microballoon, alkylaluminoxane is added later and is urged
Agent activation, last drying and moulding.
As a preference of the present invention, the polymer microballoon is styrene, divinylbenzene, acrylonitrile or acrylamide etc.
The homopolymer and copolymer microsphere of monomer.
As a preference of the present invention, the metallocene compound has structure shown in following formula,
Wherein, R1、R2、R3、R4、R5、R1’、R2’、R3’、R4' and R5' it is each independently hydrogen or the alkyl of C1-C5, M are
Metal zirconium, X are halogen.
As a preference of the present invention, the alkyl aluminum is trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl
One or both of aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride or methylaluminoxane and two or more mixtures.
Second object of the present invention is to provide a kind of preparation method of ethylene polymerization carried metallocene catalyst,
This method utilizes supercritical carbon dioxide treatment porous polymer microsphere during the preparation process, then by metallocene compound and alkane
Base aikyiaiurnirsoxan beta is supported on polymer microballoon, effectively solves the catalyst granules form and particle diameter distribution regulation of existing method preparation
Undesirable, the morphology of production is poor, is not able to satisfy the technical problem of industrialization demand.
To achieve the above object, the present invention is achieved by the following technical scheme:
A kind of preparation method of ethylene polymerization carried metallocene catalyst, specifically comprises the following steps:
1. supercritical carbon dioxide assists load: the arene solution of metallocene compound being added into polymer support, sets
In high-pressure reactor, it is passed through carbon dioxide, heating is forced into carbon dioxide and reaches supercriticality, utilizes overcritical titanium dioxide
Carbon swollen polymer carrier；
2. activation of catalyst: slow release after the completion of swelling is passed through nitrogen and replaces and crosses backward through swelling treatment for 5~10 times
A certain proportion of co-catalyst is added in catalyst intermediate and carries out activation of catalyst；
3. drying and moulding: hexane solution is added into reactor, washs 5~10 times repeatedly, by step 1. and 2. in solvent
Removing, is dried to obtain the carried metallocene catalyst of high activity.
As a preference of the present invention, 1. the arene solution is one or both of benzene, toluene or dimethylbenzene to step
And two or more mixture.
As present invention further optimization, the step 1. swelling infiltration in the supercritical carbon dioxide swelling process
Temperature is 31-60 DEG C, swelling pressure 7.5-12MPa, and swelling time is 0.5-10 hours.
As present invention further optimization, step 2. the co-catalyst be alkyl aluminum arene solution；Described
Priming reaction is to stir at 10~100 DEG C, is flowed back 1~4 hour.
As it is of the invention still more preferably, 2. 3. the described drying and moulding operation is equal for the activation and step for step
It should be carried out under the conditions of anhydrous and oxygen-free.
As it is of the invention still more preferably, mole of step 2. alkyl aluminum additional amount and metallocene compound additional amount
Than being 20~1000.
The advantages and positive effects of the present invention:
(1) present invention utilizes supercritical carbon dioxide (CO in metallocene catalyst loading process2) porous to carrier poly-
Close object microballoon swelling action so that metallocene compound and aluminium alkoxide compound be dispersed in polymer microballoon duct and
On surface, so that load rear catalyst activated centre is also evenly dispersed, obtained catalyst granules form is good, polymerization activity
Height, kinetics of polymerization reaction is steady, is easy to polymerization technique control；And resulting polymers particle shape is good, form is controllable, molecular weight
Adjustable, fine powder content is low, and bulk density is high, and mobility is preferable, is conducive to commercial plant large-scale application, can satisfy industrialization
Demand.
(2) present invention uses supercritical CO 2 to prepare carried metallocene catalyst as supercritical fluid swelling support methods,
Have the advantages that it is following uniqueness: 1. since supercritical CO 2 surface tension is extremely low, no matter the wetting of organic high molecular polymer carrier
How poor property is, nor affects on supercritical CO 2 to its swelling and metallocene compound to its scattering and permeating；2. supercritical CO 2 pair
The Swelling Capacity of carrier polymer changes with temperature and pressure, it is easy to control metallocene compound in supercritical CO 2
The degree that solubility and porous polymer microsphere are swollen, and then control metallocene compound and enter the amount in carrier, to make
The standby catalyst precursor for meeting different requirements.Exist 3. the plasticization of supercritical CO 2 can increase substantially metallocene compound
The diffusion velocity being swollen in post-consumer polymer carrier can also improve absorption dissolution journey of the metallocene compound in polymer support
Degree.4. can make metallocene compound that gradient distribution be presented in polymer support by control swelling time, will not influence life
At blend form.5. supercritical CO 2 is a kind of applied widely, environment amenable reaction medium, do not change cyclopentadienyl
Original property of metallic compound and carrier.6. slow pressure release after the completion of swelling, the polymer microballoon being swollen can still keep former
Some pore structures and performance are conducive to the generation of next step load-reaction and being uniformly distributed for catalyst active center.
Detailed description of the invention
Fig. 1 is the electron microscopic picture for the catalyst that embodiment 1 prepares.
Specific embodiment
It is detailed below by embodiment and comparative example to make those skilled in the art understand technical solution of the present invention and advantage
Describe bright technical solution of the present invention in detail, but and for limiting the scope of the invention.
Ethylene polymerization carried metallocene catalyst provided by the invention, comprising: carrier, the cyclopentadienyl gold being supported on carrier
Belong to compound and co-catalyst, zirconium loading content is 0.1~5wt% in catalyst, and aluminium content is 10~36wt%, carrier 59
~89.9wt%；The carrier is polymer microballoon, and the co-catalyst is alkyl aluminum, by the virtue of metallocene compound when load
Hydrocarbon solution is added in polymer microballoon, and using supercritical carbon dioxide swollen polymer microballoon, alkylaluminoxane is added later
Carry out activation of catalyst, last drying and moulding；The polymer microballoon is styrene, divinylbenzene, acrylonitrile and acryloyl
The homopolymer and copolymer microsphere of the monomers such as amine；
The metallocene compound has structure shown in following formula,
Wherein, R1、R2、R3、R4、R5、R1’、R2’、R3’、R4' and R5' it is each independently hydrogen or the alkyl of C1-C5, M are
Metal zirconium, X are halogen；
The alkyl aluminum is trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, a chlorine
One or both of diethyl aluminum or methylaluminoxane and two or more mixtures.
The present invention also provides a kind of preparation method of ethylene polymerization carried metallocene catalyst, prepared by this method
Supercritical carbon dioxide treatment porous polymer microsphere is utilized in journey, is then supported on metallocene compound and alkylaluminoxane
On polymer microballoon, realization is specifically adopted the following technical scheme that:
A kind of preparation method of ethylene polymerization carried metallocene catalyst, specifically comprises the following steps:
1. supercritical carbon dioxide assists load: the arene solution of metallocene compound being added into polymer support, sets
In high-pressure reactor, it is passed through carbon dioxide, heating is forced into carbon dioxide and reaches supercriticality, utilizes overcritical titanium dioxide
Carbon swollen polymer carrier；
2. activation of catalyst: slow release after the completion of swelling is passed through nitrogen and replaces and crosses backward through swelling treatment for 5~10 times
A certain proportion of co-catalyst is added in catalyst intermediate and carries out activation of catalyst；
3. drying and moulding: hexane solution is added into reactor, washs 5~10 times repeatedly, by step 1. and 2. in solvent
Removing, is dried to obtain the carried metallocene catalyst of high activity.
To make those skilled in the art more understand the preparation method of carried metallocene catalyst of the present invention, below with reference to implementation
The present invention is described further for example:
Embodiment 1
The preparation step of ethylene polymerization carried metallocene catalyst are as follows:
1. supercritical carbon dioxide assists load: to 10g polymer support (polystyrene microsphere, the micro-nano section of Suzhou intelligence
Skill Co., Ltd production, 20 μm of partial size) in be added 0.1mol/l (writing a Chinese character in simplified form into 0.1M, similarly hereinafter) bis cyclopentadienyl zirconium dichloride toluene solution
4ml is placed in high-pressure reactor, is passed through carbon dioxide, and swelling infiltration temperature is warming up to 40 DEG C, and swelling pressure is forced into
10.0MPa is utilized supercritical carbon dioxide swollen polymer carrier 4 hours so that carbon dioxide reaches supercriticality；
2. activation of catalyst: slow release after the completion of swelling is cooled to room temperature, be passed through into reactor nitrogen displacement 5~
After 10 times, it is living to be warming up to 60 DEG C of reflux, 1~4 hour progress catalyst by the 1M methylaluminoxane toluene solution 200ml added
Change；
3. drying and moulding: hexane solution 500ml is added into reactor, washs 5~10 times repeatedly, by step 1. and 2. in
Solvent removal is dried to obtain the carried metallocene catalyst of high activity.
The catalyst electron microscopic picture prepared is shown in Fig. 1；Chromium, magnesium, the content of aluminium and polymerization evaluation knot in catalytic component
Fruit is listed in table 1.
Slurry polymerization evaluation
2L reaction kettle is heated to 80 DEG C or so, 1h is vacuumized, is replaced with drying nitrogen, then blows row with hydrogen.Xiang Ju
It closes and 1L hexane is added in kettle, while the triethyl aluminum of 1ml (1M), 10ml hexene -1 and above-mentioned catalyst 10mg is added, then rise
Hydrogen 0.1MPa is added to 75 DEG C in temperature, and ethylene, which is added, after adding hydrogen makes pressure in kettle reach 1.03MPa, after being warming up to 80 DEG C,
After reaction 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
Embodiment 2
In addition to bis cyclopentadienyl zirconium dichloride to be changed into bis- (ethyl cyclopentadiene) zirconium dichlorides, the preparation method of catalytic component is same
Embodiment 1.
Embodiment 3
In addition to bis cyclopentadienyl zirconium dichloride to be changed into bis- (n-butyl cyclopentadienyl) zirconium dichlorides, the preparation side of catalytic component
Method is the same as embodiment 1.
Embodiment 4
In addition to bis cyclopentadienyl zirconium dichloride to be changed into bis- (1- butyl -3- methyl cyclopentadienyl) zirconium dichlorides, catalytic component
The preparation method is the same as that of Example 1.
Embodiment 5
In addition to bis cyclopentadienyl zirconium dichloride to be changed into bis- (pentamethylcyclopentadiene) zirconium dichlorides, the preparation method of catalytic component
With embodiment 1.
Embodiment 6
In addition to supercritical carbon dioxide being assisted swelling infiltration temperature when loading be reduced to 35 DEG C by 40 DEG C, catalyst group
Point the preparation method is the same as that of Example 1.
Embodiment 7
In addition to supercritical carbon dioxide being assisted swelling infiltration temperature when loading be reduced to 31 DEG C by 40 DEG C, catalyst group
Point the preparation method is the same as that of Example 1.
Embodiment 8
In addition to supercritical carbon dioxide being assisted swelling infiltration temperature when loading be upgraded to 50 DEG C by 40 DEG C, catalyst group
Point the preparation method is the same as that of Example 1.
Embodiment 9
In addition to supercritical carbon dioxide being assisted swelling infiltration temperature when loading be upgraded to 60 DEG C by 40 DEG C, catalyst group
Point the preparation method is the same as that of Example 1.
Embodiment 10
In addition to assisting swelling pressure when loading to be reduced to 9.0MPa by 10.0MPa supercritical carbon dioxide, catalyst
The preparation method is the same as that of Example 1 for component.
Embodiment 11
In addition to assisting swelling pressure when loading to be reduced to 7.5MPa by 10.0MPa supercritical carbon dioxide, catalyst
The preparation method is the same as that of Example 1 for component.
Embodiment 12
In addition to assisting swelling pressure when loading to be upgraded to 11.0MPa by 10.0MPa supercritical carbon dioxide, catalyst
The preparation method is the same as that of Example 1 for component.
Embodiment 13
In addition to assisting swelling pressure when loading to be upgraded to 12.0MPa by 10.0MPa supercritical carbon dioxide, catalyst
The preparation method is the same as that of Example 1 for component.
Embodiment 14
In addition to assisting swelling time when loading to be upgraded to 6.0 hours by 4.0 hours supercritical carbon dioxide, catalyst
The preparation method is the same as that of Example 1 for component.
Embodiment 15
In addition to assisting swelling time when loading to be upgraded to 8.0 hours by 4.0 hours supercritical carbon dioxide, catalyst
The preparation method is the same as that of Example 1 for component.
Embodiment 16
In addition to assisting swelling time when loading to be reduced to 2.0 hours by 4.0 hours supercritical carbon dioxide, catalyst
The preparation method is the same as that of Example 1 for component.
Embodiment 17
In addition to the bis cyclopentadienyl zirconium dichloride toluene solution of 0.1M is changed to 8ml from 4ml, the preparation method of catalytic component is the same as implementation
Example 1.
Embodiment 18
In addition to the bis cyclopentadienyl zirconium dichloride toluene solution of 0.1M is changed to 12ml from 4ml, the preparation method of catalytic component is the same as real
Apply example 1.
Embodiment 19
In addition to the bis cyclopentadienyl zirconium dichloride toluene solution of 0.1M is changed to 2ml from 4ml, the preparation method of catalytic component is the same as implementation
Example 1.
Embodiment 20
In addition to the bis cyclopentadienyl zirconium dichloride toluene solution of 0.1M is changed to 1ml from 4ml, the preparation method of catalytic component is the same as implementation
Example 1.
Embodiment 21
In addition to the additional amount of 1M methylaluminoxane toluene solution is changed to 300ml from 200ml, the preparation side of catalytic component
Method is the same as embodiment 1.
Embodiment 22
In addition to the additional amount of 1M methylaluminoxane toluene solution is changed to 100ml from 200ml, the preparation side of catalytic component
Method is the same as embodiment 1.
Embodiment 23
In addition to the methylaluminoxane toluene solution of 1M changes the triethyl aluminum toluene solution of 1M into, the preparation of catalytic component
Method is the same as embodiment 1.
Embodiment 24
In addition to the methylaluminoxane toluene solution of 1M changes the triisobutylaluminum toluene solution of 1M into, the system of catalytic component
Preparation Method is the same as embodiment 1.
Comparative example 1
The preparation step of catalyst are as follows:
1. metallocene compound loads: to 10g polymer support, (polystyrene microsphere, the micro-nano science and technology of Suzhou intelligence are limited
Company production, 20 μm of partial size) in be added 0.1mol/l (writing a Chinese character in simplified form into 0.1M, similarly hereinafter) bis cyclopentadienyl zirconium dichloride toluene solution 4ml, be placed in
In reaction kettle, then 40ml tetrahydrofuran is added into reaction kettle and makees solvent, dip loading 4 hours under the conditions of nitrogen protection；
2. activation of catalyst: evaporating solvent after the completion of load, be cooled to room temperature, be passed through after dry completion into reactor
Nitrogen replace 5~10 times after, the 1M methylaluminoxane toluene solution 200ml added, be warming up to 60 DEG C reflux 1~4 hour into
Row activation of catalyst；
3. drying and moulding: hexane solution 500ml is added into reactor, washs 5~10 times repeatedly, by step 1. and 2. in
Solvent removal is dried to obtain the carried metallocene catalyst of high activity.Chromium in catalytic component, magnesium, the content of aluminium and poly-
It closes evaluation result and is listed in table 1.
Measuring method in relation to the composition of catalyst made from each embodiment is as follows:
Zr and Al content are measured using ICP method in catalyst；
Polymerization activity calculates as follows:
Wpoly=Q/wcat, gPolyg-1Cat, wherein Wpoly is polymerization catalyst activity, and Q is in polymerization reaction 2
The yield (g) of hour interpolymer, wcat is catalyst amount.
Test condition in relation to polymer is as follows:
Melt index MI --- ASTM D1238-99.
1 catalyst of table composition and polymerization evaluation result
Claims (10)
1. a kind of ethylene polymerization carried metallocene catalyst, comprising: carrier, the metallocene compound being supported on carrier and
Co-catalyst, it is characterised in that: the carrier is polymer microballoon, and the co-catalyst is alkyl aluminum, zirconium load in catalyst
Content is 0.1~5wt%, and aluminium content is 10~36wt%, and carrier is 59~89.9wt%；By metallocene compound when load
Arene solution is added in polymer microballoon, and using supercritical carbon dioxide swollen polymer microballoon, alkyl alumina is added later
Alkane carries out activation of catalyst, last drying and moulding.
2. a kind of ethylene polymerization carried metallocene catalyst according to claim 1, it is characterised in that: described is poly-
Conjunction object microballoon is the homopolymer and copolymer microsphere of styrene, divinylbenzene, acrylonitrile or acrylamide monomer.
3. a kind of ethylene polymerization carried metallocene catalyst according to claim 1, it is characterised in that: the cyclopentadienyl
Metallic compound has structure shown in following formula,
Wherein, R1、R2、R3、R4、R5、R1’、R2’、R3’、R4' and R5' it is each independently hydrogen or the alkyl of C1-C5, M is metal
Zirconium, X are halogen.
4. a kind of ethylene polymerization carried metallocene catalyst according to claim 1, it is characterised in that: the alkane
Base aluminium is trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride or aluminium methyl
One or both of oxygen alkane and two or more mixtures.
5. a kind of preparation method of ethylene polymerization carried metallocene catalyst, it is characterised in that: specifically comprise the following steps:
1. supercritical carbon dioxide assists load: the arene solution of metallocene compound being added into polymer support, is placed in height
It presses in reactor, is passed through carbon dioxide, heating is forced into carbon dioxide and reaches supercriticality, molten using supercritical carbon dioxide
Swollen polymer support；
2. activation of catalyst: slow release after the completion of swelling is passed through nitrogen and replaces 5~10 catalysis crossed backward through swelling treatment
A certain proportion of co-catalyst is added in agent intermediate and carries out activation of catalyst；
3. drying and moulding: hexane solution is added into reactor, washs 5~10 times repeatedly, by step 1. and 2. in solvent removal,
It is dried to obtain the carried metallocene catalyst of high activity.
6. a kind of preparation method of ethylene polymerization carried metallocene catalyst according to claim 5, feature exist
In: step, 1. the arene solution is one or both of benzene, toluene or dimethylbenzene and two or more mixtures.
7. a kind of preparation method of ethylene polymerization carried metallocene catalyst according to claim 5, feature exist
Swelling infiltration temperature in: step 1. the supercritical carbon dioxide swelling process is 31-60 DEG C, swelling pressure 7.5-
12MPa, swelling time are 0.5-10 hours.
8. a kind of preparation method of ethylene polymerization carried metallocene catalyst according to claim 5, feature exist
In: step 2. the co-catalyst be alkyl aluminum arene solution；The priming reaction is to stir at 10~100 DEG C, is returned
Stream 1~4 hour.
9. a kind of preparation method of ethylene polymerization carried metallocene catalyst according to claim 5, feature exist
In: step, 2. 3. the drying and moulding operation should all carry out under the conditions of anhydrous and oxygen-free for the activation and step.
10. a kind of preparation method of ethylene polymerization carried metallocene catalyst according to claim 5, feature exist
In: 2. the molar ratio of alkyl aluminum additional amount and metallocene compound additional amount is 20~1000 to step.
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| CN114057912A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Drying method and preparation method for controlling particle morphology by using chromium-loaded silica gel |
| 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 |
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| CN114057912B (en) * | 2020-07-31 | 2023-06-16 | 中国石油化工股份有限公司 | Drying method and preparation method for controlling particle morphology of chromium-loaded silica gel |
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